Section 9

Energy

Utilization,

Conversion,

and

Resource Conservation

Richard C. Corey, B.S., Department Staff (Retired), Energy Systems Engtneertng Department, The MITRE Corporation, Metrek Dtvtsion; Member, American Socfety of Mechanical Engtneers and Afr Pollutton Control Association. (Solid and Gaseous Fuels, Combustion, Fuel and Energy Costs, Coal Concerston, Ftred Process Equipment, Heat Transport and Regeneration). (Section Editor) Projects Manager, Battelle Memortal Institute, Columbus Lab Richard Barrett, MS., ratortes; Member, American Society of Mechanical Engtneers, American Society of Heating, Refrtgerattng, and Atr Condttiontng Engineers; Institute of Energy (United Kingdom); Registered Professional Engineer (Ohio). (Steam Systems) Stafi Engineer, Gulf Science and Technology Company Robert C. Amero, B.S., (Rettred); Member, American Society of Mechanical Engineers, American Znstitute of Chemical Engineers, lnternattonal Association for Hydrogen Energy; Registered Professional Engfneer (Pennsylcanta). (Liquid Fuels, Combustton) Harold F. Chambers, Jr., Ph.D., Supervisory Technology Center, U.S. Department of Energy; (Coal Liquefaction) Mechanical Engineer, Pittsburgh Registered Professional Engineer Energy (Ohio).

Cmtsultant; Fellow, American Institute of Chemtcul Engineers; Ezekail 1. Clark, B.S., Member, Amertcun Chemical Society, American Assoctation for the Adcancement of Sctence; Registered Professional Engineer (Pennsylcunia). (Associate Sectton Editor; Coal G&cation) Neil H. Ceahs, B.S., Department Head, Energy Systems Engtneertng MZTRE Corporation, Metrek Dtcbfon. (Fluidfzed-Bed Combustion) Department, The

Willard E. Fraize, Sc.D., Senior Energy Systems Engineer, Energy and Resources Dtvtsion, The MITRE Corporation, Metrek Dtvtston; Member, American Society of Mechanical Engtneers, American Institute of Aeronautics and Astronautics. (Cogeneration) Yuan C. Fu, Ph.D., Project Manager, Ptttsburgh Department of Energy; Member, American Chemical lapan, Catalysts Society. (Coal Liquefaction) Energy Technology Center, U.S. Society, The Chemtcul Society of

H. A. Grabowski, B.S., Senior Engineering Consultant, C-E Enoironmental Systems, Combustion Engfneertng Inc.; Member, American Society of Mechanical Engineers, American Society for Testing and Mater&& (Steam Generators) Eugene Mezey, Ph.D., Senior Chemist, Battelle Memorial Znstttute, Columbus Labmutortes; Member, American Chemical Society, The Soctety of Sigma Xi, Zntemattonal Mtcrowave Power Institute, American Ceramic Institute; Fellow, American Association for the Adcuncement of Science. (Electric Heating) David E. Stutz, B.S., Research Scientist, Battelle Memortal Institute, Columbus ratories; Member, International Microwave Power Institute. (Electric Heating) Labo-

9-1

9-2

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

Indirect-Fired Equipment Fuel-Saving Methods for Existing Heaters. steam Generators. Some Fundamentals of Boiler Design Utility Steam Generators Industrial Boilers Factors lnfluencinn Performance Stacks and Chimneys. HEAT TRANSPORT Steam Systems Steam Characteristics. Water Constituents ................ Thermal Liquid Systems ............... Liquids and Their Proper&. ........... Process Systems ..................

FUELS
9-3

Cal. ., ., Other Solid Fuels Liquid Fuels. Liquid Petroleum Fuels Nonpetroleum Liquid Fuels Gaseous Fuels NaturalGes : : : Liquefied Natural Gas (LNG) Liquefied Petroleum Gas (LPG) Re-fomled Gas. OilGases ., .., Producer Gas Blue Water Gas, Carbureted Water Gas, and Coal Gas Blast-Furnace Gas Acetylene Hydrogen :: : : :: Sulfur impurities. Supercompressibility of Natural Gas Fuel and Energy Costs Cd Conversion to Liquid and Gaseous Fuels and Feedstocks for the Chemical-Process Industries Coal Gasification. Background Theoretical Considerations Types of Available Gasification Equipment Development and Lltilization Application of COPI Gas&cation Gas Purification and Refinement Economics of Coal Gasification. Direct Liquefaction Coal Background Direct-Liquefaction Kinetics Direct-Liquefaction Processes Coal-Pyrolysis PrIndirect Coal Liquefaction Fischer-Tropsch Synthesis Methanol-t+Gasoline Process. Syngas-to-Gasoline Process Ecunomia of Coal Liquefaction HEAT GENERATION Combustion Stoichiometry Theoretical Oxygen and Air for Combustion Excess Air for Combustion Products of Combustion Enthalpy of Combustion Products. Solid-Fuels Combustion on Stokers and in Suspension Fuel-Bed Firing. Suspension F&g Soreader-Stoker Firinn Solid-Fuels Combustion in Fluid&d Beds. : : : : : : : : : : : : Atmospheric and Presurized Fluid&d Beds (AFBC and PFBC) AFBC Plant Design Fluidisation Design Factors AFBC Design Ootions Combustion o? Liquid Fuels Burners for Liquid Fuels Combustion Deposits. Combustion of Gaseous Fuels. Gas Burnen Combustion Characteristics of Low- and Medium-Btu Gases. Exwrimental Evaluations of LBG and MBG Electhc Heating ......................... Direct-Resistance Heating ................... Indirect-Resistance Heating .................. Induction Heating ....................... Dielectric Heating, ...................... Microwave Heating ...................... Electric-Arc (Plasma) Heating ................. Laser Heating T Fired Proceu Equipment. Direct-Fired Equlpment

9-3 9-3 9-7 9-8 9-8 9-12 9-12 9-12 9-14 9-14 9-14 914 814 9-14 Q-14 Q-14 9-16 9-16 9-16 9-16 Q-16 9-17 Q-11 9-17 9-20 9-22 924 9-24 9-2s 9-25 Q-2.5 Q-26 Q-28 Q-34 9-35 9-35 936 Q-36 Q-36

Q-64 9-64

9-67
9-69 9-71

9-72

Cogeneration .....................

Definition and General Description. ........ Typical Systems .................. Energy-Saving Potential .............. &generation Performance of Representative Systems Operational Issues ................. HEAT REGENERATION Checkerbrick Regenerators. ................... Blast-Furnace Stoves ....................... Open-Hearth and Gla-Tank Regenerators ............ Coke-Oven Regenerators. .................... Pebble Stove. ........................... Ljungstrom Heater. ....................... Miscellaneous Systems ......................

Q-14 9-74 975 476 9-76 Q-79 9-81 9-81

9-83 9-85

9-86 9-89

990 9-90 9-90

9-91 9-91 Q-92
9-90

Nomenclature and Units

U.S.

Svmbol
AI

Definition Archimedes number Diameter Rate of power input Depth Electric field Accelerstion of gravity Isentropic enthalpy Height Pressure Rate of power input Resistivity Heating value Reynolds number Power-to-beat ratio Velocity Velocity of light FIOW ~;c~rcompr&bility Greek symbols

SI units

custonlary units

Dimensionless ft Btu/h ft V/in rt/P Btu/lb ft Ibf/in W/ins Rft Btu/lb Dimensionless Dimensionless mls cm/s kg/b Dimensionless ft/s in/s lb/h

D
D

d
9-36 9-38 9-38 Q-39 9-39 9-39 9-39 9-40 9-42 9-43 ;: 9-45 9-47 9-48 9-48 9-48 9-50 450 Q-50 452 Q-53 9-54 9-54 9-55 456 Q-57 958 9-58 9-59 9.59 9-60
E 8

h
L P P

P Q
Re R u 0 W 2

Voidage Thermal efficiency Viscaity Relative magnetic permeability Density Shaue factor

Dimensionless Dimensionless kg/(m.s) Dimensionless kg/m3

Dimensionless Dimensionless lb/(ft.s) Dimensionkss Ib/ft3

rl P c
P

FUELS
RESOURCES AND RESERVES
The resowStates-coal, and reserves of the principal fossil fuels in the United petroleum, and natural gas-follow: Quintillion (10) Btu Known reserves 4.8 0.26 0.30 Conversion factors Bituminous and anthracite coal Lignite and subbituminous coal Crude oil Natural-gas liquids Natural gas 30.2 I/kg 23.2 l/kg 38.4 j/L Z,% J/m3 (26 X ld Btu/ton) (20 X 10e Btu/ton) (5.8 X l@ Btu/bbl) (4.6 X Id Btujbbl) (1032 Btu/ft) Potential economic resnurces 3.0 2.7 2.1 Submarginal reso*ces 25.0 14.0 4.5 origin Coal originated from the arrested decay of the remains of trees, bushes, ferns, mosses, vines, and other forms of plant life

Fuel cd Petroleum liquids (crude and natural-gas liquids) Natural gas

which tlourished in huge swamps and bogs many millions of years ago during prolonged periods of humid, tropical climate and abundant rainfall. The precursor of coal was peat, which was formed by bacterial and chemical action on the plant debris. Subsequent actions of heat, pressure, and other physical phenomena metamorphosed the peat to the various ranks of coal as we know them today. Because of the various degrees of the metamorphic changes during this process, coal is not a uniform substance; no two coals are ever the same in every respect. Ckaseijcation of Cod Coals are classified by rank, i.e., acoording to the degree of metamorphism in the series from lignite to anthracite. Table Q-l shows the classification system adopted by the American Society for Testing and Materials, DUS-77. The heating value on the moist, mineral-matter-free (mmf) basis and the fixed carbon, on the dry mmf basis, are the bases of this system. The lowerrank coals are classified according to the heating value, J/kg (Btu/ lb), on the moist mmf ha&s. The agglomerating character is used to
differentiate between adjacent groups. Coals are considered agglomerating if the coke button remaining from the test for volatile matter

I bbl = 42 gal = 159 L = 0.159 m?

will support a weight of 500 g or if the button swells or has a porous cell structure.
ThP Parr fnrmulac. Fo< (Q-1) to (9-S). or the approximation for-

SOLID FUELS Coal

G-R * Elliott (ed), Chemictry of Coal Uttltitron, 2d suppl. vol., Wiley. New York, 1981. Van Krevelen. Conf, Ebvier. Amsterdam, 1961.

mulas, Eqs. (9-4) and (95), are used for classifying coals according to rank. The Parr formulas are employed in litigation cases.
F =

lOOfF - 0.15s) 100 - (M + LOftA + 0.55s)

(9-L)

TARLR 9-1

Cfauiffcation

of Coah

by Rank* Fixed carbon limits, 96 (dry mmf basis) Ek$lal or greater than 98 82 86 78 6: Less than ,.. z 2 8 14 22 31 Volatile matter limits. W (dry mmf bflSiS) Greater than Ekpal or less than 2 8 14
22

C&r& value limits, Btu/lbb (mot& mmf basis) Equal or

greater Less

Cl= Anthracitic

GOUp Metaanthracite Anthracite Semionthracited

Low-volatile

Abbreyintion ma a se Ivb mvb hvAb hvBb hbCb SubA SubB SUbC IigA IigB

than

than

Agglomerating character

II
14.w

Nonagglomerating

bituminous ccal Medium-volatile bituminous coal

31

Bituminous High-volatile A bituminous COPI High-volatile B bituminous coal High-volatile C bituminous coal Subbituminous A COPI Subbituminous B coal S&bituminous C coal Lignite A Lignite B

S&bituminous Lignitic

Annual Book of ASTM Stan&&, part 26, D 388-77.1977. This classification dm not include a few coats, principally nonbanded varieties. which have unusual ohvsical and chemical oronertin and which come within the limits of fixed carbon or calortfic value of the hinh-volatile bituminous and subbituminous ranks. All &se cvab either cc&n iesJ that 48% dry mmf fixed carbon or have more that 15,500 moist mmf Btu/lb. I To convert British thermal units per pound to joules per kilogram. multiply by 2326.
refers to coal containing its natural inherent moisture but not includinc visible water on the surface of the ccal. classify in l&-w-volatile group of the bituminous claw _ Coals having 6996 or more fixed carbon on the dry mmf basis are classified according to fixed carbon regardless of c&r&c value. There may he nonagglomerating varieties in these groups of the bituminous clas. and there are notable exceptions in the high-volatile %4&t

dlf agglomerating,

C bituminous

group. 9-3

V = 100 -

(2-2) (9-W

16,000 14,000

lOO(Q - SOS) Q=
F =

100 - (1.08A + 0.55s) 1OOF 100 - (M + l.lA + 0.1s)

Q-

1mQ
100 - (l.lA + 0.1s)

where M, F, A, and S are weight percentages, on a moist basis, respectively of moisture, fixed carbon, ash, and sulfur; F and V are weight percentages, on a dry mmf basis, respectively of fixed carbon and volatile matter; Q and Q are calorific values, Btu/lb (X 2326 = J/kg), respectively on a moist non-mmf basis and a moist mmf basii. Table 9-2 shows the principal ranks of coal mined in the major coal-producing states of the United States. Comporition and Heating Value of Coal The composition of coal is generally reported in two different ways, the proximate analysis and the ultimate analysis, both expressed in weight percent. The proximate analysis is the determination by prescribed methods of moisture, volatile matter, fixed carbon, and ash. Figure 9-1 gives the proximate analyses and heating values, on a moist mmf basis, of the various ranks of coal. It is seen that the fixed carbon and heating values increase with an increase in rank and that the moisture and volatile matter decrease. The total moisture in coal consists of inherent moisture and bed moisture. Inherent moisture, also referred to as bed and equilibrium moisture, exists as a quality of a coal seam in its natural state of depo sition. Free moisture, also referred to as surface moisture, is the part of the total moisture that is lost when coal is air-dried under standard conditions. The volatile matter is the portion of the coal which, when heated
TABLE 9-2 Print

FIG. 9-1 gram,

matter-free

Heating values and proximate analyses of coal on a moist, mineralbasis. To convert British thermal units per pound to joules per kilomultiply by 2326.

aalRanks of 6al

Mined in Various States*

0 E:

32 eI 44 Alabama Alaska Arkansas Colorado Illinois Indiana x

Iowa

Kansas Kenhrcky: Eastern.

::

Western
x

Maryland. Missouri
Montana New Mexico North Dakota. Ohio Oklahoma Pennsylvania South Dakota.

x x

Tennessee Texas
Utah Virginia Washington. West Virginia Wyoming.

in the absence of air under prescribed conditions, is liberated as gases and vapors. Volatile matter does not exist by itself in coal, except for a little absorbed methane, but results from thermal decomposition of the coal substance. Fixed carbon is the residue left after the volatile matter is driven off and is calculated by subtracting from 100 the percentages of moisture, volatile matter, and ash of the proximate analysis. In addition to carbon, it may contain several tenths of a percent of hydrogen and oxygen, 0.4 to 1.0 percent nitrogen, and about half of the sulfur that was in the coal. Ash is the inorganic residue that remains after the coal has been burned under specified conditions, and it is composed largely of compounds of silicon, aluminum, iron, and calcium and of minor amounts of compounds of magnesium, sodium, potassium, and titanium. Ash may vary considerably from the original mineral matter, which is largely kaolinite, illite, montmorillonite, quartz, pyrites, and gypsum. The ultimate analysis is the determination by prescribed methods of the ash, carbon, hydrogen, nitrogen, oxygen (by difference), and sulfur. Along with these analyses, the heating value, expressed as joules per kilogram (British thermal units per pound), is also determined. This is the heat produced at constant volume by the complete combustion of a unit quantity of coal in an oxygen-bomb calorimeter under specified conditions. The result includes the latent heat of vaporixation of the water in the combustion products and is called the gross heating or high heating value (HHV), Qh. The heating value when the water is not condensed is called the low heating value (LHV), Qt, and is obtained from QI = Qh 103Ow (g-6)

::::
x x

Compiled large :ly U.S. Bur. Mines Bull. Gad. Survey Bull. 1136

,ica
item

jta
QI = Qh - (859
PO/T) (9-6a)

Ite

where W = lb water formed/lb of fuel. The factor 1030 converts the high heating value at constant volume to low heating value at constant pressure. When dealing with gases, a useful equation is

SOUD FUELS where QI and Qh = Btu/fts of gas p = pressure, of mercury o = fts water in combustion products/fts T = temperature, OR For 60F and 29.92 inHg, the equation simplifies to QI = Qj, - 49.40 Q,+in Btu/lb (X 2326 = J/kg) can be approximated developed by the Institute of Gas Technology; Qh = 146.58C + 568.788

9-5

fuel

(9-s&) by a formula

+ 29.4s - 6.58A - 51.53 (0 + N) (9-7)

FIG. 9-2 Estimated remaining coal reserves of all ranks, by sulfur content. in the United States, Jan. 1. 1965. (From U.S. Bur. Mhes In. Clrc. 8312.)

where C, H, S, A, 0, and N are respectively the weight percentages on a dry basis of carbon, hydrogen, sulfur, ash, oxygen, and nitrogen. The standard deviation for 775 coal samples is 127. Coal analyses are reported on several bases, and it is customary to select the basis best suited to the application. The as-received basis represents the weight percentage of each constituent in the sample as received in the laboratory. The sample itself may be coal as fired, as mined, or as prepared for a particular use. The moisture-free (dry) bans IS generally the rnosr useful bans because performance calculations can be easily corrected for the actual moisture content at the point of use. The dry, ash-free basis is frequently used to approximate the rank and source of a coal. For example, the heating value of coals of a given source and rank is remarkably constant when calculated on this basis. Use of these bases is illustrated in Table 9-3. Laboratory procedures for proximate and ultimate analyses are given in the Annual Book of ASTM Standards, part 26, 1977; and in Methods of Analysing and Testing Coal and Coke, U.S. Bureau of Mines Bulletin 638, 1967. Sulfur in Coal Efforts to abate atmospheric pollution have drawn considerable attention to the sulfur content of coal, since the combustion of coal results in the discharge to the atmosphere of sulfur oxides. Sulfur occurs in coal in three forms: as pyrites (Fe&); as organic sulfur, which is a part of the coal substance; and as sulfate sulfur. The sulfate sulfur comprises at the most only a few hundredths of a percent of the coal. The organic sulfur may comprise from 20 to 80 percent of the total sulfur. Since organic sulfur is chemically bound to the coal substance in a complex manner, drastic treatment is necessary to break the chemical bonds before the sulfur can be removed. There is no economic method known at present that will remove organic sulfur, but progress is being made with so-called chemical methods for cleaning coal. Pyritic sulfur can be partially removed by using standard coal-washing equipment. The degree of pyrite removal depends on the size of the coal and the size and distribution of the pyrite particles. The sulfur content of United States coals varies widely, ranging from a low of 0.2 percent to as much as 7 percent by weight, on a dry basis. The estimated remaining United States coal reserves of all ranks, by sulfur content, are shown in Fi 9-2. Extensive data on sultur in United States coals are given in U.s Bureau of Mines Information Circular 8312. The sulfur reduction potential of United States coals is described in U.S. Bureau of Mines Information Circular 8118, which gives washability data for 455 raw-coal samples. Coal-Ash Characterietics and Composition When coal is to be burned or gasified, it is important to determine the ash fusibility, comprising the initial deformation, softening, and fluid temperaTABLE9-3

tures. The difference between the softening and initial-deformation temperatures is called the softening interval, and that between the fluid temperature and the softening temperature is called the fluid interval. The fusibility of coal ash is determined by ASTM D 1857, Annual Book of ASTM Standords, part 26, 1977. The softening temporaiture in mart o&err red IS prrough qunlitativ~ gaGlr= tn th.= Lhavior of ash on a grate and on furnace heat-transfer surfaces, with respect to the tendency to form large masses of sintered or fused ash, which impair heat transfer and impede gas Row. Likewise, the fluid temperature and the fluid interval are qualitative guides to the Eowability of ash in a slag-tap furnace. However, because ash fusibility is not an infallible index of ash behavior in practice, care is needed in using ash-fusibility data for designing and operating purposes. There is an excellent discussion of this subject in Steam: Its Ceneratton and Use, Babcock & Wilcox Co., New York, 1978. The composition of coal ash varies widely. Calculated as oxides, the composition (percent by weight) varies as follows: SiOp Ais@ Fe&is
GO MgO TiOe NanO and KaO SOS

20-60 lo-35
5-3.5 l-20 0.3-4 0.5-2.5 l-4 0.1-12

Knowledge of the composition of coal ash is useful for estimating slagging and clinkering in fuel beds, predicting the flow properties of coal-ash slag (U.S. Bur. of Mines Bull. 618) in slag-tap and cyclone furnaces, and predicting, to a limited extent, the fouling and corrosion of heat-exchange surfaces in pulverized-coal-fired furnaces. Multiple correlations for ash composition and ash fusibility are discussed in the Coal Cowersion Systems Technical Data Book, part IA, U.S. Department of Energy, 1978.
The alas rixosit)r-tempxoiturc;
slag

rc;latioruhip for oomplatcly

malted

is Log viscosity = 10 M/(T - 150) + C (9-8)

where viscosity is in poises (X 0.1 = Pa.s), M = 0.00835 (SiOa) + 0.00601 (AlaOa) - 0.109, C = 0.0415 (SiOa) + 0.0192 (AlsOs) + 0.0276 (equivalent FeaOs) + 0.0160 (CaO) - 3.92, and T = C.

Comparison of gases for Coal Analyses; High-Volatile A Bituminous Coal, Allegheny County, Pa., Pittsburgh &d Proximate weight W BSlS As-received DIY Dry, ash-free Mmsture 2.4 Volatile matter 36.6 37.5 40.8 Fixed carbon 53.2 54.5 59.2 Ash 7.8 8.0 CadXXl 75.8 77.7 84.4 Ultimate weight W Hydrogen 5.1 5.0 5.4 Oxygen 8.2 6.2 6.7 Nitrogen 1.5 1.5 1.7 Sulfur 1.6 1.6 1.8 Heatina value,_ B.t.u./lb. 13,560 13,890 15,100

On the as-received basis, the hydrogen and oxygen include the hydrogen and oxygen of the moisture NOTE: convert British thermal units per pound to joules per kilogram. multiply by 2326. To

9-6

ENERGY UTIUZATION, TABLE 94

CONVERSION,

AND RESOURCE CONSERVATION

and Hardgrow Grindability Indies Free-swelling index (FSI) Hardgrove grindability Hieh 70 66 47 111 Low 46 52 43 58 index (HGI) Average 53 60 45 96

SpocimonFrntwelling

state Alabama Illinois Kentucky Pennsylvania

Name of bed Mary Lee No. 6 Winifrede Upper Kittanning

High 8 6X 4 9

Law 1X 1 2 2x

Average 4 4!4 3 8

The oxides in parentheses are the weight percentages of these oxides when SiOs + A1sOs + FesOs + CaO + MgO = 100. Zhyrical Propertier of Coal The free-swelling index (FSI) measures the tendency of a coal to swell when burned or gasified in fixed or fluidized bed. Coals with a high free-swelling index (>4) can usually be expected to cause difficulties in such beds. Details of the test are given in ASTM D 720, Annual Book of ASTM Standards. part 26, 1977; and U.S. Bureau of Mines Report of Investigations 3989. The Hardgrove grindability index (HGI) indicates the ease (or difficulty) of grinding coal and is complexly related to physical properties such as hardness, fracture, and tensile strength. The Hardgrove machine is usually employed (see ASTM D 409). It determines the relative grindability or ease of pulverizing coal in comparison with a standard coal, chosen as 100 grindability (see Sec. 8). The FSI and HGI of some United States coals are given in Table 9-4. See Bureau of Mines Information Circular 8025 for FSI and HGI data for 2812 and 2339 samples respectively. The bulk density of broken coal varies according to the specific gravity, size distribution, and moisture content of the coal and the amount of settling when the coal is piled. Following are some useful approximations of the bulk density of various ranks of coal:
lb/f? Anthracite Bituminous Lignite 50-58 42-57 40-54 kg/m3 801-929 673-913 641-865

Size stability refers to the ability of coal to withstand breakage during handling and shipping. It is determined by twice dropping a 22.7-kg (5OJb) sample of coal from a height of 1.83 m (6 ft) onto a steel plate. From the size distribution before and after the test, the size stability is reported as a percentage factor (see ASTM D 440). The frfabfltty test measures the tendency of coal to break during repeated handling. It is actually the complement of size stability and is determined by the standard tumbler test (ASTM D 441-45). Spierss Tech&al Data on Fuels gives the specific heat of dry, ash-free coal as follows: Btu/(lb.OF)
Anthracite Bituminous 0.22-0.23 0.24-0.26

1Rkg.K)
921-963 1004-1088

The relationship between specific heat and water content and between specific heat and ash content is linear. Given the specific heat on a dry, ash-free basis, it can be corrected to an as-received basis. The specific heat and enthalpy of coal to 1090C (2000F) are given in Coal Conoersfon Systems Technical Data Book, part IA, U.S. Department of Energy, 1978. The mean specific heat of coal ash and slag, which is used for calculating heat balances on furnaces, gasifiers, and other coal-consuming systems, follows: Temperature range
OC OF

Coke Coke is the solid, cellular, infusible material remaining after the carbonization of coal, pitch, petroleum residues, and certain other carbonaceous materials. The varieties of coke, other than those from coal, generally are identified by prefixing a word to indicate the source. e.e.. oetroleum coke. To indicate the mocess bv which a coke is manufactured. a orefix also is often used. e.e.. own coke. Transformutbn of coal info coke. The mechanism of the formation if coke whencoal is carbonized is a complex of physical and chemical phenomena that are not perfectly understood. Some of the physical changes, which are interrelated when certain ranks of coal or blends are heated, are softening, devolatilization, swelling, and resolidification. Some of the accompanying chemical changes are cracking, depolymerization, polymerisation, and condensation. More detailed theoretical information is given in Coal, by Van Krevelen (Elsevier, Amsterdam, 1961), and Chemistry of Coal Ufiltzatfon, by Lowry (Wiley, New York, 1945 and 1963). High-temperature coke (900 to 115OX). This type is most commonly used in the United States; nearly 20 percent of the total bituminous coal consumed is used to make high-temperature coke for metallurgical applications. About 99 percent of this type of coke is made in slot-type recovery ovens, and the remainder in beehive and other types of ovens. Blast furnaces use about 90 percent of the production, the rest going mainly to foundries and gas plants. A U.S. Bureau of Mines survey of 12 blast-furnace coke plants, whose capacity is 30 percent of the total production in the United States, provides an excellent picture of the acceptable chemical and physical properties of such coke. The ranges of properties are given in Table 9-5. The typical by-product yields per ton of dry coal from high-temperature carbonization in ovens, with inner-wall temperatures from 1000 to 1150% (1832 to 2102OF). are: coke, 653 kg; gas, 154 kg (11,200 f?); tar, 44 kg (10 gal); water, 38 kg; light oil, 11 kg (3.3 gal); and ammonia, 2.2 kg. Foundry coke. This coke has different requirements from blastfurnace coke. The volatile matter should not exceed 2.0 percent, the sulfur should not exceed 0.7 percent, the ash should not exceed 12.0 percent, and the size should exceed 3 in. Low- and medium-temperature coke (500 to 75OOC). Cokes of this type are not now produced in the United States to a significant extent. However, there is now interest in low-temperature carbonization as a source of both hydrocarbon liquids and gases to supplement petroleum and natural-gas resources. The Fischer assay is an arbitrary but precise analytical tool for determining the yield of products from low-temperature carbonization. A known weight of coal is heated at a controlled rate in the absence of air to 500C, and the products are collected and weighed.
_I_~ ,

TABLE9-5

Chemicaland PhysicalPqwtios of High-TomPwaturo CokesUsed in tha United States Prcmertv Volatile matter ............... Ash Sulfur ................. ::: :: Stability factor ... .......... Hardness factor. ............. *y&l~,rL apecrnc grilvt~y ........... (water 1.0) =Ranee 0.8-1.4 wt. 96. as-received 7.5-10.7 wt. 96. as-received 06-1.1 wt. W. as-received 39-58 (l-in. &mbIer) 60-68 (%-in. tumbler)

Mean specific heat Btu/(lb.F) o.ela

0.224 0.232 0.235 0.272 E 971 984 1139

::::::

I/(kg.K)

& 98 0- 813
O-1038 O-1093 O-1371

a* 100
32-1500 32-1900 32-2tXM 32-2500

.ou-.JII

Comparison of Properties of Coke Produced by EM-ACA and Indwwal Methods. U.S. Bur. Mines Rep. Invest. 6354. To convert inches to centimeten. multiply by 2.54.

SOLID FUELS
TABLE9-6 Fiihw-Assay Yieldsfrom Various Ranksof Cool (As-R~~oivod Basis) ASTM classification by rank ClasS Bituminous 1. 2. 3. 4. 5. Group Low-volatile bituminous Medium-volatile bituminous High-volatile A bituminous High-volatile B bituminous High-volatile C bituminous Coke. weight % 90 63 76 70 67 59 56 37 Tar, gal/ton 8.6 16.9 30.9 30.3 27.0 20.5 15.4 15.2 Light oil, gal/ton 1.0 1.7 2.3 2.2 1.9 1.7 1.3 1.2 GPS, ftS/ton 1760 1940 1970 2010 1800 2660 2260 2100 water, weight % 3 4 6 11 16 23 26 44

9-7

Subbituminous Lignite

1. Subbituminous A 2. Subbituminous B 1. Lignite A

NOTE To convert gallons per to to liters per kilogram, multiply by 0.004; to convert cubic feet per ton to cubic meters per kilogram. multiply by 3.1 X lo-.

yields of products for various ranks of coal. Pitch coke and petroleum coke. Pitch coke is made from coaltar pitch, and petroleum coke is made from petroleum residues from petroleum refining. Pitch coke has about 1.0 percent volatile matter, 1.0 percent ash, and less than 0.5 percent sulfur on the as-received basis. There are two kinds of petroleum coke: delayed coke and Buid coke. Since they contain the impurities from the original crude oil, the sulfur is usually high, and appreciable vanadium salts may be present. Ranges of composition and properties are as follows:
Table 9-6 gives the approximate

species. These values are accurate

Other Solid Fuels Char Char is the nonagglomerated, nonfusible residue from the thermal treatment of solid carbonaceous material. Coal chars are obtained as a residue or a coproduct from low-termperature carboni&ion processes and from processes being developed to convert coal to liquid and gaseous fuels and to chemicals. Such chars have a sub stantial heating value. The net amount of char from a conversion prvaries widely; in some instances it may represent between about 30 and 55 percent of the weight of coal feed; in others no net or excess char is produced; i.e., the entire char yield is consumed as in-plant fuel. The analyses of feed coals and resulting chars from two coal-conversion processes are given in Table 9-7. The volatile matter, sulfur, and heating values of the chars are lower, and the ash is higher, than in the original coal. Wood Higher heating values are 20,004 X 109 J/oven-dried kg of hardwood species and 20,930 X 10s J/oven-dried kg of softwood
TABLE 9-7 Rot- Examplesof Anab

enough for most engineering purposes. U.S. Department of Agriculture Handbook 72 (revised 1974) gives the specific gravity of the important softwoods and hardwoods if heating value on a volume basii is needed. Peat Peat is partially decomposed plant matter that has accumulated underwater or in a water-saturated environment. It was the precursor of coal but is not classified as coal. Peat is sold under the term peat moss or moss peat and currently is used in the United States mainly for horticultural and agricultural applications. Interest is growing in its use as a fuel in certain local areas. Although analyses of peat vary widely, a typical high-grade peat has 90 percent water, 3 percent fixed carbon, 5 percent volatile matter, I.5 percent ash, and 0.10 percent sulfur. The moisture-free heating value is approximately 20,930 X 10s J/kg (9000 Btu/lb). Ckrcool Charcoal is the residue from the destructive distillation of wood. It absorbs moisture readily, often containing as much as 10 to 15 percent water. In addition, it usually contains about 2 to 3 percent ash and 0.5 to 1.0 percent hydrogen. The heating value of charcoal is about 27,912 X 10s to 30,238 X 10s J/kg (12,000 to 13.000 Btu/lb). Tanbark Tanbark is the residue remaining after bark has been used in tanning operations. usually contains from 60 to 70 percent It water and has a heating value of 5815 X ld to 6978 X 10s J/kg (2500 to 3000 Btu/lb). Bogarre Bagasse is the solid residue remaining after sugarcane has been crushed by pressure rolls. It usually contains from 40 to 50 percent water. The dry bagasse has a heating value of 18.608 X 10s to 20,934 X 10s J/kg (8000 to 9000 Btu/lb). Solid Wartee and Biomarr Large and increasing quantities of solid wastes generated per capita are a significant feature of affluent societies. In the United States the rate exceeds 5 lb per capita per day, or nearly 290 million tons per year, and it is grooving rapidly. Table 9-8 shows the composition of various solid wastes. On a moisture-free basil, the composition of miscellaneous refuse is surprisingly uniform, but size and moisture variations cause malor difficulties in efficient, economical disposal.

of Coal Feedsand ResultingCharSfr om Various CoaUanv~n

Process. Coal bed.

Composition and properties Analysis, wt. W: Volatile matter Fixed carbon Ash Sulfur Heating value. B.t.u&

FMCf
Pittsburgh-Federal Coal, dry basis Char, dry basis 3.7 66.8 9.5 1.9 13,400 Illinois No. 8 Coal. dry basis 36.8 50.0 11.4 3.8 12,600 Char, dry basis 3.5 76.4 20.1 3.1 11.670 Coal, dry basis 32.7 52.3 14.1 4.3 13,200

IGTi
Pittsburgh Char, dry basis 1.2 77.5 21.3 1.7 12,ux)

36.8 :::::
57.0 6.2 2.9 14,470

Nelson et al.. Study of the Idenrificatla and Assessment of Potenttil Markets for Chars from Various Procesc(ng Systems, Battek Memorial Institute, Columbus. To convert Brlthh therrnal units per pound to joules per kilogram, multiply by 2326. tFMC prinvolves multistage tluidized-bed pyrolysis of coal to produce a liquid, residual char, and some gas. tiGT process involves hydrogasification of coal to produce a gas of pipe-line quality (about loo0 Btu/ft) and char.

9-8

ENERGY UTIUZATION, TABLE 9-8

CONVERSION,

AND RESOURCE CONSERVATION

WastcFuol Analvur*
Heating value, Btu/lb 7,572 8,613 7,652 8,484 10,996 11,054 8,899
19,161 12,283 7,907 13,202 11,428

Percentage composition by weight V&tiles

84.6 849 93.6 33.3 81.2 80.87 81.06 99.02 75.73 15.08 100.00 75.06

Tvw of waste Paper Wood Bags Garbage Coated fabric: rubber Coated felt: vinyl Coated fabric: vinyl Polyethylene film Foam: scrap Tape: resin-covered glass Fabric: nylon Vinyl scrap

Moisture
10.2 20.0 10.0 72.0 1.04 1.50 1.48 0.15 9.72 0.51 1.72 0.56

Ash
6.0 1.0 2.5 16.0 21.2 11.39 6.33 1.49 25.30 5673 0.13 4.56

Sulfur
0.20 0.05 0.13 0.52 0.79 0.80 0.02 0 1.41 0.02 0 0.02

Dry combustible

Densit Ib/ft Y*

78.80 88.61 93.67

98.51

23.9 10.7
10.1

74.70 43.27 99.87 95.44

5.7 9.1 9.5 6.4 23.4

From Hescheles, MECAR Conference on WasteLX.qwd, New York, 1968; and Refuse Collection Practfce,3d ed.. American Public Works Association, Chicago, 1966. To convert British thermal units per pound to joules per kilogram, multiply by 2.326: to convert pounds per cubic font to kilograms per cubic meter, multiply by 16.02. The fuel value of most solid wastes is usually sufficient to enable self-supporting combustion, leaving only the incombustible residue and reducing the volume of waste eventually consigned to sanitary landfill to only 10 to 15 percent of the original volume. The heat released by the combustion of waste can be recovered and utilized, although the cost of the recovery equipment or the distance to a suitable point of use for the heat may make heat recovery economically infeasible. Biomass (e.g., crop residues and cattle manure) is an important source of energy currently being examined for engineering feasibility and economics. Energy from Biocm~sion of Waste Mat&ah, by D. J. DeRenzo (Noyes Data Corp., Park Ridge, N.J., 1977), is a useful reference. Coal-Oil Mixture (COM) COM is viewed as a near-term method for extending domestic fuel supplies and for reducing foreign oil imports. The most attractive feature of the COM concept is that the technology for producing and burning coal-oil slurries exists; they can be burned in many existing boilers with few modifications. Coal for the mixture is pulverized wet or dry until about 80 percent passes through a 200-mesh screen. Then it is blended with oil and a surfactant, which helps keep the coal in suspension. Boiler tests indicate that COM can be burned in boilers and some fired process equipment designed for oil bnd gas without significant derating or expensive retrofit work, with about 50 percent coal by weight. It is generally agreed that COM is not economically attractive for boilers producing less steam than 45,360 kg/h (100,000 lb/h). COMs are nonnewtonian &ids in the pseudoplastic classification; that is, their viscosities decrease with increasing velocity gradient. Once COMs start Bowing, their viscous nature approaches that of a heavy oil. A useful reference for COMs is Can Coal-Oil Mixtures Make It as Industrial Fuels? by J. W. Eberle and R. H. Hickman [Me&. Eng., 24-28 (March 1978)]. UQUID FUELS Liquid Petroleum Fuels The principal liquid fuels are made by fractional distillation of crude petroleum (a mixture of hydrocarbons and hydrocarbon derivatives ranging from methane to heavy bitumen). As many as one-quarter to one-half of the molecules in crude may contain sulfur atoms; and some contain nitrogen, oxygen, vanadium, nickel, or arsenic. Desulfurization, hydrogenation, cracking (to lower molecular weight), and other refining processes may be performed on selected fractions before they are blended and mar-

Density: 15OC 2 2

I
0.1
Ho. 9-3

III,rlll
1

I1111111
10
Kinematic viscosity

I I I lllll
lal

I1111111

lllll(

1000

ia

00

at 100 OF, mm2/s St)

Viscosity, boiling-range, and gravity relationships for petroleum fuels.

LIQUID FUELS keted as fuels. Viscosity-gravity-boiling-range relationships of common fuels are shown in Fig. 9-3. The highly viscous oil extracted from tar sands is also a grade of crude petroleum which can be hydrogenated and refined into conventional petroleum products. Speci$cacatione Specifications developed by the American Society for Testing and Materials are widely used to classify fuels. Table 9-9 shows ASTM Fuel Oil Specihcation D 396. Note footnote F, covering low-sulfur residual fuels of high wax content, which require the same heated storage and handling as No. 6 hut, when warm, are in the No. 4 or No. 5 viscosity range. (D 396 omits kerosine, a lowsulfur, clean-burning No. 1 fuel for lamps and freestanding flueless domestic heaters that is covered by Federal Specification VV-K2IId.) In drawing contracts and making acceptance tests, refer to ASTM Standards, Parts 23 and 24 (American Society for Testing and Materials, Philadelphia, annually). Part 23 contains test methods and specifications (&s&cations) for burner fuel, motor and aviation gasoline, diesel fuel, and aviation and gas-turbine fuel. It also contains ASTM D 270, with sampling procedures for bulk oil in tanks, barges, etc. Part 24 contains test procedures for water and sediment and alternative procedures for sulfur determination. Fuel specifications from different sources may differ in test limits on sulfur, density, etc., but the same general categories are recognized worldwide: kerosine-type vaporizing fuel, distillate (or gas oil) for atomizing burners, and more viscous blends and residuals for commerce and heavy industry. Typical specifications are as follows: Soecifier Canadian Government Specification Board, Department of Defence
Production, Ottawa, Canada Deutschen Normenawhusses. Berlin 15 British Standards Institution, British Standards House, 2 Park Street, London, WlA 2Bs JP Federal swxifications. United States DIN 51803 B.S. 2869 ,IS IcL109 JIS K2204 JIS K2205 VV-F-815 NUlllb.X Catenorv

9-9

may serve as fuel in nearby furnaces or may be cooled and blended to make commercial fuels. Diluted with 5 to 20 percent distillate, the blend is No. 6 fuel oil. With 20 to 50 percent distillate, it becomes No. 4 and No. 5 fuel oils for commercial use, as in schools and apartment houses. Distillate-residual blends also serve as diesel fuel in large stationary and marine engines. However, distillates with inadequate solvent power will precipitate asphaltenes and other highmolecular-weight Colloids from visbroken (severely heated) residuals. A blotter test, ASTM D 2781, will detect sludge in pilot blends. Tests employing centrifuges, filtration, or microscopic examination havealsobeenused. No. 6 fuel oil contains from 10 to 500 ppm vanadium and nickel in complex organic molecules, principally porphyrins. These cannot be removed economically, except incidentally during severe hydrcdesulfurization (Amero, Silver, and Yanik, Hydrodesulfurized Residual Oils as Gas Turbine Fuels, ASME Pap. 75-WA/GT-8). Salt, sand, rust, and dirt may also be present, giving No. 6 a typical ash content of 0.01 to 0.5 percent by weight. Ultimate analyses of some typical fuels are shown in Table 9-10. Hydrogen content of petroleum fuels can be calculated from density with the following formula, with an accuracy of about 1 percent for petroleum liquids that contain no sulfur, water, or ash: H = 26 15s (9-9)

where H = percent hydrogen and s = relative density at 15OC (specific gravity at 60/60F). Schmidt (Fuel oil Manual, 3d ed., Industrial Press, New York, 1969) claims improved precision of the formula by replacing 26 with different constants:
API gravity O-9 lo-20 21-30 31-45

5GP-2

Fuel oil, heating

Relative fuel density at 15C 1.0754-1.0065 1.008%0.9935 0.9935-0.8757 0.8757-0.8013

Constant 24.50 25.00 25.20 25.45

Heating (fuel) oils

Petroleum fuels for oil engines and burners E%rori..e Gas oil Fuel oils Fuel oil. burner

Gravity
c;ialimed

is usually determined
end cxprcwd

at ambient temperature
in

with speP x~lo

hydrometcn

deg.-s

API (at 60F),

that relates inversely to specific gravity s at 60/600F also the abscissa scale of Fig. 9-4): Degrees API = 141.5/e 131.5

as follows (see (9-10)

Foreign specifications are generally available from the American National Standards Institute, New York; United States federal specifications, at Naval Publications and Forms, Philadelphia. Equipment manufacturers and large-volume users often write fuel specifications to suit particular equipment, operating conditions, and economics. Nonstandard test procedures and restrictive test limits should be avoided; they reduce the availability of fuel and increase its cost. Bunker-fuel specifications for merchant vessels often cover only viscosity, flash point, water and sediment, and ash content. Deepdraft vessels carry residual (e.g., No. 6 fuel oil) or distillate-residual blend for main propulsion, plus distillate for startup, shutdown, maneuvering, deck engines, and diesel generators. Main-propulsion fuel is identified by its viscosity in centistokes at 50C (e.g., marine diesel 40). Obsolete designations include those based on Redwood No. 1 seconds at lOOoF (e.g., MD 1500) and the designations Bunker A for No. 5 fuel oil and Bunker B and C for No. 6 fuel oil in the lower- and upper-viscosity ranges respectively. Chemical and Physical Properties Petroleum fuels contain paraffins, isoparaffins, aromatics, and naphthenes, plus organic sulfur, oxygen, and nitrogen compounds that were not removed by refining. Olehns are absent or negligible except when created by severe refining. Vacuum-tower distillates with a final boiling point equivalent to 454 to 566% (850 to 1050F) at atmospheric pressure may contain from 0.1 to 0.5 ppm vanadium and nickel, but these metal-bearing compounds do not distil1 into No. 1 and 2 fuel oils. Black, viscous residuum directly from the still at 200C or higher

Specific gravity is widely used in countries outside the United States, and with the adoption of SI units the American Petroleum Institute favors density at 15OC instead of degrees API. The hydrogen content, heat of combustion, thermal expansion, specific heat, and thermal-conductivity data herein were abstracted from Bureau of Standards Miscellaneous Publication 97, Thermal Properties of Petroleum Products. These data are widely used, although newer correlations have appeared, notably that by Linden and Othmer [C/rem. Eng., 54(4,5) (April and May 1947)]. Heat of combustion can be estimated within 1 percent from fuel gravity by using Fig. 9-4. Corrections for water and sediment must be applied for residual fuels, but they are insignificant for clean distillates. Figure 9-5 shows viscosity-temperature relationships for typical petroleum fuels. Between the cloud point and the boiling point and at pressures below 6.9 MPa (1000 Ibf/in*), they are practically newtonian liquids. At low temperatures where solids begin to separate, viscosity depends on the rate of shear. Pour point ranges from -60C ( -80F) for some kerosine-type jet fuels to 46C (115F) for waxy No. 6 fuel oils. Cloud point (which is not measured on opaque fuels) is 5 or 10C higher than pour point unless the pour has been depressed by additives. The drop in viscosity with increasing temperature is greater for some fuels than for others. Generalized viscosity charts hecome less reliable at temperatures substantially removed from the specification temperatures of 38 or 50% (100 or 122OF).

9-10 TAME 93

ENERGY UTIUZATION,
ASTM D 396-Note

CONVERSION,

AND RESOURCE CONSERVATION for Fuel Oib

Water

79: Dotaibd Roauhnont

Flash point. (Z, Grade of fuel oil No. 1: P distillate oil intended for vapwizing pot-type burners and other burners requiring this grade of fuel No. 2: P distillate oil for general-purpose heating for we in burners not requiring No. 1 fuel oil No. 4: preheating not usually required for handling or burning No. 5 (light): preheating may be required, depending on climate and equipment No. 5 (heavy): preheating m*y be required for burning and, in cold climates, for handling No. 6. preheating required for burning and handling Min.

and sediment, volume 96

Ash, weight 96

Distillation temperatures, C (OF) point Max 215 (420) Min.

90%

lint

-6 (20)

-6 (20)

0.10 0.10

1.10

:tepripted. with permission, from the Annual Book of Standor& _ . tt is the intent ot these ctassitications that failure to meet any requirement of P given grade dm not automatically place a oil in the next lower grade unless in fact it meets all requirements of the lower grade. aln countries outside the United States other sulfur limits may apply. CLmver or higher pour points may be specified whenever required by conditions of storage or use. When a pour point less than - 18C (0F) is specified, the minimum viscosity for grade No. 2 shall be 1.7 cSt (31.5 SUS) and the minimum 90% point shall be waived. Viscwity value in parentheses are for information only and not oece+rprily limiting. The amount of water by distillation plus the sediment by extraction shall not exceed 2.00%. The amount of sediment by extraction shall not exceed 0.50%. A deduction in quantity shall be made for all water and sediment in excess of 1.0%. Where low-sulfur fuel oil is required. fuel oil falling in the virosity range of a lower numbered grade down to and including No. 4 mpy be sup lied by agreement between purchaser and supplier. The visc&ty range of the initial shipment shall be identified, and advance notice shall be required when cR,.gmg from one viscosity range to another. This notice shall be in sufficient time to permit the user to make the necessary adjustments. Where low-sulfur fuel oil is reauired. Grade 6 fuel oil will be clpsified as low DOUI+ 15OC (60F) max., or high pour (DOmax.). Low-pour fuel oil should be used u&s all tanks and lines are t&ted.

Thermal expansion of petroleum fuels can be estimated as volume change per unit volume per degree:
where c = c =

c = (1.685

+ 0.0(x39 x C)/s X F)/s

(g-11) (9-M

c = (0.388 + 0.00045 heat capacity, heat capacity, kJ/(kg.OC)

Density kg/dm, lSC >0.9660

-0.6499

Volume change/unit API gravity Below 14.9 15.0- 34.9 35.0- 50.9 51.0- 63.9 64.0- 78.9 79.0- 88.9 89.0- 93.9 94.0-100.0 CoefficientlF
0.00035 o.om4o O.OOEO O.OOO60 o.oao7o 0.00060 O.OW35 O.OOWO

volume

Coefficient/C
0.00063

-0.7754 -0.7239 -0.6724 -0.6419 -0.6277 -0.6112

o.w2 O.@X@O 0.00106 0.00126 0.00144 0.00153 0.00162

s = relative Specific heat varies the specific heats at calculations related Tabk V-10.

Btu/(lb.F) density at 15% (specific gravity, 60/60F) with temperature, and an arithmetic average of the initial and final temperatures can be used for to the heating or cooling of oil. Analyses of Potium
No. 4 fuel 011 123.2A.PI )

Typical Uhimato

Fuob
Hagh SlfW. No. 6 (15.5A.P.I.)

Compwtion. %

No. 1 / No. 2 fuel 011 fuel od (41 5h P.1.l (23A.P.I.l

LOW rulfur. No. 6 EO. (12.6A PI)

ASTM-IP Petroleum Measurement Tables (ASTM D 1250 IP 200) are used for volume corrections in commercial transactions. Specific heat capacity of petroleum liquids between 0 and 205C (32 and 400F) having a relative density of 0.75 to 0.93 at 15W can be calculated within 2 to 4 percent of the experimental values from the following equations:

UOUID FUELS

9-11

lSwbolt viscositv. so
Universal at 3WC (lOOoF) Min. Fur01 at SOT (122F) Min.
Max.

Kil nematic viscosity. cStD l-

At 36~C Min.
1.4

CWF)
Max. 2.2

M40(
Min. 1.3

104F) MUX. 2.1

T At

5ov

122F) Max.

Specific gravity 6O/WF (OAPI) Max.

0.6499

Copper strip

Min.

No. 3

0.5

(35 min)

(32.6)

2.OC

3.6

1.9c

3.4

0.6762 (30 min)

No. 3

0.5

(45)

5.6

26.4

5.5

24.6 58

(>W

z-26.4

65F

124.0

c-300)

(2-w

(40)

Z-65

lQ4F

Xi6

166

(42)

(81)

(xm

(>45)

WQ)

>92

&BP

The thermal conductivity of liquid petroleum products is given in Fig. 9-6. Thermal-conductivity coefficients for asphalt and paraffin wax in their solid states are 0.17 and 0.23 W/(m.K) respectively for temperatures above 0C (1.2 and 1.6 Btu/(h.fP)(F/in)l Fuel systems for No. 1 and No. 2 fuel oil are not heated. Systems for No. 6 fuel oil are usually designed to preheat the fuel to 32 to 49C (90 to 120F) to reduce viscosity for handling and to 74 to 93C (165 to ZOOOF) to reduce viscosity further for proper atomization. No. 5 fuel oil may also be heated. (See Table 9-9.) Steam or electric heating is employed as dictated by economics, climatic conditions, length of line, and frequency of use. (See Fig. 9-7.) Pressurerelief arrangements are recommended on sections of heated pipe lines when fuel could he inadvertently closed between valves. Fuel can expand several percent between 15 and 100% (59O and 212OF). Fuel-pump capacity exceeds burner capacity; excess flow recirculates through pressure-relief valves in the pump (for simple No. 2 fuel systems) or in the fuel header (for multiple-burner heavy-fuel systems). CommerciDl Codderationr Fuels are sold in gallons and in multiples of the 42-gal barrel in the United States. Table 9-11 shows units used elsewhere. Transactions exceeding 5000 to 10,000 gal usually involve volume corrections back to 15.6OC (60F) for accounting

purposes. Fuel passes through an air eliminator and mechanical meter when loaded into or dispensed from trucks. Larger transfers such BSpipe-line, barge, or tanker movements are measured by fuel depth and strapping tables (calibration tables) in tanks and vessels, but positive-displacement meters that are proved (calibrated) frequently are gaining acceptance. After an appropriate settling period, water in the tank bottom is measured with a plumb bob or stick smeared with water-detecting paste. Receipts of tank-car quantities or larger are usually checked for gravity, appearance, and flash point to confirm product identification and absence of contamination. Safe@ Comiderationr Design and location of storage tanks, vents, piping, and connections are specified by state fire marshals, Underwriters codes, and local ordinances. In NFPA 30, Flmmuble and CombuPtiMe Lkpguidp Code, 1977, published by National Fire Protection Association, Quincy, Massachusetts, liquid petroleum fuels are classified as follows for safety in handling: Class I (Eammable) liquid has a flash point below 37.8C (lOOoF) and a vapor pressure not exceeding 0.28 MPa at 37.8C (40 Ibf/in* absolute at lOOoF). Class IA includes those liquids having flash points below 22.8C (73OF) and boiling points below 37.8C (lOOoF).

9-12

ENERGY UTIUZATION,

CONVERSION, AND RESOURCE CONSERVATION Shale oil has been hydrotreated and refined in demonstration tests into relatively conventional fuels. Refining in petroleum facilities is possible, and blending with petroleum is most likely. Coal-Detioed Fuels Liquid fuels derived from coal range from highly aromatic coal tars to liquids resembling petroleum. Raw liquids from different processes show variations that reflect the degree of hydrogenation achieved Also, the raw liquids can be further hydrogenated to refined products. Properties and cost depend on the degree of hydrogenation and the boiling range of the fraction selected. A proper batance between fuel upgrading and equipment n&&cation is essential for the most economical use of coal liquids in boilers, industrial furnaces, diesels, and stationary gas turbines. Coal-tar fuels are high-boiling fractions of crude tar from pyrolysis in coke ovens and coal retorts. Grades range from free-flowing liquids to pulverizable pitch. Low in sulfur and ash, they contain hydrocarbons, phenols, and heterocyclic nitrogen and oxygen cornpounds. Being more aromatic than petroleum fuels, they burn with a more luminous flame. From 15 to 205C (60 to 400F) properties include: Specific heat capacity 1.47-1.67 kJ/(kg.OC) [0X1-0.40 Btu/ (lb.OF)] 0.14-0.15 W(m.K) [0.080-0.085 Btu/fts Thermal conductivity

160000 I50000

150000 140000

E g > : % s Y G a 0. > & z :

14oooo 130000

E a i c c 8 r B 120000 ; i P

130000

120000 110000

(F/ft)l

110000 100000

100000 0 IO 20 30 40 50 60 70

a0

90 100

API qrslt

FIG.

Heat of combustion of petroleum fuels. To convert British thermal 94 units per U.S. gallon to kilojoules per cubic meter, multiply by 2.787 163 E+ 02

Class IB liquids have flash points below 22.8C (73OF); boiling wints. at or above 37.8V (lOOoF). Class IC includes thoseliquid; having flash points at or above 22.8C (73OF) and below 37.8V (lOOoF). Class II combustible liquids have flash points at or above 37.8OC (100F) and below 60% (140OF). Class IIIA combustible liquids have flash points at or above 60% (140F) and below 93.4OC (ZOOoF). Class IIIB liquids flash at or above 93.4% (ZOOOF). NFPA 30 details the design features and safe placement of handling equipment for flammable and combustible liquids. Crude oils with flash points below 37.8% (lOOoF) have been used in place of No. 6 fuel oil. Different pumps may be required because of low fuel viscosity. Handling precautions related to flammability are covered in Petroleum Safety Data Sheet PSD 2215, Crude Oil as Burner Fuel, American Petroleum Institute, Washington. Nonpetroleum Liquid Fuels Table 9-12 shows typical data on liquid fuels from tar sands, oil shale, and coal. Tar Sands Canadian tar sands are strip-mined and extracted with hot water to recover heavy oil (bitumen). The oil is processed into naphtha, kerosine, and gasoline fractions, which are hydrotreated, in addition to gas, which is recovered. Tar sands are being developed in Utah also Oil shale is nonporous rock containing organic keroOil S/&e gen. Raw shale oil is extracted by pyrolysis in a surface retort, after mining, or in situ after rubblizing the rock with explosives. PyrolyEi= orncks the korogcn, yielding raw ahe& 4 high in nitrvt;cu, w.y-

34; kJ/kg (150 Btu/lb) Heat of vaporisation Heat of fusion See the monograph edited by W. H. Huxtable, Coal Tar Fuels (Association of Tar Distillers, London, 1961). Properties of hydrogenated-coal liquids, largely unreported as yet, will no doubt fall between coal-tar fuel and petroleum. The EDS, H-Coal, and SRC-II processes hydrogenate coal to yield hydrocarbon liquids. Distillates between 177 and 510C (350 and 950F) are low-sulfur liquids in the viscosity range of No. 2 to No. 5 fuel oil. Ash content ranges from nil to a few ppm. High-ash residuals are minor fractions, often to be consumed in process rather than marketed. SASOL in South Africa is using coal gasification followed by synthesis to produce gasoline and diesel fuel (Fischer-Tropsch process). There are proposals in the United States to use the same gasification process to provide for the synthesis of methanol as a liquid fuel. Fermentation ethanol can be considered as a fuel supplement in countries with sufficient land, sunshine, and water to grow food, feed, and fiber at surplus levels. With Bash points of 11 and 14C (51.8 and 57.2OF) respectively, methanol and ethanol must be handled with due regard to tlammability Coal-derived fuels are discussed in greater detail in a later subsection.

GASEOUS FUELS Natural Gas Natural gas is a combustible gas that occurs in porous rock of the earths crust and is found with or near accumulations of crude oil. Being a gas, it may occur alone in separate reservoirs. More commonly, it forms a gas cap entrapped between petroleum and an impervious, capping rock layer in a petroleum reservoir. Under high-pressure conditions, it is mixed with or dissolved in crude oil. .Natural gas consists of hydrocarbons with a very low boiling point. Methane is the main constituent, with a boiling point of -1540~ (-245F). Ethane, with a boiling point of -89% (-128OF) may be present in amounts up to 10 percent; propane, with a boiling point up to -42C (-44OF), up to 3 percent. Butane, pentane, hexane, heptane, and octane may also be present. Physical properties of these gases are given in Table 9-13. Although there is no single composition that may be called typical natural gas, Table 9-14 shows analyses of natural gas in 14 large cities in the United States. Natural gas termed dry has less than 0.013 L of gasoline/m3 (0.1 gal/1000 fts). Above this amount, it is termed wet. The terms wcat and wur arc used IO denote rhe absence or presence of HsS.

gen, and &fur.

Maximum viscosity -for typical storage

2000 500 200 100 50 20 10 6 4

Maximum

viscosity

for pumping and handling

Steam atomization Mechanical atomization

0.6

"'T-3o 0
FIG. 9-5

50

100

150

59

200 190

300 170

4oO'F 2qo"c

Viscosity-temperature

relationships for typical petroleum fuels

I.1

1.0

-0.9 2
-0.8
5 ;

o=

2
-0.7

-0.6

d-II
100
I I I I

250

300 600

350 700

400

450 c

I
100

I
200

I,

0
FIG. 9-6

I 300

I I I I I,
400

I II
500

I I I I I I I I I I,,,,

I
800 F

Thermal conductivity of petroleum liquids. 9-13

9-14

ENERGY UTIUZATION,

CONVERSION, AND RESOURCE CONSERVATION The proven reserves of natural gas in the United States total about 210 trillion cubic feet. Production in 1977 was about 20 trillion cubic feet. This reserves-to-production ratio of 10.5 suggests that natural gas from conventional sources will be seriously depleted by the end of the 1980s. Unconventional natural sources, such as tight sands, Devonian shales, and geopressure zones, would increase natural-gas reserves significantly but at much higher costs. Surface coal gasification processes now being developed may provide substitute natural gas that is more economical than unconventional natural sources. The subsection dealing with coal gasification describes the technologies for making low-, medium-, and high-Btu gas (substitute natural gas) currently being developed. Liquefied Natural Gas (LNG) The advantages of storing and shippin natural gas in liquefied form derive from the fact that 0.03 ms (1 ft ) of liquid methane at - 162C (-26OF) equals about 18 m3 (630 fts) of gaseous methane. Temperatures higher than - 162OC can be used if the liquid is stored under pressure. For example, the liquid state is maintained at 22.4 bar (325 lbf/in*) and -103C (-155OF). The critical temperature of methane is -82C (116F), and the corresponding critical pressure is 46.4 bar (673 Ibf/ ins). One ma(264 gal) weighs 412 kg (910 lb) at -164% (-263OF). The heating value is about 24 MJ/L (86,000 Btu/gal). The heat of vaporization of LNG at 1 bar is about 300 J/m3 (10 Btu/standard fts). It requires 232 MJ to vaporise 1 m30f liquid methane (6575 Btu/fta). LNG is stored in metal double-wall or prestressed concrete tanks, frozen-earth storage, or mined quarries or caverns. Liquefied Petroleum Gas (LPG) The term liquefied petroleum gas is applied to certain specific hydrocarbons which can be liquefied under moderate pressure at normal temperatures but are gaseous under normal atmospheric conditions. The chief constituents of LPG are propane, propylene, butane, butylene, and isobutane, mixed in any proportion or with air. LPG produced in the separation of heavier or more dense hydrocarbons from natural gas is mainly of the paraffinic (saturated) series. LPG derived from oil-refinery gas may contain varying low amounts of olefinic (unsaturated) hydra carbons. LPG is widely used for domestic service, supplied either in tanks or by pipe lines. It is also used to augment natural-gas deliveries on peak days and by some industries as a standby fuel. &formed Gas Although applicable to any gas transformed by suitable treatment, the term re-formed is ordinarily applied to lower-thermal-value gases obtained by the pyrolysis and steam decomposition of high-thermal-value gases such as natural gas, propane, butane, or refinery oil gas. It is sometimes used to meet peakload requirements. These gases, with heating values from 30 to 41 MJ/ Oil Gases m3 (300 to 1100 Btu/fts), are made by thermal decomposition of oils ranging from naphtha to heavy-residuum high-carbon oils. Although of minor importance now in many countries, the lower-Btu gases were distributed as manufactured gas by certain utilities, whereas the high-Btu gases were used primarily to supplement peak-load requirements by companies serving natural gas. Producer Gas This gas is generated by blasting a deep, hot bed of coal or coke continuously with a mixture of air and steam. The products of the process are CO, Ns (from the use of air), small amounts of Hz, and some COI. Because of the large percentage of nitrogen in the gas, the heating value is low [4.4 to 5.3 MJ/ms (125 to 150 Btu/fts)]. Blue Water Gas, Carbureted Water Gas, and Coal Gas These are combustible gases produced from coal or coke (in some cases enriched with oil, natural gas, or LPG) which have continuously declined in use in recent years to an extremely small share of the market. Blast-Furnace Gas This gas is a by-product in the manufacture of pig iron in blast furnaces and is generally used for heating purposes within the plant. The heating value, approximately 3.2 MJ/m (90 Btu/fts), is too low for sale to others. Acetylene Acetylene is used primarily in operations requiring high flame temperature, such as welding and metal cutting. In order

Dlophrogm Pressure

rehef gouge

valve -

---+C
Supply and

return lines
High-pressure supply line, far any number of branch circuits

Pressure Shutoff

gauge
valves

----_,_c

Main-inlet valve far clrcult

shutoff branch

Duplicate pumps with mtegrol pressure-relief wives

Low-oressure return line

Shutoff Duplex

valves oil filter------. Check Suction Shutoff valve-.____ line----wlwe _ oil)----. Far overhead

Tank suction (not required

heater for light

Oil-storage

tank-

Traps FIG. 9-7 Oil-storage

North American

Mfg. Co., Ckwhnd,

tank and main circulating loop. (Combustion Handbmk.

Ohfo &#uJS.)

TABLE

9-l

Commercial Units of Fuel Moaruromont

Multiply by this factor ta get APIpreferred metric unit Cubic meter, m3 1 1.589 873 E - 01 4.546092E-03 3.785 412 E - 03 1.000000E-03 1.13652.3E-03 9.463 529 E -04 Kilazrem. kc 1.016 047 E + 03 O.O71847E+O2 1.01I0 000 E + 03 Cubic decimeter, dm 1.000000E+@3 4.546092E+OO 3.785 412 E + M) :.136523E+00 9.463 529 E - 01 Tonne. t* 1.016 047 E + 00 0.071 847 E - 01 1

Customary unit Volume m3 (264.2 U.S. gal) bbl (42 U.S. gal) Imperial gal (1.201 U.S. gal) us. gal L (0.2642 U.S. gal) Imperial qt (0.3002 U.S. gal) U.S. qt (0.2.wO us. gal)
UPU

Long (U.K.) tan (2240 lb) Short (U.S.) ton (20~1 Ib)t Metric ton (tonne; 2204.616 lb)

Allowable (not official SI) unit. f Not commonly used far petroleum measurement.

TABLE9-12

Chamctwisks of TypicalNonpholeum Fuels Conventional coal-tar fuels from retortine CTF50 CTF 400 1.234 10.3 9-18 At 121% 90.1 5.4 2.4 1.4 0.7 0.15 16.5 36837.9 15.800 to 16.300 Typical coal-derived fuels with different levels of hydrogenationb Minimal 175-280 ,974 8.1 3.1-3.4 At 38OC 86.0 9.1 3.6-4.3 0.9-1.1 (0.2 <O.OOl 9.4
280-500

Synthetic crude oils, by hydrogenation Oil shale 0.817 6.8 Ta1 sand& 0.864 7.2

Mild 160-415 0.964 8.0 3.6 At 38% 87.8 9.7 2.4 0.6

Mild 175-400 0.9607 8.0

Severe 12.5-495 0.914 7.6 2.18 At 38C 89.0 11.1 0.5 0.09 0.04 8.0

Distillation rant C Density, kg/m , 15C lb/US. gal, 60F Viscosity. mm*/s Ultimate analysis, % Carbon Hydrogen Oxygen Nitrogen Sulfur Ash* C/H ratio, weight

1.018 8.5 2-9 At 38C 87.4 7.9 3.6 0.9 0.2 TriKY 11.0 38.4-40.7 16.500 to 17.500

1.072 8.9 5w30 At 38C 89.1 7.5 1.4-1.8 1.2-1.4

o'4io'5
11.9

0.07
9.1

89.6 10.1 0.3 0.04 0.004 8.9

86.1 13.84 0.12 0.01 0.02 6.2

87.1 12.69 0.04 0.07 0.10 6.9

CTF 50, 100, etc., indicate approximate preheat temperature, OF, for atomisation of fuel in burners (terminology used in British Standard B.S. 1469) bPmperties depend on distillation range, as shown, and to a lesser extent on coal source. Using recycle-solvent process. dTar sands, although a form of petroleum, are included in this table for comparison. Inorganic mineral constituents of coal tar fuel: 5 to 50 ppm: Ca, Fe, Pb, Zn (Na. in tar treated with soda ash) 0.05 to 5 ppm: Al, Bi. Cu, Mg, Mn. K. Si, Na, Sn Less than 0.05 ppm: As, B, Cr. Ge. Ti. V, MO Not detected: Sb. Ba. Be, Cd, Co, Ni, Sr, W, Zr Inherent ash is trace or <O.l%, although entrainment in distillation has given values as high as 0.03 to 0.1%.

TABLE 9.13

PhysicalProperties light Hydrocarbona of

a
Moleculurolllmeofp*oa.ft.t.. ~~~%%r:::::::::::::::::::::::::::: k&bon.. ...................................... whydmgm.. .................................... 8Dm@ @tlr: ofllquld Qmt4e - I). ............................. Ofliquid. A.P.I.................................. ofguftiI). ................................. W taa$@lmcIB: e ~!~$$i&~:::.:::::::::::::::::::::::::: ....................

!sii

zi! 10.41

!!3E
Zi: Il:P)

-s&G::::

0.631 2.G

. . d~qbyd..d..;bi...,i:: ..... :.::::::: :: ::: EEl&pfi0tbtmaphri0-i.. ........... =~.%rl%-~: .......

B.t.u./lb:li~~::::...: B.t.u./pl.hquid.. .:. .................... ......... . ........... r-w:.!::?:?::~::.:::.:::::::::::::: AtOT.. ....... . :..: At 33T .......................................... AtmF.. ....................................... AtWF.. ........................................ At IWF ......................................... At IWF.. ....................................... At I3O.F ... ....... .: ... .. .......

Yrz 0155 572.7 -43.7

4.023 21.110 110,a!3 -1: -II -6 4 :I I53 02

::::: ........

..I.. .........................................

I&eat of npLxintl.m atbxilin# II& pint: B.t.u./lb ......................................... B.&p;. ......................................

Ofliquid.atCC,ad6PF..B.t.u. (lb. F.). ......... Of~.atC,sndWF.,B.t.../ 0 6T .I( .) ............. Of mu. J C. and f@F .. B.t.u./Ob.)CF.).

................

............

Johnson and Auth (eds.), Fuels and Combwth Handbook, McGraw-Hill, New York, 1951. To convert British thermal units per cubic foot to megajoules per cubic meter, multiply by 0.0373; to convert British thermal units per pound to megajoules per kilogram, multiply by 0.00232; to convert British thermal units per gallon to megapules per cubic meter, multiply by 0.277; and to convert cubic feet to cubic meters, multiply by 0.0283. Cnl/(lb~mol)(at 60F) X 0.008 = ma/ (kg.mol)(at 1fYC). tIdeal gas = 379.5 ft3. tApparent values for dtssolved methane at 60F. @ased on perfect gas.
9-15

ZX

9-16

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

TABLE 9-14

Analyses of Natural Gas,t

Components of gas, 46 by volume
I H.3XLiIES

City Baltimore, Md. Birmineham. Ala. Boston,vMass. Columbus, Ohio : : Dallas, Texas Houston. Texas Kansas City, MO. Los Angeles, Calif. Milwaukee, Wis. New York, N.Y. Phoenix, Ariz. Salt Lake City, Utah San Francisco, Calif. WashIngton, D.C..

Methane

Ethane 3.40 2.50 3.82 3.58 7.25 4.80 6.42 8.00 5.19 3.29 8.11 5.29 7.01 2.84

Propane 0.60 .67 .93 0.66 2.78 2.00 2.91 1.90 1.89 0.73 2.26 1.69 1.93 0.63

Butanes .32 .28 .22 .48 .30 so .30 .13 .55 .28 .24

1 Pentanes t

olus

CO

N2
2.14 0.39 1.11 2.47 0.13 17.10 2.80 2.73 0.31 1.37 0.82 1.43 0.42

0.60

0.50

::

93.54

86.30
92.50 72.79 86.50

TEUX

permission tram Gas Engineers Handbook, American Gas Association, Industrial Press, New Yorl f Average analyses (1954 data) obtained from the operating utility company(s) supplying the city. The gas supply may vary considerably from these dataespecially where nwxe than one pipe line supplies the city. Also, as new supplies may be received from other sources, the analyses may change. Peak shaving (if used) is not accounted for in these data. NOTE:TO convert British thermal units per cubic foot to megajoules per cubic meter, multiply by 0.0373.

__ . . by _ neproauced

! :I
:

89.01 94.52 87.37 91.17 88.69 95.15

.lO .snl
.16

.03 .05

.lO .02 .09 .oo .03 .oo .05

1.06 0.94 .85 63 .27 .22 so .70 .61 .29 62 .62

Misc.

Heating vahIe,t B.t.u./cu. ft. 1051 1024 1057 1028 IO93 1031 945 lo84 1051 1049 1071 lo82 lo86 lo42

Specific gravity 0.590 ,599 .!?a4 ,597 .641 ,623 ,695 638 ,627 ,595 J33.3 ,614 ,624 ,586

.oo

to transport acetylene, it is dissolved in acetone under pressure and drawn into small containers which are filled with porous material. Hydrogen Used primarily in the production of ammonia and chemicals, in the hydrogenation of fats and oils, and as an oven reducing atmosphere, hydrogen is limited as a fuel to certain special industrial purposes such as cutting and welding. It is made industrially by electrolysis of water, by thermal cracking of natural gas and other hydrocarbons, and by the steam-re-forming reaction. Hydrogen as a nonpolluting fuel gas has been getting considerable attention. Sulfur Impurities Most natural gas is free from sulfur compounds; however, some wells deliver gas containing levels of hydrogen sulfide and sulfur which must be removed before delivery. Pipe-line-company purchase contracts specify maximum limits of impurities; actual HIS and sulfur (after purification) seldom exceed 0.002 and 0.02 g/m3 (0.1 and 1.0 gr/lOO fta) respectively. Hydrogen sulfide in manufactured gases may range from approximately 2.30 g/m3 (100 gr/lOO ft3) in blue and carbureted water gas to several hundred grains in coal and coke-oven gases. Another important sulfur impurity is carbon disulfide, which may be present in amounts varying from 0.007 to 0.07 percent by volume. Smaller amounts of carbon oxysulfide, mercaptans, and thiophene may be found. However, most of the impurities are removed during the purification process and either do not exist in the finished product or are present in only trace amounts. Supercompressibility of Natural Gas All gases deviate from the simple gas laws to a varying extent. This deviation is called supercompressibility and must be taken into account in gas measurement, particularly at high line pressure. For example, since natural gas is more compressible under high pressure at ordinary temperatures than is called for by Boyles law, gas purchased at an elevated pressure gives a greater volume when the pressure is reduced than it would if the gas were ideal. The supercompressibility factor may be expressed as follows: 2 = (RT/PV)Os where Z = supercompressibility factor A = universal gas constant T = gas temperature, absolute P = gas pressure, absolute V = molar gas volume For determining supercompressibility factors of natural-gas mixtures, see A.G.A. Manual for the Determination of Supercompress&t&y Factors for Natural Gas, American Gas Association, New York, 1963; and A.G.A. Gas Measurement Committee Report No. 3,
1969.

FUEL AND ENERGY COSTS Fuel costs vary widely from one area to another because of the cost of the fuel itself and the cost of transportation. Any meaningful cost comparison between fuels would require current costs based on the amounts used at a particular geographical location, utilization efficiencies or energy-ratio data for the equipment involved, the effects of form value, etc. Although the costs given in Table 9-15 will not apply to specific locations, they do give fuel-cost trends. Figures 9-8 and 9-9 are charts for comparing fuel and energy costs. COAL CONVERSION TO LIQUID AND GASROUS FUELS AND FEEDSTOCKS FOR THE CHEMICAL-PROCESS INDUSTRIES Converting coal to environmentally acceptable synthetic gaseous and liquid hydrocarbons would supplement the dwindling reserves of petroleum and natural gas of the United States and help reduce national dependence on imported fuels. Coal gasification yields a wide variety of useful products for the residential, utility, and industrial markets. A medium-Btu gas (MBG), produced by gasifying coal with oxygen and steam, can be upgraded to substitute natural gas (SNG) for distribution in existing natural-gas pipe lines, or MBG can be used for firing boilers and kilns and as a feedstock for the catalytic synthesis of chemicals. A 1owBtu gas (LBG), produced by gasifying coal with air and steam, can be used close to gasifier sites to fire boilers, kilns, and several other industrial processes that now depend on petroleum and natural gas. Coal liquefaction, effected by hydrogenating coal at high temperature and pressure, yields low-ash, low-sulfur boiler fuels for electric

TABLE 9-15

Time-PriceRelationshipsfor Fossil Fuels

Bituminous coal and lignite, $/ ton Natural gas at wellhead, cents/loo0 standard ftS 10.4 14.0 15.6 17.1 52.0 Crude petroleum at wellhead, $/ bbl 2.77 2.88 2.66 3.18 6.851

1955 1960 1965 1970 1975

4.50 4.69 4.44 6.26 18.75

SOURCE: MIneral Facts and Problems, U.S. Bur. Mines Bull. 667, 1975. All average annual prices f 1974.

COAL GASIFICATION

9-17

IZ

I
A

20

10
Y

FIG. 9-O Comparing power-plant fuel costs. The difference in fuel costs between alternative generating plants is found easily with the nomograph. Knowing fuel costs in cents per million British thermal units and plant heat
rates in British thermal units-per kilowatthour makes it possible to find a fuelcost differential factor in dollars ner hour-megawatt. This number. when multiplied by unit output in rnega&tts and unit &rating hours, gives the differ-

ential fuel cast in dollars. (Courtesy Power.)

power generation, process heating, and making high-grade fuels such as gasoline and chemical feedstocks. Coal pyrolysis, or thermal decomposition, and the catalytic hydrogenation of carbon monoxide (from coal gasification) are also sources of liquid fuels and chemical feedstocks. Bodle, Vyas, and Talwalker (Clean Fuels from Coal Symposium II, Institute of Gas Technology, Chicago, 1975) presented the chart in Fig. 9-10, which shows very simply the different routes from coal to clean gases and liquids. Coal gasification and liquefaction are old technologies; current research, development, and demonstration efforts are aimed toward technical and economic improvements in some of the old, or firstgeneration, technologies and toward seeking new ways to accomplish the same ends: cheap and clean coal-conversion processes.

COAL GASIFICATION CEN~~LREFEREN~E~: Fuel Cmtjicaffm,symposium sponsored by American

Chemical Society, 157d meeting, Sept. 12-13, 1966. Von Fredersdorff and Elliott, Chemfstry of Coal Uttltzatia, suppl. vol., ed by H. H. Lowry. Wiley, New York, 1963. ChemLstry of Cwl Uttliurtbn, 2d suppl. vol., ed by M.A. Elliott, Wiley, New York, 1981.

Background Converting coal to combustible gas has been practiced commercially since early in the nineteenth century. The first gas-producing companies were chartered in 1812 in England and 1816 in the United States to produce gas for illumination by the heating or pyrolysis of coal. This method of producing gas is still in use as a by-product of the carbonixation of coal to produce coke for metallurgical purposes. The advantages of a gaseous fuel as a source of heat and power increased the use of coal for gas generation. The gas producer, in which a downward-moving bed of coal or coke is reacted with air and steam, was extensively used to prepare a gas of relatively low thermal content per unit volume, 3.7 to 6.0 MJ/ms. The development of the cyclic water-gas process in 1873 permitted the continuous production of gas of higher thermal content, II.2 to 13.0 MJ/m? By adding oil to the reactor, the thermal content of

the gas was increased to from 18.6 to 20.5 MJ/ms. This type of gas, carbureted water gas, was distributed in urban areas of the United States as a fuel gas for residential and commercial uses until its displacement by lower-cost natural gas began in the 1940s. At approximately that time, development of oxygen-based gasification processes was initiated in both the United States and other countries. An early gasification process developed by Lurgi Kohle u Mineralijltechnik GmbH at that time, which operated at elevated pressure, is still in use, as are many producer-gas systems. Table 9-16 lists the composition of the coal-derived gases produced by these methods. Theoretical Considerations The chemistry of coal gasification can be depicted by conveniently assuming coal as carbon and by listing the several well-known reactions involved; see Table 9-17. Reaction (g-13) is the combustion of carbon and oxygen, which is highly exothermic. This reaction supplies most of the thermal energy for the gasification process. The oxygen may be used as pure oxygen or be contained in air. Reactions (g-15) and (9-16) are endothermic and represent the conversion of carbon to combustible gases. These are driven by the heat energy supplied by Reaction (9-13). As hydrogen and carbon monoxide are produced by the gasification reaction, these gases react with each other and with carbon. The reaction of hydrogen with carbon as shown in Reaction (9-14) is exothermic and can contribute heat energy. Similarly, the methanation reaction (9-18) can contribute heat energy to the gasification. These equations are interrelated by the water-gas-shift reaction (g-17), the equilibrium of which controls the extent of Reactions (9-15) and (916). It has been shown by several authors (cf. Gumz, Gas Producers and BkastFurnaces, Wiley, New York, 1950; and chapter on gasification by Elliott and van Fredersdorff, Chemistry of Coal Utlkaetion, suppl. vol., ed by Lowry, Wiley, New York, 1965) that all the reactions could be based on three fundamental reactions: the Boudouard reaction (g-16), the heterogeneous water-gas reaction (g-15), and the equation for methane formation by the hydrogasification reaction (9-14). The equilibrium constants for these reactions are sufficient to calculate all the reactions listed. It is not possible to calculate accurately actual gas composition by using the relationships of Reactions (9-13) to (9-18) in Table 9-17. Since the gasification of coal always takes place at elevated temperatures, thermal decomposition, or pyrolysis, takes place as coal enters the gasification reactor and is exposed to these temperatures. Reaction (9-19) treats coal as a compound of carbon and hydrogen and postulates its thermal disintegration to produce carbon (coke) and methane. Reaction (9-20) assumes the stoichiometry of hydrogasifying part of the carbon to produce methane and carbon. These reactions as well as those involving the other elemental constituents of coal take place during gasification. It is possible to utilize these reactions and their relationships with each other for predicting the effects of changes in the operating parameters of gasification. At higher temperatures, endothermic reactions are favored at the expense of exothermic reactions. We can expect a decrease in methane production as Reactions (9-14) and (918) will proceed at a lower rate, CO production will be favored, and all reaction rates will increase in the direction in which heat absorp tion takes place. An increase in pressure will favor those reactions in which a smaller number of moles (or volumes) is formed At higher pressures, production of COs will be favored as well as that of methane. The knowledge of stoichiometry, equilibrium conditions, and rates for these gasification reactions provides a sound basis for modcling and extrapolating gasification systems. A great deal depends on the gasifier system, coal reactivity and particle size, and method of contacting coal with gaseous reactants (steam and air or oxygen). It is generally believed that oxygen reacts completely in very short distances from the point at which it is mixed or comes in contact with coal or char. The heat evolved acts to pyrolyze the coal, and the char formed will then react with carbon dioxide, steam, or other gases formed by the combustion and pyrolysis of coal and char. The assumption made in Table 9-17 that the solid reactant is carbon is probably close to being correct. The conversion of coal to char and the type of char formed affect the kinetics of gas-solid reactions. While the reaction rate does vary with tem-

Cosl of eleclriclty.

$;kWh

Typical Heating V&KS Fuel oil, Btu/gal No. 1 No. 2 No. 4 No. 5 No. 6 Propane, Btu/gal Natural gas. Btu/f? Coal. Btu/lb Bituminous S&bituminous Lignite Steam, Btu/lb Electricity, Btu/kWh Resistance heating Heat pumps 137,400 139.600 145,1clo 148,800 152,400 91,500 1035 11.50&14,oQo 8,3cc-11,500 6,30&8,300 1,012 3,413 up to 13,oQo

To convert British thermal units per gallon to kilograms per cubic meter, multiply by 278.7; to convert British thermal units per cubic foot to kilojades per cubic meter, multiply by 37.3; to convert British thermal units per pound to kilojoules per kilogram, multiply by 2.326; and to cunvert British thermal units per kilowatthour to kilojo& per kilowatthour, multiply by 1.055. FIG. 9-9 9-18 Comparing pr cces-alergy cxxts. (courtesy Power.)

COAL GASIFICATION

9-19

Clea gaseous fuels

Hz, steam or synthesis gas Preparation : Hydrocarbon Clean hqwd fuels

Cool-deriyed

liquid

Slurry

Hz

preparot1on Dissolution an solvent t HZ Direct desulfurizotion by physical, chemical or thermal treatment

Alr pyritic SUlflJr

Solidification

Solvent w refined COOI b Cool

Clean solid fuels

The production of clean fuels from coal. (Boaed on W. &d&z, FIG. 9-10 Coal Symposium II, Institute of Gas Technology, Chicago, 1975.)

K. VYOJ, and

A. Tdudker,

Clean

Fuels

from

perature as in all chemical reactions, the overall rate of reaction is controlled probably by the chemical reaction rate below 1000C (1832F). Above this, pore diffusion has an overriding effect, and at very high temperatures surface-film diffusion probably controls. Thus, for many gasification processes the reactivity of the char is quite important. This may depend not only on parent-coal characteristics but also on the method of heating, rate of heating, and particle-gas dynamics. The importance of these concepts can be illustrated by the extent TABLE9- 16 Rq2wi.s of coocDwiied Gas.8

to which the pyrolysis reactions contribute to gas production. In a moving-bed gasifier (e.g., producer-gas gasifier), the particle is heated through several distinct zones of carbonization, char devolatilization, char gasification, and fixed-carbon combustion. As much as 15 to 17 percent of total gas production is liberated in the coal carbonization, almost 2.3 percent may be produced by char devolatilization, and some 60 percent is generated by actual gasification of the remaining char. This emphasizes the importance of coal quality or reactivity.

Carbureted water Coke-oven gas

Reactant system Pyrolysis Producer gas Water gas b3.s Air plus steam

Synthetic coal
%-

Steam (cyclic-air)

Steam (cyclic-air)

Oxygen plus steam at prersure

15.6 40.6 10.9 31.3 2.4 10.6 (290) Fuel, chemicals

Andysis,

volume 46
6.8 47.3 33.9 2.2 6.0 3.0 22.0 (590) Fuel, chemicals 27.0 14.0 3.0 4.5 50.9 0.5 5.6 KY 42.6 49.9 0.5 3.0 3.3 0.5 11.5 (306) Fuel, chemicals 33.4 34.6 10.4 3.9 7.9 9.6 20.0 Ki

Carbon monoxide, CO Hydrogen, Hp Methane, CH, Carbon dioxide, CO2 Nitrogen, Np Othert Fuel value. hlJ/ms (Btu/ ftss)
Analyser

and fuel valuea vary with

the type of coal and operating

conditions

tOther contents include hydrocarbon gases other than methane, hydrogen r&de, and small amounts of other impurities.

9-20

ENERGY UTIUZATION,
TABLE 9-17

CONVERSION,

AND RESOURCE CONSERVATION

Chemical Reactions in Coal Gasification

Reaction heat. kl/lkcmol) Solid-gas reactions Combustion Hydrogasification steam-carbon Boudouard Gas-phase reaction Pr@XSS Number

Reaction

c + op-cop C + 2Hz.CH, C + Hz0 - CO + Hz c+cop-2co

+393,7QO +74,900 - 175,440 - 172,560

(Q-15) (Q-16)

CO + HpO - Hp + CO* CO + 3Hp - CH, + HpO

+2,653 +250,340 Pyrolysis and hydropyrolysis

Water-gas shift Methanation

CHx
CHx + mHn

(1-:)C+($)CH,

Pyrolysis

(Q-19)

[1-(F)]C+(F)CH,

Hydropyrolysis

(Q-20)

Types of Available Gasification Equipment The fundamental chemistry and physics of gasification motivate the design of existing and advanced gasifiers. The equations listed in Table 9-17 show that a logical means of contacting a solid particle with a gaseous reactant is necessary, that the transfer of heat within the gasifier (and to the gasifier) is a critical parameter, and that variations in pressure and temperature alter the composition of the gas produced. In addition, the type of coal and the composition of both organic and inorganic constituents have a strong influence on gas composition and applicability of various gasification systems. Several gasification Moving bed

Ash
Fluidized bad

Temperature

oC

Coat o-5mm

Gas

Gas

systems designed for contacting particles of coal with gaseous reactants at temperatures above 700C (1292F) are shown in Figure 9-11. The three main types of reactors shown in Figure 9-11 are in actual commercial use: the moving bed (often referred to as a fixed bed), the fluid&d bed, and the entrained or suspension flow reactor. These differ in size consist of coal fed, reactant and product flow, residence time, and reaction temperatures. This type of gasifier was one of the earMoving-Bed Reactorr liest used. It requires a coal particle size of 2 to 50 mm and is commercially used with air or oxygen. Steam and oxygen (air) are introduced, and ashes leave at the bottom of the reactor; coal is fed, and product gases leave at the top. The low temperature differentials between incoming and outgoing flows indicate the efficient transfer of heat between gaseous and solid reactants and products. Noteworthy is the relatively low temperature of product-gas effluent, which for some coals is below 500% (932F). This low temperature results in a minimum of energy contained as sensible heat in the product gases with a resultant decrease in oxygen usage and an improved thermal efficiency. The countercurrent Bow, low exit-gas temperature, and use of a mechanical grate at the bottom of these moving-bed systems cause some disadvantages. To protect the grate, steam in greater quantity than required for reaction is injected to reduce the bottom temperature. This impresses a negative thermal input and reduces overall efficiency. The coal as it enters is subject to pyrolysis as it passes down the gasifier, and tars and oils which must be recovered and/or utilized are produced. The resultant mixture of organic liquids and water condensate must be separated and the water purified prior to discharge. Finally, the need to dispose of the portion of the run-ofmine coal which is too fine to be used for feed can be an economic burden. Reasonable procedures are available for meeting some of these
prnhlemP Snnme nf thrrp ~~~rr,=ntly Ling ~atili?~J in nthe7 ,vwntries

90

m Temperature

MO

Residual Entrained

char

Gas

oC :

suspension

Ash

Coal

Ash FIG. 9-11 Coal-gasification systems

may require modification to meet Environmental conditions in the United States. Considerable progress has been made toward this end by the Lurgi Kohle u Mineralijltechnik GmbH for their Lurgi gasifier. While many moving-bed gasifiers are available, the Lurgi is currently the only gasifier that is commercially available for operation at elevated pressure. Units are routinely being operated at pressures of 30 bar (450 psig). An outline sketch of the pressurized Lurgi gasifier is shown in Fig. 9-12. Also shown is the outline of the first step in purifying the gas: a multiple-venturi water scrubber. The maximum reactor size for the Lurgi gasifier is currently 3.9 m (12.8 ft) in internal diameter. The capacity of this size of gasifier depends on coal quality and has been able to handle approximately 750-GJ coal input/h, equivalent to more than 25,ooO kg/h (55,115 lb/h) of coal or 70,000 m3/h (245,700 ft3/h) of gas production. While stirrers have been designed to break up agglomerates so that caking coals can be handled, limited commercial experience is available with such coals.

COAL GASIFICATION

9-2 1

Condenrate

Prccerr

steam

Steam and oxygen

Crude gas

Ash

FIG. 9-13

Winkler gasifier

Ash

FIG. 9-12

Lurgi gas&r.

Fluidized-Bed Reactors The commercial gasification of coal with oxygen (air) and steam began with the use of a tluidized-bed reactor developed by Winkler (German Patent 437,970, filed Sept. 28, 1922). The coal is usually ground to sizes below 8 mm (%s in), which allows the entire run-of-mine coal output to be utilized. In contrast to the moving-bed reactor, the iluidized-bed reactor is essentially a completely mixed, partially cocurrent reactor. In the Winkler generator, coal is injected into the fluidized bed and the reactant gases are injected at two levels in the iluidized bed to maximize carbon conversion. The present commercial units are operated at essentially atmospheric pressure and are used primarily with reactive coal or with chars derived from lignite carbonisation. Figure 9-13 shows an outline sketch of a Winkler gasifier. The fluidized-bed reactor normally operates at higher temperatures than the moving-bed reactor and, being a completely mixed system, results in a higher outlet-gas temperature. This reduces efficiency but does destroy tars and oils and reduces the water-contamination problem. The major problem in any fluidized-bed system is the extent of carbon conversion and the carry-over of fine particles from the reactor. Normally, this carry-over has a high carbon content and must be collected and used for boiler fuel to avoid economic losses. The gasifiers currently in commercial use have internal diameters in excess of 4 m and are 20 m in height. Production of more than 50,000 ms/h of gas is achieved by the Winkler gasifier (equivalent to 540 CJ/h or 18,000 kg/h of bituminous coal) even though the gasifier is operated at atmospheric pressure.

The Winkler gasifier cannot handle agglomerating coals, as the formation of such agglomerates would disrupt the uniformity of the fluidized bed Similarly, coals containing ash of low fusion temperature could cause difficulties by forming ash agglomerates. Efforts in solving these problems and increasing operating pressure are being actively pursued. Entrained or Suspension Gasification Entrained gasification in the Koppers-Totzek gasifier, shown in Fig. 9-14, takes place at temperatures close to 15OOC (2732OF), using fine particles of coal at short residence times. The process is cocurrent with coal particles entrained in the turbulent reactant gases. The Koppers-Totzek pro cess, currently operated at atmospheric pressure, is the most widely utilized commercial example of entrained gasification. More than 50

FIG. 9-14

Koppers-To&k

gas&r.

9-22

ENERGY UtlUZATION,

CONVERSION,

AND RESOURCE CONSERVATION tory life, and slag control. The rapid reaction rate requires good control to prevent an exces of oxygen should the coal feed be interrupted. There is no reservoir of carbon, as is available in either the moving- or the fluidized-bed reactors. Operation at atmospheric pressure is a handicap, and considerable development effort is in progress to provide a pressurized system. Present capacity at atmo spheric pressure can reach 360 GJ/h (360 X lo6 Btu/h) per gasifier, equivalent to 13,000 kg/h (28,660 lb/h) of bituminous coal for the two-headed gasifier shown in Fig. 9-14. Recent development and commercial adaptation of a four-headed unit have doubled these throughputs. Development and Utilization Both government and industry are sponsoring large development programs aimed at alleviating the various disadvantages of presently available commercial gasifiers. These programs involve all types of gasifiers and have as major objectives increased operating pressures, reduced reactant consumption, decreased capital costs, and improved product quality. Many of these developments have reached the pilot-plant stage and appear to justify commercial consideration. Table 9-18 lists several commercial and developmental gasification systems. The data are all based on 100 kg (2205 lb) of moisture-and-ash-free (maf) coal. The two moving-bed systems shown have essentially the same reactor configuration except that the BG/Lurgi unit eliminates the grate, utilizing a slagging bottom with a large reduction in steam input. This raises the average temperature and increases throughput. The critical difference is the reduction in specific steam consumption (kg steam/kg coal gasified) by a factor of almost 5. This reduces unreacted steam in the gasifier and thereby the total gas volume, which in turn reduces solids carry-over and gas-handling costs downstream from the gasifier. The lower steam input results in a reduced Hs/CO ratio and reduced CH, and COs concentration in the product gas. Carbon conversions are similar for both moving-bed units. The problems of tars and oils are also similar, but progress has been made in recycling heavy tars and contained fines back to the gasifier. The effect of increasing pressure is shown dramatically by comparing the two fluidized-bed gasifiers in Table 9-18. The HYGAS unit operates at much higher pressures and, by using staged fluid&d beds, achieves a low gas-exit temperature. The result is a large decrease in specific oxygen consumption (kg oxygen/kg coal gasi-

gasifien of this type have been built, mostly for producing ammoniasynthesis gas. Because of the short reaction time, usually only a few seconds, coal particles are very rapidly devolatilized and lose any inherent characteristics of the original coal. All types of coal can be handled in Koppers-To&k gasifiers. The high operating temperature effectively gasifies all hydrocarbons, tars, or phenolics which may be formed during gasification. This reduces gas-purification and watercondensate-handling problems. Pulverized coal (90 percent less than 200-mesh) is screw-fed from hoppers to burners in which oxygen and steam convey coal at velocities in excess of flame-propagation rates into the gasifier. The temperature at the burner nozzles may reach 1900C (3452OF). Gas temperatures at the reactor exit may be close to 1500C (2732OF). At these high temperatures, the mineral content of the coal is in molten form, and part of it is removed from the gasifier as a slag or melt. Part of the ash is carried overhead in particulate form and is removed in water scrubbers. While the Koppers-Totzek type of gasifier can handle all types of coal, careful attention must be paid to ash characteristics. Generally, one can characterize two general classes of slags produced from coal ash: a short slag, in which the temperature differential between softening and flow point is small; and long slags, in which this temperature differential is large and there are phases of sintering, clinker formation, softening, and finally flowing. The short slags are ideally suited for high-temperature entrained gasification. In addition to this general description, there are important criteria of slag viscosity. This should be less than 2.5 Pa.s (250 P) for suitable drainage of slag from powdered-fuel-slagging systems operating at atmospheric pressure. The slag chemistry is also critical, as high-silica slags present problems of both high viscosity and the potential of silica vaporization at temperatures of 1650C (3362OF). [For detailed data on slag behavior and characterizations, see Hoy, Roberts, and Wilkins, Inst. Gas Eng. J., 444469 (June 1965)]. The entrained gasifier offers many advantages: the ability to handle a wide variety of coals, the elimination of tar and oil formation, and a conveniently disposable water-condensate and solid residue. The latter is generally free of carbonaceous matter and low in leachability. There are problems of handling high temperatures, refrac-

TABLE9-18

Commmial

and Dwolopmontal

GasiioGon

Processes, Oxy~wwBbwn
BG,%q,i .1.&& pilot plant 440 20 2100 337 461 275 1744 2.5 60.6 27.8 7.6 1.5 14.2 0.46 1939 517

Reactant Consumption,
Fluid&d bed
planta

and Gas Production

Entrained Bow K~&S,J-TlA.,
commercial

Moving bed
Lur_si e-tr. commercial

WinI&.,
commercial

IIYcx.S, PiI1 340 70 6900 213 1642 24.7 24.0 30.5 19.4 1.4 14.5 1.27 1850 542
304 684

Trr.w,
Phe

yilu1

Gas exit temperature, OC Pressure. bar Feed capacity, GJ/(h.gasifier) Reactants and products per 1000 kg -lb Oxygen, nM
Oxygen, kg

560 750 247 352 1336 2050 29.7 16.9 39.1 11.3 1.0 12.3 2.1
30

700 atm 600 490 700 516 1900 20.0 34.0 41.0 3.0 2.0 10.7 1.21 1596 413

1290

atm 380
587 638 300 2016 71 56.7 32 8 1.4 11.6 0.56 1645 462

1290 40 410 657 953 2136

Steam, kg Dry raw product gas, nMs Gas analysis, volume 96 Carbon dioxide, COs Carbon monoxide, COP Hydrogen, Hs Methane. CIC
Otherd

.C

Fuel value, MJ/nM H&O, volume ratio Product utilization Equivalent synthesis gas, nMs/lOOO kg coal Equivalent SNG. (CH& nMs/lO@l kg c!clal

10.6 51.6 35.1 0.1 2.6 11.1 0.68 1966 470

pilot Plants are of various sizes: BC/Lurgi. 12,ooOkg/h; HYCAS, 2500 kg/h; -rexam, E@Okg/h. bu on moisture-and-ash-free (maf) coal with fuel value approximatelv 30 G[/lOOOkc. _ Texaco feeds coal slurried with water (60% coal); no other st&m added . dIncludes nitroaen and various imourities (Ha. COS. NH*. etc.). Synthes_is &uned equal to &n of Hs: dd, and h X ?Hi &entration. gas Methane potential assumed equal to methane (CH,) concentration plus %(Hs + CO) concentration

COAL GASIFICATION fied). The much higher pressure favors methane production and a higher COs level in exit gas. The results shown for the developmental HYGAS processes are tentative; additional operation to confirm them is required. Winkler is operating a single-stage tluidized-bed pilot plant at pressures up to 10 bar. While elevated pressure will decrease compression costs (oxygen volumes are one-fourth or less of the volume of product gas), carbon conversion is not appreciably improved. The HYGAS process, by utilizing several fluid&d beds, does achieve some improvement. Two processes, Westinghouse and U gas, report succes in agglomerating the ash particles by allowing higher temperature at the bottom of the bed. The low-carbon agglomerates are discharged preferentially owing to their larger size. Several processes utilize the high heattransfer capability and solids mobility to supply external heat to the gasification reaction. The COs acceptor process uses the exothermic absorption of COs by calcined limestone or dolomite to supply heat for the steam-carbon reaction. Pilot-plant tests have demonstrated technical feasibility but not economic viability. The COGAS process supplies heat by burning part of the char externally with air and recycling the hot char to the steam-carbon reactor. The use of nuclear heat has been suggested in Germany, where high-cost coal could be saved by this means. All processes operated without the use of oxygen can effect a saving since the oxygen plant is of an order of magnitude of capital cost similar to that of the gasification system. However, these processes cannot be considered as operational in the commercial sense. Operation at elevated pressure can benefit the performance of an entrained-flow gasifier by reducing compression cost. KruppKoppers, the parent firm supplying the Koppers-Totzek gasifier, has joined with Shell Oil to develop a pressurized version. This version should provide a gasifier of higher throughput and gas production at a lower cost primarily through a reduction of compression cost. In Table 9-18 data are provided for a pressurized Texaco unit. Both atmospheric and pressurized entrained-tlow gasifiers have an exit-gas temperature above 1250C (2282F), and this results in a high oxygen requirement. Efficient heat recovery and utilisation of thermal energy in the gas&r exit gases are mandatory for recovery of the energy required for oxygen production and gas compression. For elevated-oressure oneration of entrained-flow easifiers. a reliable coal-feed system is a critical requirement. No carbon inventory
in rhr msifkr ip avnilnhlr tn ~vnid hirrh nxvw=n mnrentrationc if rnal

9-23

feed is-interrupted. The Texaco ga&er I& a pumped coal-waterslurry feed. The water content of such a slurry must be minimized to avoid high thermal penalties. The higher oxygen usage due to evaporating the water of a 65 percent coal-water slurry may be noted in Table 9-18 when the Texaco results are compared with those of Koppers-Totzek. The use of coal-derived gases as a fuel is a well-known technique, but other important uses of such gases are addressed in Table 9-18. Conversion of raw product gas to a synthesis gas by re-forming its methane content is calculated for each of the processes. Similarly, conversion of product gas to methane is estimated by adjusting the hydrogen-tecarbon-monoxide ratio by the water-gas-shift reaction followed by methanation. Those processes which produce high methane concentration in the raw product gas are best suited for producing synthetic natural gas or methane (see HYGAS data). For such conversions, the ratio of hydrogen to carbon monoxide is an important factor, and this ratio is listed for each process. The processes using high temperatures and low steam-to-coal ratios produce a gas rich in carbon monoxide. For producing hydrogen or hydrcgen-rich synthesis gases, the carbon monoxide may be reacted with steam in a catalytic reactor external to the gasifier. The added steam must be considered in any overall evaluation of a gasification process. For example, if a hydrogen-to-carbon monoxide ratio of 2 is required in using a BG/Lurgi gasifier, an additional 437 kg (961 lb) of steam would be required for converting carbon monoxide to hydrogen. This would increase total steam consumption from 275 to 712 kg/ 1000 kg coal (0.275 to 0.712 lb/lb coal). While this would still be less steam than required by the Lurgi grate-type gasifier, the advantage of dependence on product-gas requirements is an important factor to be considered.

For this reason, any attempt to calculate the efficiency of gasification should be related to final product requirements and plant design. All the data are available in Table 9-18 to calculate the heating value of products and relate them to the energy input in the 1000 kg of coal used as a basis. However, use of the crude product gas as a final product can be misleading, as shown by the added steam required for producing a 2: 1 synthesis gas. In addition, the energy used in the actual process must be considered, and this will depend on the use of waste heat to produce steam, power, or other needed energy forms for process use Also given in Table 9-18 is an estimate of the possible coal throughput for a single gasifier of each type. The commercial extrapolations for coal throughput for pilot-plant processe.s are based on published data. The process proponents have shown varying optimism. The oxygen-blown gasifiers shown in Table 9-18 are probably of greatest industrial interest. In addition to producing a fuel gas undiluted by nitrogen, they offer a potential of supplying synthesis gas for chemical use and synthetic natural gas (SNG) for pipe-line transport, which extends the marketability of oxygen-blown gasification systems. In some cases, air-blown gasifiers may offer an advantage when fuel gas is desired. The use of air as a reactant does eliminate the capital cost and power required for operating an oxygen plant. This saving is negated to some extent by the need to purify larger volumes of product gas diluted with nitrogen. The lower fuel value of these product gases prevents economical pipe-line transport and mandates use of the fuel gases close to the point of production. Some estimates do show a 10 to 15 percent lower cost per unit of heating value for the products of air-blown gasification versus oxygen-blown product gases. Data are provided for two air-blown systems in Table 9-19. The gases produced are similar in characteristics to the producer gas shown in Table 9-16. This table can be conveniently compared with Table 9-18, so that downstream gas volumes and purification-unit sizes can be estimated and compared for oxygen- and air-blown gasifiers. Owing to the use of air, larger volumes of lower-fuel-content product gas are obtained. As in the case of oxygen systems, a higher gas exit temperature requires more air usage and results in a lower fuel value. It should be noted that the Combustion Engineering gasifier shown in Table 9-19 is not a commercial system, but the data are based on pilot-plant nperatinn which has heen ex~rarmlated to a commercial siw. In an attempt to improve the heat recovery of the high-temperature-gasifier product, the Combustion Engineering gasifier injects coal feed

TABLE 9-19 Commwcial and Dovolopmontal Gasifiws; Ai-RbwnRoactont Consumption and Gas Production Moving bed Lllrgi, grate-type; Entrained flow, Combustion

Engineering;
Dibt Dht

commercial
Gas exit temperature, OC Pressure, bar Feed capacity, CJ/h/gasifier Reactants and products per 1006 kg malt 535 20 750

927 atm 2700

Air, nMs

Air, kg Steam. kg Dry, raw product gas, nM3 Gas analysis, volume 96 Carbon dioxide, CO* Carbon monoxide, CO Hydrogen, Hn Methane, CH, g~~vn, Nn Fuel value, MJ/nMi

1920 2560 1650 2695 13.5 16.5 23.8 4.0 41.3 0.9 6.4

3561 4880 Non.? 5322 5.1 22.3 11.2 57.4 4.0 4.0

Pilot plant has capacity of 4500 kg/h of COPI. tBsed on moisture-and-ash-free (maf) coal with a fuel value of 30 GJ/1000

/ kg.

tlncludes sane hydrocarbons, moisture, and sulfur compounds.

9-24

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION anation reaction is highly exothermic, and the heat released is usually utilized to produce steam, which may be used for heating or for providing power. The centrality of gasification to all coal-conversion processes is illustrated by the end products and their potential uses. The mixture of hydrogen and carbon monoxide produced as synthesis gas may be used to prepare chemicals or converted to liquid hydrocarbons (indirect liquefaction). By altering the steam-togas ratio in the shift reactor, pure hydrogen may be produced for use in ammonia manufacture and petroleum refining. Finally, for direct liquefaction, or hydrogenation of coal, hydrogen must be supplied generally through gasification of coal or unreacted residua of the hydrogenation process. Most of the processing steps Gas Purification and Refinement shown in Fig. 9-15 upstream and downstream of the actual coal-gasification unit are of conventional design. The handling, storage, size reduction, and feeding of coal are discussed in other portions of this section and in other sections of this handbook (see Solid Fuels: Coal and Solid-Fuels Combustion on Stokers and in Suspension in this section and also Sets. 7 and 8). The removal of particulates and drop lets of oil and tar from raw product gases is also a generally well known processing step. Figure 9-12, depicting a Lurgi gasifier, includes a gas washer of relatively simple but effective design. Additional information on gas scrubbing is available in Sets. 14 and 18, where the engineering of such systems is discussed. Adjustment of gas composition by the water-gas-shift reaction, using an external catalytic reactor, is shown in Fig. 9-15 and has been previously discussed. The recent development of sulfur-resistant catalysts for this reaction allows some choice as to the location of this processing step. Designers of total plant systems have shown a preference for locating the shift reactor immediately after the particulate-removal units; in a pressurized system, this allows for a high gas exit temperature. This location permits the use of steam in the gasifier product gas in the shift reaction and eliminates the need for reheating gases after complete sulfur removal. An important function of the gas-purification section of a coal-gasification plant is the removal of COs and HaS (acid gases). A variety of chemical and physical solvents are offered by various proprietary processes for removing acid gases. Table 9-20 lists one or two typical solvents for each class of absorbents. The alkaline amines and hot

into these hot gases to enrich the product gas through pyrolysis of the coal. It is not possible to identify all the gasifiers under development or in use throughout the world in this brief discussion. It should be noted that many brands of small air-blown moving-bed gasifiers are commercially available. Most of these are analogous to the Lurgi shown in Table 9-18, except that they operate at atmospheric pressure. This decrease in pressure would reduce methane formation and decrease gasifier throughput. Other gasifiers under development utiliae molten salts, metals, or slags as a medium to improve contact between solid and gaseous reactants. Many of these systems are in too early a stage of development to provide meaningful product-gas and reactant usage information. The use of alkali catalysts to increase the rate of steam-carbon and methane formation is reported as showing promise in bench-scale and process-development units (PDUs). The data indicate that lower operating temperatures may be achieved and the use of oxygen eliminated because of the exothermic methane-forming reactions. Further data on catalyst recovery and downstream processing are needed to establish the technical and engineering feasibility of such processes. Application of Coal Gasification While Table 9-19 mentions some of the products that can be obtained by refining the raw-gas output of the gasifier, application of coal gasification involves considerable processing downstream of the gasifier. Figure 9-15 is a composite flow plan indicating some of the complexities of such processing. The area denoted as Gasification includes the supply of coal and gaseous reactants (air or oxygen and steam). The particulate matter, dust, and tars must be removed and the sulfur content lowered to meet regulations for the combustion of gaseous fuels. At this point, the gasifier output has been converted to a usable fuel: lowBtu fuel gas for air-blown gasifiers and medium-Btu fuel gas for oxygen-blown gasihers. The area denoted as Product Refinement includes more complete removal of sulfur to avoid deactivation of catalysts; adjustment of gas composition using the water-gas-shift reaction [see Reaction (g-17), Table g-171; and, to produce high-Btu or pipe-line gas (also called SNG), complete conversion to methane [see Reaction (g-18), Table g-171. As can be noted from Table 9-17, the water-gas-shift reaction is slightly exothermic but requires the addition of steam, which results in an energy drain on the overall process. The meth-

-Garilication_~~ FIG. 9-15 General

Product Rellnenlenf-

systems description: surface-coal gasification.

DIRECT COAL UQUEFACTION TABLE9-20 Acid-Gas-RemovalSystems Coal GasScation for Operating ranges, CO1 partial pressure LOW LOW Moderate Moderate High High Moderate Selectivity H&/CO9 1 3 6 9 7 9 1 COp/HC 8 a 9 9 2 3 3 Utility requirementst 10 7 4 4 2 1 5

9-25

solvents Amines MEA TEA Hot carbonate Benfield Giammarcp Vetrocoke Physical solvents Methanol (R&is& selexol Mixed solvents Methanol plus DCA

sowxx Fleming and Primack (IGT), presented at gist National Meeting, AIChE. Kansas City, MO, April 1976. Arbitrary number scale, 1 to 10: 1 = poor and 10 = excellent selectivity. futility consumption, 1 to 10: 1 = low and 10 = high utility use. tMEA, methylethanolamine; TEA, triethanolamine.

carbonate solutions react chemically with acidic gases. These solvents require heating to regenerate them and remove the acid gases. As a result, utility consumption is high. Physical solvents can be regenerated with only minor use of heat energy but operate only at elevated pressure. An important characteristic is solvent selectivity. For cleansing a gas to be used as a fuel, the only acidic components which must be removed are those containing sulfur. For such systems, a physical solvent such as Selexol (trade name of the Allied Chemical Company) would be ideal. The amine solvents, which were originally developed for use with natural gas, have excellent selectivity vi&vis hydrocarbons. For facilities which require total removal of sulfur compounds and carbon dioxide for downstream processing over sensitive catalysts, more than one removal step may be required to avoid catalyst damage. Economics of Coal Gasification Many estimates of the costs of coal gasification have been provided in the literature since the early 1970s. Usually, these estimates were outdated by the time they were published. Double-digit inflation increased the costs of almost all capital equipment, labor, and materials. Even though the prices of petroleum and natural gas increased sharply, fuel gases made from coal have not yet become competitive with these naturally occurring products. Unfortunately, the accuracy of these published estimates is not dependable. A very large portion (as much as 70 percent) of production cost is related to capital investment for the plant. It is in estimating capital investment that most published estimates go astray. These capital costs are obtained by a system of factors. The costs of major capital-equipment items are estimated and these costs multiplied by various factors to generate costs of installation, piping, instrumentation, electrical needs, etc., associated with these items. These factors have been shown to be not representative of plants handling large volumes of gases and solids but to be more typical of liquid-processing plants such as oil refineries or chemical plants. As a result, errors of as much as 30 percent have been found when a factored estimate was compared with a line-by-line material-takeoff estimate. Using 1978 dollars and assuming utility financing in which 75 percent of the capital cost is borrowed, it is estimated that synthetic natural gas produced from lignite will cost from $5 to $S.50/10e Btu (1.05 GJ). Such a plant, producing 125 to 250 million scfd (3.5 to 7.0 m3), will require a capital investment of $9KKl to $10,003 per daily 10s Btu of production. This is equivalent to approximately $2.5 billion for a plant producing 250 million scfd of SNG. It should be noted that these costs will vary with inflation and also with the costs of borrowed funds. This results in a doubling of the effects of inflation, since interest rates are driven upward by rising costs and decreasing currency values. In spite of major research and development efforts, it appears doubtful that major reductions in cost can be achieved. Almost 80

percent of the capital cost of coal-gasification plants consists of conventional equipment, which will not be altered appreciably by new gasification technology. Improvements will be small in size and slow in being used and will depend on actual commercial implementation

of state-of-the-art systems. Only through profit-oriented will reliable and practical improvements be real&d.
DIRECT COAL LIQUEFACTION

operation

GENWUL REIFRENCES~ Don&h, Chemistry of Coal Uttlflafton, suppl. vol., ed by Lowry, Wiley, New York, 1963. Gcrin. Chemistry of Coal Uttltmt(on, 2d suppl. vol., ed. by Elliott, Wiley, New York, 1981. Wu and Starch, Hydrogenatkm of Coal and Tar, U.S. Bur. Mines Bull. 6%. 1968 Background The primary objective of any coal-liquefaction pro cess is to increase the hydrogen-carbon ratio and remove sulfur, nitrogen, oxygen, and ash from the coal. Table 9-21 shows the hydrogen-carbon ratios in proceeding from coal to crude petroleum and gasoline, together with the four techniques for accomplishing these objectives. Direct coal liquefaction refers to any process approach in which coal and hydrogen are reacted at high pressure and temperature either with or without hydrogen donor solvent and catalyst. The first three techniques in Table 9-21, direct hydrogenation, solvent extraction, and pyrolysis, follow this approach. The fourth, catalytic hydrogenation of carbon monoxide, or indirect liquefaction, first converts coal to a synthesis gas, followed by purification and use of a catalyst to form liquid products. An alternative indirect-liquefaction route converts purified synthesis gas to methanol, for fuel use or conversion to gasoline. The technology of coal liquefaction to synthetic fuels is not new.

In 1913 Dr. Friedrich Bergius discovered the technique of adding hydrogen to coal at a pressure of 200 atm (2940 Ibf/ina) and a temperature of about 45OC (842F). Under these conditions most oxygen was hydrogenated to water, some nitrogen to ammonia, and most sulfur to hydrogen sulfide. Hydrogen was also chemically combined with the coal to produce a liquid similar to petroleum. Later research at I. G. Farben led to the discovery of catalysts which increased the speed of hydrogen addition to coal. Interest by the US. Bureau of Mines began in 1924 with A. C. Fieldner visiting several
TABLE 9-21 Basic Approachesof Coal Conversionto liquid Hydrocarbons 1. Direct hydrogenation at elevated temperature and pressure, with or without catalysts 2. Solvent extraction (hydrogen donor) 3. Pyrolysis 4. Catalytic hydrogenation of carbon monoxide Bituminous coal HIC 0.8 Lignite 0.7 Crude petroleum 1.8 Gasoline 1.9

9.26

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION Bate of dissolution = rate constant X fraction of undissolved solid organics X coal-solvent ratio rA = kc,exp -E/RT exp (0.006684 Pns)(C,J(l - r)(C/S) (9-21) where T,, = rate of dissolution, g/(h.cms) reactor volume c, = weight fraction of organics in unreacted coal ko= rate constant, g/(h.cm3) reactor volume PHp = I.. drogen partial pressure, psia X= conversion, solid organics/solid organics in original coal 1 t . .. c/s = coal-solvent weight rat10 By assuming an Arrhenius temperature dependency, calculated and experimentally reported conversions agreed well for the following values:

facilities in Germany, France, and England to become familiar with their coal research. Production of synthetic liquid fuels and chemicals from coal in Germany became very noticeable in the mid-1920s. In 1927 the U.S. Bureau of Mines started a laboratory research pro gram on the thermodynamics and kinetics of chemical reactions for the production of alcohols and hydrocarbons from carbon monoxide and hydrogen. By 1939 gasoline was being produced by coal hydrogenation in Germany at 1 million tons/year and in England at 150,000 tons/year. Research at the Bureau of Mines was also conducted to verify claims of Fischer and Tropsch in 1926 on the discovery of a catalytic technique to produce liquid hydrocarbons similar to petroleum by using water gas at atmospheric pressure and a temperature of 135 to 250% By using a cobalt-copper-manganese catalyst at 275C, about I.7 gal of oil/1000 fts of gas which contained 34 weight percent of motor fuel could be produced German commercial plants operated at from 1 to 10 atm (14.7 to 1470 Ibf/ins) at catalyst temperatures of 1800 to 21O~C. In the early 1950s the Bureau of Mines constructed and operated a demonstration plant at Louisiana, Missouri, using the technology of catalytic hydrogenation of coal and carbon monoxide to produce liquid fuels. Research in the chemistry of coal liquefaction since then has produced several modifications of the four types of liquefaction processes. These include catalytic hydrogenation in fixed and ebullated beds, zinc halide hydrocracking, reaction of carbon monoxiderich synthesis gas and steam with coal, and a combination of solvent extraction and catalytic hydrogenation in two-stage liquefaction. Currently, the most advanced direct coal liquefaction processes are solvent-refined coal (SRC), Exxon donor solvent (EDS), and HCoal. These are compared in a generalized flow diagram, Fig. 9-16, and discussed in greater detail later. Direct-Liquefaction Kinetics All direct-liquefaction processes may be considered to consist of three basic steps: (I) coal slurrying in a vehicle solvent, (2) coal dissolution under high pressure and temperature, and (3) transfer of hydrogen to the dissolved-coal products. In the temperature range of 350 to 450% (662 to 842OF) the coal is dissolved in about 1 min. Solvents are assumed to promote thermal cracking of coal into smaller, more readily dissolved fragments. These may be stabilized through reactions with each other or with hydrogen supplied either by a donor solvent or in a gas phase. Data on Illinois, River King (hvCb), and Kentucky No. 9 (hvBb) coals were used by Wen and Hahn to obtain a rate equation for coal dissolution under hydrogen pressure. These data included a temperature range of 375 to 500C and pressures up to 136 atm (O-2090 psig). An empirical rate expression was proposed as

Constant

Illinois.

River Kim? (h&b)

Kentuckv

No. 9 (hvBb)

212.5 g/(hcm3) 11 kcal/(a~mol~

15.3 g/(h.cm) 4.5 kcnl/(g~mo~)

The small values of activation energy suggest that the dissolution rate is controlled by counterdiffusion of organic components from the coal surface and dissolved hydrogen from the solvent-hydrogen mixture. Also, the rate of dissolution appears to be exponentially dependent on hydrogen partial pressure. A free-radical mechanism was also proposed for coal dissolution in hydrogen donor solvents. Initial dissolution was considered a thermal process, with a net rate dependent upon the type of solvent and its effectiveness in stabilizing free radicals. The greater a solvent hydrogen donor capability, the more effective it is in terminating radicals. An overall rate-limiting step in the process appears to be rehydro genation of the donor solvent. A mixture of Kentucky No. 9/14 (hvBb) coal and creosote oil was used in the study at a 3: 1 solvent-to-coal ratio. Hydrogen solubility was experimentally measured over 100 to 4oOC and 500 to 3000 psia, simulating the high temperature and hydrogen partial pressure of coal-liquefaction reactors. The first-order-reaction model obtained from hydrogen-absorption data expressed total hydrogen consumption as H, = H&l - exp (c&t)] (9-22)

CCNl -..-+

Grind and Dry

--x-+

Sklrry Coal and Solvent

._._._.-.a+._._

Lt. Ends

H,S. NH,, H,D, CH.

Ash FIO. 9-16

Direct-coal-liquefaction general&d flow diagram.

DIRECT COAL UQUEFACTION = &I HT hydrogen consumed in reaction, g HI, = total hydrogen, t = o, g hydrogen in liquid phase, g ;, I total hydrogen at time t, g t- time, min kL = I. first-order rate constant,. min- . Solubility ot hydrogen in the coal-liquetaction sented by a Henrys-law coefficient:
H, =

9-27

wherecr

solvent was repre-

B = SIhl,
where S = solubility, g Hs/g oil Pus = hydrogen partial pressure, psia I3 X 10. p, Hz/k oilpsia) 5.95 6.94 7.75 9.65
T, OC (I T. =C

100 200 300 499

,163 ,193 ,196 ,211

335 400 410 435

An Arrhenius plot of hydrogen-transfer rates gave an activation energy of 21 kcal/mol and a frequency factor of 1.06 X ld min-. From these values it appears that mass-transfer effects are small and that the hydrogen consumption rate was kinetically controlled. Solvents and heat facilitate thermal degradation of coal to form relatively low-molecular-weight free radicals. These may be stabilised by hydrogen transfer from a hydroaromatic solvent. The functions of dissolved gaseous hydrogen and catalyst are to rehydrogenate the solvent. Catalysts are considered to be primarily responsible for nitrogen and sulfur removal and the formation of light liquid products. A first-order hydrogen absorption in creosote oil was proposed with creosote oil being considered a good representative for steadystate, coal-derived solvent. The progress of coal conversion was measured on the basis of a fraction of organic products soluble in benzene or pyridine. At conversion above 90 percent these results will be very similar. The rate of consumption of gas-phase hydrogen in the liquefaction reactor was expressed as - rH1 = ; %
= k&P, PHy) (9-23)

The liquid holdup Rr may be estimated by use of the Lockhart-Martinelli correlation for large-diameter reactors or the Nicklin correlation for smaller diameters, less than 7 cm. Temperature, reactor hydrodynamics, and catalyst affect the overall gas-absorption coefficient (kp). Values of (k@) are presented in Fig. 9-17 and show that increasing temperature and turbulence increase kp for both catalyzed and noncatalyzed systems. As shown in Fig. 9-18, increasing turbulence, which reduces diffusion barriers, has more effect on catalyzed systems when reaction rates are higher. The pressure effects on the coal-dissolution coefficient were observed to be Puzfor PH2 > 50 atm. Bituminous coals begin to soften in the 325-350C temperature range. Rapid mixing will increase both heat and mass transfer in this regime by reducing diffusion resistance to hydrogen at the solid-liquid boundary. The effect of the slurry Reynolds number on the coaldissolution rate is shown for three coals in Fig. 9-19. Increased hydrogen absorption for catalytic as compared with noncatalytic systems is due to the further hydrogenation of coal liquids to lighter products and to sulfur and nitrogen removal. The conversion reaction from coal to oil has been modeled as a series of steps: Coal + solvent preasphaltene asphaltene oil with some gas formation accompanying each step. In a study using Illinois No. 6 coal, Burning Star Mine (hvCb), and process-derived heavy distillate (232 to 454%) data were obtained at 13.8 MPa (2060 Ibf/in) and 400 to 475C. Activation energies for the steps of the reaction series were determined to be Activation energy, kcal/(n.mol) 15 21 32 At 450C (843F) stoichiometries sented as

Reaction steo Preasphaltene - asphaltene Asphaltene - oil coal - preasphaltene for the reaction steps were repre-

Coal + 3 solvent - preasphaltene Preasphaltene - 2 asphaltene asphaltene - 3 oil which appears consistent with published molecular-weight values of solvent (250), preasphaltene (1000) and coal (2250). A more complex reaction model was proposed from the results of a kinetic study of thermal liquefaction of Belle Ayr subbituminous coal. Data were obtained over a temperature range of 400 to 470% (752 to 878OF) at 13.8 MPa (Zoo0 psig) by using two solvents, hydrogenated anthracene oil (HAO) and hydrogenated phenanthrene oil (HPO), at a coal-solvent ratio of 1: 15. Results were correlated with the following model; cl;, _+w
Asphaltem

where rHp = rate of consumption, (g.mol)/(cmr~ S = surface area for absorption, cm*
NH2 = mole of hydrogen, g. mol

h)

ks = z$de
Pm =

mass-transfer

coefficient,

(g.mol)/(cmrh.

P Hp( =

Integrating

hydrogen partial pressure, atm hydrogen partial pressure at gas-liquid interface, atm this over the reactor length, -ln
OHPO/YH~,)= k&PTVdFC (9-24)

where kp

;;emr)all gas-absorption

coefficient,

(g.mol)/(h.cms.

liquid holdup total pressure, atm VR = reactor volume, cm3 Fc = total gas flow rate, (g.mol)/h

RI = PT =

Activation energies and frequency factors for the various steps of this model were determined as follows: Activation e;o;y kcal/(g
Coal-HP0 26.9 4.3 6.6 10.5 33.9 25.6

Frequency factor, min- Coal-HA0 Coal-HP0 2.1 x 10s 4.94 9.63 X 10 E :: :z 1.53 x 10

Reactor Coal - oil ConI- preasphaltene Coal - asphaltene coal-gas Preasphaltene - asphaltene Asphaltene - oil

Rate constant K. b K. K, K, L

Coal-HA0 14.1 13.8 15.6 21.5 12.6 16.0

1.12 6.72 9.66 1.42

x X x X

10 ld lop ld

9-28

ENERGY UTIUZAlION,

CONVERSION,

AND RESOURCE CONSERVATION

1.3

1.4 03/T(K-1 (0)

1.5

10

10 Slurry Reynolds number

Re,

10

Effect of the slurry Reynolds number on the rate of coal dissolution for Kentucky, Illinois, and West Virginia coals.
FIG. 9-19

s . 84
2
0 7 10-S 1.34 1.36 1.38 1.40 1.42 103/T(K-) (b) on the coal-dissolution-rate coefficient (n) Noncatalytic systems. (b) Catalytic

ond, contrasting results were obtained in the catalytic-activity experimental results for iron. Thus, differences in the composition of coalash minerals will determine their effectiveness for hydrogenation or hydrodesulfurization activity in coal liquefaction. Direct-Liquefaction Processes

FIG. 9-17 Effect of temperature including hydrodynamic influence systems.

Magnitudes of K , K,, K., and K, indicate the importance of direct reactions wit t coal, where K, and K, are hydrocracking reactions in the conversion process. Data for K, and K, from the experiments with HP0 show the effect of an effective hydrogen donor solvent on product yield and indicate that oil production from coal will be increased by the use of a good hydrogen donor solvent. The ability of coal minerals to catalyze the hydrogenation creosote oil and Kentucky coal has been investigated. Catalytic materials investigated are listed in Table 9-22. Hydrogen partial pressure was used as a measurement of hydrogenation activity for these materials as shown in Fig. 9-20. Desulfurization results are contained in Fig. 9-21. Data for both tests of catalytic activity are in general agreement for all except two materials. First, pyrite was determined to be an effective hydrogenation catalyst but poor for desulfurization. Set-

Ill1

Temp 445C

o-52

0 2

5 02 2

3 103 2

Slurry Reynolds number AeL FIG. 9-19 Effect of slurry Reynolds number on the hydrogen-absorption-rate coefficient {or catalytic and noncatalytic coal-liquefaction systems.

This process was initiated by the Pittsburgh & Midway Coal Mining Co. in the early 1960s. SRC-Z process. In the SRC-1 (solid-fuel) operating mode, shown in the flow diagram of Fig. 9-22, pulverized coal is mixed with process-derived solvent. After adding hydrogen, the slurry is pumped through a preheater and into a dissolver which operates at 425 to 470C (800 to 878OF) and a pressure of 10 to 14 MPa (1450 to 2030 lb/in). Coal conversions of 92 to 95 percent are achieved during the residence time of 20 to 60 min. The dissolver effluent is separated into gases and slurry in a separator. The raw gas is scrubbed with a dilute caustic solution to remove hydrogen sulfide and carbon dioxide. A portion of the scrubbed gas is purged to prevent accumulation of noncondensables (C,-Cd hydrocarbon gases and CO), but most of the gas is recycled back into the process. The slurry product, after being cooled to 315OC (6OOOF) and depressurized to 0.8 MPa (116 lbf/in), is passed through a precoated rotary drum or leaf filter to separate undissolved coal and mineral matter from the SRC solution. In a commercial plant, these residues would be sent to a gasifier to produce process hydrogen. The filtrate is vacuum-distilled to separate the solvent from the nondistillable product (SRC), which is then solidified by cooling. The SRC product is almost ash-free (<O. 16 percent) and has a sulfur content of 0.6 to 0.9 percent and a heating value of approximately 37.2 MJ/kg (16,009 Btu/lb). Typical operating conditions and product yields for SRC-I are shown in Table 923. Studies have indicated that bituminous coals of Kentucky No 9 and No. 14, Illinois No. 6, and Indiana V are attractive for use in the SRC process but that Wyodak subbituminous coal and Utah bituminous coal are not. It appears that certain components of mineral matter in coal, iron compounds in particular, may have a catalytic effect on hydrogen transfer, resulting in an increase in coal conversion. High-vitrinite and low-oxygen contents of the coal are also desirable to achieve high SRC yield at low hydrogen consumption. SRC-ZZ process. The SRC-11 process is an improved version of the SRC process, recycling a portion of the reactor effluent slurry in place of the distillate solvent of the original SRC-I process. Because of increased severity of operating conditions in the SRC-11 process, the primary product is a liquid distillate fuel with a 217 to 455% (42.3 to 851F) boiling range. The fIow diagram of the SRC-II operating mode is shown in Fig. 9-23. The general process is the same for both modes from the slurry-mix tank through the dissolver. In the SRC-II mode, however, the dissolver slurry is split into two streams; one is recycled to the slurry mix tank, while the other is passed into a vacuum-flash unit. The vacuum-flash condensate is fractionated to

Solvent-Refined Coal (SRC)

TAME 9-22

Derriotion SDeties

of Ceal Minerals or Catalvtic Aaents Studied Classification Carbonate Carbonate Carbonate Kaolin Descrivtio An isomorphorus mixture of CaMg(CO& and CaFe(CO& A crystalline form (hexagonal scalenohedral class of the hexagonal system) of CaCOa. Often, to a small extent the Ca is replaced by iron, magnesium, and manganese Clay, sand, bitumen, and other mechanical impurities may be present. A double salt with equal molecular quantities of CaC03 and MgC03 and not a isomorphous mixture of these two compounds; usually found in a curved rhombohedral form. A common type of clay; often found in minute pseudohexagonal (monoclinic) crystals; chemically, a acid aluminum silicate, H,Al,Si& or 2HeO-A&03-2SiOo (He0 = 14%) Iron is often present is small amounts. A lamina-type silica substance. having a monoclinic crystal structure, and chemically classified as a acid Dotassium aluminum orthosilicate. H~KAI&iO.h or ~H&KvO-~AIQOV 6SiOz(Hzd = 4.5%). Often, the potassium ii pa&$ rep&xl by;odi&, and s&e varieties contain a excess of silicon over that indicated A cubic structure of Fe&. having in its crystalline structure a rock-salt type of arm ement of Fe*+ and S%ions, with iron being octahedrally surrounded by S and each S atom $ avlng one S and three Fe atoms as neighbors. Uncommonly, Ni, Co, or sometimes both are found substituted for Fe. Obtained from M&hewn, Coleman, and Bell (90-955 pure). A crystalline form of SiOl, a member of the triagonal trapezohedral class of the hexagonal system. A crystalline form of FeCOs, with the brown to gray crystals usually being rhombohedral. Calcium, magnesium, and manganese are usually present in small amounts as replacing elements. Commercial catalyst from Laporte Industries, Inc. (Comox 451, 1.5.mm extrudute); surface area = 300 m/e. ore volume = 0.66 mL/e. Chemical analvsis: 3.7. 12.8. 0.06. 1.4. and 0.03% Coo. M&,~Na~O. NazO + Kz, SiOp,-and SOa respectively. Reagent-grade hydrogen-reduced iron from Mallinckrodt, Inc. Solid residue from hydrogenation-of-creosote oil in presence of 15% by weight of Fe& at 425T, stirrer setting of 2OtM r/min, and 3OOO psig of initial hydrogen pressure Obtained from filter cake from Wilsonville SRC pilot plant. Analysis: 55.2% ash content and 13.6% S for -325mesh material; and, prior to screening. 30% filter aid, 53.6% ash, and 2.9% s. Obtained by burning Kentucky No 9/14 mixture (7 2% ash) in a muffle furnace at 1CCVC; analysis: 13.7% iron. Obtained from W. H. Curtis and Co.

Ankerite (ferriferrous dolomite) Calcite Dolomite Kaolinite

Muscovite

Shale

Pyrite

Sulfide

Quartz Siderite CUM-AI

Accessory Carbonate

Iron

Reduced pyrite SRC residue Cd

ash

Kaolin

Minerals obtained from David New, Minerals and Books, Providence, Utah. NOTE:Al1 agents were ground to -325 mesh prior to use, except muscovite. which was ground onlv to -80 mesh because of its laminar silica structure. and except as indicated.

Initial 3oooc----------___-____-----_-_

pressure,

3000 psig

Species FIG. 9-20 Comparison of hydrogenation activity of catalyst

9-29

9-30

ENERGY

UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

Original % sulfur in creosote oil

FIG. 9-21

Comptin

of desulfurization

activity

of catalyst.

yield naphtha and middle and heavy distillates. The vacuum residue is heavy oil, unreacted coal, and mineral matter. The increased conversion to light products in the SIG11 process results in a higher hydrogen consumption of about 4 to 5 percent, as compared with 2 to 2.5 percent for the SIX-1 process. This is caused by the longer residence time, higher operating pressure, and recycle of coal solution with mineral matter, allowing more hydrocracking in the dissolver.
MMEUP HYDROGEN

Because the mineral residue is separated as vacuum-flash bottoms along with the undissolved coal, the solid-liquid separation step of the SRC-I mode can be eliminated in the SRC-II mode. The degree of dissolution of coal and the distribution of products depend greatly on the reactivity of the coal feed. Three high-volatile bituminous coals have been tested to determine the effects of dissolver temperature, coal-slurry feed rate, and coal concentration on product yields. The material balance runs with western Kentucky coal, Illinois No.

RECYCLE HYDROGEN

I
A

.HC GAS
)PURGE GAS

I
COAL

GAS
PURIFICATION

I--+

TO SULFUR RECOVERY

UNIT

Ir
+

RECYCLE SOLVENT b PROCESS SOLVENT

T ---)

SEPARATOR OIL __) PRODUCT FRACTIONATDN b NAPHTHA

PREHEATEA

DISSOLVER

RESIDUE

SRC

FIG. 9-22

SK-1

process scheme.

DIRKT TARlR 9-23 SRGI Product Yiilds from Pilot Plant

Operating Coal Coal (maf) feed rate solvent feed rate Hydrogen purity in feed gas Dissolver outlet temperature Dissolver pressure conditions Western Kentucky 9 and 14 1837 kg/h (4050 lb/h) 2860 kg/h (6305 lb/h) 94 mole 5% 724 K (642=F) 10.3 MPa (1500 Ibf/in)

COAL LIQUEFACTION

9-31

Hp consumption

2.4 weight 96 maf coal Product yield, weight X maf coal

36

C,-C, Light

hydrocarbon oil, 193T-

gas (385OF)

3.7

Wash solvent, 193-249C (365-4~UYF) frocess sohent. 249-254=C (480-860F) SK Ash Unreacted coal

5.1 4.0 4.4 63.0 96 5.4

::I
20 22

24
Feed

26
slurry

28
cmcenfrotm.

x)

32
wght

34
percenl

36

38

6 coal,and Blacksville No. 2 Pittsburgh Seam coal indicated that a higher distillate yield was obtained at decreased coal concentration and increased dissolver residence time. This is shown in Fig. 9-24 for western Kentucky coal. The test results with the three coals are summarized in Table 9-24. The western Kentucky and Illinois No. 6 coals
are more reactive than the Blacksville No. 2 Pittsburgh Seam coal. Exxon Donor Soloent (EDS) Process The Exxon Research &

Effect of coal concentration and nominal FIG. 9-24 on total distillate yield in the SRC-II operating mode 13.1 MPa). 46OT.

dissolver (western

residence Kentucky

time coal,

Engineering Co. has developed the EDS process, which also liquefies coal with a hydrogen donor solvent under hydrogen pressure. The solvent, however, is a catalytically hydrogenated recycle stream fractionated from the middle boiling range, 201 to 455OC (395 to 85OF), of the liquid product. The liquefaction system is an upflow, tubular plug-flow reactor which is divided into four sections illustrated in Fig. 9-25. The hydrogenated recycle solvent is mixed with fresh coal feed and pumped through a tubular preheat furnace into the liquefaction reactor. The reactor operates at 427 to 471C (309 to fBOF) and 10.3 to 13.8 MPa (1490 to 2000 lbf/inr), similar to the conditions of SRC-II. The reactor effluent is separated by distillation into light hydrocarbon gases, naphtha, distillates, and vacuum bottoms. The vacuum bottom, 63WC+ (1180F+), may be treated with air and steam in Exxons proprietary Flexicoking process to produce some heavy oil,
MAKEUP HYDROGEN

a low-heating-value flue gas, and a mineral-ash residue. The process hydrogen is produced by the steam reforming of Ci-Cd hydrocarbon gases produced in the hydrogenation reactors. The hydrogenation of the recycle solvent is conducted in a conventional fixed-bed catalytic reactor by using hydrotreating catalysts such as cobalt molybdate or nickel molybdate. Coal conversion and liquid yield strongly depend on the molecular composition, boilingpoint range, and other properties of the solvent. Exxon uses its pro prietary Solvent Quality Index (SQI) as the main criterion of solvent quality and correlates product yields with SQI. The SQI can be controlled by adjusting the hydrotreater temperature, and coal conversion, product yields, and hydrogen consumption decrease significantly when the SQI is less than a certain value. This critical SQI appears to depend on the coal type and liquefaction conditions, and solvent quality requirements are significantly reduced when molecular hydrogen is present in the reactor. The solvent has two major roles in the liquefaction process: (1) to stabilize the liquid products by donating hydrogen to the coal and (2) to disperse and transport the coal particles through the liquefac-

RECYCLE HYDROGEN t

b PURGE GAS

COAL

RECYCLE SLURRY

FIG. 9-23

SRC-II process scheme.

9-32

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

TABLE 9-24

SRC-II Product Yields from Pilot Plant Coal Western Kentucky Nos. 9 and 14 Ooera\ina conditions Illinois No. 6 Blacksville No. 2 River King Pittsburgh Seam

Dry coal feed rate, kg/h (lb/h) Feed-slurry composition, weight !% Dry coal Solvent SRC Ash (in recycle slurry)

900

(1984)

911(2008)
29.5

906 (1997) 30.3 29.8 24.1 8.3 7.5 1.00 91.6 456 ($53) 14.09 (2044) 3.5

29.5

334
23.9

Undissolved coal (in recycle solvent) Nominal dissolver residence time, h

Hydrogen purity in feed gas, mole p6 Average dissolver temperature, C (OF) Dissolver pressure, MPa (Ibf/in*) Hn consumption. weight 9b maf coal

8.2 5.0 0.98

89.8

35.6 20.0 11.0 3.9 0.97

93.7

461 (862) 13.34 (1930) 4.8

457 (855) 13.44 4.7

Product vield. weinht %maf coal C&C, hydrocarbon gas Na htha, 177OC- (341F-_) Mi Bdie distillate, 177-28OC (341~536F) + heavy distillate, 28%454C (550-849OF) SRC, 454C+ (849OFf) Undissolved coal 18.4 14.2 28.2 26.1 6.6 15.8 17.0 303 23.0 5.0 13.5 11.9 22.3 36.8 11.9

tion system.

The specific

feature

of the EDS process is that the cat-

alyst used in the process is not in contact with the high-molecularweight asphaltenes, preasphaltenes, or mineral matter, thereby preventing fast deactivation of the catalyst. The use of vacuum distillation provides a residue,_which in addition to Flexicoking, may be used as a fuel or feed to gasification for hydrogen generation. Several coals including bituminous, subbituminous, and lignite coals have been tested Different coals gave different liquid-yield response with a change in operating conditions. For Illinois No. 6 bituminous, Wyoming subbituminous, and Texas lignite, the conversion increased only slightly after 40 min. The low-rank coals gave slightly higher conversion, owing to higher yield of water and carbon oxides. The C, 638% (811 K) liquid yields, on the other hand, is adversely affected at long residence times owing to the cracking of liquids to gases. The optimum residence time is about 40 min for Illinois No. 6, 60 min for Wyoming, and 25 to 40 min for Texas lignite. Table 9-25 shows the liquefaction product yields at these preferred operating conditions. These results have been confirmed in a 2.%ton/day pilot plant. H-Coal Process This process has been under development by Hydrocarbon Research, Inc., since 1964. Operation at laboratory and process-development-unit (PDU) scales of up to 3 tons/day has been

confirmed by a 600_ton/day pilot plant using various coals and demonstrating satisfactory control of catalyst bed expansion. This process can be operated in either a fuel-oil mode or a syncrude mode, depending on the type of fuel desired. The flow scheme of the H-Coal process is shown in Fig. 9-26. Coal, which has been ground to -60 mesh and dried, is mixed with recycle oil, pumped to 20 MPa (2900 Ibf/in), and mixed with compressed hydrogen. The mixture is preheated to 371C (7OOF) and fed to the bottom of the ebullated-bed catalytic reactor. The catalyst is kept in a fluidized state by the upward flow of the slurry and gas through the reactor. Catalyst activity is maintained by the addition and withdrawal of small quantities of catalyst to and from the reactor. The reactor also contains an internal tube for recirculating the reaction mixture through the catalyst bed. The reactor temperature is kept at 454% (849OF). Vapor products leaving the top of the reactor are cooled to separate a liquid condensate. The gas stream is sent to a scrubber to absorb light hydrocarbons, ammonia, and hydrogen sulfide. The remaining hydrogen-rich gas is recycled. The condensate from the reactor vapors is released to atmospheric pressure and fed to an atmospheric still. The liquid-solid product from the reactor is let down to the atmosuheric-oressure flash separator. The lighter hydrrr carbon liquids that are tlashed off are sent to the atmospheric still.

CATALYTIC

HYDROGEN

H,

LIQUEFACTION

DISTILLATION

FLEXICOKING

FUELGAS

FtG. 9-25

Flow scheme of the Exxon donor solvent process

DIRECT COAL LIQUEFACTION

TABLE 9-25 EDS Product Yields Illinois No. 6 bituminous
Residence time. min 40

9-33

TABLE 9-26 Wyoming subbituminous 60 -4.6 22.3 0.9 9.3 33.3 38.8 Texas lignite B-40 -3.9 21.7 17 9.1 33.3 38.1

H-Coal Product Yiildr Fuel-oil

mode syncrude mode

Yields. weight 96 maf coal $+.,0 HsS + NHj G-C3 g= Cd. 638OC (118OOF) liquid 638;~Lts(l180F+) 10.3 MPa. 449oc

-4.3 12.2 4.2 7.3 38.8 41.8

Coal feed rate, Mg/(h.ms) Recycle oil-coal ratio Reactor temperature, T (OF)

1.35
2.1

0.53
2.1 453 (847)

Hydrogen partial pressure, MPa (Ibf/ins) Yields, weight 96 of dry coal Cl-C3 C,, 204C (399=F) 205-524C (401-975OF) 524=C+ (975OF+) unconveried coal Ash H.0
Nii3

453 (847) 12.1 (1750) 7.71 16.90 18.28 32.45 6.75 10.95 6.67
0.53

12.6 (1827) 9.97 2.366 23.21 19.25 5.68 11.67 7.37

0.84

product from the flash separator is further separated with a hydroclone, with a liquid-solid separator, and by vacuum distillation. The atmospheric still yields light and heavy distillates, and the vacuum still yields heavy distillates and residual fuel. A portion of the heavy distillate and hydroclone overflow is recycled as the slurry vehicle. The severity of operating conditions of the H-Coal process affects the type of fuel produced. In the fuel-oil mode, a relatively hiah slurr;space velocity of 1.25 Mg/(h.ms) of reactor is used. The re&tor space velocity can he related to the residence time of the slurry phase in the H-Coal reactor. The hydrogen partial pressure is lowered to about 12 MPa (1740 Ibf/ins); hydrogen consumption is usually less than 4 weight percent based on dry coal. In general, at lower hydrogen partial pressures there is less Hz pickup by the oils, resulting in higher residuum and lower distillate yields. Table 9-26 shows the product yields obtained at PDU by using an Illinois No. 6 bituminous coal. The catalyst was cobalt molybdate on an alumina support. A 0.49 percent sulfur fuel oil [205C (399F+)] was produced at 3.3 weight percent hydrogen consumption. Table 9-26 also shows the results obtained in the syncrude mode

The bottoms

W
co + co* Total Hs consumption, weight pb of dry coal Sulfur in 205OC+ (399F+) oil, weight X

2.55
1.01

2.65
0.95

103.80 3.80 0.49

105.25 5.25 0.26

operating at a space velocity of 0.53 Mg/(h.ms). In general, with all other variables held constant, the decrease of the space velocity decreases the residuum yield but increases the naphtha yield. The hydrogen consumption is higher in the syncrude mode, at 5.25 weight percent based on dry coal. The total liquid yield was 73 weight percent and 76 weight percent on an maf coal basis for the syncrude and fuel-oil modes respectively. As with the SRC processes, one of the major problems has been solids separation. The H-Coal process uses hydroclones to remove about two-thirds of the solids from recycled liquid employed as the vehicle. In the syncrude mode, the separation of unreacted coal and ash from the liquid can be accomplished by vacuum distillation. In

Hydrogen -

H y drogyt

i-$rcarbqn

gas

Condenser 20 MPa Regenerated catalyst j llquld

111

I\X..

I SOild

Recycle tube

Coal
preparallon

Fired preheater 371 C Recycle RG. 9-26

L Impeller shaft I

Vacuum still Yl=

Residual fuel

heavy distillate

H-Coal process scheme.

9.34

ENERGY UTIUZATK)N,

CONVERSION,

AND RESOURCE CONSERVATION

FIG. 9-27

COED

coal pyrolysis

the fuel-oil mode, however, an efficient solid-liquid separation method is needed.An antisolvent-precipitation method has been selected. Coal-Pyrolysis Processes Another approach to coal liquefaction is pyrolysis, which produces synthetic crude oil, gas, and char as demonstrated in the COED process shown schematically in Fig. 927. Crushed coal is dried and heated to successively higher temperatures in a series of Euidized-bed reactors. In each stage, a portion of the coals volatile matter is released, with each stage maintained slightly below the temperature at which it would agglomerate and detluidize. Typically, four stages of 316, 454, 538, and 816OC (600, 850, 1000, and 15OOF) were used, but operations varied owing to the different coal-agglomerating properties. Process heat was generated by burning char in the last stage and circulating hot char and gases to the other stages. Volatile products were condensed in a recovery system and pyrolysis oil filtered to remove fines. The filtered-oil product was hydrotreated in a fixed-bed reactor with hydrogen at 371 to 427OC (700 to 8OOF) to remove sulfur, nitrogen, and oxygen, thus producing a 25 to 30 API synthetic crude. Typical operating conditions and pyrolysis yields for two bituminous coals, Utah A and Illinois No. 6, are presented in Tables 9-27 and 9-28. These results were obtained from a 36-ton/day coal pilot plant at Princeton, New Jersey. Higher net oil product yield, 1.23 versus 1.10 bbl/ton, was obtained from the Utah coal than from the Illinois coal. The major problem with any pyrolysis process is the high yield of char. Flash Pyrolysis and Hydropyrolysis Pyrolysis of coal at elevated temperatures for a s&t r&idence time, c&d flash pyrolysis, produces gases, liquids, and char. The increase in hydrogen content in the gases and liquids is the result of removing carbon from the process as a char containing a significantly reduced amount of hydrogen. Several processes have been tested on a relatively small scale.

None have demonstrated economic potential, although the technical concepts may be valid. Flash hydropyrolysis, which is the rapid pyrolysis of coal in the presence of pressurized hydrogen, could improve the oil product quality and liquid yields. It requires large usage of hydrogen. The Occidental Research Corporation (OK) flash pyrolysis process consists of rapidly pyrolyzing coal particles at a temperature of 621 to 679% (1149 to 1254OF) in an entrained stream of hot coal char and gas. The process takes advantage of the high heating rates that are made possible by recycling the hot char, and it gives the highest liquid yield of the pyrolysis processes. The process has been tested in a S-ton/day PDU. Flash hydropyrolysis, the noncatalytic short-residence-time hydropyrolysis of coal, is a process for producing light aromatic liquids and gaseous hydrocarbons. Product distribution and yields are greatly influenced by temperature and time because of competitive reactions between fragmentation of repolymerization. Several research organisations are undertaking developmental programs by using bench-scale units to determine operating conditions for maximizing the production of high-quality distillate liquids by rapidheat-up noncatalytic hydropyrolysis. In the Brookhaven National Laboratory unit pulverized coal is mixed with hydrogen preheated to 775C (1427OF), and the mixture is fed into the top of a downflow tubular reactor. With North Dakota lignite at temperatures in the range of 78 to 750C (1337 to 1382OF) and 13.8 MPa, the maximum yield of the heavier liquid hydrocarbons (> C,) is approximately equal to that of the BTX yield. The Institute of Gas Technology used a coil reactor in its bench-

TABLE 9-28

Typical Propertier of p/ro@s

Utah

Oils
A seam Illinois No. 6 seam

Properties of derived coal: elements analysis

TABLE 9-27

Pwdnir

Yield Data
Illinois No. 6 wzam Utah A seam

Net yields, weight Char Oil Gas Liquor Net lkes~ yields Char, lb/ton Oil, bbl/ton Gas, rf/ton Liquor, gal/ton

9b dry

coal 59.5 19 3 15.1 6.1 1190 1.10 6610 14.6 54 5 21.5 18.3 5.7 1090 1.23 8545 13.7

Weight X, dry C&O Hydrogen Nitrogen Sulfur Oxygen Ash API gravity, 60F Moisture, weight % Pour point, OF Viscosity, SUS 2lOOF Solids, weight %, dry basis Gross heating value, Btu/lb

83.8 9.5 09 0.4 5.0 0.3 -3.5 0.5 100 390 3.8 16,lCQ

79.6 7.1 1.1 2.8 8.5 0.9 -4 0.8 100 1333 4.0 15050

INDIRECT COAL LIQUEFACTION

9-35

Coal+
oxygen Steam Ho. 9-20 + +

Gaslflcatlon tocorbon monoxide + and hydrogen

Purlflcotlon synthesis ws

of +

Liquefaction via catolytlc synthesis

Product

Generalized

Bow diagram

for indirect

liquifaction.

scale unit to investigate hydrocarbon yields from North Dakota lignite at operating pressures of 3.5 to 13.8 MPa. At 13.8 MPa, carbon conversions and yields of hydrocarbon liquids were higher. During normal operations, pulverized coal is gravity-fed to the reactor from a feed hopper, and carrier gas is supplied on a once-through basis. The residence time of the reactants is varied by altering the coal and the carrier-gas Bow rates. On the basis of the results of bench-scale studies, a 23- to 45-kg/h riser reactor PDU has been designed. Recent bench-scale studies with Illinois No. 6 bituminous coal showed that yields of hydrocarbon liquids were greater than those obtained from North Dakota lignite under similar processing conditions. To explore methods for handling caking coals, silica sand has been mixed with coal as a dry diluent. Cities Service Co. tested several bituminous coals and lignites in a bench-scale unit to determine operability in a small-diameter, entrained-tlow hydropyrolysis reactor and relative reactivity toward carbon conversion. The tests were made at an average temperature of 704OC (1299F), hydrogen partial pressure of 15.2 MPa, and a residence time of about 3 s. Carbon conversion ranging from 35 to 75 weight percent was obtained with carbon selectivities of about 30 to 35 percent to liquids. Rocketdyne has been testing its flash-hydropyrolysis process in a l-ton/h PDU to study residence time and reactor hydrogen requirements. Pulverized coal is fed from a high-pressure feeder into the entrained-flow reactor, where it is mixed rapidly with high-temperature hydrogen by using a rocket-engine injector element. The reactor is generally operated at temperatures in the range of 760 to 1037C (1400 to 1898F). The residence time is 20 to 200 rns, and the operating pressure is in the range of 3.4 to 10.3 MPa (493 to 1493 Ibfjir?). A hydrogen-to-coal-feed ratio as low as 0.16 by weight was

achieved. Overall conversions of about 60 percent can be obtained, yielding a plant thermal efficiency of about 75 percent if the char is gasified to supply the process hydrogen.

INDIRECT COAL LIQUEFACTION GENERAL REPERENCES: Lowry

and (ed.), Chemistry Of Coal LJtiliZ(ltiGn, vols I

II, Wiley. New York, 1945. Lowry (4.). Chemf.stry of Coal UrUitatfon, suppl. vol., Wiley. New York, 1963. Starch, Golumbic, and Anderson, The Fischer-Tropsch and Related Syntheses, Wiley, New York. 1951. Fischer-Tropsch Synthesis A general schematic approach for all indirect-liquefaction processes is shown in Fig. 9-28. All use the basic Fischer-Tropsch (F-T) reactions to produce liquids from hydrogen and carbon monoxide. The F-T synthesis differs from the direct-liquefaction processes described earlier in that it involves catalytic reactions between mixtures of hydrogen and carbon monoxide, so-called synthesis gas (syngas), which can be made by steam-oxygen gasification of coal or other hydrocarbons. The F-T synthesis produces largely paraffinic and olefinic hydrocarbons instead of the predominantly aromatic hydrocarbons from direct coal liquefaction. The basic reactions in the F-T synthesis follow: (en + l)HZ + nC0 2nHz + nC0 = C,H,.+, + nH,O = C.H1. + nH~0

(9-E) (9-26) (9-27) (9-28)

(9-29)

(n + l)He + 2nC0 nH, + 2nCO

2nH2 + nC0

= C.Hs.+z + nCOz = C.H,,+ = C.&+,OH

nCOp + (n - 1)H20

aCoal Prep.
FIG. 9-29

High Trmprrature and Moderato Presruro

Simplified process diagram for the SASOL-I Fischer-Tropsch process

9-36

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION duce high yields of high-octane gasoline and only trace amounts of oxygenated organics or hydrocarbons having molecular weights higher than those in gasoline. Some of the Mobil catalysts produce olefinic gasolines, and others produce aromatic gasolines. Some reject oxygen in the form of water, and others do so in the form of carbon dioxide. The other by-products of the Mobil catalysts are LPG materials, CI hydrocarbons, and methane. Preliminary aging tests suggest that some of the catalysts can be regenerated, and some also exhibit relatively long service lives. This preliminary work had been done in microscale units having the capacity for about 10 cm3 of catalyst in a fixed bed. Larger units (100 cm3 of catalyst) for both fixed- and Ruid-bed operation have now been built and are in shakedown testing. ECONOMICS OF COAL LIQUEFACTION

Reactions (9-25) and (9-27) yield paraffins, (9-26) and (g-28) olefins, and (9-29) alcohols. SASOL (an acronym in Afrikaans for South African Coal, Oil, and Gas Corporation) is the only commercial F-T plant in operation. The first plant, SASOL-I, was completed in Sasolburg in 1955; it is shown schematically in Fig. 9-29. Two additional plants, SASOL II and III, are now in operation. SASOL-I includes both fixed- and fluid&d-bed Synthol reactors. SASOL-II uses only fluidized-bed reactors since they produce a higher percentage of transportation fuels. A typical Synthol product slate follows: Product
Methane Ethane and ethylene Propane and propylene Butanes and butylenes Cs to 375F fraction 375 to 75OF fraction 750 to 970F fraction Heavier than 970F fraction Chemicals Total Yield, percent/weight 11.0 7.5 13.0 11.0 37.0 11.0 3.0 0.5 6.0 loo.0

Gasoline. It has been estimated that the installed cost of a SASOL-II type of plant in the United States would range from $2.5 to $36 billion (based on 1979 dollars), depending on where it was constructed. This corresponds approximately to $60,000 per daily barrel. Other approaches have been investigated for selectively making specific materials from syngas. Some have culminated in wellknown, widely used processes such as those for making methanol and acetic acid. More particularly, the approaches being pursued by the Mobil Research and Development Corporation are especially attractive because they show great promise of being the basis for making high-octane gasoline on a large scale from coal via syngas and methanol or directly from syngas without simultaneously making byproducts for which it may be difficult to find markets. Thus Mobils approaches appear to avoid one of the major stumbling blocks to the use of Fischer-Tropsch chemistry for making gasoline from coal, namely, the many higher-molecular-weight hydrocarbons and oxygenated organics produced by that chemistry along with the gasoline. Methanol-tc-Gasoline Process Mobil has developed a family of proprietary catalysts which make a mixture of hydrocarbons in the gasoline range with high selectivity from methanol. The mixture has a research octane number in the 93 to 94 range; the only by-products are water, a relatively small quantity of LPG materials, and even smaller quantities of methane and Cn hydrocarbons. Practically no materials having molecular weights above the gasoline range are pro duced. Because of the selectivity of the Mobil catalysts and because methanol can be made with great selectivity from syngas, which could tX made from coal, the Mobil catalysts provide a potentially promising route for making gasoline on a large scale indirectly from coal without simultaneously making any by-products which might be difficult to market. Syngas-to-Gasoline Process Mobil has also developed another group of proprietary catalysts which convert syngas with notable selectivity directly into a mixture of hydrocarbons in the gasoline range. Unlike the Fischer-Tropsch catalysts, the Mobil catalysts pro-

An example of process economics is included here to show a method for this type of calculation. Results obtained should be regarded as estimates based on conceptual plant designs and on a relative rather than an absolute basis. A product-value technique was used in determining product cost from a plant with a variety of products having different properties. This technique calculates a price for a reference fuel, in this case premium gasoline, and all others are determined from this reference. The basic assumption here is that particular product prices will remain in a fixed ratio with time. Solid fuels were priced on their heating value relative to fuel oil. Fuel oil is defined as industrial No. 6 or bunker C, and No. 2 is considered the same as diesel fuel. Naphtha is a general distillate product used for the production of gasoline, diesel, or other products. All naphtha were assigned values related to a cost of upgrading to gasoline. Liquid petroleum gas (LPG) consists primarily of propane and butane, and gasoline is low-octane as obtained from a simple Fischer-Tropsch process. Value factors for these products are shown in Table 9-29. TABLE9-29 Value Factws for Enorgy Products (Raferenco to Premium Gas&ml
Energy Value

Heating value, Product

SRC solid Char Tar oil Fuel oil No. 2 oil (diesel fuel) N&ha LPG Gasoline Premium gacolinet Methanolt Methyl fuel8 Butane Propane All fuel gases9 Electricitv

1978 price. $
26.32/tori 14.68/bbl 12.35jbbl 14.92/bbl 14.92jbbl 12.04/bbl 15.75ibbl 17SOjbbl 13.ll/bbl lr.lO/bbl 31.06/10s Wh

ld Btu 32.0 16.0 5.0 6.3 5.2 5.2 4.0 5.0 5.0 2.7 2.6 3.5 3.2 3.4

price, $1 l@Btu 1.75 1.65

2.96

factor. f, SO .47
I35

1.95 2.67 2.67 3.01 3.15 3.50 3.50 3.36 3.75 3.76 3.50 9.10

.56 .a2 .62 :Z 1.00 1.00 .36 1.07 1.06 1.00 2.60

No sales in 1978; energy price assumed as 10% less than that of fuel oil. f Premium gasoline is reference fuel; f = 1.00 tNo significant market in 1978; energy value awmed as same as premium gasoline $No market in 1978, energy price 4% below methanol for water content. ~Severe price regulation for natural gas in 1978; energy value set at 1.00.

HEAT GENERATION
GENRUL Mars: Field, Gill, Morgan, and Hawk&y, Combustion of Puloerized Cool, British Coal Utilisation Research Association, Leatherhead, England. 1967. Jmt and Croft. Explosions and Combustion Processes in Cases, t&Craw-Hill, New York, 1946. Spalding, Some Fun&menials of Combustion, Academic, New York. 1955. Thring, The Science ofFlnmes and Furnaces, Wiley, New York, 1962.

Kolecuw&t 12.01 2.016 32.OOO Z:!" 44.01 16.O4l 30.067 ai 8::: 72.144 E:I$

Hat Lb. cu. / t.

of am B&u/lb.

u. ft. combustible Flu4 ~OdUcta Net Air 4.76 2.33 2.38 9.53 E:$ a.97 E:E s&II M.lI (5.26 3.0 ::: ::: ::?I 10.5 2.5 '::! 3.0 0.75 3.983 6.545 I.0 I.5 ::z iE 55 73 :::: 50.02 II.91 '::I: 'i:F ::G

Sib!/

%&k-F.
l.ooo

/lb. a DR

B.t.u./cu.

t
N

1
Nr
i3.M i lb.41 0.57 1.90 I13.m I I i::3 I II.91 I I 11::; I I1.e.I I Il.81 II.74 At?

,Grow
325 327.

Net 215 37l

,Gross

COI I.0

El0
1.0

COI
a.94 ....

N; 0.M 1.41 1.90 13.26 :::

::EE %E ::t:: 13.443 'E 0.1170

KS 6.365 ::::1 ::iE ::ii ':G c!i 5.400 ::E 0.2no3 ::EZ ::YE 0.0456 ::!i: 3.567 '::Z 'A:X 21.914 0.97Ut 1.4504 I.9336 I.9336 2.4190

14.093 14D93 61.100 51423 4.347 23.879 22.320 21.661 ::iE 21.091 21.052 20.970 2094o 4.347

X
1.1 7.53 1::: 24.47 24.47 M.II 3:;: 35.76 El 22.59 22.59 28.23 KI 39.52 9.41 'Z 11.29 3.32 ::3

Il.53 3.66 n.34 . 2.47 1.57

I.0 I.0 2.0 3.0 ::: ::: 5.0 6.0 ::: ::: 5.0 ::: 11.0 2.0 I::: 2.0 80 1.0 I.0

$:?i 19:944 19.680 IE 19:47ll 19.3% 19.4o3 EC 19:496 19.382 19.363

::: ::: 5.0 ::: !:i 2.0 ::: 4.0 6.0 3.0 ::i I.0 ::: ::: I.0

::Fi ::!i Z :::: 3.53 3.42 :::: :::: ::X 3.17 3.07 ::!i 2.08 I.41 I:!!

1:: 1.55
I:Z I:E ::I: 3.14 :::: X 13.70 X E 6.10 ::; 3.38 :::: ::ii I.37 1.92 I:E I:Z 1.29 0.69 ::E E 1::: I.59 0.53

EE K ll:E 11.81 II.74 I:3 II.39 Il.39 II.39 18.22 I::: 10.22 9.97 4.98 ::s E

1614 SE ZE 3751 z hii IZ 441 647

1513 is z g IZ l8:65O 21.500 17.298 10.259 13.161 9.668

I I I I I I

17.480 17.620 17.760

kiti 10.53 '!:i Z 4.69

z.! I:

32.06 X6 10.016 28.9

0.0911 0.1733 EE

'!:Z 21.017 13.063

596

From American Gas Association. To convert pounds per cubic foot to kilograms per cubic meter. multiply by 16.02; to convert cubic feet per pound to cubic meters per kilogram, multiply by multiply by 2329. 0.062; to convert British thermal units per cubic foot to joules per cubic meter. multiply by 37.3 X IO? and to convert British thermal -units per pound to joules per kilogram, 60F and 30 inHg dry = 15.6OC and 76.2 cm. t All gas volumes corrected to 60F and 30 inHg dry. (Carbon and sulfur are considered as gases for molal calculations only.

9-38

ENERGY UTIUZATION,

CONVERSION, AND RESOURCE CONSERVATION in pounds is obtained by multiplying cubic feet by 0.0891, the density of oxygen at the same conditions. The w~lume of theoretical air is obtained by using a coefficient of 1710 instead of 359 in Eq. (Q31). Table Q-30 gives the theoretical oxygen and air requirements and the gaseous products of combustion (POC) for a wide variety of cornbustible substances. Table Q-31 gives the theoretical air requirements on the basis of the higher heating value and the maximum, or theoretical, carbon dioxide content of the POC for several industrial fuels. The close agreement among theoretical air requirements suggests that a good approximation of the air requirements is 7.7 lb/IO,000 Btu (HHV) for coal and coke and 7.4 for petroleum oils. If only the lower heating value of the fuel is known, the HHV can be calculated from Eq. (Q6) or (Q-7). More than the theoretical amount Excess Air for Combustion of air is necessary in practice to achieve complete combustion. This excess air is expressed either as a percentage of the theoretical air or as the total air divided by the theoretical air. The former is most frequently used. The latter is sometimes called the excess air number. If, for example, it is 1.25, there is 2.5 percent exces air. Figure Q-30 shows the relationship of oxygen in the POC to excess air for various industrial fuels. If it is desired to know the percentage of excess air A, under the operating conditions of a particular combustion process, it can be calculated from

COMBUSTION STOICHIOMETRY Theoretical Oxygen and Air for Combustion The amount of oxygen or air just sufficient to burn the carbon, net hydrogen, and sulfur in a fuel to carbon dioxide, water vapor, and sulfur dioxide is the theoretical oxygen or air. The general expression for combustion of a fuel is (Q-30) 0 m and n being the number of atoms of carbon and net hydrogen, respectively, in the fuel. For example, this relationship shows that 1 n-101 methane (CH,) requires 2 mol of oxygen for complete comof bustion to 1 mol of carbon dioxide and 2 mol of water. If air is used, each mole of oxygen is accompanied by 3.76 mol of nitrogen. The theoretical weight or volume of oxygen or air required to burn a given weight of a fuel is of primary interest in engineering calculations for the design of equipment. The volume of theoretical oxygen needed to burn any fuel can be calculated from the ultimate analysis of the fuel as follows: = ft3 oxygen/lb fuel (9-31)

Op = mCOp + ; He0

where C, Hp, and S are the decimal weights of these elements in 02, 1 lb of fuel. (To convert cubic feet to cubic meters, multiply by 0.0283; to convert cubic feet per pound to cubic meters per kilogram, multiply by 0.0623.) The coefficient 359 is the volume in cubic feet of 1 mol of oxygen at OC (32F) and 1 atm. The weight of oxygen
Net hydrogen total hydrogen (0.125 X oxygen in fuel).

4 =

OS
0.266N* - 02

100

TABLE

9-3 1

Thowotical

Air and CO, fovCombustionof Industrial

where 0s and N2 are the percentages by volume of these gases in the dry POC, as determined from an Orsat analysis or other volumetric methods for analyzing POC Equation (Q-32) is applicable only when the nitrogen in the fuel is negligible and there are no combustible gases, such as carlxon monoxide or hydrogen, in the POC. If these gases are present, the percentage excess air is Op - 0.5(C + Hz) (W Ax = 0.266N2 - O2 + 0.5(CO + HP) (Q-33)

n ... . . . .

..

~ 7.62-7.76

IQh-vol+lnA..
[*bb&umk.w~. Lip ortbD&ot4..

7.%7.75 . &h-mlat~LB.. .................. 7.56-7.75 7.54-7.67 Hi@-volat&c.. ..........

.......... 7.56-7.57

Texas..

................................... ........... .

60

...... .. ,...,...

. ... .

,..,...,

I...... .

.. I

7.32-7.41
I

brhuia -__ . . . .. :i ..,,..,,,

$fi&:::; ::-:.,::::::::: :::.::::::

From Johmn and Auth (eds.), Fuels and ~omb~.~rron McGraw-Hill, New York. 1951, p, 355. (lb/lo,000 Btu) x 43 = k, tHigher heating value.

2 3 4 5 6 7 6 Oryqen in flue 90s. by volume

in the tlue us

IO

II
fuels

12

Relationship of oxwen FKI. 9-30 (Barley Meter Co.)

to rxces~ air for various

If only the carbon dioxide content of the POC is known, * I = 79oo((CCz), - COP1 CO$lOO - (CO&]

where (COP), is the maximum volume percentage of carbon dioxide obtainable in the dry POC for a given fuel, and COs is the actual percentage found in the dry PCC. Tables 9-30 and 9-31 give the values of (COP), for several fuels and other combustible substances. The products of combustion consist, in Products of Combustion the case of solid fuels, of solid residue which may contain unburned combustible and gases previously referred to as POC. The amount of residue will exceed the ash content of the original solid fuel by an amount equal to the unburned combustible in the residue. It may be estimated by determining the ash content of the residue. The weight of dry gas in the POC may be calculated from cd _ C, - C, 4(CO*) + 01 + 709 100 I 3(C4 + 0,)

I (9-W
(9-36)

where Cd = lb dry gas/lb fuel fired, Cf and C, are the percentages by weight of carbon in the fuel and the residue respectively, and COs and 0s are the percentages by volume of these gases in the PCC. Equation (9-35) assumes hydrogen to be absent or negligible in the dry POC. The weight of wet gas in the POC is C, = Cd + 0.09Hp

where G, = lb wet gas/lb fuel fired; and Hz is the total hydrogen, percent by weight, in the as-fired fuel. ENTHALPY OF COMBUSTION PRODUCTS
0 400 803 1203 1603 Zoo0 2400 2803 32C0 3600 4co3

Figure 9-31 gives the enthalpy of combustion products above lS&C (tWF). To illustrate its use, assume that a Eue gas at 1093C (2tK0F) contains, in percent per volume, 13.7 COs, 3.9 Op, 7.7 HpO, and 74.7 Ns. The enthalpy of the tlue gas at the specified temperature would be (0.137 X 59) + (0.039 X 38) + (0.077 X 48) i(0.747 X 38) = 41.85 Btu/ft3, or 1553 kJ/ms. SOLID-FUELS COMBUSTION SUSPENSION ON STOKERS AND IN

Temperature, "F FIQ. 9-31

Heat content of various @.sesabove 60F in British thermal units per cubic fmt (to convert to kilojoules per cubic meter, multiply by 37.3). T - (F - 32) X X.

There are basically two modes for burning solid fuels: in a fuel bed or in suspension. There are several variations of both modes, each suited to a particular system. Table 9-32 lists the kinds of equipment used to burn different types of solid fuels. Fuel-bed firing is accomplished with mechanFuel-Bed Firing ical stokers, which are designed to achieve continuous or intermittent fuel feed, fuel ignition, proper distribution of the combustion air, free releare of the gaseous combustion products, and continuous or intermittent disposal of the unburned residue. These aims are met conventionally with three types of stokers: underfeed, crossfeed, and overfeed, which differ mainly in the relative directions of the flow of fuel and air. The principles of these types of stokers are shown schematically in Fig. 9-32, and capacities are given in Table 9-33. Both fuel and air have the same relative direction in the underfeed stoker, which is built in single-retort and multiple-retort designs. In the single-retort, side-dump stoker, a ram pushes coal into the retort toward the end of the stoker and upward toward the tuyere blocks, where air is admitted to the bed. This type of stoker will handle most bituminous coals and anthracite, preferably I.9 to 5 cm (K to 2 in) and no more than 50 percent through a O.&cm (%-in) screen. Overfire air or steam lets are frequently used in the bridgewall at the end of the stoker to promote turbulence. In the multiple-retort stoker, rams feed coal to the top of sloping grates between banks of tuyeres. Auxiliary small sloping rams perform the same function as the pusher rods in the single retort. Air is admitted along the top of the banks of tuyeres, and on the largest units the tuyeres themselves are given a slight reciprocating action

to agitate the bed further. This type of stoker operates best with caking coals having a relatively high ash-softening temperature. Coal sizing is up to 5 cm (2 in) with 30 to 50 percent through a O&cm (%in) screen. The fuel flows at right angles to the air Bow in the crossfeed stoker. The most common of this type is the traveling-grate stoker, which is built in two types, the chain grate and the bar grate. Coal feeds by gravity into a hopper at one end of the moving grate. As the grate paws under the hopper, it carries a bed of fresh coal toward the furnace. Only a small amount of air is fed at the front of the stoker, to keep the fuel mixture rich, but as the coal moves toward the middle of the furnace, the amount of air is increased, and most of the coal is burned by the time it gets halfway down the length of the grate. Fuel-bed depth varies from 10 to 20 cm (4 to 8 in), depending on the fuel, which can be coke breeze, anthracite, or any noncoking bituminous coal. Figure 9-33 illustrates a variation of the traveling-grate stoker, which is widely used for sintering ore. Combustion air is drawn downward through the bed of ore and coal, and combustion products are removed beneath the grate. The fuel and air flow in opposite directions in the overfeed stoker. Except for certain types of gas producers, in which coal moves downward toward a grate against upward movement of the air (or oxygen and steam) through the grate, there is no combustion system that operates purely in the overfeed mode. However, the spreader stoker approximates overfeed action. A portion of the fuel burns in suspension, and the remainder burns on a dump, undulating, or moving grate. Spreader stokers with cecillating, pulsating, or traveling grates have been widely employed because they will burn all typesoT coal,

940

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

TABLE 9-32

Burning Equipment for Solid Fudr

Stokers

Fuel
Coke breeze Anthracite Bituminous coal: 17-2796 volatile 27-352 volatile Strongly coking Weakly Pipelme Lignite coking

c
E.Pi.

w.

Va.,

cent.Pa.

w.

Pa., w. Va.,

Ky., Ohm, Utah Ind., Iowa, Ill., Cola., W. Ky.

N:Dak., Mont.. S: D& wyo., Tex

slurry

Low-temp. Bud-coal char Petroleum coke, 9-14% volatile Fluid petroleum coke, 4-596 volatile Wood and bark]

Bagasse
From Baumeister and Marks, Standard Handbook good application. but there are many factors affecting equipment. t c = coarse sizes only. Aux = auxiliary fuel-coal, t Bark and wood are also burned on inclined grates for Mechanical the burning Engineers, of fuel, and 7th ed ,, McGraw-Hill, 1967. Equipment indicated will usually of fuel properties that guide the indiwdual selection variatior

IS

resl.

c,f b

oil, or gas.
and in Dutch-oven pile furnaces.

respond rapidly to load changes, and operate efficiently, with comparatively low excess air. Low gas velocities through the furnace are necessary to minimize fly-ash erosion, and dust collectors must be used to minimize dust emissions from the stack. (Since spreader firing combines the features of fuel-bed and suspension firing, the combination is discussed later under Spreader-Stoker Firing.) Suspension Firing Suspension firing of pulverized coal is used much more often than fuel-bed firing of coarse coal in the United States. This mode of firing coal affords higher steam-generation capacity, is independent of the caking characteristics of the coal, and responds quickly to load changes. However, pulverized-coal firing is

TABLE 9-33

Cupacitior of Mechanical Stokers

steam
Type Single retort (underfeed) Multiple retort (underfeed)

Maximum grate
heat release, loo0

generation, ICOO lb/h

5-50 40-300 lo-300 IO-300

Btu/(h.fP)t
:: 300 loo0

Traveling (crossfeed)
Spreader ~overfeed) To obtain tTo obtain

kg/s, multiply by 1.26 X lo-. J/(m*.s), multiply by 3.16.

ICI r;rTz, Y

Basic types of mechanical

stokers.

(a) Underfeed

(b) Crwfeed.

(c)

FiG. 9-33

Improved sintering

prcca.

(Courtesy

of Chemical

Engineering.)

SOLID-FUELS COMBUSTION rarely used on boilers of less than 45,360 kg/h (100,000 lb/h) steam capacity, since stokers are more economical for units of lower capacity. The various burner and furnace configurations for pulverized-coal firing are shown schematically in Fig. 9-34. The U-shaped flame, designaied as fantail vertical firing (Fi-& 9-34a), was d&loped initially for pulverized coal before the advent of water-cooled furnace walls. Because a large percentage of the total combustion air is withheld from the fuel stream until it projects well down into the furnace, this type of firing is well suited for solid fuels that are difficult to ignite, such as those with less than 15 percent volatile matter. Although this configuration is no longer used in central-station power plants, it may find favor again if low-volatile chars from coal-conversion processes are used for steam generation or process heating. Modem central stations use the other burner-furnace configurations shown in Fig. 9-34, in which the coal and air are mixed as rap idly as possible in and close to the burner. The primary air, used to transport the pulverized coal to the burner, comprises 10 to 20 percent of the total combustion air. The secondary air, comprising the remainder of the total air, mixes in the burner with the primary air and coal in a manner to promote rapid mixing. The velocity of the mixture leaving the burner must he high enough to prevent Ilashback in the primary air-coal piping. In practice, the velocity in the primary air-coal pipe is maintained at about 31 m/s (100 ft/s). In tangential firing (Fig. g-346) the burners are arranged in vertical banks at each comer of a square (or nearly square) furnace and directed toward an imaginary circle in the center of the furnace. This results in the formation of a large vortex with its axis on the vertical centerline. The burners consist of an arrangement of slots one above the other, admitting, through alternate slots, primary airfuel mixture and secondary air. It is possible to tilt the burners upward or downward, the maximum inclination to the horizontal

ON STORERS

AND IN SUSPENSION

941

RQ. P-35 Circular burner for puhwized oool, oil, or gas (From Bautiter, Marks Standard Handbook for Mechanical Engineers, 7th Ed.. McGraw-HIU, New York, 1967.) being 30. enabling the operator to control superheat and to permit selective utilizntion of furnace heat-absorbing surfaces. Basically the turbulence needed for mixing is generated in the furnace instead of in the burners. The circular burner shown in Fig. 9-35 is widely used in horizontally fired furnaces and is capable of firing coal, oil, or gas in capacities as high as 174 GJ/h (165 million Btu/h). In cyclone firing (Fig. 9-34d) the coal is not pulverized but is crushed to 4-mesh size, admitted with the primary air in a tangential manner to a horizontal primary, cylindrical chamber called a cyclone furnace. The finer particles bum in suspension. while the coarser ones are thrown by centrifugal force to the outer wall of the cyclone furnace. The wall surface, having a sticky coating of molten slag, retains most of the coal particles until they burn. The secondary air, which is admitted tangentially along the top of the cyclone fur-

Primary

ndary

Fantoil (a)

Multiple

intertube

Plan wew of furnace (b) Tonpentlal Firing

Vertical Fuing

Mulhple

Intertube (c) Haizontal Firing

Circular

U
(d) Cyclone RG. 9-34 Flrmq (4 Opposed -inclined

ond coal
Firing

Burner and furnace configurations for pulverizec-cosl firing

9-42

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

time necessary for cleaning the grates. Continuous-cleaning grates do not need to be zoned for ash removal; the higher grate heat releases possible make such grates economical. Small units can be equipped with grates installed at a slight slope and using a vibrating or oscillating motion to propel the ash to the end of the grate. The stoker is in motion only a small portion of the time, and the fuel bed moves forward as one mass, so there is no serious intermixing of ash and burning coals. These units are restricted by the size of grate, weight of fuel bed, and physical size of the driving apparatus. Large spreader stokers are normally equipped with traveling grates. Grate heat-release rates used in sizing spreader stokers are listed in Table Q-34. The figures given in the table are for normal designs and will vary for a particular installation, depending upon the coal used and the load factor of the particular unit. Excess air is usually 30 to 40 percent for stationary and dumping grates, while continuous-cleaning grates are operated with from 22 to 30 percent excess air. Preheat air can be supplied for all types of grates, but the temperature is usually limited to 120 to 15OC (250 to 300F) to prevent any excessive slagging of the fuel bed. Overfire air nozzles are located in the front wall underneath the spreaders and in the rear wall from 0.3 to 0.9 m (12 to 36 in) above the grate level. These nozzles use air directly from a fan or inspirate air with steam to provide turbulence above the grate for most effective mixing of fuel and air. They supply about 15 percent of the total combustion air. The size range of spreader stokers extends into that for which multiple-fuel firing is generally considered necessary. It is usually easy to increase the height of the furnace and install oil or gas burners in the upper portions of the furnace. During firing of this auxiliary fuel

Cyche furnace. (From Baumetster, for Mechanical Engineers. 7th ed., McCrawHt11, FIG. 9-36

Mark; Standard New York, 1967.)

Handbook

nace, completes the combustion of the coarse particles at a firing rate of about 18.6 GJ/(h.ms) [500,000 Btu/(h.fts)]. Slag drains continuously into the main boiler furnace and then into a quenching tank. Figure 9-36 shows the cyclone furnace schematically. Spreader-Stoker Firing Spreader stokers burn coal by propelling it into the furnace. A portion of the coal burns in suspension (the percentage depending on the coal fineness), while the rest burns on a grate. In most units coal is pushed off a plate under the storage hopper onto revolving paddles (either overthrow or underthrow) which distribute the coal on the grate (Fig. 9-32c). The angle and speed of the paddles control coal distribution. The largest coal particles travel the farthest, while the smallest ones become partially consumed during their trajectory and fall on the forward half of the grate. A few spreaders use air to transport the coal to the furnace and distribute it, while others use mechanical means to transport the coal to a series of pneumatic jets. The performance of spreader stokers is affected by changes in coal sizing, the main problem being the size consist of the fuel fired The equipment can distribute a wide range of fuel sizes, but it distributes each particle on the basis of the size and weight of the particle. Normal size specifications call for 1.9~cm (%-in) nut and slack with not more than 30 percent less than 0.64 cm (X in). Approximately 30 to 50 percent of the coal is burned in suspension. If excessive fines are present, more coal will be burned in suspension, more coal particles will be carried out of the furnace, and very little ash will be available to provide a protective cover for the grate surface. If sufficient fines are not present, the capacity of the unit will be reduced because the grate is not designed to burn the entire capacity of the furnace, usually resulting in excessive live coals being dumped to the ash hopper. The grates used with spreader stokers are of several types, as shown in Fig. 9-37. Stationary grates are the cheapest to install, but they must be divided into zones for cleaning and ash removal. In the dumping-grate stoker the grates themselves can be dumped, thereby olimhrting tlrc h&g UCa.&~>. TlrL psvvider DVIIIC: reducr~on In the

TARE 9-34

Grate

Hoat Relwses

in Sproadr

Stokm

Grate heat release 1000 B.t.u./(hr.)(sq. ft.) Grate type Without dust collector For bituminous coals With dust collector

Stationary: Maximum continuous load 2.hr. peak Dumping: Maximum continuous load 2-hr. peak Oscillating: Maximum continuous load 2-hr. peak Travel& 1000 Ib./hr. continuous boiler

350
400 375 450

400 450 475 525 555 62.5

loo axl 725

200 300 7lJlJ 7z.5 775 800

For Iowa coal, subbituminous coal. lignite. wood. and bagasse Stationary: Maximum continuous load 2-hr. peak Dumping: Maximum continuous load 2-hr. peak Oscillatinn: Maxi&m continuous load Matimum continuous load 2.hr. peak Trawling: loo0 Ib./hr. continuous boiler capacity Maximum continuous load 2-hr. peak (d) Traveling

(a)

Stat ionory

(b)

Cumpmg

6.50 Refractory with clinker chill 700 Water-cooled

800 furnace All furnaces

loo 150 850

200 300 850 850 9001ooo

(cl osclllotlnp
Ao. 9-37

Types of grates used with spreader stokers.

NOTE: convert British thermal units per hour-square toot to joules per To square meter-second. multiply by 3.16.

SOLID-FUELSCOMBUSTION IN FUJIMZED BEDS

TABLE 9-35 Factors for Selecting Mechanical Stokers

943

FaCtOrS Initial capital investment Handling fine coal Handling caking coal Handling ash Maintenance and operating costs Fly ash and carbon loss Draft loss through fuel bed Minimum exees air, percent Ability to handle load changer

Chain or trawling grate Least POX PO01 Good Intermediate Lowest Intermediate 30 Fair

Spreader Least POOr Good Excellent Lowest Largest Lowest 2.5 Excellent

Underfeed Most PCOr PO01 Fair Largest Lawest Largest 45 Fair

the grate must be protected from overheating by a very deep bed of ash or a firebrick cover, both with slight air leakages. The carbon content of the ash passing out of the furnace varies from 30 to 50 percent. Overall efficiency of a spreader stoker can be increased by rebuming this fly ash. It is returned to the stoker grate by a gravity or pneumatic feed system. The reinjected ash must be retained on the fuel bed to keep the fly-ash loading in the boiler passes low. Table 9-35 shows some of the factors for selecting mechanical stokers. The heart of any solid-fuel suspension-firing system Pulverizers is the pulverizer. Air is used to dry the coal, transport it through the pulverizer, classify it, and transport the specified fines to the burner, where the transport air provides part of the air for combustion. The pulverizers themselves are classified according to whether they operate under positive or negative pressure and whether they are slow-, medium-, or high-speed. Pulverization occurs by impact, attrition, or crushing. The capacity of a pulverizer depends on the grindability of the coal and the fineness desired, as shown by Fig. 9-38. Capacity can also be affected by excessive moisture in the coal. Capacity can be restored by increasing the temperature of the primary air; Fig. 9-39 indicates the temperatures needed. For pulverized coal-fired boilers, the coal size usually is 65 to 80 percent through a 200-mesh screen, which is equivalent to 74 pm. The kinds of pulverizers and their characteristics are discussed in Sec. 8.

loo
FIG. 9-39

Lb. air/lb.

coal pulvermd

Effect of moisture in coal on pulveriser capacity. Sufficient drying can be accomplished to restore capacity if air temperatures are high enough. (Combustion Engineer, Combusifon Engtneertng Inc.. New York, 1966.)

SOUD-FUELS COMBUSTION IN FLUIDIZED BEDS

Proceedtnns of the Fourth IntemattomaI Conference GENERUREPOIMCES: on Flutdtzed-Bed Combwtton, De. Q-11, 1975, The MITRE Corporation, McLean. Va. 22102. Pmceedtngs of the Workshop on Uttltty/lndu.strtal Implementation of Flutdtzed Bed-Comtwtton Systems, Atlanta, Ga., Apr. 27-28, 1976, The MITRE Corporation. McLean, Va. 22102. Pmceedtnga of the Flutdtzed-Bed Cm&&ton Technology Exchange Workshop, Apr. 13-15, 1977. The MITRE Cormration. McLean. Va. 22102. Proceedtnns of the Ftfth Inter&tonal Confer& on Flutitzeed-Bed Combustton, D&&&r 1677, The MITRE Corporation, McLean, Va. 22102. An Assessment of Flutdtzed-Bed Ccmbwtron Based on the Papers of the Ftfth btemattonul Conference. December 1979, The MITRE Corwration, McLean. Va. 22102. Prcieedags of Sixth Intematkmal Conf&m on Flutdtzed-Bed Cornbustton, Atlanta, Ga., Apr. Q-11, 1960, U.S. Department of Energy, CdNF-

- ,

of

theStatus

the

KlO428, vols. 1-3. Atmospheric and Pressurized Fluidized Beds (AFBC and PFBC) Fluidized-bed combustion (FBC) involves the combustion of fuel in a bed of solid particles, which is tluidized (held in suspension) by the injection of air at the bottom of the bed. When coal is burned in this manner, the bed can consist of inert solids, coal ash, or a sorbent such as limestone or dolomite. Limestone or dolomite in the bed reacts with the sulfur dioxide formed during combustion of the coal and forms a solid sulfate which can be discarded as a dry solid. Variations in the technology include atmospheric-pressure tluid&d-bed combustion (AFBC) and pressurized tluidized-bed combustion (PFBC). Figure 9-40 shows various applications of AFBC, and Fig. 9-41 shows PFBC-cycle concepts. In the early 196Os, Great Britains National Coal Board, the British Coal Utilisation Research Association, and the Central Electricity Generating Board began investigating FBC. After the energy crisis in 1973, AFBC and PFBC of coal developed rapidly, mostly in the United States, Great Britain, and the Federal Republic of Germany, for use in utilities, process industries, and the institutional sectors. FBC has great potential to burn efficiently and cleanly a wide variety of fuels, ranging from high-sulfur, high-ash c&s of all ranks and grades to industrial-process wastes and municipal sludges. Some of the potential advantages of FBC, compared with pulveri&-coal firing, are: 1. Less sulfur dioxide emissions, because much of the sulfur is captured by fuel-bed additives such as limestone or dolomite

o.23~

70 00 Grlndablllty index,A.S.T.hl.

90

100

Variation of pulveriser capacity with the grindability of the coal FIG. 9-38 and the fineness to which the coal is ground (Bobcock G Wtlcox Co.)

Saturotedsteam outlet

Feed water inlet

Feedwoter inlet +

Hot gases process needs

for

Fluldized Working fluid Inlet

bed

Fluidized

bed -

C
-------------

Fuel and sarbent inlet Air Inlet (fluidizing ond process)

*_

Ash disposal (c

(d) boiler.

Atmospheric-fluid&d-bed-combustion boiler-combustor arrangements. (a) Saturated-steam FIQ. 9-40 (b) Superheater-steam generator. (c) Indirect-proces heater. (d) Direct-process heater.

Steam turbine

Stock

Steam

turbme

. Stock

Ash disposal

Condenser heat recovery

Ash disposal

Ash

disposal ICI

(0)

lb) tuber in bed

Prffsurized-Eutdized-bed-combustion concepts. (a) Steam-cc&d FIG. 941 bed CC)Bed cooled by excess air (300 percent); no in-bed tubes.

(b) Air-cooled tubes in

946

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

3 CO/S

FIG. 946 XK

Calcium-sulfur-ratio

effect on SO* capture

RQ. 943

Carbon-combwtion

efficiency as P function

of bed temperature.

75 -

70-" " " " " ' 0 1 2

10

1112

Gas velocity. If/s Ro. 944

Carbon-combustion

efficiency as B function of gas velocity.

11 0
~NX 9-45

I 5 Gas vekmty, o/s

I 10

Dependency

of bed grid area on gas velocity.

The relationship of bed area to velocity is illustrated in Fig. 9-45. Decreasing velocity rapidly increases the required square feet of grid or bed area needed per unit of output. SOs removal or S retention in situ is a unique feaSOs Removal ture of the AFBC process. Sulfur contained in the fuel is oxidized to Sop during the combustion process. This SO, chemically reacts, in the presence of oxygen, with the sorbent to form a stable, solid sulfate in the bed. SOs emissions are thereby controlled in the combustion vessel itself, eliminating the need for downstream SOa cleanup of the Eue gas. Sulfur capture depends on a number of design and operating variables as well as on the sorbent used. A primary variable, which can be readily controlled, is the calcium-tosulfur mole ratio. Also of importance is the bed temperature, since the SOs-sorbent reaction is temperature-dependent. These two effects are illustrated in Fig. Q46. Typical experimental trends are shown for SOa capture plotted against the Ca/S ratio for several bed temperatures. An optimum sulfur-capture temperature of around 643% (1550OF) is common for many sorbents. Increasing the Ca/S mole ratio increases sulfur capture, but it is desirable to minimize calcium addition because this represents greater sorbent costs, parasitic heat loss through calcination, and increased disposal problems. Other variables that affect sulfur capture include bed depth and gas velocity. Deeper beds allow longer gas residence time, i.e., provide more contact time with the sorbent, and thereby increase sulfur capture. Low velocity also increases gas residence time and, therefore, increases sulfur capture. These variables along with the Ca/S ratio can be balanced to achieve efficiency of sulfur capture. Fig. Q47 presents calculated curves which illustrate this sulfur-capture trade-off. In this figure, two curves are shown, with sulfur-removal efficiency plotted versus the Ca/S ratio. In curve A, the performance of a low-velocity bed (4 ft/s) shows high sulfur capture at relatively low velocity. Curve B shows that high Ca/S ratios are needed for high sulfur capture at higher bed velocities. Heat-transfer rates to tubes immersed in AFBCs Heat Transfer are higher than those to tubes in conventional pulverized-coal-fired boilers. This feature of AFBCs allows relatively high volumetric heat release and absorption rates, which result in relatively small boilers. The heat-transfer rate depends on the bed particle size as shown in Fig. 9-48. Bed particle size, however, is largely a dependent variable in a given design and is not readily controlled or changed. Bed-partitle-size distribution depends on sorbent and fuel-feed size, sorbentattrition rate, carry-over rates, and fuel-ash properties. The heattransfer rate is nearly independent of gas velocity in the AFBC, provided the velocity is above the point for minimum Euidiaation. Nitrogen Oxidea Emissions Emissions of nitrogen oxides are limited by current New Source Performance Standards (NSPS) to less than 0.7 lb NOa/lOa Btu. In the AFBC bed, combustion occurs at relatively low temperatures [760 to 930% (1400 to 1700F)], compared with the much higher temperatures typical of pulverized-coal-

SOW-FUELS COMBUSTION IN FUJIDIZED BEDS fired boilers. These low temperatures do not allow significant oxidation of atmospheric nitrogen, so the AFBC process is characterixed by low NO, emissions. Nitrogen oxides formation in the AFBC results primarily from oxidation of fuel-bound nitrogen. The reaction of carbon monoxide and NO, in the gas-burnout zone apparently further reduces NO. emission from the AFBC. Fuel nitrogen content and percent of excess oxygen are the two main variables affecting NO, emission. Over the excess-oxygen range of 0 to 10 percent, NO. emissions are generally below the current NSPS level as well as the proposed level of 0.6 lb NOs/l@ Btu. Experimental data on NO. emissions taken since the late 1966s from major FBC experimental facilities are shown in Fig. Q-49. Superimposed on the graph are three levels of emission control: moderate, intermediate, and stringent. These three levels are those that

9-47

95 -

90-

cl

El Ao. 949 NO,

Boiler capocity,

MW,

emissions from AFBC facilities.

s_85

iP
i

80-

ff
!
755 f

m65 -

601
0

10

11

1
12

sorbent type
Average diameter, pm Preswre. kPa Bed temperature, OC Excessair, percent Velocity, m/s
Bed depth. m
PI@. 9-47

A 500
101

loo0
101

840 20
1.38 1.22

840 20
3.scl 1.22

can be achieved by (1) normal or routine operation, (2) a well-maintained system operating with some optimixation of design conditions, and (3) optimixation of all design parameters so that the system is performing at its technological limit. Figure 9-49 shows that as AFBC systems increase in size, the range of NO. emissions decreases. When capacities approach those expected for commercial use (Le., greater than 5 to 10 MWt), the range of NO, emissions falls below even the most stringent levels identified for possible emission standards. Fluidization Design Factors In addition to the AFBC process considerations, the design of an AFBC combustor must follow the design principles associated with fluidixation as discussed in Sec. 20: Fluidized-Bed Systems. Information useful in the design of coalfired AFBCs is presented in the following paragraphs. The information is based on the Coal Conoersfa Systems Data Book, prepared by the Institute of Gas Technology for the U.S. Department of Energy (HCP/T2266-01). Shape Factorr of Variour Mater&& Shape factors for nonspherical particles are often required in tluidiaation studies. Shape factor rj~ defined as the ratio of the area of a sphere, with a volume is equivalent to that of the particles, divided by the actual surface area of the particles. Some values follow:

Material
Coal dust, pulverised Coal, anthracite Goal, bituminous Limestone

Shape factor 6 0.73 0.63 0.63 0.45

Sulfur-capture tradeoff

Relation of Minimum Fluidized-Bed Voidage to Average Particle Diameter Minimum iluidized-bed voidage c,,, is often required in tluidization studies. Fig. 950 gives c,,,, as a t unction of particle diameter for various materials. Minimum Fluidizafion Velocity The Kunii-Levenspiel correlation is recommended for estimating minimum fluidization velocities. (Q-37) where Re,,,) =

Dp,u,1_ c1
Ir

Reynolds number ration velocity

at minimum

fluidi-

OW4
FIG. 9-U

Ar = @&
001

004 Portlcle 8" we.

01

B=
hf = Pa =

Effect of Particle size on bad-totute heat transfer.

shape factor minimum fluidized-bed voidage particle density of fluidizing solids, lb/f?

- ps)g = Archimedes number

9-48

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION no bed (infinite expansion) at superficial gas velocities equal to or greater than the terminal velocity of the particles. Superficial velocities in the data used are less than 60 percent of the terminal velocity for the average particle diameter for the bed. Projections to higher relative velocities should be made cautiously. hnsporf Disengagement Height (TDH) Fluidized beds are usually operated with a wide size distribution of solids, containing a substantial portion of fines. More fines are also created by attrition and by virtue of reacting solids, and the exiting gases may exceed the terminal velocity of many of these fine particles, thereby carrying them out of the reactor. In addition to the entrainment of fines, solids are carried into the freeboard by erupting bubbles. However, as the particles ascending the freeboard space lose their kinetic energy, some particles will return to the bed, depending on particle size and particle density. As a result, particle loading in the escaping freeboard gas drops rapidly to a certain point beyond which it attains a constant value at which the terminal velocity of the accompanying particles is close to or less than the velocity of the exiting gas stream. The freeboard height corresponding to the constant entrainment rate is known as the transport disengagement height (TDH), which determines the optimum distance for gas exit ports above a fluidized bed. TDH is discussed in Sec. 20: Fluidized-Bed Systems. AFBC Design Options The effects of major design and operating variables on AFBC performance characteristics were presented in the preceding subsection. However, technical parameters should be selected only after consideration of economic and site-specific factors. Some of the factors to be considered are: 1. Availability and costs of fuel and sorbent 2. Fuel and sorbent tlexibility (reliability of sources) 3. Space available for AFBC system 4. Space available for solids receiving, preparation, and storage 5. Local environmental regulations 6. Impacts of energy costs on product costs (energy intensiveness of application or process) 7. Load-following requirements compared with load-following capability of the AFBC system COMBUSTION OF LIQUID FUELS

D, = average particle diameter, ft ps = density of fluidizing gas, lb/f? U mf = minimum fluidization velocity, ft/s or = viscosity of fluidizing gas, Ib/(ft.s) g = acceleration of gravity, 32.2 ft/s* When reliable values of shape factor and voidage at minimum fluidization velocity are not available, the following correlation is useful: U,,,f = (fi/p&,) [(25.25) + 0.0651 Arps - 25.25 (9-38)

(To convert pounds per cubic foot to kilograms per cubic meter, multiply by 16.02; to convert feet per second to centimeters per second, multiply by 30.48.) Bed Expansion on Fluidization The following equations are recommended: For Dw 5 2.5 in,

4=1+
L mf

0.762(U -

U,,,,)s70p~oB3

p~wyv~o.445

(9-39)

and for Du

> 2.5 in,

&
Ld

= 1+

10.978(U

- Umf)0738D;oo6p~376 p3? om mf Ps

(9-40)

= column diameter, ft = height of minimum tluidized bed, ft .$ = height of tluidized bed, ft U = superficial gas velocity, ft/s U,,,f = minimum Buidization velocity, ft/s p, = particle density of fluidizing solids, lb/f? pg = density of fluidizing gas, lb/f? D, = average particle diameter, ft = l/[C(X,/D )] The experimental data on which the correlation is b &are limited to a maximum bed diameter of 1 ft. Extrapolations to very large bed diameters must be made with caution. Second, the correlations in their present form do not account for the fact that there would be
L

where &

I
I

0
FIG. 9-50

0.015

0.020

0.1

DP, in

diameter. .

Relation of minimum fluid&d-bed voidage to average particle

Burners for Liquid Fuels For combustion, liquid fuels are vaporized or atomized in the combustion air. Distillate fuel oil can be burned with a blue flame if it is completely vaporized and homogeneously dispersed in the air before burning. Blue-flame combustion is a two-step mechanism, the first step being hydroxylation of the fuel. Yellow flame indicates glowing carbon from fuel pyrolysis in oxygen-deficient parts of the Eame. Droplets of fuel may be partly volatilized, leaving the residue to decompose and burn as coke particles. Either a blue or a yellow Eame may be preferred, depending on the need for conductive versus radiant heat transfer. Both types can give complete combustion if the flame is not quenched prematurely. Time, temperature, and turbulence are the criteria for good combustion. In vaporizing burners, reflected heat continually converts liquid fuel into vapor, sustaining the flame. This principle is used in blowtorches, pot-type home-heating furnaces, and all wick burners such as kerosine lamps, stoves, and cigarette lighters. Gasoline-burning mantle-type lamps and catalytic heaters use a more volatile fuel plus a catalytic surface to promote rapid combustion. Vaporizing burners are built in capacities up to 30 to 40 dms fuel/h and are designed for kerosine, naphtha, No. 1 fuel oil, gasoline, etc. (No. 1 fuel oil cannot be used in pressure-type vaporizing burners because of excessive carbonaceous deposits in the vaporizing tube) Atomizing oil burners spray fuel at pressures of 0.69 to 2.1 MPa (100 to 300 Ibf/in) or atomize it with air or steam at pressures of 0.003 to 1.4 MPa (0.5 to 200 Ibf/in). Several types are shown in Fig. 9-51. Quantities of power and steam or compressed air required are shown in Table 9-36. Combustion air is blown into the furnace with the fuel spray. Vanes and baffles are built into the air stream to assure proper airfuel mixing. The air-handling parts, the fuel-spray pattern, and the furnace shape are matched to avoid tlame impingement, a cause of

COMBUSTION OF LIQUID FUELS

9-49

90

FIG. 9-51 Principal types of oil burners. (a) Pressure-type vaporizing burner; oil travels through coil of pipe. Uses kerosine or gasoline, 0.1 to 6 gal/h at 5- to 5&lbf/in* fuel pressure, with B turndown ratio of 3:l. For blowtorches, lamps, and portable torch-type burner equipment. (b) High-pressure steam- or air-atomizing burner, injector or venturi type. Uses all grades of oil, No. 1 to No. 6, with heavy oil heated to flow. Oil pressure, low; steam pressure, 40 to 175 Ibf/in. Uses 5 to 10 percent of air or 2 to 4 lb of steam for atomizing. On boilers, 2 percent of the steam output is wed for atomisation. Steam helps heat oil and assists in combustion to reduce soot. (c) Horizontal rotary-cup atomising oil burner. Uses any grade of fuel, No. 1 to No. 6. Heavy oil must be heated to 150 to 330 SSU. Oil pressure, low; air pressure, 0.25 to 3 Ibf/in*. Turndown ratio of 5:l. Capacities of 1 to 2.50 gal/h. For use on automatic-fired boilers. (d) Low-pressure air-atomizing burner, variable-pressure type. Uses all grades of oil, No. 1 to No. 6. when supplied at viscosity of 60 to 90 !XJ. Oil pressure, 5 to 20 Ibf/in*; air pressure, 0.5 to 5 lbf/in*. Pnmary air pressure. constant; secondary air pressure varies. Turndown ratio of 4:l. Capacity of 1 to 200 gal/h. (e) Mec hanical or oil-pressure atomizing burner, return-flow type, showing general operating principle and typical design. Uses all grades of fuel oil, No. 1 to No. 6. with heavv oil heated to 150 SSU. Oil oressure. 300 Ibf/i& air oressure. low or natural draft. Turndown ratio bf 10: 1. C&cities of 10 to loo0 gal/h: cf) Complete &&&al or oil-pressure atomizing burner unit. Air supplied by natural draft of low-pressure blower. Used on boilers and rotary kilns Domestic burnen of this type use oil at lwlbf/in* pressure. (Hauck hffg. Co.)

soot or hard-carbon deposits and/or refractory spalling, washout, or slagging. Except in small domestic furnaces, oil spray and air usually enter the furnace through an ignition tile. The tile configuration, matched with the oil-spray pattern, stabilizes the flame. Furnace volume is established to allow time for complete combustion. Heatrelease rates depend on fuel properties, excess-air concentration, airfuel mixing, and allowable smoke levels. TABLE9-36 CompresawLAir, foe Atomiring Burners
Steam,

and Power Requirements Requirements per cm/s (0.951

gal oil/h)

Atomizing medium Low-pressure air, 6.9 kPa High-pressure air, 0.52 MPa Steam Mechanical Rotary-cup burners Hydraulic-power equivalent.

Power, kW 0.071

Fluid 4.5-6.7 dm3/s 1.1-1.4 dm3/s 0.85-3.5 kg

0.284
0.651 0.0227 0.0355

Coal- and shale-derived liquids generally contain more nitrogen than petroleum and form more NO, when burned. Also the high C/ H ratio in coal-derived liquids gives luminous flames and potentially more smoke. Combustion modifications are being developed to control stack emissions without requiring drastic upgrading of the fuel. Staged combustion involves primary burning with insufficient air (to prevent NO, formation in the highest temperature zone), followed by the introduction of more air to complete combustion. In multiburner boilers, this may be accomplished by firing some burners rich and others lean. (See KVB, Inc., Reference Guideline for Industrial Boiler Manufacturers to Control Pollution with Combustion Modification, EPA 600/8-77-0@3b, November 1977.) For gas turbines, staged combustion in each burner is a promising prospect. See Fig. 9-52. High-intensity burners permit clean combustion at low excess-air levels through finer fuel atomization and better air-oil mixing. Figure 9-53 shows nozzles in which oil is sprayed through a gas, steam, or air whistle and atomized by sonic energy. Typical oil pressure might be below 0.4 MPa (60 Ibf/in); atomizing air or steam, at 0.34 to 0.4 MPa (50 to 60 Ibf/in*); windbox (combustion air), at 0.025 to 2.5 kPa (0.1 to 10 in water).

9-50

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION and suffer catastrophic corrosion. Molten vanadium compounds are particularly corrosive. Combustion air often carries dust. A classical example in limestone areas is the diopside formed in the flame by limestone and silica dust and deposited on refractories as a glass. Spalling occurs when the furnace cools because diopside and refractory shrink at different rates. Ashes are mixtures, and fusion is not sharply defined. Final liquefaction may occur at 160 to 125YZ higher than initial sintering. VsOs melts at 673C (1243F), but oil-ash fusion temperatures range from below 540 to over 1995C (1999 to 2ooOF), depending on relative concentrations of tluxes (principally sodium) and refractory compounds (such as silica, magnesia, and alumina). Vanadium corrosion usually occurs above 675C (1250F), and sulfidation (attack of nickel alloys by sulfates) above 999C (1650OF). Magnesia, epsom salts, and other compounds are added at Mg/V weight ratios of 3: 1 or 3.5: 1 to prevent corrosion and dewsition bv raising the ash fusion temperature. There is disagreement over the value of alumina as a coadditive to overcome the slight tendency of magnesia to form deposits. Calcium compounds are considered undesirable because they form hard, adherent, insoluble deposits. Manganese compounds and sometimes lead and copper compounds are used as combustion catalysts to reduce soot and smoke. There are also many additives sold to benefit the fuel-handling system. These may contain solvents or dispersants to combat sludge, emulsifiers or demulsifiers for water in the fuel, corrosion inhibitors, and other functional ingredients. Fuel suppliers should be consulted for possible adverse reactions between the additive and fuel, and claims for the additive should be evaluated cautiously, but their potential usefulness for specific problems should not be overlooked. COMBUSTION OF GASEOUS FUELS

Quick quench slots for dilution Ro. 9-52 (Adapted air

Rich-lean-burner concept for liquid fuel with bound nitrogen. from Pierce, Mash, and Smith, Advanced Combustion Systems for Stationary Gas Turbine Engines, 001.II: Bench Scale Evaluation, EPABOO/780417b.)

Combustion Deposits Residual fuels cost less and yield more heat per gallon than distillates, but they usually have higher sulfur content plus ash-forming ingredients. In and near the combustion zone, molten ash can cause corrosion and deposits; in areas below 160C (350F), water and sulfur compounds in flue gas condense into corrceive acid solutions. During combustion, the ash-forming materials oxidise and interact to form a variety of compounds. If they solidify before striking a solid surface, ash particles are likely to paas through the equipment. However, parts of a boiler (or gas turbine or diesel engine) which operate above the ash fusion temperature may accumulate deposits
Resonator chamber

onicenergy

core

Sonicore Fuel Nozzles Sonic Energy Combustion Wilmington, Delaware Systems,

Swirl

Combustion of gas takes place in two ways, depending upon when gas and air are mixed. When gas and air are mixed befMe ignition, as in a bunsen burner, burning proceeds by hydroxylation. The hydrocarbons and oxygen form hydroxylated compounds which become aldehydes; the addition of heat and additional oxygen breaks down the aldehydes to Hs, CO, COs, and HsO. As carbon is converted to aldehydes in the initial stages of mixing, no soot can be developed even if the flame is quenched Cracking occurs when oxygen is added to hydrocarbons after they have been heated, decomposing the hydrocarbons into carbon and hydrogen, which, when combined with sufficient oxygen, form COs and HsO. Soot and carbon black are formed if insufficient oxygen is present or if the combustion process is arrested before completion. A gas burner is primarily a proportioner and mixGas Burners ing device. In industrial furnaces in which long, lazy flames are essential, slow and gradual mixing of air and gas is necessary. When a short, bushy Rame is needed, the burner should be designed to achieve rapid and thorough mixing of air and gas. Figure 9-54 illus-

Vortimetric Sheridry

atomiser

Gulf Canada Ltd., R&D Dept. Park, Ontario ASME Paper 71.WA/Fu.3 Sonic fuel nobles. oil is sheared by pressure waves of sonic fre. Ao. 9-S) quency in a stream of air. gas, or steam. (a) Sonicore fuel nozzle. (Sonic Energy

CombutrOn &Ma, Wlfm(ngtcm, Def.) (b) Vortimetric atomirer. (R&D %nZflmmt, Gulf hwda Limfted, Sheridan Park, Ont., ASME Pap. 71WA/FuS.)

(8)
Ao.

fbl

9-54

Schematia of gas-burner principles.

COMBUSTION OF GASEOUS FUELS

9-51

J&- -Gasfine
Gas valve Wnll posting

~///...,.

, Shuiter / /Spud holder / 1 Burner body I j /Nozr/e I! 1 , I \ruunnel\

f//f

Burner

cement

Ro. 9-55 Atmospheric industrial gas-burner installation with individual air control to each burner.

trates simply the principles of gas burners. In burner A, the gas enters the furnace through a burner port and induces a flow of air through the port. Mixing is poor, and a long tlame results. The flame can be shortened with a ring burner B, in which gas Rows through an annular ring and induces air Bow both around and within the annulus of gas. When both air and gas are under pressure, burner C may be used. In each of these burners, the gas must flow through the port into the furnace at a velocity high enough to prevent the flame from burning back (flashback) into the burner. Burner shapes and arrangements should avoid tlame impingement on furnace walls or heattransfer surfaces. Variations of these principles are found in commercially available burners such as the following. Premix burners burn by hydroxylation and are used for many natural-draft applications when accurate furnace conditions must be maintained. Figure 9-55 indicates a common natural-draft industrial-type burner with air being aspirated at the spud and burner throat. Figure 9-56 shows another type of premix burner, in which high-pressure air is used to aspirate the gas. The governor diaphragm controls the amount of gas admitted to the aspirator.

RQ. 9-57 Carburetor for maintaining B preset ratio of gas and air over a wide load range. adjusting to the total volume handled. (C. hf. Kemp Mfg. Co.)

Governor
dlaphram Gas mlel

Burners used for close air control, such as for generating inert gas, must exercise close control over both the fuel and the air admitted to the burners. Figure 9-57 shows a typical carburetor arrangement used for this control. The high-velocity burner shown in Figure 9-58 can be adapted for use with various gaseous fuels. Although it is not strictly a premix burner, its temperatures and mixing produce results similar to those of premix burners. The rate of llame propagation must be exceeded in premix burners to assure that ignition cannot travel back into the burner. Figure 9-59 indicates the rate of flame propagation at various air-gas ratios for several gases.

FKI. 9-56 Premix burner in which a proportional mixer uses air velocity to draw in a measured amount of gas. (Surface Combustta Dtv~~(on. MidlandRaps Corp.)

Air M. 9-58 High-velocity burner. High heat release produces combustion results similar to hydroxylation. (?%ermal Research and Engfneerlng Co.)

9-52

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION rings can extend to the outside of the burner tile. These rings use very small holes and give better dispersion of gas in the air, though they can plug up easily. One burner has a spider in the burner inlet through which gas is emitted in all the several radial arms. The spider is drilled to emit gas from the sides of the bars to provide a reaction from the emission of high-pressure gas, causing the spider to turn. The spider can be attached to a fan so that forced draft is provided by the movement of the spider. The spider arrangement provides high turbulence for the close regulation of excess air. Control of gas burners is accomplished by regulating only the flow of gas in aspirating burners or by regulating both gas and air flows when these are controlled separately. Combustion Characteristics of Low- and Medium-Btu Gases Low-energy gas from various coal-gasification procqs is a source of clean fuel for utilities, industrial boilers, and industrial processes. The combustion characteristics of low-Btu gas (LBG) and mediumBtu gas (MGB) can best be desqibed by comparison with natural gas. Combustion characteristics for comparison include oxygen or air requirements, flue-gas Bow rates, tlame temperatures, and flue-gas composition, including pollutant emissions. All these factors bear on the interchangeability of LBC and MBC in the context of flame characteristics and stability. Results of experiments by the Institute of Gas Technology on utility-type burners and industrial burners follow. Table 9-37 shows adiabatic flame temperatures calculated for natural gas and manufactured gases. MBGs have adiabatic flame temperatures near that of natural gas. Adiabatic flame temperatures for LBGs are lower than that of natural gas, owing to the nitrogen in the air and fuel. The lower flame temperatures will result in lower heattransfer rates per unit load surface area in radiant furnaces. Figure 9-61 shows that for a given tlue-gas temperature significantly less heat is available from the tlame of a low-Btu gas than from the flame of a fuel gas from a medium-Btu gasifier or natural gas.

$6 +
;5

0 20 10 Per Cent Gasin

40 30 Primary AirSGas

60 70 Mixture

Ro. 9-59 Flame velocities of various gas-air mixtures Data on individual gases from Bur. Stand. .I. Res., 17,7-43 (1936); data on natural gas, coke-oven gas, and carbureted water gas from Combustion, American Gas Association, 1932. (As compiled by EIIiotf and Denues, U.S. Bureau of Mines, for Marks, Mechanical Engineers Handbook, McGrawHUl, New Y&, 1941.)

Nozzle-mix burners mix air and gas at the burner tile. As shown in Fig. 9-60, these burners can take four arrangements. The burner may be a standard forced-draft register with the gas emitted from holes drilled in the end of a supply pipe This type is easy to build, but large holes are used and gas mixing becomes a problem; these burners frequently produce a luminous gas flame. Small-diameter pipe can be inserted at the center of the burner, or large-diameter

GA

C~n~r~ion

System

Technical Data Book, Institute of Gas Technol-

ogy, Chicago,

November

1980.

register

w
lgnltl
tube
GOS WPP

(a)

Blunt Pipe

(bl Small Al,

Rmg

Gas
suPPlY

(d)
FIG. P-60

Turbme
Various ways of mixing gas and air at the burner.

COMBUSTION OF GASEOUS FUELS

TABLE 9-37 Typical Properties of Cleaned Manufactured Gases

9-53

MBGs Natural bws Composition, 5% CH4 CO Con HZ Hz0 NZ GH6 966 0.0 0.52 0.0 0.0 0.46 1.82 0.3 1020 0.62 3551 1300 Koppers-Totzek oxwen 0.5 52.9 9.2 34.5 1.9 1.0 Lurgi oxygen 9.4 18.5 29.4 40.2 1.9 0.6 Winkler 0XYE.e 3.0 32.9 20.0 41.2 1.9 1.0 Wellman-Galusha oxygen
0.9

LBGs Wellman-Calusha air 2.6 26.9 7.4 14.3 1.9 46.9 Winkler air 0.6 21.4 6.9 12.1 1.9 56.5

GHs Who

0.70

S .

. .

S .

39.2 16.2 40.4 1.9 1.4

. .
267 0.66 3574 325

.
159 0.83 3114 175

.
116 0.85 2818 12.5

Higher heating value. Btu/scf Specific gravity (calculated) Adiabatic flame temperature, OF (stoichiometric) Wobbe no., Btut

288 0.68 3684 3.50

285 0.70 3360 335

&o 0.67 3511 325

Small amounts may be present after cleaning procews tHigher heating value/(specific gravity)*. NOTE To convert British thermal units per standard cubic foot to kilocalories per cubic meter (15C saturated), multiply by 8.98; OC = (OF - 32) X %

For example, if furnaces fired by MBG from a Koppers-Totzek oxygen-blown generator (KTO) and by LBG from a Wellman-Galusha air-blown generator (WGA) each had an exit flue-gas temperature of 1316% (2400F), the KTO-fired furnace would be losing approximately 74 percent. Conversely, for a given percentage of the input enthalpy to be transferred in the furnace, flue gas from LGB would have to be discharged from the furnace at a significantly lower temperature. For example, to have 30 percent of the input enthalpy available in the furnace, the WGA fuel gases would have to be cooled to 1099V (2010F), while the KTO fuel gases could be discharged at 1543% (2810OF). Table 9-38 shows the combustion air required and volume of cornbustion products per 1000 Btu of manufactured gases and natural gas. Manufactured gases require slightly less combustion air than natural gas, and air blowers and air ducts sized for natural-gas operation will be more than adequate for LBG. The larger gas volumes required for a given Btu input for MBG and LBG will make gas piping, pressure regulators, and control valves undersized for most conversions. The combustion-product

Bows for low-Btu gases are considerably larger than for natural gas. This requires larger tlues, stacks, and induced-draft fans. Table 9-38 also gives the flammability limits calculated by the method given in the Gus Engineers Handbook (1977). The values were calculated by using the fuel-gas compositions in Table 9-37. These calculated limits of tlammability are approximate values only. Accurate flammability predictions require that the fuel in question be subjected to experimental measurement. Experimental Evaluations of LBG and MBG Research programs have provided information on utilizing manufactured gases in the following areas: I. In industrial-process burners designated for natural gas 2. As utility boiler fuel 3. Pollutant emission The results of these investigations may be summarized as follows: 1. When used in burners designated for natural gas, manufactured MBG generally produce stable flames and give thermal performance, flame temperature, and heat-transfer rates similar to those of natural-gas flames. Flame lengths may be longer or shorter, depending on the exact burner design.

El0 J

f : 8 ; 2
g

70 60 50
40 30 20 WGA WA = Wellmon-Galusha = Wmkler air-blown air-blown

w g

0 400

KKJ

800

10031xx,1403160018002ooO220024002603280;)xxx)3xx)340036003800 Flue-gas

temperature,

OF

FIG.

941

Variation of available heat with fuel type C = (OF - 32) X %.

9-54

ENERGY UTIUZATION,
Stokhiimohk

CONVERSION,

AND RESOURCE CONSERVATION resistance heating is most often used for heating metal rods and billets prior to rolling or forging, for melting glass in combination with other heat, in boilers for hot water, and for heating salt baths for the heat treatment of metals. Indirect-resistance heat in ovens and furnaces has many applications, from drying to melting. Induction heating is used to heat metals for melting, forging, brazing, and hardening, as well as in many other less frequent applications. Dielectric and microwave heating is used for drying many materials from wood to foods, for processing plastic materials, and for an increasingly large application of microwaves in residential and commercial food heating. Table 9-39 presents the major advantages and disadvantages of electric heating. It should be emphasized that one of the major advantages often listed for electric heating is high efficiency. This is usually very true for electrical efficiency, that is, the percentage of electrical energy converted to usable heat. There is therefore less wasted heat in the users plant. However, the generation of electricity from fossil fuel is only about 30 percent efficient; therefore, overall efficiencies of electric heat vary from I5 percent in a dielectricheating application to 30 percent in a direct-resistance-heating application. Direct-Resistance Heating Resistance losses (PA) in conductors are in general undesirable, but they can be desirable when the conductor is the load to be heated. This method is used in the iron and steel industry to preheat metal rods and billets prior to rolling or forging and for annealing similar shapes. Billets to be heated efficiently should have a length much greater than the diameter; otherwise, relative heat losses to the contacts will be large. For low-resistance metals such as copper, the L/D ratio should be greater than about 10. For relatively high resistance metals such as steel, the ratio can be lower. Cross sections of the rod should also be uniform for uniform heating. Energy consumption for heating to forging temperatures is approximately 300 kWh/ton. Comparable induction heating systems seldom realim better than 350 to 450 kWh/ton. Resistance heating systems also cost about 75 percent of the cost of an induction heating system. The power supply for direct-resistance heating can be either threephase or single-phase. It consists essentially of stepdown transformers and contactors with power-factor-correction capacitors often included. The whole system must also be strong to withstand the forces between high-current-carrying conductors, as currents of the order of ld A are not uncommon in the load circuit. Contacts through which the current is transferred give rise to major design problems. Large areas of contact, with consequently low resistance, are good heat sinks and produce cold ends. Small contact areas with little heat withdrawal have high resistance and cause power losses and local overheating. Contacts also often must support the load. Careful design with some compromises is therefore called

TABLE 9-38

Combustion Quantitin

Calculated
scf/lCK@Btu Fuel Natural gas Koppers-Totzek oxygen Lurgi oxygen Winkler oxygen Wellman-CaIusha oxygen Wellman-Galusha air Winkler air 1.0 3.5 3.5 3.7 3.7 6.3 8.6 Air 9.44 7.40 8.10 7.60 6.90 7.80 7.50 Products 10.4 9.4 10.6 10.0 9.3 12.8 14.7 tlammability limits, 96 fuel in air Lower 5.0 7.5 7.5 7.5 7.5 16.5 20.5 Higher 15.0 71.0 50.5 62.5 68.5 645 685

2. When used in natural-gas burners, manufactured LBG may need enlarged fuel nozzles, continuous piloting, or downrating to prevent blowoff. They give reduced flame temperatures and heattransfer rates compared with natural-gas flames in the same furnace. Preheating the fuel and/or combustion air can increase flame temperatures and heat-transfer rates but would then require specially designed burner equipment with refractory linings and very large fuel low passages. 3. Using hot manufactured gases directly from the gasifier, without cleanup to avoid loss of the sensible heat, can produce NO, and SO. emissions greatly above those for cleaned fuels or natural gas.

ELECTRIC HEATING Industrial electric heating can be divided into three basic categories: resistance heating, both direct and indirect; induction heating; and dielectric heating. The choice of which method to use depends on many factors. Resistance heating is the generation of heat by Joules law, that is, PR Iin relatively conducting materials by passing current through them by direct contact. Induction heating is also fR heating, but the current is induced in the conductor by placing it in an alternating magnetic field. Dielectric heating is the generation of heat in a nonconductor by placing it in an alternating electric field, with the mechanisms of heating being primarily dipole rotation losses. A discussion of laser heating is also included in this analysis because it is powered by electric energy. This is not an in-depth analysis but a guide to making choices. For further study see Brown, Hoyler, and Bierworth, Radfo Frequency Heatfng, Van Nostrand, New York, 1947; Copson, Microuwe Heatfng, AVI Publishing Co., Westport, Corm., 1962; and Davies and Simpson, Induction Heattng Handbook, McGraw-Hill, London, 1979. The applications for electric heating are many. In general, directTABLE9-39
Comparison of glactrk-Heating Mothodr

Resistance heating Direct Indirect

X X X X X X

Induction heating
X X X X X X X X X X X

Dielectric heating
X X X X X X X X X X

Clean:-no pollutants
Easilv controlled: accuratelv controlled Efficient: leu h&t to sur&dings Lower capital investment Lower maintenance Electricity readily available Performing task impossible with fossil fuel Electricity generated by coal or nuclear reaction Heating electrical nonconductors Heat generated internally High electrical efficiency possible No direct contact Disadvantages High cost of energy Uniformity of hept sometimes difficult Only limited energy sometimes available Low conversion efficiency from fossil fuel Hiah cart of conversion from mesent eauirxnent

X X X X

X
X X X X

ELECTRIC HEATING for. Multiple-end contacts have been used with both peripheral and end contact. Direct-resistance heating of liquids such as molten glass or molten salts is also used. Glass above llOOC is molten and has a resistivity sufficiently low for direct heating; current is passed between electrodes immersed in the melt. The electrodes must withstand both the high temperatures and the movement of the melt. Molybdenum or tin oxide electrodes are normally used Salt baths used for metal treatment have similar electrode problems. Graphite or corrosionresistant steel is normally used. Generation of steam by passing current directly through water is also now common practice. The preceding discussion assumed 60-Hz resistance heating. Highfrequency resistance heating is also commonly used. This method takes advantage of both the skin effect, or shallow penetration of high-frequency current, and the proximity effect, in which the current follows the path of lowest reactance rather than that of lowest resistance. Such large applications as tube-seam welding and such small applications as selective area-surface hardening are uses of high-frequency resistance heating. Indirect-Resistance Heating Indirect-resistance heating includes surface resistance heaters, immersion heaters, uninsulated heating elements in furnaces and ovens, and infrared heaters. Factors affecting selection include the temperature coefficient of resistance, creep resistance, atmosphere of use, thermal-shock resistance, and need for high resistivity. Industrial heating elements, for use in air, fall into four groups: nickel-base and iron-base, for metallic elements; and silicon carbide and molybdenum disilicide for nonmetallic elements. The most widely used nickel-base heating elements consist of 80 percent nickel and 20 percent chromium and are generally recommended for a maximum element operatmg temperature of 1ZOOG. They form a coating of chromium oxide which protects the material from excessive oxidation. However, they are not recommended for use in furnace atmospheres which contain traces of sulfur because of a low-temperature reaction with nickel.

9-55

For slightly higher element temperatures, up to 1375C (WOOoF), iron-base alloys are widely used. These consist mainly of iron, chromium, and aluminum. In air, the aluminum oxidizes and forms a tightly adhering film of alumina which protects the material from oxidation. These alloys, as well as the nickel-chromium series, can readily be shaped into coils or sinuated strips. For element temperatures above 1375V (2500F) nonmetallic materials are needed. Silicon carbide elements can be used up to 16OOX (2912OF). These elements are made in the form of a straight rod, sometimes with a spiral cut. One of the characteristics of silicon carbide is that resistance increases with time (this property is called aging), making it necessary to use electrical equipment which provides for numerous voltage settings. Another type of nonmetallic element, molybdenum disilicide, pro vides element temperatures up to 17OOOC (3092OF) while avoiding

the aging problems of silicon carbide. These elements are made of a cermet containing 90 percent M&s and 10 percent ceramic additives. They soften at high temperatures and in general are made in U-shaped sections. Table 9-40 summarizes the data on the types previously discussed and also includes others such as graphite and platinum. Platinum has the disadvantage of high cost but the advantage of low corrosion. Graphite has the advantage of highest temperature use, high blackbody radiation coefficient, high resistance, high thermal-shock resistance, and low thermal expansion but the disadvantage of oxidation at low temperatures in an oxidizing atmosphere.
Resistance heaters are used for many relatively low temperature applications in which direct contact is made with the insulated ele-

ment. These include applications from plastic-sealing heat sources to melting soft metals. As flexible insulated heaters, these heaters are also used for heating pipes in many industrial areas. Elecrrlc furnaces and uveus a&c u& fur a r*i& ralr~~ uI pfiv cesses ranging from annealing, hardening, and forging metals to drying many materials in hot air. Ovens are usually defined as operating up to about 450% (842OF) and furnaces as operating above this temperature. The dominant mode of heat transfer in ovens and

TABLE940

Materials Uwd for RristancaHwting

Maximum operating tenmerature in drv air, C 350 1200 1250
1100 1075 1050 400 1050

Elomonts Mean temperature coefficient of resistivitv over operating range

LOW-power

Material

Resistivitv at 2ooc, ll:m 1.72 X 10-s 103 124 112 111 105 49 x 10-s X 10-s x 10-s x 10-s x 10-B x10-s

Principal applications

tipper Nickel-based alloys SO-20 Ni-Cr SO-20 Ni-Cr + Al 60-15-25 Ni-G-Fe 50-1832 Ni-G-Fe 37-18-43-2 Ni-&F&i 44-56 Ni-Cu Iron-based alloys 72-22-4 F&r-Al 72-22-4 Fe-G-Al Refractory metals Platinum W-10 Pt-Rh 60-4-O Pt-Rh Molybdenum Tantalum Tungsten NOl&aL Graphite Molytdenum disilicide Silicon carbide Lanthanum chromite

surface heaters

17 x 10-S 24 X lo-

Furnace heating elements; resistance heaters Furnace beating elements; lower ccst Furnace heating elements; lower cust Furnace heating elements; lower cust Furnace heating elements; lower ccrt Resistance heaters; domestic appliances Furnace heating elements Furnace heating elements Furnace heating elements Small muflle furnaces Small mufile furnaces Small mufEe furnaces Vacuum furnaces; small muffie furnaces in hydrogen atmarphere Vacuum furnaw infrared lamps; vacuum furnaces Vacuum furnaces; reducing atmospheres Small glass-melting furnaces; forehearths Furnace heating elements; oxidizing and reducing atmospheres

+ Co 78-16-4 Fe-CT-AI + Yt, C

1375 1300 1300 1550 1800 175Ot 2500

18cQt

139 x 10-8 145 x 10-a 134 x 10-8 11 19.7. 17.4 5.7 x x x x 10-8 10-8 10-8 10-e

4.7 x 10-S 3.2 X lo- 12 x 10-S 3.92 2.0 2.0 5.5 x x x x 10-S 10-3 10-3 10-s

12.5 X lo- 5.6 x 10-a

3.2 X lo- 5.94 x 10-S

mt
1800 1600 1800

1000 x 10-8
40 x 10-a 1.1 x 10-S

-2.66 x lo- 1.02 x 10-4 -2.63 x lo-

2 x 10-s

Approximate compoJitions only. t Not in air.

9-56

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

TABLE 9-41 Maior Applications of Induction Heating Approximate frequency range, Hz 60-10 k 10 k-10 M 10 k-10 M 60-3k 10-500 k ~10 k 10-500 k 50-500 k

furnaces is radiation, although convection and conduction from air heated by the elements make a large contribution, depending upon the furnace type. A large number of different construction methods are used for furnaces. The most common include box furnaces with heating elements in the furnace cavity, forced-convection furnaces with heaters external to the cavity, hot-retort furnaces with the load sealed from the outside air and the heating elements, low-thermal-mass furnaces using fiber insulation rather than ceramic refractories, cold-retort furnaces with heat reflectors protecting the heat from the walls, and muffle furnaces with the heater outside a refractory tube. The choice for various applications includes such factors as the atmosphere desired, start-up and shutdown times, and the maintenance scheculing required. Furnace insulation consists mostly of oxides of aluminum, silicon, magnesium, and zirconium. Furnaces for heat treatment generally use high-grade aluminosilicate bricks for lining. Filer insulation of aluminates and silicates has a very low thermal conductivity and low heat capacity and is used for low-thermal-inertia designs suitable for batch processing. High-purity alumina and zirconia fibers have recently pushed the upper temperature limits of fibers to about 1700C (3092OF). However, if temperatures above this level must be used, carbon powder, either in submicrometer size or pelletized, is the only satisfactory insulation. Its thermal conductivity is somewhat higher than that of fibrous insulation, but it is still a satisfactory insulator. Infrared (IR) heating, or radiant heating, is advantageous because the work need not be contacted by the heating elements or by circulating air. The heaters must have a line of sight to the surface to be heated. Although generation of heat and delivery to the load are more efhcient than in other furnace or oven methods, infrared heating can be less efficient overall because the portion of the energy used depends upon the absorptivity of the load. The radiation is controlled by re5ectors, which also contribute to the efficiency. The intensity distribution of an IR source varies with the temperature, and more power 1s radlared at shorter wavelengths as the temperature increases. IR sources of relatively low temperature are normally used for heating nonmetallic materials which absorb at long wavelengths. High-temperature sources with most output at shorter wavelengths are required to heat metals which absorb them better. The advantages of IR heating are: 1. It can heat up portions of a process or product. 2. Less floor space is needed than for other ovens. 3. Production can be increased easily by adding heating units to current units to heat more at local areas or more overall. 4. High-flow exhaust systems can be replaced with lower-flow systems because air is not heated excessively. 5. Product temperatures up to 65OC (1202OF) are practical. Early IR systems were simply on-off controlled heaters. Current silicon-controlled-rectifier (SCR) controls make possible closed-loop automatic temperature control. There are three major types of IR heaters: wide-beam, with about a 100 reflector and low power density; multibeam, with several reflector angles available to establish desired power densities and coverage; and heavy-duty, which have power ratings up to 20 or 30 kW, have a medium beamwidth of about 60, and are selected for mechanical ruggedness. Three types of heating elements are available: 1. Quartz lamps, which are the most radiation-efficient, and are tungsten elements in a clear evacuated quartz enclosure 2. Quartz tubes, which have a nickel-chrome element in a quartz enclosure and are used for wide-beam heaters and a broad selection of power levels 3. Metal rods, which consist of a nickel-chrome element surrounded by magnesium oxide insulation with an outside metal sheath and are used in heavy-duty heaters Induction Heating Induction heating provides a means for the precise heating of electrically conducting objects. In some cases, it is the only practical method of supplying heat to the work material. It is clean, fast, and repeatable and lends itself to automatic cycling. No contact is-required between the workload and the heat source, and

Application Melting Surface hardening Brazing and soldering Forging Tube wlding Annealing Strip heating Semiconductor-zone refining

heat may be restricted to localized areas or to a surface zone of the load. Induction heating occurs when electrically conductive materials, such as metal workpieces, are immersed in an alternating magnetic field. This field is usually produced by an electrical coil energized by a suitable source of alternating-current electric energy. The ac magnetic field induces voltages in the conductive material, and these voltages cause circulating currents (eddy currents). The magnitude of the induced currents is determined by the effective magnitude of of the workpiece. The flow the induced voltage and the impdance of induced current generates I R losses and heat in the workpiece. Additional heat is produced in magnetic workpieces as the result of hysteresis losses; this heat is usually small, but in some cases involving strong magnetic fields the heat resulting from hysteresis losses can become significant. Table 9-41 lists major applications of induction heating. Induction heating is efficient and practical if certain basic relationships dealing with the frequency of the magnetic field and the properties of the workpiece are satisfied. Although the relationships are not sharply critical, they must be satisfied to the extent that a suitable degree of skin effect is produced in the workpiece. Skin Jf,=,+ in the phmnmmnn h, whit-h th P r,rrrentc flming in the urn&piece tend to be most intense at the surface, while currents at the center are near zero. As a consequence of this distribution the currents produce a greater rate of heating near the surface. Skin effect is present in every successful induction-heating application. Consideration of the operating frequency should be the first step in the design of a successful induction-heating installation. To achieve efficient induction heating, there must be a proper ratio of workpiece diameter (or thickness) to reference depth. For a given workpiece diameter, the thinner the current-carrying layers, the greater the rate of heat generation in the surface, other factors remaining constant. If minor effects are ignored, the effective depth of the current-carrying layer depends on the frequency of the ac magnetic field and on the electrical resistivity and magnetic permeability of the workpiece. Frequency is the only one of these factors that can be readily manipulated. The current density in a workpiece decreases exponentially from

FIG. 942

Reference depth for common materials as a fun&on of frequency.

ELECTRIC

HEATING

9-57

TABLE

942

Average Loads

Coupling

Efficiencies

for Induction

Heating

of Ckm-Coupled

I
Copper Helical-around work Helical-internal One turn-around work One turn-internal. Hairpin Pancake 0.01 1 FIG. 943 10 100 1000 Percent of critIcal frequency type of furnace, the currents are induced directly in the charge; in others, the currents are induced in a conductive case containing the charge, and the heat is radiated inward to the furnace charge. Since the coil currents may be as high as 15,000 A, the coil conductors are usually hollow to permit water circulation for cooling. Compared with resistance heating, the power factor of induction heating is relatively poor at 60 Hz because of the reactance effects. This tends to lower the overall plant power factor, which may incur power penalties from the utility company. Power-factor-correction capacitors are normally used. Power sources to the induction coil fall into four categories, and the type to be used usually depends upon the frequency range desired. The four types are supply frequency (60 Hz), solid-stateconverted systems, motor-alternator systems, and vacuum-tube systems. Table 9-43 summarizes the four systems with their features and frequency limits. Some supply-frequency magnetic multipliers are still used, but they are generally being replaced by solid-state systems. Since about I965 solid-state systems have also been increasingly replacing motor-alternator systems in the middle-frequency range. The main advantages of solid-state systems are possibly higher efficiency and no warm-up time, and the main advantages of motoralternator systems are fixed frequency and easier maintenance. The features may be advantages or disadvantages depending upon applications. Vacuum-tube radio-frequency power supplies have long been used for shallow, rapid surface-heating applications. The upper frequency limit of solid-state systems is about 50 kHz, and these systems cannot currently compete with vacuum-tube supplies above that frequency. Dielectric Heating Dielectric heating is the term applied to the generation of heat in nonconducting materials by their losses when subject to an alternating electric field of high frequency. The frequencies necessary range from 1 to 200 MHz. Heating of nonconductors by this method is extremely rapid. This form of heating is applied by placing the nonconducting load between two electrodes, across which the high-frequency voltage is applied. This arrangement in effect constitutes an electric capacitor, with the load acting as the dielectric. Although ideally a capacitor has no losses, practical losses do occur, and sufficient heat is generated at high frequencies to make this a practical form of heat source. The frequency used in dielectric heating is a function of the power 0.30

0.20 0.25
0.15 0.25 0.20

Relationship between relative efficiency and critical frequency.

the surface. The rate of decrease can be compared from one application to another by means of reference depth. Reference depth, which has actual physical significance in certain special cases, is defined by d=5m\/;;7;f (9-41) where d is the reference depth, cm; p is the resistivity of the work, il.m; p is the relative magnetic permeability of the work, dimensionless; and f is the frequency of the alternating magnetic field of the work coil, Hz. Figure 9-62 shows reference depth versus frequency for various common metals. It can be shown that if the ratio of workpiece diameter to reference depth drops below about 4: 1, the efficiency of heating decreases. The critical frequency is defined as the frequency at which the workpiece-to-reference-depth ratio is 4.5:1 for round bars; if heating sheet from both sides, the ratio is 2.25: 1. Figure 9-63 shows the efficiency of heating as a function of this critical frequency. For a shallow depth in a large workpiece, a high frequency is selected. There is no concern about critical frequency, since the diameter will be many times the skin depth. However, for the fastest through-heating, a frequency close to the critical frequency must be chosen, and the calculations of reference depth and efficiency become more important. The rate of heat generation for induction heating is proportional to the coil ampere-turns squared. The electrical resistivity of the work governs the rate of heat generation in it by IR. In a magnetic load, there are also developed hysteresis losses which are negligible compared with the 1% losses unless exceptionally strong fields are present. In heating a nonmagnetic load that has a low resistivity, large currents must be used in the work coil to achieve high heating rates. Coil losses therefore tend to be high and efficiency low when heating a low-resistivity workpiece. The efficiencies for heating various types of loads with various types of coils are given in Table 942. Induction furnaces operating at frequencies from 60 to 1000 Hz are useful for obtaining temperatures up to 3000C (5432OF). In one

TABLE

943

Induction

Power

Sources

Source Line-frequency Motor-alternator Solid-state

Frequency range M) Hz 500 Hz-10 kHz 500 Hz-50 kHz

Power range 100 kW-100 MW

Effeciency, % 9&95

Features High efficiency; low cost; no complex equipment; deep current penetration LOWsensitivity to ambient heat; low sensitivity to line surge; fixed frequency; low-cost maintenance; spares not needed No standby current; high efficiency; no moving parts; protection needed outdoors; no warm-up time; impedance matching the changing loads Shallow heating depth; localized heating; highest cost; impedance matching the changing loads; lowest efficiency

10 kw-1 MW
10 kW-1 mW

75-85
75-95

Vacuum-tube

50 kHz-10 MHz

l-500 kW

65-75

9-58

ENERGY

UTIUZATION,

CONVERSION,

AND RESOURCE

CONSERVATION cost has come within range of an increasing number of users. The range of applicability of microwave heating is determined by economic factors, which include but may not be limited to price per pound of the finished product, existence of special features such as instantaneous heat programming or differential heating, savings in storage space or tooling which result from a significant reduction in heat-cycle time, reduction in raw-material costs for equal-quality final product, reduction of in-process shrinkage and/or loss, and superiority of the final product. The conversion of utility-power-line power to microwave power into the product is estimated at 50 percent. Basic microwave-power sources cost about $25OO/kW, the microwave energy applicator about $5OO/kW, and tube replacement costs about $0.06/h (all 1980). Microwave-power sources for industrial use are available in l-, 5-, 20-, and 30-kW modules, which can be ganged to meet specific process-power requirements. Two distinct areas for the use of microwave energy in chemical processing are developing. One area utilizes the direct absorption of microwaves to effect rapid and efficient heating of dielectric materials without heating the surroundings or associated low-dielectricloss materials. This form of radiant energy is being studied or used for large-scale food processing (cooking, sterilization, freeze drying, etc.) and for such industrial processes and products as ceramics, chemicals, coatings, electronics, forest products, graphic arts. paper, pharmaceuticals, plastics, rubber, and textiles. Typical functions performed are bonding, curing, deinfestation, drying, foaming, fusing, heat treating, polymerisation, and sealing. Utilization in many cases goes beyond just a replacement for or complement to a heating cycle. This is, in part, due to the ability of microwaves to penetrate dielec11ic urac~-rialr nud LUlx abwrbcd tbrougtwut the entt~ exposed WAume and thereby to generate heat uniformly. It is also, in part, due to the selectivity inherent in microwave heating. For example, in drying moist materials, the microwave power is absorbed in the wettest regions and essentially passes through the dried regions. This selectivity of heating offers a means for self-limiting the energy taken up by heterogeneous materials, and overheating is unlikely. With these combined effects, microwave heating often can do a heating job more quickly, in less space, without undue superficial heating, without thermal lag, and, therefore, with rapid control. The other area of microwave energy under development involves chemical synthesis by means of microwave-coupled plasmas. As an accurately controlled, monochromatic source of electromagnetic radiation, microwaves supply the alternating electric field necessary for the continuous ionization of a gaseous substance passed through this field. The ionized gas, or plasma, offers several routes to chemical synthesis: the plasma contains ionized species and electrons; it can supply radicals and/or excited atomic and molecular species; and it can be used as a precise ultraviolet-light source for photochemical reactions. Electric-Arc (Plasma) Heating Electric heating by means of plasma formation has rather significant usage. The plasma is formed from gases or vapors of reactive or diluent constituents of a process stream and electrons in voltage gradient. A plasma is a partially ionized gas containing molecules, atoms, ions, electrons, and free radicals, each moving with a certain velocity. The plasma is in thermal equilibrium when the average energy of each species is the same and the laws of thermodynamics apply. Thermal equilibrium is approached at pressures of 101.325 kPa (1 atm) and at power levels sufficiently high to maintain an electron concentration of >lO cm-s. Plasmas having these properties are known as arc discharges. Devices that supply the electric power to form and employ arc discharges are the electric-arc furnace, the induction plasma, and the plasma jet. The principle of electric-arc heating is that when an electric circuit is interrupted (by an air gap), current will continue to flow if the current is high enough to vaporize some of the conductor and thus fill the gap with a conducting vapor path. The electric-arc furnace is capable of operating at temperatures up to the order of 3500C (6332F). At such temperatures, the electric furnace has no eco nomic competitors. The main uses are in the purification of ores, changing an undesirable crystalline structure of an ore, and synthesis

desired and the size of the work material. Practical values of voltages applied to the electrodes are 2000 to 5000 V/in of thickness of the work material. The source of power is exclusively by electronic (vacuum-tube) oscillators which are capable of generating the very high frequencies desirable. Units with up to 500-kW output are in commercial use. Some of the more common uses of dielectric heating are wood drying, curing, and gluing; preheating of plastics; processing of rubber and synthetic materials; food processing; and drying and heat treatment of textiles. The basic requirement for dielectric heating is the establishment of a high-frequency alternating electric field within the material or load to be heated. Once the electric field has been established, the second requirement involves dielectric-loss properties of the material to be heated. The dielectric loss of a given material occurs as a result of electrical polarisation effects in the material itself. There are at least four recognized types of such polarization: two which occur as a result of the field itself, or induced polarisation; and two which are inherent and are determined by the arrangement of the component particles of the material itself. These loss mechanisms are (1) electronic polarization, (2) atomic polarisation, (3) dipole orientation, and (4) space-charge polarization. The latter two are most prominent in dielectric heating. The volume rate of power input P, to a dielectric material can be expressed in watts per cubic inch as P, = 1.41E2fe, tan 6 X lo-* (Q-42)

where E = electric field, V/in; f = frequency of electric field, Hz; L, = relative dielectric constant of the work; and tan 6 = dielectric loss tangent of the work. or the complement of the power factor single, that is:, the or& bctwocn the roltago and currr;nt in ~lr~ dielectric material. The product of t, and tan 8, called the loss factor, is often listed in tables of dielectric properties of materials for various frequencies (see Table 9-44). Microwave Heating Microwave heating is simply dielectric heating at still higher frequencies, done in a cavity where the wavelength is of the order of the cavity size rather than large compared with the applicator, as in low-frequency heating. The two predominant frequencies used in microwave heating are 915 and 2450 MHz. Since microwave heating is 10 to 100 times higher in frequency than the usual dielectric heating, from Eq. (Q-42) it can be seen that a lower voltage is needed if the loss factor is constant. However, the loss factor is generally greater at microwave frequencies. Also at microwave frequencies there is a definite skin depth in high-lossfactor materials analogous to the skin depth in induction heating. The skin depth is 0s (Q-43) I where d is the penetration depth, in; o is the velocity of light, in/s; and f, e,, and tan 6 are as in Eq. (9-42). Skin depth is important in heating foods, for example, in which it is quite large in frozen foods with a small loss factor but small in room-temperature foods such as unfrozen meat. Microwave heating is rapidly becoming the key to new techniques and processes. This form of heating has begun to proliferate as its

TABLE 9-44

Typical Dielectric loss Factors for Various Materials Loss factors 0.11 0.175 0.29 0.20 0.62 0.015 0.044 0.25 0.50 0.45 0.16

Material Spruce wood, dry 6% moisture

10% moisture.

Paper. Text&e Hard rubber Porcelain Cellulose acetate Cellulose nitrate .............. ................... Phenol formaldehyde Urea formaldehyde .....................

FIRED PROCESS
of compounds not available in the natural state by fusing different raw materials. The arc furnace is therefore used extensively in the metallurgical, abrasive, refractory, and electrochemical industries. The arc is established by momentarily bringing together two electrodes, or one electrode and the charge (which frequently acts as a second electrode), and then separating them. The vapor produced on separation provides the conducting path. The preferable method of operation is with a short arc which gives rise to high currents. Voltages up to 250 V are normally used in arc furnaces in conjunction with tap-changing transformers to obtain the most suitable voltage. Typical electrode materials are graphite and carbon. Graphite is more expensive and purer and has greater strength and higher CUTrent-carrying capacity than carbon. Severity of operation and purity requirements dictate the type of electrode to be used. Carbon arcs are the most intense source of heat, with a temperature of about 5500% (9932F). Electrodes are consumed in the heating process by oxidation and by contact with the furnace charge. In the directarc furnace, the voltage is applied between two or more electrodes located above the charge, which in most cases is a nonconductor of electricity at room temperatures but becomes a conductor at higher temperatures. To fuse the charge, layers of coke are placed on the surface between electrodes. When the electrodes are lowered into the coke bed, a current flows, generating heat, which in turn melts the furnace charge near it. The charge then becomes conductive, and current will flow from electrode to electrode through the molten bath. Heat is generated by radiation from the electric arc between electrodes and bath and through the resistance-heating effect in the bath. Arc furnaces may be single-phase or three-phase. For balanced electrical loads on the power supplies three-phase is desirable. However. cingbphscp flwnawc pmprly connwtwl tn different ringlo. phase power can also maintain an overall balanced system. Furnaces with capacities of 250 to 10,000 kVA are in commercial use. Sizes in the range of 1000 to 2000 kVA are most common. Since the position of the electrode is critical, automatic regulators are used to control the position of the electrodes to maintain constant current, voltage, or power--whichever is desired. The plasma jet can be operated with direct or alternating current. The water-cooled metal electrodes are nonconsumable, and the gap between the electrodes is made conductive by passing an easily ionized, unreactive gas such as argon or helium between them. The gas velocity attains supersonic levels. For the purpose of heating, reactive gases can be added either to the inert gas stream at low levels before passing through the electrode region or, at high levels, to the heated inert gas outside the electrode region. Pure reactive gases cannot be used because of the reactivity of the electrodes with them. Similar restrictions exist when a particulate solid is a reactant. Because of the high velocities encountered in the plasma jet device, contact time in the maximum heat-flux region is extremely short. Temperatures in excess of 8COOC (14,432F) exist in gas issuing from such a device. The limitations set by the electrodes in the electric-arc and plasma-jet devices are eliminated in the induction plasma generating device. Power from a radio-frequency source operating up to 20 MHz is transferred to the thermally ionized gas by inductively coupling to the partially conductive gas. The energy transfer occurs by inducing high-frequency current in a very thin annulus on the outside of the load, much as current would be induced in a thin-walled steel tube located in the same position within the multiturn coil. At a frequency of 4 MHz and power levels up to 10 kW only monatomic gases can be used to initiate the arc. Reactive diatomic gases can be metered into an argon plasma and heated. The plasma is extinguished at a critical ratio fixed by the type of gas added and the reactor geometry. At higher frequencies and output power levels, larger amounts of a diatomic gas can be metered into the argon plasma without the gas being extinguished. Since no electrodes are exposed to the plasma region, more types of reactions at elevated temperatures can be undertaken than in the plasma jet or the electric (carbon)-arc devices. The induction plasma device is useful as a clean heat source for crystal growth or spheroidization and for high-temperature chemical processes which are endo-

EQUIPMENT

9-59

thermic overall. For exothermic reactions, rapid quenching of the heated products is required. Laser heating is accomplished by the absorption Laser Heating of light energy on a material surface, except in the case of semitransparent materials, which can absorb light energy beneath the surface. The absorption of light energy by a material surface may vary from 1 to 99 percent, depending on the specific material and the condition of mechanical and/or chemical surface preparation. The uniqueness of laser heating results from the high level of energy shaping which may be accomplished optically with the monochromatic, coherent laser light energy. Energy densities delivered to a material surface can easily exceed 10s W/cm* in a small focal spot or may be reduced to much lower levels for broad-area coverage, depending on the heating requirement. While the cutting and drilling of metals, plastics, ceramics, and organics are the most widely practiced applications for laser heating, the greatest amount of laser energy is consumed in the transformation hardening (heat treating) of steels and cast irons to improve the wear performance of specific locations on mechanical components. Laser welding of automotive-transmission components is also beginning to consume larger amounts of laser energy. Although hundreds of different laser types have been successfully operated, continuous-wave CO* lasers provide by far the greatest amount of industrial laser energy. These machine tools provide output powers of 50 to 15,OCKl W in the far-infrared (10.6~Km) wavelength and may be operated continuously or in pulsed fashion. The lasing medium is a mixture of low-pressure CO*, NP, He, and sometimes 02 or CO which is excited by an electric-glow discharge. Laser light energy is extracted from the excited medium by means of an optical resonator composed of at least two mirror surfaces, one of
whia-h ic partially ,rzanrpwen+ 14 pmviAer the n,,tp,,t helm
Flew.

trical conversion efficiencies for CO1 lasers range from 5 to 14 percent, and their operating costs per watt of delivered power are the lowest for any industrially significant laser-heating equipment.

FIRED PROCESS

EQUIPMENT

Twenty-four major energy-intensive industries depend on directfired or indirect-fired equipment for drying, heating, calcining, melting, and chemical processing. Some of these industries used coal and producer gas at first and switched to natural gas or oil when these fuels were less expensive than coal. There is a strong movement now to return to coal and coal-derived gases and to adapt to coal processes that conventionally used other fuels. This subsection will deal with both direct- and indirect-fired equipment, with the greatest emphasis on indirect firing for chemical-process industries. Steam generation for process heat and electric power production is the largest user of indirect firing and is handled separately under Steam Generators. Direct-fired combustion equipment is that in which the flame and/or products of combustion are used to achieve the desired result by direct contact with another material. Common examples are rotary kilns, open-hearth furnaces, and submerged-combustion evaporators. Indirect-fired combustion equipment is that in which the flame and products of combustion are separated from any contact with the TABLE 9-45 Industrv Fmd Lumber Paper Petroleum Rubber and elastics Glass
Cement Lime Ore beneficiation Coke Iron and steel

Industrial Amhations

of Direct and Indirect Firina Direct

x

Indirect
x x x x

x x x x x x

9-60

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION ery. Here, crude oil entering the fired heater as a 371C (700F) liquid might exit near 232OC (450F) with about 60 percent of the charge stock vaporized. Fired heaters in this application raise Reactor-Feed Preheater5 the charge-stock temperature to a level necessary for controlling a chemical reaction taking place in an adjoining reactor vessel. The nature of the charge stock and the heater operating temperatures and pressures can vary considerably, depending on the process. The following examples illustrate the diversity of the applications performed by reactor-feed preheaters. . Single-phase-single-component heating such as steam superheating in the reaction sections of styrene-manufacturing proIn this service, the fluid temperature across the fired heater cesses. increases from an inlet temperature of about 371C (700F) to an exit temperature of about 816C (15OOF). . Single-phase-multicomponent heating, such as the heating of mixtures of oaportted hydrocarbons and recycle hydrogen gas prior In this service, the charge to catalytic re-forming in a refinery. stock enters the fired heater at about 427OC (8CWF) and exits at approximately 538C (1OOOOF). In re-farmers, the fluid pressure may range from about 1.723 X 10s Pa (250 psig) to 4.137 X 10s Pa (600 psig). Severe restrictions on fluid pressure drop are normally associated with this service. * Mixed-phase-multicomponent heating, such as the heating of mixtures of liquid hydrocarbons and recycle hydrogen gas for reacFluid temperatures typically run tion in a refinery hydrocracker. from 371C (700F) at the inlet to 454C (850F) at the outlet. Operating pressures may reach 20.685 X 10s Pa (3000 psig), depending on the process. Heat Supplied to Heat-Transfer Media Many plants furnish heat to individual users via an intermediate heat-transfer medium. A fired heater is generally employed to elevate the temperature of the recirculating medium, which is typically a heating oil: Dowtherm, Therminol, molten salt, etc. Fluids flowing through the fired heater in these systems almost always remain in the liquid phase from inlet to outlet. Heat Supplied to Viscous Fluids Often heavy oil must be pumped from one location to another for processing. At low temperatures, at which the oil may have so high a viscosity as to render pumping infeasible, a fired heater is employed to warm the oil to a temperature that will facilitate pumping. In this category are heaters in which a chemical Fired Reactors reaction occurs within the tube coil. As a class, these units represent the fired-heater industrys most sophisticated technology. The following two applications typify the majority of installations. - Steam hydrocarbon-re-former heaters, in which the tubes of the combustion chamber function indivtdually as vertical reaction In reformers that yield vessels filled with nickel-bearing catalyst. hydrogen, fluid outlet temperatures range from 788 to 899OC (1450 to 1650OF). - Pyrolysis heaters, used to produce olejins from gaseous jeedstocks such as ethane and propane and from liquid feedstocks such as naphtha and gas oil. In cracking heaters, in which chemical reactions occur in the coil, the tubes and burners are arranged so as to assure pinpoint firing control. Fluid outlet temperatures in heaters designed for liquid feedstocks are in the 816 to 899OC (1500 to 1650F) range. The principal classification of fired heaters relates to the orientation of the heating coil in the radiant section, i.e., whether the tubes are vertical or horizontal. Vertical arrangements are shown in Fig. 9. 64; horizontal arrangements, in Fig. 9-65. Salient features of each follow. Here the tube coil is placed Vertical-Cylindrical; All Radiant vertically along the walls of the combustion chamber. Firing is also vertical, from the tloor of the heater. Heaters of this type represent a low-cost, low-efficiency design that requires a minimum of plot area. Typical duties are 528 X 10s J/h to 21 GJ/h (0.5 to 20 million Btu/h). Vertical-Cylindrical; Helical Coil In these units, the coil is arranged helically along the walls of the combustion chamber, and firing is vertical from the floor. Although these heaters are grouped

TABLE 946
Industries

AverageEnergy Consumption

Rote in Process

Industry Glass containers Cement Lime Steel (ore beneficiation. furnace, open hearth, products

10 Btu consumed/ ton product 12.0 :.: 24.0 40.2 4.9 20.6

blast stove,

blast

soaking pits) Copper (roasting, smelting, refining, melting)

Structural clay Plastic products

SOURCE: M E. Fejer et al., Assessment Applkafirm for Direct Coal Combwtkm, Institute of Gas Technology, Chicago, National Science Foundaliorr Cont. NSF-024, October 1976. To convert l@ British thermal units per ton to megajoules per kilogram, multiply by 1.16.

principal material in the process by metallic or refractory walls. Examples are steam boilers, vaporizers, heat exchangers, and melting pots. Table 9-45 shows the 11 industrial applications of both these types of fired process equipment. Direct-Fired Equipment Table 9-46 gwes the average energy consumption in seven major industries that use direct firing. Table 947 shows the kinds of equipment used in the direct-fired cement and lime industries and the respective energy consumption per ton of product. Details of the equipment are described in a report entitled Assessment Application for Direct Coal Combustion, issued in 1977 by the National Science Foundation. Section 20 of this edition describes and illustrates rotary dryers, rotary kilns, and hearth and multiple-hearth furnaces. Indirect-Fired Equipment The following discussion is based largely on articles by Herbert L. Berman [Fired Heaters I, II, III, and IV, Chem. Eng. (June 19, July 31, Aug. 14, and Sept. 11, 1978)]. Process-industry requirements for fired heaters are divided into a half-dozen general service categories. Column Reboilera The charge stock taken from a distillation column is a recirculating liquid that is partially vaporized in the fired heater. The mixed vapor-liquid stream reenters the column, where the vapor condenses and releases the heat of vaporization. Depending on the particular application, reboiler heater outlet temperatures generally faj] in the range of 204 to 288OC (400 to 550F). Fractionating-Column Feed Preheater8 The charge stock (usually all liquid, although some feeds may contain a nominal amount of vapor at the inlet) is sent to the fired heater following upstream preheating in unfired equipment. A typical example of this service is the feed heater for an atmospheric distillation column in the crude-oil unit of a petroleum refin-

TABLE 9-47 Energy Consumptionof Various Cement-and LimeManufacturing Roceues PrOCESS

Cement Wet Long kilnf Calcinator and short kiln Semiwet: preheater and short Dry Long kiln Suspension preheater Semidry grate preheater lo6 Btu/ton

kiln

5.9 4.7 36 4.7 3.2 3.4 7-8 5-6 4.5-5.0 4.5-5.0

and short kiln and short kiln

Lime
Rotary long kiln+ Rotary short kilnt Vertical kiln Rotary-hearth kiln

To convert lo6 British thermal units per ton to megajoules per kilogram, multiply by 1.16. tMost common in the United States.

Radtant coil ._

Extended -surface area

-Radtant

coil--

Burner5 , /
1 I

Termjnal

mamfolds

FtG. 9-64 Vertical-tube-fired heaters can be identified by the vertical arrangement of the radiant-section coil. (a) Verticalcylindrical; all radiant. (b) Vertical-cylindrical; helical coil. (c) Vertical-cylindrical, with cross-flow-convection section. (d) Vertical-cylindrical, with integral-convection section. (e) Arbor or wicket type cf) Vertical-tube, single-row, double-fired [From Chem. Eng., 100-101 (June 19, 1978).]

P-61

u lcll
JPaa@ll

l-II
a00

a00

oao

.-__
coil -----_______

a00

_------Convect~on

117[ -

000

Fi
000 0000 000 0000

oooo OOQQ

i/ 0 0 0 0000 n
0 0 0 0 0
0

y Q0 0

3 3 0 0 0 0 0 3 0

a
0 0

1
,Convectlon coil
,A Convection
coil-.,
I

lu
a@00 @@@ 0000 000

i==l
000
0 0 .Q fdl FW 9-U Six basic designs box. (c) Cabin with dividing Horizontal-tube, single-row, used in horizontal-tube-fired bridgewall. (d) End-fired double-fired [From Chem.

II----l

0800333~~~~3~
0

=To -

stack

Radiant

coil-

8 n
-*.

n
000 000 000 600 800 0 0 0 0 0 8 8 0 0 0

___--0

heaters. Radiant-se&on coil is horizontal. box. (e) End-B& bo x. with side-mounted Eng., NL?-IO.~ (tune 19, IN%).]

(a) &bin. convection

(b) Two-~11
section. cf)

9-62

FIRED PROCESS
with others having vertical-tube designs, their in-tube characteristics resemble those of horizontal-tube heaters. This design also represents low cost and low efficiency and requires a minimum of plot area. Heating duties are the same as for the preceding heater. Vertical-Cylindrical, with Cross-Flow Convection These heaters, also fired vertically from the Boor, feature both radiant and convection sections. The radiant-section tube coil is disposed in a vertical arrangement along the walls of the combustion chamber. The convection-section tube coil is arranged as a horizontal bank of tubes positioned above the combustion chamber. This configuration provides an economical, high-efficiency design that requires a minimum of plot area. The majority of new verticaltube fired-heater installations fall into this category. Typical duty range is 10.6 to 212 GJ/h (10 to 200 million Btu/h). Although this Vertical-Cylindrical, with Integral Conoection design is rarely chosen for new installations, the vast number of existing units of this type warrants its mention in any review of fired heaters. As with the preceding types, this design is vertically fired from the floor, with its tube coil installed in a vertical arrangement along the walls. The distinguishing feature of this type is the use of added surface area on the upper reaches of each tube to promote convection heating. This surface area extends into the annular space formed between the convection coil and a central baffle sleeve. Medium efficiency can be achieved with a minimum of plot area. Typical duty for this design is 10.6 to 106 GJ/h (10 to 100 million Btu/h). This is a specialty design in which the radiant Arbor or Wicket heating surface is provided by U tubes connecting the inlet and outlet terminal manifolds. This type is especially suited for heating large Bows of gas under conditions of low pressure drop. Typical applications are found in petroleum refining, in which this design is often employed in the catalytic-re-former charge heater, and in various reheat services. Firing modes are usually either vertical from the floor or horizontal between the riser portions of the U tubes. This design type can be expanded to accommodate several arbor coils within one structure. Each coil can be separated by dividing walls so that individual firing control can be attained. In addition, a cross-tlow convection section is normally installed to provide supplementary heating capacity for chores such as steam generation. Typ ical duties for each arbor coil of this design are about 53 to 106 CJ/ h (50 to 100 million Btu/h). Vertical-Tube, Double-Fired In these units, vertical radiant tubes are arranged in a single row in each combustion cell (there are often two cells) and are fired from both sides of the row. Such an arrangement yields a highly uniform distribution of heat-transfer rates (heat tlux) about the tube circumference. Another variation of these heaters uses multilevel sidewall firing, which gives maximum control of the heat-flux profile along the length of the tubes. Multilevel-sidewall-firing units are often employed in fired-reactor services and in critical reactor-feed heating services. In addition to the twin-cell furnaces already mentioned, single-cell models are available for smaller duties. As a group, these represent the most expensive fired-heater configuration. The typical duty range for each cell runs from about 21 to 133 GJ/h (20 to 125 million Btu/h). tube coils of these Horizontal-Tube Cabin The radiant-section heaters are arranged horizontally so as to line the sidewalls of the combustion chamber and the sloping roof, or hip. The convectionsection tube coil is positioned as a horizontal bank of tubes above the combustion chamber. Normally the tubes are fired vertically from the floor, but they can also be fired horizontally by sidewall-mounted burners located below the tube coil. This economical, high-efficiency design currently represents the majority of new horizontal-tube fired-heater installations. Duties run from 10.6 to 106 GJ/h (10 to 100 million Btu/h). Two-Cell Horizontal-Tube Box Here the radiant-section tube coil is deployed in a horizontal arrangement along the sidewalls and roof of the two combustion chambers. Vertically fired from the Bow, this is again an economical, high-efficiency design. Typical duties range from 106 to 266 GJ/h (100 to 250 million Btu/h).

EQUIPMENT

9-63

Again the Horizontal-Tube Cabin with Dioiding Btidgewall radiant-section tube coil is arranged horizontally along the sidewalls of the combustion chamber and along the hip. The convection-section tube coil takes the form of a horizontal bank of tubes positioned above the combustion chamber. A dividing bridgewall between the cells allows for individual firing control over each cell in the combustion chamber. A typical duty range for this design is 21 to 105 GJ/h (20 to 100 million Btu/h). End-Fired Horizontal-Tube Box The radiant-section tube coil is disposed in a horizontal arrangement along the sidewalls and roof of the combustion chamber. The convection-section tube coil is arranged as a horizontal bank of tubes positioned above the combustion chamber. These furnaces are horizontally fired by burners mounted in the end walls. A typical duty range for this design is 5.3 to 53 GJ/h (5 to 50 million Btu/h).

End-Fired Horizontal-Tube Box, with Side-Mounted ConoecHere the radiant-section tube coil is disposed in a hortion Section
izontal arrangement along the sidewalls and roof of the combustion chamber. The convection-section coil is arranged as a horizontal bank of tubes positioned alongside the chamber. The unit is horizontally fired from burners mounted on the end wall. These furnaces are found in many older installations and occasionally in new facilities that burn particularly poor grades of fuel oil containing a high ash concentration. This relatively expensive design provides duties ranging from 53 to 212 GJ/h (50 to 200 million Btu/
h).

Horizontal-Tube, Double-Fired Horizontal radiant tubes are arranged in a single row and are fired from both sides to achieve a uniform distribution of heat-transfer rates around the tube circumference. Such heaters are normally fired vertically from the Boor. They are often selected for critical reactor-feed heating services. For increased capacity, the concept can be expanded to provide for a dual combustion chamber. A typical duty range for each cell of this design is about 21 to 53 GJ/h (20 to 50 million Btu/h). Fuel-Saving Methods for Existing Heaters Because of increased fuel costs, industries that operate process heaters must give serious consideration to improving fuel-burning efficiency. They can now justify increased costs for more efficient major equipment and control instrumentation. In todays environment, industrial-boiler and process-heater efficiency not only is measured in British thermal units but must also reflect the much greater dollar cost of those units. Figure 9-66 illustrates one of the two basic methods of improving design for fuel conservation: air for conbu.stion. Reduction of total air to the 1. Optfmite left of the zone of maximum combustion efficiency will result in increasing unburned-fuel loss. Heat loss is rapid when all the fuel is not burned. To the right of the zone of maximum combustion efficiency, the losses rise with increasing excess air.

Save

Total

air percent

FIG. 9-66 One of two basic methods of improving design for fuel conservation. Air is optimized for combustion. Heat is trapped out of flue gas (with air heaters or ecanomizers). [From Combustion, NJ-16 (November 1978).]

9-64

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

In the industrial market, boilers have been designed to burn a wide range of fuels and operate at pressures up to 12.4 MPa (1803 Ibf/in*) and steaming rates extending to 455,006 kg/h (l,OOO,C@O lb/h). High-capacity shop-assembled boilers range in capacity from 4500 kg/h (lo,@30 lb/h) to about 250,ooO kg/h (550,000 lb/h). These units are designed for operation at pressures up to 11.1 MPa (1650 psig) and 763 K (950F). Figure 9-69 shows a gaseous-liquid fuel-fired unit. While most shop-assembled boilers are gas- or oil-fired, designs are available to burn pulverized coal. The significant increase in the cost of fuels and the greater reliance on coal have provided the incentive toward large-capacity field-erected boilers operating at higher pressures with superheat and possibly reheat. A field-erected coal-fired industrial boiler is shown in Fig. Q-70. Boilers designed for service in electric power utility systems operate at both subcritical-pressure [pressures below 221.1 bar (3206 lbf/ in*)] and supercritical-pressure steam conditions. Subcritical-pressure boilers range in design pressures up to about 18.6 MPa (2700 Ibf/in*) and in steaming capacities up to about 2946 Mg/h (6,500,OOO lb/h). A subcritical-pressure boiler is shown in Fig. 9-71. Supercritical-pressure boilers have been designed to operate at pressures up to 344.5 bar (5006 psig). In practice, the 241.2-bar (3500-psig) cycle has been firmly established in the utility industry, and boilers with steaming capacities up to 4219 Mg/h (9,300,ooO lb/h) and superheat and reheat temperatures of 614 K (1065F) are in service. Some Fundamentals of Boiler Design Boiler design involves the interaction of many variables: water-steam circulation, fuel characteristics, firing systems and heat input, and heat transfer. The furnace enclosure is one of the most critical components of a steam generator and must be conservatively designed to assure high boiler availability. The furnace configuration and its size are determined by combustion requirements, fuel characteristics, emission standards for particulate matter, and the need to provide a uniform gas flow and temperature entering the convection heat-absorbing surfaces to minimize ash deposits and excessive superheater metal temperatures, Discussion of some of these factors follows. Circdution and Heat Tramjer Circulation, as applied to a steam generator, is the movement of water or steam or a mixture of both through the heated tubes. The circulation objective is to absorb heat from the tube metal at a rate that assures sufficient cooling of the furnace-wall tubes during all operating conditions, with an adequate margin of reserve for transient upsets. Adequate circulation prevents excessive metal temperatures or temperature differentials that would cause failures due to overstressing, overheating, or corrosion. The heat transfer from the tubes to the fluid depends primarily on turbulence and heat flux. Turbulence is a function of mass velocity of the fluid and tube roughness Turbulence has been achieved by designing for high mass velocities, which ensure that nucleate boiling takes place at the inside surface of the tube. If sufficient turbulence

330 0 $ 310

Dew points for sulfurfree flue gas % Excess Dew point OF C

air

0.01

0.05 Sulfur

0.1

0.5

1 .o

5.0

10.0

in Fuel Oil, Percent/Wt.

zlt3~-67

Maximum flue-gas dew point versus percent of sulfur in typical oil

An additional factor is that when excess air is increased, flue-gas temperature rises, and this compounds with excess-air loss Excess-air loss rises at a slower rate than does the loss from unburned combustibles by a factor of about 6 (316% stack temperature); therefore, it is important to keep the flue gas out of the combustibles range. There is a aone, then, of maximum combustion efficiency where the sum of the losses is at a minimum. The extent of overlap between combustible gas and excess oxygen depends on the particulars of a given installation, the type of burners, and the fuel fired. 2. Recowr heat in flue gas. If the &e-gas temperature is high, this thermal-energy loss can be reduced by installing heat exchangers that absorb energy from the stack gases. Air heaters and feed preheaters are well-known examples of such equipment. Corrosion problems in air heaters are associated with high flue-gas dew points because of SOs formation from sulfur in the fuel. The curves in Figs. 9-67 and 9-68 can be used to determine safe upper limits for dew points in fired heaters burning liquid or gaseous fuels.

STEAM GENERATORS
Steam generators are designed to produce steam for process requirements, for process needs with electric power generation, and solely for electric power generation. In each case, the prime incentive is to design the most efficient and reliable boiler for the least cost. Many factors influence the design and selection of the type of steam generator, and some of these will be discussed later in connection with industrial and utility boilers,

360 0

Dew points for sulfurfree flue gas % Excess Dew Point

0.01

0.05

0.1

0.6

1.0

5.0

10.0

H2S in Gas Fuel, PercedVol. EJU6

Maximum flue-gas dew point versus percent of HpS in typical gas

FtG. 9-69

Shop-assembled boiler.

Ro. 9-70

Cad-fired industrial boiler.

FIG. 9-71 9-66

Subcritical-pressure

utility

boiler.

STEAM GENERATORS
Steam water mixture

9-67

Film boiling

Heat *

Transition boiling _-_-__

Nucleate

boiling

me---

357

water
FIG. V-72

Tube-metal
from nucleate boiling (DNB) on tube-metal temperature

454 temperature,

566 oC

Effect of

departure

is not provided, departure from nucleate boiling (DNB) occurs. DNB is the production of a film of steam on the tube surface that impedes the Bow of heat to cool the tubes. This phenomenon is illustrated in Fig. 9-72. Satisfactory performance is obtained with tubes having helical ribs on the inside surface, which generate a swirling flow. The resulting centrifugal action forces the water droplets toward the inner tube surface and prevents the formation of a steam film. The internally rifled tube maintains nucleate boiling at much higher steam qualities and with much lower mass velocities than those in smooth tubes. This improvement is shown in Fig. 9-73. Circulation ratio, defined as the weight of circulating flow divided by the weight of steam generated, is an empirical criterion for eval-

uating the performance of circulation systems. In modern practice, however, the most important criterion in drum boilers is the prevention of conditions that lead to DNB. Utility Steam Generators Steam-Generator Circulation System Circulation systems for utility application are generally classified as natural circulation and forced or pump-assisted circulation in drum-type boilers and as oncethrough 5ow in subcritical- and supercritical-pressure boilers. The circulation systems for natural- and pump-assisted circulation boilers are illustrated schematically in Fig. 9-74. Natural circulation in a boiler circulation loop relies only on the
Rifled tube

Ho. 9-73

Maximum

allowable percent of steam to avoid departure

from nucleate

boding (DNB).

9-48

ENERGY

UTIUZATION,

CONVERSION,

AND

RESOURCE

CONSERVATION

(0) FIG. 9-74

(b)

Circulation systems. (a) Natural circulation. (b) Pump-assisted circulation

difference between the mean density of the fluid (water) in the downcomers and the mean density of the tluid (steam-water mixture) in the heated furnace walls. The difference in these densities pro vides the drive that causes flow in the loop. The actual circulating head is the difference between the total gravity head in the downcumer and the integrated gravity heads in the upcoming legs of the loop containing the heated tubes. The circulating head must balance the sum of the Bow losses due to friction, shock, and acceleration throughout the loop. In a once-through system, the feedwater entering the unit continuously absorbs heat until it is completely converted to steam. The

total mass Bow through the waterwall tubes equals the feedwater flow and, during normal operation, the total steam Bow. The key fact of circulation at supercritical pressures (above 221.1 bar, or 3206 lbf/ in) is the existence of a single-phase tluid at any temperature, and there is no need for a steam drum. Fuel Characteristics Fuel characteristics have a major impact on the design and operation of a coal-fired boiler. Coals having a low volatile matter usually require higher ignition temperatures, and those with less than 12 to I4 percent volatile matter may require supplementary fuel to stabilize ignition. Generally, western United States coals are more reactive and, consequently, easier to ignite, but

cl 0
W4

1.0BWm6D

1.16W~l.OBO

1.26Wx1.24D

1.29Wx1.26D

1.07H

EASTERN BITUMINOUS
Ro. 9-75

MIDWESTERN BITUMINOUS SUB-BITUMINOUS

WILCOX SEAM

VEGUA-JACKSON SEAM

TEXAS LIGNITE

NORTHERN PLAINS LIGNITE

Effect of coal rank on furnace sizing.

STEAM GENERATORS
content they require higher air temperatures to the mills for drying the coal to attain proper pulverization. Extremely high-ash-content coal could create problems in ignition and stabilisation. The ash constituents and the quantity of ash will have a decided influence on sizing the furnace. Accordingly, a thorough review of coal characteristics is needed to establish the effect on the design and operation of a boiler. In designing and sizing furnaces, particular attention is required for the following fuel-ash properties: 1. Ash fusion temperatures in terms of their absolute values and the spread between initial deformation temperature and 5uid temperature 2. Ratio of basic to acidic ash constituents 3. Iron-to-calcium ratio 4. Ash content, kg/l,O%,OOO kJ (lb/million Btu) 5. Ash friability These characteristics translate into the furnaces shown in Fig. 975 for five United States coals. Note the progressive increase in furnace size in terms of plan area, volume, and burning zone as lowergrade fuels are fired to develop equivalent steam-5ow capacity. There are wide variations in coal properties within the coal ranks as well as several subclassifications (e.g., subbituminous A, B, C) of these fuels. These variations require a different size of furnace for each classification. Coal properties in5uence pulverizer capacity, the sizing of the air heater, and other heat-recovery sections of a steam generator. Furnace size and heat-release rates are designed to control slagging characteristics. Consequently, heat-release rates, in terms of net heat in ut to plan area, range from 4,420,OOO W/m2 [1.4 million Btu/(h W/m8 [2,100,000 Btu/ fib;] f or severely slagging coals to 6620,000 (h.ft*)] for low-slagging fuels. Finng-gysfem Heat Znput Heat input is a critical design criterion in establishing the combustion of fuel with regard to minimizing the formation of the oxides of nitrogen (NO,) in the combustion process. To accomplish these functions, the designer considers the following design parameters: * Design and size of burners and their arrangement in the furnace . Clearances from burners to water-cooled surfaces * Furnace release rate, (kg.cal)/m* (Btu/ft*) effective projected radiant surface or EPRS * Furnace-gas residence time for combustion and NO, emissions . Furnace exit-gas temperatures, K (OF) . Combustion rate, kJ/m8 (Btu/fta) . Burner-zone release rate, W/m8 [Btu/(h.fta)] Firing systems can be classified into two groups: . Wall firing, in which individual flames are formed by burners in the front, rear, and/or side walls of the furnace . Tangential firing, in which fuel and air are introduced into the furnace from delivery nozzles located in the corners of the unit A major difference between the systems is that in wall firing there is little interaction among the Barnes from individual burners; in tangential firing, reactants from all coal nozzles interact, forming a cyclonic name mass and making the furnace a single burner. The furnace of large coal-fired steam generators absorbs about one-half of the heat released, so that the gas temperature leaving the furnace is about 1376 K (2000F). Superheater8 and Reheaters The superheater raises the temperature of the steam generated by the boiler to some point above saturation. The thermodynamic advantage of superheating steam is shown in Fig. 9-76, which compares the available head above a given exhaust condition with the total heat in the steam. Another important point is to minimize moisture in the last stages of a turbine to avoid blade erosion. With continued increase of evaporation temperatures and pressures, a point is reached at which the available superheat temperatures are insufficient to prevent excessive moisture from forming in the low-pressure turbine stages. This condition is resolved by removing the vapor for reheat at constant pressure in the boiler and returning it to the turbine for continued expansion to condenser pressure. The thermodynamic cycle using this modification of the Bankine cycle is called the reheat cycle. Figure 9-77 illustrates the surface arrangements in a high-pressure boiler.

9-69

because of high moisture

FIG. V-76

Improved prime-mover performance wit hs ,uperheat.

Economizers Economizers improve boiler efficiency by extracting heat from the discharged 5ue gases and transferring it to feedwater, which enters the steam generator at a temperature appreciably lower than the saturation-steam temperature. Industrial Boilers A common definition of an industrial boiler is a stationary water-tube boiler in which some of the steam is generated in a convective tube bank. The percentage of total heat absorp tion in the boiler bank varies considerably with boiler steam pressure and temperature and feedwater temperature. For a typical coal-5red boiler producing 90,720 kg/h (200,000 lb/h): Boiler pressure w, total steam 45 30 16 10 kg/cd 14 42 105 126 lb/in 200 600 1500 1600 Steam temperature, T 167 399 510 536 Feedwater temperature, T 116 116 177 177

The thicker plate for operation at higher pressures increases the cost of boiler drums. As a result, it is normally not economical to use a boiler bank for heat absorption at pressures above 109 kg/cm* (1550 psig). Industrial boilers are used over a wide range of applications, rang-

ing from large power-generating units, for which emphasis is placed on maximum efficiency and sophisticated control systems, to small low-pressure units for space or process heating, for which the principal aims are simplicity and low first cost. While an industrial boilers primary function is usually to provide

TABLE 9-48

Solid-Waste Fuels Burned in industrial Boilers HHV, kl/kg a374-11,KKl 11&x30-13,956 9304-11,630 10,467-18,lxx 11,397-15,119 16,282-18,608 12,cKa5-15,119 18,608-19,306 26,749~45.822 27,912-45,822 27,912-30.238 39.077 27.912 40,705 40,705 4652-27,912 13.695-18.608

waste
gag= Furfural residue Bark General wood wastes coffee grounds Nut hulls Rich hulls ComclJbs Rubber scrap Leather Cork scrap ParaffiIl CMlophane plastics Polyvinyl chloride Vinyl scrap Sludges Paper wastes

To convert kilojoules per kilogram to British thermal units per pound, multiply by 4.299 X 10-l produce an even higher carbon loss. The lower carbon loss produced with the pulverized-coal unit results from increased combustion efficiency obtained from the finer coal particles that enter the furnace (normally 70 to 80 percent will pass through a ZOO-mesh screen). In contrast, the coal particles that enter the furnace with a spreader stoker are much coarser, with a I9-mm top size and not more than 50 percent passing through a KS-mm screen. The coal itself also affects the total fuel-cost difference between these firing methods. For efficient operation of a spreader-stokerfired boiler, the coal must have the proper mixture of coarse and fine particles. Normally, double-screened coal is purchased to obtain the proper mixture. One cannot depend on run-of-the-mine coal to have the optimum balance of coarse and fine material. The fine coal particles are burned in suspension above the grate, while the larger particles burn on the grate surface. If the amount of fine particles is too great, excessive suspension burning will occur with the following possible results: . Higher stack particulate-matter loading . Furnace pulsations . Possible heat damage to the distributors . Higher carbon loss and smoke If the amount of coarse coal is too great, there will be insufficient suspension burning with these possible results: . Loss of ilame stability . Higher carbon loss and smoke If it is decided not to use double-screened coal, there will be a loss in efficiency as the coal sizing diverges from the optimum. The question of whether the reduced efficiency obtained with unsized coal is offset by the higher cost for double-screened coal cannot be answered on a general basis. The answer depends on such factors as degree of coalsizing variation, quality of operators, boiler or stoker size, and coal classification. A pulverized-coal-fired boiler requires only that the coal entering a mill be IX-in top size. Coal of any size can be purchased and crushed at the plant site if the proper size is not available at the mine. In addition to designing for a range of coals, liquid, gaseous, or other solid fuels may be considered. Because pulverized coal is suspension-fired, as are conventional liquid and gaseous fuels, the furnace is properly proportioned for this function. Oil or gas is required for unit warm-up; therefore, the required piping, combustion controls, and fuel-firing equipment are in place. These fuels can be fired to carry load with little or no design or equipment modifications. Firing a liquid fuel derived from coal or a coal-oil slurry would also be possible because the furnace has been designed to cool the gases below the ash-softening temperature before these gases enter the closely spaced generating bank section. Well-prepared solid wastes may also be burned in suspension. Up to 20 percent of the total heat input may be added. Bark, bagasse,

RG. 9-77

Typical boiler superheater-reheater arrangement

energy in the form of steam, there are a number of applications in which steam generation is incidental to a chemical process, e.g., a chemical recovery unit in the paper industry, a carbon monoxide boiler in an oil refinery, or a gas-cooling waste-heat boiler in an openhearth furnace. Within a given industrial plant, it is not unusual for industrial boilers to serve a multiplicity of functions. For example, in a paper-pulp mill the chemical-recovery boiler is used to convert black liquor into useful chemicals and to generate process steam. At the same plant a bark-burning unit recovers heat from otherwise wasted material and also generates power. Industrial boilers burn oil, gas, coal, and a wide range of product and/or waste fuels as shown in Table 9-43. Current statistics show that pulverized-coal firing is the choice for larger boilers, above 113,398 kg/h (WO,@Xl lb/h). For boilers in the medium-size range, 45,359 to 113,398 kg/h (100,090 to 250,009 lb/ h), stoker-fired boilers dominate, although the percentage of pulverized-coal-fired boilers in this range is increasing. The higher thermal efhciency of a pulverized-coal-fired boiler makes it attractive toward the upper limit of the medium-size range. A major factor to consider when comparing a stoker-fired boiler with a pulverized-coal-fired boiler is the reduction in efficiency due to carbon loss. A properly designed pulverized-coal-fired boiler can maintain an efficiency loss due to unburned carbon of less than 0.4 percent. A continuous-ash-discharge spreader-stoker-fired unit will typically have a carbon loss of 4 to 8 percent, depending on the amount of reinjection. Dumpgrate, underfeed, or overfeed stokers

STEAM GENERATORS and refuse have all been successfully suspension-fired in a pulverized-coal-fired boiler. These wastes are normally blown into the furnace pneumatically through ports located above the burners. For a stoker-fired boiler, firing liquid or gaseous fuels is more difficult The firing equipment must be placed high above the stoker to protect it from the radiant heat produced by the auxiliary burners. The placement of firing equipment high in the furnace reduces the effective furnace volume. For long-term operation, it may be necessary to cover the stoker with refractory. For short-term operation, considerable quantities of air are required to cool the stoker, resulting in large quantities of excess air, which is inefficient. While firing liquid or gaseous fuels in a stoker-fired boiler is more difficult, the stoker is ideally suited for firing other unsized solid fuels. Bark, bagasse, or refuse can normally be fired on a stoker to supplement the coal with a minimum amount of additional equipment. Also, these waste fuels can comprise a higher percentage of the total heat input in a stoker-fired boiler than in a pulverized-coal-fired boiler. Design Criteria Industrial-boiler designs are tailored to the fuels and firing systems involved. Some of the more important design criteria include: * Furnace heat-release rates, both W/m3 and W/m2 of effective projected radiant surface [Btu/(h.fts) and Btu/(h.fts)] . Heat release on grates * Flue-gas velocities through tube banks . Tube spacings Table 9-49 gives typical values or ranges of these criteria for gas, oil, and coal. The furnace release rates are important and establish maximum local absorption rates within safe limits. They have a bearing on completeness of combustion and therefore on efficiency and particulate emissions. Limiting heat release on grates (in stoker firing) will minimize carbon loss, control smoke, and avoid excessive By ash. Limits on flue-gas velocities for gas- or oil-fired industrial boilers are usually determined by the need to limit draft loss. For coal firing, design gas velocities are established to minimize fouling and plugging of tube banks in high-temperature zones and erosion in lowtemperature zones. Convection tube spacing is important when the fuel is residual oil or coal, especially coals with low ash-fusion or high ash-fouling tendencies. The amount of the ash and, even more important, the characteristics of the ash must be specified for design. The recommended TABLE 9-50 Boilers,mm

9-7 1

RecommendedMinimum Tube Spacingfor Industrial Superheater Platen Spaced 102 102 152 152 Boiler Front 254 2.54 50.6 38 Rear 25.4 25.4 38 25.4 Economiser 76 76 76 76

Oil and clean gases Coal Low ash; high AST High ash; low AST Bark. baea.w

305 305 305 305

Ash-softening temperature.

TABLE 949 F,,mWW

Tv~ical Dostan Parameters

for IndustrialBoilers Heat-release rate, W/ & nf FPRCt 630,800 551,~630.800 220,780-378,480 %52,320-410,020

minimum tube spacing for industrial solid-fuel-fired boilers is shown in Table 9-50. Natural-circulation and convection boiler banks are the basic design features on which a line of standard industrial boilers has been developed to accommodate the diverse steam, water, and fuel requirements of the industrial market. Figure 9-78 shows the amount of energy available for power by using a fire-tube boiler, an industrial boiler, and subcriticaland supercritical-pressure boilers. Condensing losses decrease substantially, and regeneration of air and feedwater becomes increasingly important in the most advanced central-station boilers. The boiler designer must proporton heat-absorbing and heatrecovery surfaces in a way to make the best use of heat released by the fuel. Waterwalls, superheaters, and reheaters are exposed to convection and radiant heat, whereas convection heat transfer predominates in air heaters and economizers. The relative amounts of these surfaces vary with the size and operating conditions of the boiler. Factors Influencing Performance Some of the dominant factors influencing performance are fouling, slagging, moisture in the coal, grindability of the coal, and heating value of the coal. The volatile constituents in coal ash (i.e., NarSO, or CaSOI. NasSO,) cause fouling and can be used as a fouling index of a given coal. Two factors that affect fouling are deposit hardness and the rate of deposition. Deposit hardness is affected by chemical composition, temperature, and, to some extent, time. The rate of deposition depends on the volatile constituents of coal and the amount of ash in the coal. In general, fouling is related to the sodium and potassium compounds in the ash, and it becomes severe as the level increases above 4 to 5 percent NaaO and KaO for high-calcium, low-iron ash coals. Slag deposits are caused primarily by the physical transport of molten or partially fused ash particles entrained by the gas stream. When the particles strike the wall or tube surfaces, they become

Natural gas-fired Oil-fired coal: pulverized coal Spreader stoker Stoker, coal-fired Continuous-discharge spreader Dumpgrade spreader Overfeed travelinn crate Flue-gas velocity: type Fuel-fired Gas or distillate oil Residual bil Coal (not lignite) Low-ash High-ash Single-pass Bailer m/s 30.5 30.5 19.6-21.3 15.2 Bailer m/s 30.5 22.9 15.2 NA1

Grate heat-release
W/n?

rate,

2,CL50,000-2,207,6OO 1,419,3oo-1,734,7oo 1.261.ooo -1.734.700 Baffled Economiser m/s 30.5 30.5 15.2-18.3 12.2-15.2
ICI

lb)

To convert watts per square meter to British thermal units per hour-foot. multiply by 0.317. iEffective pro+cted radiant surface. 1Not available.

Id1

FIG. 9-78 Sankey diagrams for various types of boilers. (a) Fire-tube boiler. (b) Industrial boiler. (c) Subcritical-pressure boiler. (d) Supercritical-pressure boiler.

9-72

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION higher degree of fineness than subbituminous coals and lignites to ensure carbon burnout. The grindability of coals varies over a wide range. Pulveriser output related to pulveriser base capacities for various grindability indices is shown in Fig. 9-79. Grindability can be a significant factor in limiting rated boiler output when coal having a looererrindabihty than that for which the pulveriser was sized is The heating value of coal has a significant intluence on boiler performance. The greatest potential for variations in the pulveriser output rate is the result of fuel heating-value variations. The lower heating value of hgnites and subbituminous coals creates a potential limitation in boiler output because it takes more coal for a given heat input. Heating values range from 12,000 Btu/lb (27,912 kJ/kg) for an eastern bituminous coal to 6800 Btu/lb (15,817 kJ/kg) for northern plains lignite. The range of firing rates of various United States coals to yield comparable heat inputs for a given unit is shown in
Table 9-51.

chilled and solidify. The strength of their attachment is influenced by the temperature and physical contour of the surface, direction, force of impact, and melting characteristics of the slag. Coals with low ash-fusion temperatures have a high potential for slagging [below 2200F (1477 K)]. Normally, slagging is confined to the radiant surfaces, but it also occurs in the convection superheater if the gas temperature exceeds good design practice. Slagging characteristics affect the furnace design, requiring a significant increase in furnace volume to reduce the potential for deposit formation. High moisture in coal influences furnace performance. Excess surface moisture compounds the difficulties of handling coal at the exit of the bunker into the inlet of the feeder and at the feeder outlet into the pulveriser. Wet coal within the pulveriser causes it to ball up and inhibit grinding. Such problems are typical with coal having a high inherent moisture in the fuel, up to 30 percent. In these cases, providing sufficient high-temperature air will obviate pulverisation problems. The high moisture in the fuel lowers the flame temperature, reducing local furnace absorption and ignition stability, especially during start-up. High moisture also reduces boiler efficiency, owing to heat losses up the stack. The grindability index is a measure of the relative eax of pulverising coal. The fineness required for both good ignition and complete combustion of coal depends on a number of factors, including volatile matter, agglomerating properties, and particle reactivity. In terms of rank, low-volatile bituminous coals must be pulverized to a

Stacks and Chimneys Theoretical Draft The theoretical draft is that which is pro duced by the manometric difference in static head of equal columns of atmospheric air and combustion gases. The theoretical draft of a smokestack or a chimney can be calculated readily from the formula

24 (KIT/~)

ZA
/

14.1 (SOT/hr)

I I 20

10

I 15
Pulverizer

I
kg/s 200 mesh)

capacity

(55 grind - 70% through

Ro. 9-79

Pulveriser capacity: grindability

index. To convert kilograms per second to tons per hour, multiply by 3.543.

STEAM GENERATORS TABLE 9-51

Ranae of United States Ceal Promertiar

9-73

Eastern
bituminous

Midwestern bituminous 23.300 12 26 145,160

Subbituminous C 19,540 21 71 291,900

Texas lienite 16,980 32 9-l 336,ooo

Northern lignite 15,820 37 119 360,500

HHV, kJ/kg
Moisture, 95 Moisture, kg HgO/CJ Fuel fired, kg/h

27,900
6 204,3;

Based on QF = 12,500 Cl/kg.

where Ap, = theoretical stack draft, in water; L = stack height above furnace, ft; P = barometric pressure, inHg; T = ambient temperature, OR; and T1 = average stack temperature, OR. Figure 9-800 may be used to estimate the exit-gas temperature required to obtain the average stack temperature for masonry or steel stacks. Actual Draft To obtain the actual draft for a chimney or stack, the losses that occur with Bow must be deducted from the theoretical draft. These losses include both friction and exit velocity. They may
be evaluated by the following equation:

where Apf = stack flow loss, in water; u = stack exit velocity, ft/s; g = dimensional constant, 32.17; f = friction factor from Fig. 980b; L = stack height above furnace, ft; D = stack diameter, ft; and ps = average density of gases in the stack, Ib/fts. To apply Fig. 980b the Reynolds number may be approximated by the equation
24,000

Nae =

X W

D(T, + 715)

(9-46)

(9-45) /

where T, = average stack temperature, OF W = gas Bow, lb/h The actual draft may be obtained by subtracting the frictional losses from the theoretical draft. This quantity is known as the nat-

FtG. 9-800

Exit-gas temperatures from stacks

80,000w-400p-655F.-1337h -------_---___-_)I

Ow

Reduclnq valve (and desuperheater)

t-----+=+---1

lo5

5
Reynolds

lo6
number,

2
NR~

10

FIG. 9-Mb

Friction factors for stacks. (Bobcock G Wilcox Co.)

FIG. 9-80~ Steam-plant-cycle diagram showing by-product generation of electric power and process steam. Heat supplied in steam = 97 kJ/h (92 X lo6 Btu/h). Heat supplied in fuel = 121 kJ/h (115 X 106 Btu/h). Net plant electric send-out = 4700 kW.

9-74

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

pressures by dilution when condensable acid gases occur. When corrosive conditions warrant the extra expense, chimneys and stacks are frequently lined with glass, acid-resistant brick, or acid-resisting cement. Steel stacks may be purchased lined with bonded glass for erection as a unit, or they may be lined in place with brick after erection. Masonry stacks are erected in place of either brick or reinforced-concrete design. Either steel or masonry stacks may be lined after erection with special coatings applied by hand or by pressure spraying (guniting). It is advisable to inspect stacks for internal corrosion at periodic intervals. Water washing after cooling is advisable to expose the surface for inspection if the stack is heavily coated with soot.

ural draft of the chimney, since it is produced without mechanical means. When it is insufficient to overcome the tlow resistance of the system, fans must be added. If the fans supply air at pressures above atmospheric to the burners and combustion space, they are called forceddraft fans. If the fans handle the products of combustion, they usually operate at pressures below atmospheric and are called induced-draft fans. Special Problem Frequently stacks are required to handle gases of a highly corrosive nature. Even the gases of conventional fuels may contain sufficient amounts of contaminants such as sulfur trioxide to attack steel and concrete rapidly. Efforts should be made to maintain temperatures above the dew point or to reduce partial

HEAT TRANSPORT
GENERALREFWIMCES: The Dowtherm Handtook, Dow Chemical Company, Midland, Mich., 1960. G&ringer, Handbook of Heat Transfer Media, Reinhold. New York. 1962. High Temperature Heating Media, Chem. Eng. Prog., 59(S), 33-53 (1963) Keenan and Keyes, Thmodynamtc Properttes of Steam, Wiley, New York, 1956. Kent. Mechanical Engineers Hnndhk, vol. 2: Pourer, 12th ed., Wiley, New York, 1950. Kern, Process Heat Transfer, t&Craw-Hill, New York, 1950. McAdams. Heat Transmissia, 3d ed., McGraw-Hill, New York, 1954. Marks, Mechonlcal Engineers Handbwk, 7th ed, McGraw-Hill, New York, 1950. Liquids and vapors used to transport heat and give it up to process require a unique combination of properties. High boiling points and low pressures reduce hazards and permit economical designs, while high heat capacity improves the ability to carry heat and spread it evenly through the process system. The tluids must also be commercially available and economical to use. Solid materials are also used for heat transport. These materials have never reached the importance of liquids and vapors, primarily because of the difficulty of transporting the solid particles through small pipes and bent tubes. Pebbles, sand, and iron balls can be heated to higher temperatures than liquids and have found application in air and gas heaters for high-temperature equipment. The commonly used heat-transport fluids are listed in Table 9-52, along with their useful temperature ranges and corresponding pressure ranges. Historically, the open flame is the oldest source of heat known to man. Basic simplicity and low equipment cost have enabled it to survIvc In many lodusrrlal processes. The open ftame as a heat source for industrial-product heating has several limitations, however. These include low fuel efficiency, minimum control over uniformity of heat absorption, and correspondingly poor control over local temperatures in the product material. The burners, fuel supply, and controls must be at the operating point, making the units unwieldy and not suitable to locations of advantage to the manufacturing operations. As a result of these limitations, fluids adaptable control long ago supplanted tlame for process work. to much closer

STEAM SYSTEMS
System Characteristics To utilize the energy that is stored as chemical energy in fuels, the chemical energy must be converted to a more usable form, generally either electrical energy or mechanical energy, to drive machines, or thermal energy, as a source of process heat. Although some fuel energy is converted directly to mechanical energy (as in combustion engines) or to thermal energy (direct-process heating), the most popular systems involve the use of steam as an intermediate medium. Steam is the most widely used heat-transport fluid owing to its nontoxic nature, stability, low costs, and high heat capacity. It has limitations, too: its high vapor pressure and its low critical point. Most commercial sytems start with energy in the form of chemical energy in fuel. Combustion of the fuel in the furnace converts the chemical energy to thermal energy in the form of high-temperature combustion products. In a boiler, heat is transferred from the cornbustion products to water, thus producing steam. The steam may then be used for driving machinery (Including turbmes) or for heating (process or space). The use of steam can be via three types of systems: systems (in which nearly all the steam is used 1. Steam-electric to drwc a turbine-generarorj systems (in which steam is used both to drive a 2. Cogeneration turbine-generator and for heating, usually in series) 3. Steam systems (in which steam is used as a heat-transfer medium for heating purposes only) Steam-electric and steam systems are discussed in the following paragraphs. Cogeneration systems are dealt with in another part of this subsection. Steam-Electric Systems Steam-electric systems utilize superheated steam to drive turbine-generators to produce electrical energy. Unless special circumstances exist, economics are unfavorable for small- to moderate-size process plants to consider steam-electric systems. The unfavorable economics include the high capital cost of the furnace-boiler system, the generally lower operating efficiency of small boiler systems, high operating and maintenance costs, and the cost of capital equipment for meeting air-pollution-emissions regulations for the combustion process. Special circumstances that can justify the operation of small steamelectric systems include the availability of a low-cost fuel, such as a waste or by-product fuel. Industries can make use of such by-product fuels as bark, black liquor, bagasse, sawdust, blast-furnace gas and coke-oven gas, and fluid coke, either as main fuels or in combination with conventional fuels such as coal, oil, or gas. Cogeneration systems greatly increase the opportunities for a process plant to generate electric power economically.

TAME 9-52

CommonlyUsed Heat-Transport Fluids*

Chlorinated biphenyls NaK Mercury Flue gas or air

:~z&

30-2000

: O-180 O-100

See Table 9-54 for more detailed data. To convert pounds per square inch gauge to kilopascals, multiply by 0.15; C = (OF - 32) x %.

STEAM Steam Systems* Steam systems include those systems in which steam is generated and used for process and/or space heating and, less frequently, for the direct driving of machinery. Although industrial steam can be generated at high pressure (up to 12.4 MPa) and temperature, most industrial steam systems are limited to about 1.724-MPa (2.5~lbf/in) steam pressure and 204OC (400F) steam temperature. In an industrial steam system, the major component is the furnace-boiler unit; another major component is the condenser, if one is used. Furnace-boiler units are constructed as integrated units; design varies with size and fuel. Small gas- and oil-fired boilers, with capacities up to 31.7-Mg (70,000-lb) steam per hour, are usually fire-tube boilers. Most solid-fuel-fired boilers and larger gas- and oil-fired boilers are water-tube design. Water-tube boilers for industrial steam generation are of drum-type design. Water-tube boilers may be shop-assembled packaged boilers or field-erected. Gas- and oil-fired boilers of capacities to 113.4.Mg (250,mlb) steam/h can be installed as package units (to 550,COO lb/h if shipment is possible). Coal-fired boilers with capacities above about 11.3-Mg (25,000-lb) steam per hour are partially or totally field-erected. Because of the high cost of field erection, it may be more economical to install several smaller boilers than one large boiler. Also, because the minimum firing rate of boilers is about one-third of the design firmg rate, the use of several smaller boilers provides a much higher turndown ratio. A typical steam-plant cycle for generation of process steam and electric power is shown in Fig. 9-8Oc. This is the cycle of an industrial power plant that requires the delivery of 5000 kW of electric energy and 22.7 Mg/h (50,000 lb/h) of dry saturated process steam at 137.9 kPa absolute (20 psia). Because all power cannot here be generated as a by-product of the process steam flow, a condensing element is added to the turbine and operated at 2.54 cmHg (1 inHg) absolute pressure. The heat balance of Fig. 9-8Oc is for one set of load conditions. Careful analysis of load curves is necessary for the selection of the most economical cycle. Most industrial steam systems utilize saturated steam; thus, superheaters are rarely used. Also, when low steam temperatures are used, there is no need for an economizer or an air preheater. However, pulverized-coal firing requires air preheat to achieve ignition and combustion stability. The cost of coal-fired boilers is about 4 times the cost of packaged gas- and oil-fired boilers. Modern industrial boilers operate at efficiencies of about 85 percent. including a condenser in the steam system provides opportunities for reusing the clean steam condensate, as opposed to providing clean boiler water continuously. The choice of whether or not to include a condenser in the system will vary with plant design and size, water availability, and water quality. The cost of return-water piping and a condenser becomes less attractive for widely dispersed plant facilities and as steam use decreases. Conversely, high steam (and, therefore, water) use and limited water availability may make a condenser attractive. Factors that must be considered when selecting an industrial boiler include: . Fuels, including projected costs and availability * Steam requirements: temperature, rate of delivery, and pressure * Load profile; turndown . Boiler feedwater: source and treatment * Space requirements, including fuel storage . Air pollution emissions and regulations . Energy to drive auxiliaries . Operating personnel required Water Constituents Water, as the working fluid of steam systems, is one of the most widely dispersed natural substances but is never found in a pure state, suitable for direct feed to a boiler. Water in its natural state is usually turbid with solid matter in fine suspension. Even when clear, natural water contains solutions of salts and acids that will quickly damage steel or copper-bearing metals in
See Steam Generators for further details on equipment.

SYSTEMS

9-75

steam systems. Recycling steam condensate from process heating is desirable to take advantage of the relatively pure condensate. Because of atmospheric dissipation and contamination from process equipment, some raw makeup is constantly required. Various constituents in waters may be classed in accordance with the troubles that may result from their presence: 1. Corrosive substances 2. Scale-forming substances 3. Foam-producing substances Corrosive substances are usually in the form of acid solutions or as dissolved gases such as carbon dioxide, oxygen, hydrogen sulfide, or ammonia. Oxygen and carbon dioxide are dissolved in the feedwater by aeration and unavoidable contact with the atmosphere. Since the solubility of oxygen decreases with an increase in water temperature, the most common method of removal is the deaeration of water, in which the water is heated to the boiling point by direct contact with steam and the heated water is allowed to cascade over trays. The trays increase the exposed surface and permit easier dissipation of the oxygen. Deaeration is also effective in removing other dissolved gases, and all modern steam systems use any of several types of deaerators. In addition to deaeration, use is made of chemicals, such as sodium sulfite, which combines with oxygen and is introduced into the boiler with a chemical feed pump. At higher boiler pressures sodium sulfite is less desirable, because of an increase in the dissolved solids produced by the end-product sodium sulfate and a decomposition into sulfur dioxide and hydrogen sulfide which contribute to corrosion. Hydrazine removes dissolved oxygen without increasing dissolved solids at high pressures with the following reaction: NIHd + 02 2H20 + N2

High residuals of hydrazine in the water must be avoided to prevent the decomposition-product ammonia from attacking copper-bearing alloys in the system. Reused water that is high in acidity must be treated to maintain a proper alkaline environment in which the pH is between 10.5 and 11.0. Bicarbonate alkalinity in the boiler can hydrolyze under the action of heat, and liberate carbon dioxide, which will be carried along with the steam to form a corrosive carbonic acid product with the condensate in process heat exchangers or condensate piping. Present-day practice calls for water treatment to prevent corrosion in the recycling system by means of neutralizing or filming amines. Neutralizing amines combine with CO1 and neutralize its acidity. Filming amines do not combine chemically but act by forming an impervious, nonwettable film on metal surfaces which acts as a barrier between metal and condensate, preventing both oxygen and carbon dioxide attack. Steam systems in which the bulk of condensate is unrecoverable are more often subject to difficulties caused by scale-forming sub stances. The makeup water invariably has constituents which will be scale-forming when present in the water in concentrations in excess of their solubility. Some materials exhibit a decrease in volubility with an increase in temperature, and the scales commonly deposited in boilers belong to this class Chemical treatment in the preboiler system is successful in reducing most scale-forming substances to a soft sludge, which is removed before it can enter the boiler, while sludges formed by internal treatment may be collected in quiescent zones of the boiler and removed through blowdown pipes. Water recovered from process heating causes foaming within the boiler from the presence of organic, inorganic, or insoluble materials, when they are present in sufficiently large quantities. Oil and the products of decomposition of sewage and humic matter are the chief causes of foaming, and these products should be strictly excluded from condensate returns. The foaming effect of these materials is especially true in the presence of high alkalinities, and the alkaline concentration of boiler water should be limited for this reason. Table 9-53 summarizes recommended limits for impurities in water used in boilers. Continuous or intermittent blowdown of the boiler water to keep concentrations below recommended limits is the most effective way of preventing foaming. When the blowdown

9-76

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

leaving behind the higher-boiling-point fractions, which carbonize. When this begins, the carbon forms a skin on the heating surface of the vaporizer, and this increases the thermal resistance so that decomposition is greatly accelerated. In this manner, a Dowtherm vaporizer may be filled completely with carbon in a few hours. To prevent overheating and decomposition, Dowtherm vaporizers are of liquid-tube or fire-tube natural-circulation design or liquidtube forced-circulation design. Small laboratory vaporizers are frequently heated by electricity. A natural-circulation vaporizer as in Fig. 9-81 is arranged with few bends or restrictions to allow fast recirculation of the Dowtherm liquid, and is designed with ample furnace capacity. Good flame-shape control prevents hot spots from forming along the vaporizer tubes. Dowtherm E, a specially processed o-dichlorobenzene which boils at 177OC (SOOF) and has a freezing point below zero, is commonly used between 177 and 260% (350 and 5CUF). No trace of decomposition of Dowtherm E has been noted in tests conducted at temperatures and heat loads considerably higher than those recommended for commercial installations. There is some evidence that aluminum can catalyze the decomposition of Dowtherm E to form hydrochloric acid. This acid is likely to corrode severely the polished surfaces of precision tools, machines, and sheet or formed metals. Aluminum should not be used with Dowtherm E. Znorganic Salta Molten mixtures of inorganic salts, one of which is a eutedic consisting of 40 percent NaNOs, 7 percent NaNOs, and 53 percent KNOs, are widely used in salt baths and petroleum refining when high temperatures are maintained and when the system is kept in continuous operation. A melting point of 14VC (288F) precludes their use in low-temperature systems and requires that the circulating fluid be kept hot and molten throughout its Bow path. The salt mixture need not be pressurized higher than required to overcome the pressure drop of the system. Inorganic-salt mixtures are nontoxic and chemically stable up to 427 to 454C (800 to 850F) in the absence of contaminants. Between 454 and 593% (850 and llWF), which is the maximum operating temperature, the salt undergoes a slow thermal decomposition, which is largely a thermal breakdown of the nitrite to nitrate, alkali metal oxide, and nitrogen: 5NaNOp 3NaNOs + Na20 f NI

TABLE 9-53

Recommended limits for Boiler-Wahr Constituents

Parts per milhon

NOTE:To convert parts per million (by weight) to micrograms per liter, multiply by l/198; to convert pounds per square inch to kilopaxaln. multiply by 6.695

results in large quantities of heat being lost to the system, much of this heat may be recovered by passing the blowdown through heat exchangers used to heat feedwater or air, which returns some of the heat to the unit.

THERMAL-LIQUID

SYSTEMS

Thermal liquids used for process heating and cooling may be in the form of liquids, vapors, or a combination of both. In addition to steam, thermal liquids include hot water, mercury, NaK, diphenyldiphenyl oxide (Dowtherm A), odichlorobenzene (Dowtherm E), molten salt mixtures, mineral oils, arylaryloxysilane (Hydrotherm 750-200), tetraaryl silicate (Hydrotherm 700-160), and chlorinated biphenyls (Therminols). Physical properties of these materials are given in Table 9-54. High-temperature hot water is a favorable system for process temperatures of 149 to 204% (300 to 400F) but requires pump pressures greater than the saturation pressure of 17.5 kg/cm (250 Ibf/in*) to maintain the water in liquid form. Hot-water systems are stable, with simple equipment, and easy to control. Corrosion is at a minimum when air is excluded from the system. Deleterious solids in the water do not build up to high concentrations in the absence of evaporation, and scale formation and foaming are at a minimum. Dowtherm A (Dow Chemical Company) presently dominates the 204 to 399C (400 to 750F) field of indirect process heating. This &id is an organic compound of high heat stability, a eutectic mixture containing 73.5 percent diphenyl oxide and 26.5 percent diphenyl by weight. At its freezing point of 12.2C (54OF) Dowtherm A contracts slightly, thereby removing the possibility of damage to process equipment when shut down under cold-weather conditions. At room temperatures it is a clear, almost colorless liquid, which darkens rapidly in use without change in physical characteristics, and has a characteristic rose-geranium odor. It does not react chemically with metals commonly used in heat-transport systems and is not toxic to humans, presenting no appreciable hazard to health in heat-transfer use and requiring no special precautions. Dowtherm A is quite stable at moderately high temperatures. Many vaporizers and accessories have operated for years at Dowtherm temperatures of 343OC (65OOF) with no decomposition. At higher temperatures decomposition may occur in two ways. Above about 399% (750F) two molecules of diphenyl may react to yield one molecule of p-diphenylbenzene and one of benzene. The pdiphenylbenzene dissolves in Dowtherm A, but the benzene, being a noncondensing vapor in practical Dowtherm heating installations, escapes into vent pipes. There is a similar reaction in the case of diphenyl oxide. The second form of decomposition is more troublesome When Dowtherm A is severely overheated, such as by tlame impingement on the tubes of a vaporizer or by forcing the heater beyond its rated capacity, complete decomposition into carbon and hydrogen may take place. The formulation of carbon occurs when inadequate circulation caused by the accumulation of materials holds the Dowtherm in a stagnated condition. The lighter fractions then distil1 off,

Liquids and Their Properties

This reaction is evidenced by the slow evolution of nitrogen gas, and it is accompanied by a gradual rise in the freezing point of the mixture [Alexander and Hindin, Ind. Eng. Chem., 39, 1044 (1947)]. The nitrite is also subject to slow oxidation by atmospheric oxygen above 454OC (85OOF) with formation of sodium nitrate. This reaction is eliminated by excluding air or blanketing the salt with an atmosphere of inert gas such as nitrogen. Other reactions will gradually alter the composition of the salt: (1) absorption of carbon dioxide to form carbonates which may settle out in the system; and (2) absorption of water vapor to form alkali metal hydroxides. These reactions do not interfere with process operation but if allowed to continue will ultimately affect utility of the system. They may be eliminated by blanketing the molten salt with nitrogen. Ordinary carbon steel may be used successfully in molten-salt equipment up to 454% (850F). Above this temperature more resistant alloys are recommended. Copper equipment has been used satisfactorily at moderate temperatures, 316V (SOOF), but cast iron is not recommended because of a reaction between the molten salt and the iron which results in embrittlement or fissuring. Mineral oils Conventional mineral oils are of low cost and readily available for process use and are valuable in systems operating from - 1.1 to 316C (30 to SOOF). They need not be pressurized in this range. The paraffinic-type cylinder oils are often employed in open systems to about 232C (450F), such as are used in tempering metal. At higher temperatures the conventional mineral oils are used in closed systems, up to 316C (SOVF), in which temperature region the oils become susceptible to thermal cracking. This decomposition, similar to the controlled cracking process used to produce gasoline from heavy oils, is not nearly so severe as the cracking that occurs in petroleum refining but will produce volatile materials that reduce

TABLE 9-54

Ph+cal

Prowrties of Thermal Fluids

Dowthem A

Thmal

Specific gmvity at 212E : Melting point, F. F. (am. prarure, Flub pint. COC. F. heat of hquid. B.t.u.;&F.) : : : Hut of vqmiutio. B.t../lb. Heat of fusion. B.l.u./lb. Cube,1 erpmi coeffiwnt Absolute vkccsily of liquid. centipoise Surface term (cantact with ati). dynes/cm. cmductiwty hqud. B.t .,(hr.)(q. h.~F./R.)

Boding point. Speeik

::

165 147 0.997 1.191 53.6 -6.7 495.8 352 255 l.OWZ12F.) O.S28(496F 0.4,2$2F .) 970.2 125.0 119.0 143.3 64 39 Oar24 O.maU 0.2B4(212F.1 O.LW&WOF 0.30(4OOF. ) 72.8 43 37 0.393 0.078 0064

18 0.958 32 212

The Dow Chemical Company. f E. I. du Pont de Nemoun h Co.. Explosives Department, Wilmington, De1 1 Mobil Oil Corp. QAmerican Hydrotherm Corp. 1 Monsanto co. NOTE: To convert British thermal nits per pound-degree Fahrenheit to joules per kilogram-kelvin. multiply by 4.187 X Id; to convert atmospheres tokilograms per square centimeter, multiply by 1.0333, to convert British thermal units per pound to kilojoules per kilogram, multiply by 2.326; to convert centipoise to grams per centimeter-second, multiply by 0.01; and to convert British thermal units per hour-square fee-degrees Fahrenheit per foot to watts per square me!e-kelvin. multiply by 5.678. C = (F - 32) X %.

I
WK,

Dowtherm E

Fused Salt HI Tect NsNO,

NaNO,

011 Mobiltherm 6001

Oil Mobiltherm Ii&t

Hydrthern$ 75wxm

Hydrotherm$ 700-180

Therminoll FR-2

Mercury

NaK 44 wt.% K

Hg

KNO, 92 1.9!,(3OOF.) 0.90 288 20 (po, point) .,.......... >@JO 0.373000F.) 35 O.lXO20 1.7(BWF.) 035 0.5BO$%F )

0.930

-20 (pour point: >a 250 0.5WOOF.)

5 (P

1.11 PQ

108 40 (pw p0i.q ,..... 0 64(5OOF.)

1.38 20 (p paint) 644 ,.33.$&F.)

475 O.WrnL)

O.ooo35 O.XS&WOF) 0.067

OClKl35 0.87&300F.) 0.0652 0.572z0E O.OYN

0 6tW0OF.l

O.OOlU9 0.63(5OOF.) 0.057

0.972

9-78

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

als, copper, and copper alloys. There is a slight attack on aluminum and magnesium metals. Hydrotherm organosilicate heat-transfer tluids are applicable for heating and cooling operations from -4.56 to 357C (-50 to 675OF). Since these lluids do not freeze and stay pumpable below -17.8OC (OOF), neither reheating nor steam tracing is required. Hydrotherm silicate heat-transfer tluids are noncorrosive toward mild steel and copper and its alloys, even at high temperatures. However, magnesium, aluminum, zinc. titanium, and their alloys are attacked. Organosilicate liquids do not present a potentially serious fire hazard. Hydrotherm 700-160, a tetraaryl silicate, is an ambercolored liquid with a slight phenolic odor that has good thermal and chemical stability. It does react with oxygen, and so contact with the atmosphere should be avoided. In the presence of moisture hydrolysis takes place; free phenols are released and a silicate sludge is deposited. Thermally, a re-forming reaction occurs at elevated temperatures, above 357C (675F). Low-boiling products, primarily monohydric or dihydric phenols, are formed and a gradual increase in viscosity occurs. Therminol FR heat-transfer liquids are a series of chlorinated biphenyls of increasing chlorine content. Many important physical characteristics such as viscosity, density, and pour point vary from lowest- to highest-molecular-weight members of the series. One reason for their succes as a heat-transfer medium is that they do not support combustion. Their spontaneous ignition temperature is about 649C (1200F). Therefore they can be considered fire-resistant. These compounds are relatively inert liquids, resistant to the action of water, dilute alkalies, dilute acid solutions, air, and oxygen. They are readily soluble in most of the common organic solvents and drying oils. All these &ids are stable below 316OC (600F). At higher temperatures thermal decomposition takes place, higher polyphenyls are formed, gaseous HCI is liberated, and viscosity increases. The vapors at high temperatures are at a level of toxicity such that adequate provision must be made for ventilation when leakage occurs, and system vents should be remote from normal operating areas. Although the compounds are not severe skin irritants, they should not be in repeated contact with the skin. Because of its low pour point, Therminol-FR-2 is widely used at temperatures between 10 and 316V (50 and 6COOF). Mercury is useful in thermal-liquid systems. Its stability as an element makes it suitable for high temperatures, in the range of 316 to 538OC (600 to lOC@F). Experimental work shows that it has no corrosive effect on metals commonly used in practice. Mercury is toxic to humans, and mercury systems must include elaborate precautions to prevent the escape of mercury vapor to the surrounding atmosphere. The low latent heat of vaporization of mercury makes it unattractive to use as a vapor at low temperatures when heat must be given up during condensation. The high cost of mercury, in comparison with other thermal liquids commercially available, precludes it use at temperatures below 316V (6OOOF). Sodium-potassium alloys are used for heat transfer instead of the pure elements because these mixtures have lower melting points. The two most popular alloys are, by masts percent, 56 Na-44 K and 22 Na-78 K. The latter is approximately the eutectic composition. In comparison with the pure elements, NaK alloys have a lower thermal conductivity, whereas vapor pressure, density, specific heat, and viscosity fall between values of the two elements. The chemical prop erties of NaK alloys are almost identical to those of sodium; however, the alloys are more reactive. Increased chemical activity can be ascribed to the presence of potassium, which has a greater reactivity than sodium. Upon contact with the atmosphere, potassium is oxidized to the superoxide, KOz; and explosions have been caused by reaction of the superoxide with hydrocarbon gases used as cleaning media. The use of hydrocarbons in NaK systems should be discouraged. Experiments at 204OC (400F) have revealed that sodium monoxide, rather than potassium superoxide, precipitates from NaK alloys. Other reactions of potassium not duplicated by sodium are an attack on silicon and the formation of an explosive carbonyl on contact with carbon monoxide. Carbon steel and low-alloy steels show good resistance to attack up to 538C (lOCWF), and they can sup plant more expensive stainless-steel alloys. Oxygen impurities above

Explosion port \

flG. 9-81

Dowvtherm vaporizer. (Foster Wheeler Corp.)

the flash point of the oil. At the same time, the decomposition yields heavier products, which after long periods of operation flow less readily, leading to formation of coke deposits. Mobiltherm 600 and Mobiltherm Light (Mobil Oil Corp.) are aromatic mineral oils of lower viscosity than conventional mineral oils and can operate between - 1.1 and 316% (30 and SPOOF) for the former and at -25C (-15F) but not above (400F) for the latter. They will not be broken down by temperature when used in the recommended range. Their tlash points thus remain unchanged after many hours of service life. When the aromatic oils are subjected to excessive temperatures, thermal cracking will occur in a form similar to the decomposition of conventional mineral oils. Sludge and coke deposits do not readily occur with such aromatic mineral oils, as they have a powerful solvent action, and some installations have operated for years without changing oil or cleaning the system. Neither aromatic mineral oil is suitable for operation in an open system, in direct contact with air. Oxidation results in deterioration of the oil, a chemical breakdown that is accelerated when the oil is at an elevated temperature. All process systems must include a coldoil expansion tank, in which the temperature of the oil will not exceed 54V (130F). The expansion tank prevents the hot oil of the process system from coming into contact with air. The aromatic oils should not be used with copper or copper-bearing-alloy parts, since these metals are powerful catalysts which promote oxidation and sludging. Iron and carbon are preferred for the entire system. Other oils, whether lubricating or mineral oils, should not come into contact with aromatic oils, as this causes the solvent power of the oil to be lowered and may result in harmful sludge being deposited in the system. Silicon Compounds Three types of silicon compounds are in use as heat-transfer media: silanes, silicones, and silicates. Silanes are substituted hydrides of silicon; silane itself has the form SiH,. The silicone Euids in use are usually polymers. The basic structure is of the form Si-0-Si, with organic radicals attached directly to the silicon atoms. Silicates are the salts or esters of the silicon acid in which the central atom is silicon. The organic heat-transfer fluids are generally esters. The organic constituents usually comprise alkyl, aryl, or alkaryl groups. Hydrotherm 750-200 is an arylaryloxy- (mixed) silane used at temperatures from 63 to 371C (145 to 7GPF). It is a transoarent amber fluid with a slightly phenolic odor. There appear to be no chronic or other pathological effects from exposure to vapors; skin tests show dermatitic effects similar to those of phenol. The substance is lethal on injection or ingestion. There is negligible corrosion in ferrous met-

THERMAL-LIQUID Process Systems

SYSTEMS

9-79

Dowtherm Dowtherm process sytems are either gravity-return or pumped-return. The most desirable system is the gravity system,
in which the vapor rises from the vaporizer to the heated vessels, condenses, and flows back to the vaporizer by gravity. No moving

li

ri I
1 Temperature 1 controller,

B-?-

storage tank

Drains to

I
H 1 p. \-------AC-

W. 9-92 Dowthem~ gravity-return system. V. C = maximum and minimum liquid levels in vaporiser drum; M, H = range of liquid heights in condensate leg between A and B to cause flow through system. Dotted lines show the vapor path; solid lines, the liquid path. (Faster Wheeler Corp.) 100 ppm markedly accelerate corrosion. Alkali metals react with the skin and eyes, causing thermal and alkali burns. Oxide smoke or hydroxide mist is irritating and corrosive to the throat and lungs. Toxicity Many instances of potential hazards have been described in this discussion of heat-transfer &ids, and this paragraph is intended to emphasize the problems. Toxicity and ecology are extremely important from both an operating and a process standpoint. There is always a chance that a beat-transfer fluid will leak from a system, e.g., packing glands on valves, pumps, and heat exchangers. If this happens, operators, maintenance personnel, and the environment in general may be overexposed to fluids known to be hazardous. Polychlorinated biphenyls (PCBs), especially, must be used with great caution.

parts are required. It is essential that the gravity-return-system pip ing be suitably proportioned to the limitations of the headroom available between the bottom of the heated vessel and the liquid level in the vaporizer. This involves the frictional loss in the vapor piping, the user, and the condensate return. Figure 9-82 is a gravity-return system, and Fig. 9-83 shows the pumped-return system. Pumps should generally be of cast-steel construction with a deep watercooled stuffing box designed for metallic-foil packing. Transport of heat at two different temperatures may be accomplished with Dowtherm in a single vaporizer by supplying the higher-temperature process with vapor and the lower-temperature process with Dowtherm liquid. Close control of the vapor temperature is achieved by maintaining the pressure in the vaporizer, while the liquid temperature is controlled by circulating only part of the process returns through the heating unit. In such an installation, illustrated in Fig. 9434, the Dowtherm vaporizer provides vapor at the desired temperature for two high-temperature users. A liquidDowtherm circulating system heats the low-temperature users. In this system, the hot liquid is withdrawn from the vaporizer and returned to it after passing through the heating elements of the vessels. A three-way valve, which divides the return-liquid flow, provides automatic control of the liquid circuit. Part of this flow returns to the vaporizer to be reheated, while the remainder bypasses the vaporizer and flows directly to the circulating pump section. The amount of heat put into the liquid system is controlled by varying that part of the flow returning to the vaporizer. As Dowtherms have extremely low surface tension and viscosity at high temperature, more than ordinary care is necessary in the fab rication and erection of equipment to prevent leakage. There is ordinarily more or less evidence of leakage at pump stuffing boxes, relief-valve outlets, etc. Welded construction in accordance with ASME specifications is advisable whenever possible. The wide range of temperature requires adequate provision for expansion of piping. The high temperature renders ordinary relief-valve springs unsafe, and only special tungsten-steel-alloy relief-valve springs are suitable. Other relief-valve parts and other fittings should be steel rather than brass or bronze. The condensate line of a gravity-return system should include the *called Hartford loop. This consists of a line connecting the lower vaporizer drum and the vapor space above the upper drum. The con-

Heating

r------------~--------~-------~

Storoqe
Ro. 9-92 Dowtherm

Ionk system.

pumped-return

(Foster Wheeler Corp.)

9-80

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

ermostat-controlled

st;;,e$!
FIQ. 9-U

charge
pump

Cwculcting Pump (Foster Whm&r Corp.)

Combination vapor and liquid heating with Dowtherm.

densate return is brought into this line at a point just above the top of the tubes in the vaporizer. With this loop it is impossible to draw liquid out of the vaporizer up through the condensate line after the liquid level in the vaporizer falls below the point at which the condensate line enters this connection. If the liquid level is drawn lower than this point, vapor will be drawn back into the condensate line, and the resulting water-hammer effect will give warning that the liquid level is too low. Other recommended safety features include installation of a storage tank of sufficient capacity to contain the entire system charge. It should be buried or otherwise located where not exposed to fire. The drain valve from the vaporizer should be accessible so that, in the event of an uncontrollable vaporizer fire from a tube leak, the liquid in the vaporizer can be drawn off promptly. Emergency drainage of the vaporizer requires considerable judgment, however, since damage to dry heating surfaces from burning fuel may cause considerably more damage than would result from a relatively small Bre or tube leak. RecycledDowtherm needs no treatment to maintain purity. Periodic analysis is recommended to detect contamination or deterioration Repurification requires shipment of the complete charge to the reprocessing plant. For this reason remote locations ftnd it economical to install continuous-reclamation equipment in the process plant. Zmrganic Salts Inorganic-salt mixes are heated electrically for pilot-plant units and for larger processes in gas- or oil-fired units with capacities up to 4396 kW (15 million Btu/h). They may be either fire-tube or circulating furnace design. In each design the initial charge is melted by means of steam coils or electric immersion heaters. For moderate heating applications, to about 316% (6CUF), an

indirect salt-bath heater, including both the molten salt and a flow coil for the product to be heated, is placed in a ftre-tube design (Fig. 9-85). Gases passing through the fire tube maintain the salt in a molten state with precise control over the temperature of the product passing through the Bow coil. Advantages for this indirect heater are its safety of operation, even heat distribution to the tlow coil, high efficiency, and elimination of Bow-coil failure because of flame impingement or localized overheating. The maximum size of these heaters of 2344 kW (8 million Btu/h) can be supplemented by installing several heaters in battery fashion. Heating and cooling are accomplished in one unit, shown in Fig. 9-86, for processes in which reactions taking place at a high temperature level require removal of exothermic heat. Once the salt initiates the exothermic-process reaction, it maintains the reaction temperature by switching the flow of molten salt from the heating unit

Ao.

9-85

Fire-tube salt-bath heater. (E. I. du

Pant

de Nemours

G Co.)

RG. 9-w Circulating-salt system for heating and cooling operation. (Bethlehem Corp.)

COGENERATION to the steam generator that is mounted integrally with the heating unit. By means of a three-way valve, all or a portion of the salt flow can go to the cooler. Controls on the system maintain temperature levels by forestalling pump operation when the salt temperature falls below the desired level and sounds an alarm if the salt temperature exceeds a safe limit of the process. because of the high melting point of the inorganic-salt mix, salt lines and valves must be traced or steam-jacketed to prevent freezing by solidified salt, especially for intermittent operation. Submerged centrifugal pumps are used to circulate the salt and are of a type which permits no contact of the salt with the packing gland. Remelting of salt, or fusing of the initial charge, is done with electric immersion heaters or steam coils that pass below the surface of the bath. Heating a solid bath of salt from the bottom alone can develop sufficient pressure to rupture equipment or expel the molten salt through the solid surface. Combustible solids, such as wood, coke, paper, plastics, cyanides, chlorates, and ammonium salts, and active metals, such as aluminum and magnesium, are potential hazards. Magnesium, except as an alloying agent in low concentration, must not come in contact with the salt mix. The salt itself is not flammable but will support combustion Water from spray sprinklers or low-velocity fog nozzles is recommended as fire protection. Mineral Oib Conventional mineral oils are not affected by contact with air at temperatures of about 232OC (450F), but aromatic mineral oils must always be used in a closed system with a cold-oil expansion tank to prevent the hot oil from contact with air. Figure 9-87 is a layout for indirect heating with hot-oil recirculation. The heater may be direct-fired, with combustion gases passing over the tubes through which the heated oil circulates, or electrically heated, with the oil Rowing through narrow channels over the heating source. Other heater designs utilize high-temperature steam passing through heating coils with the circulating oil outside. The heat source must be such that excessive temperatures are avoided. Large heating-surface areas and moderate temperature differences between the oil and the heat source are preferred to minimize thermal breakdown of the aromatic oil. In electric heaters this is achieved with a power input of not more than 1.9 W/cm* (12 W/in) of heating surface; for oil- or gas-fired radiant heaters the input should not exceed 126 to 158 kW/mx [40,000 to 50,OCQ Btu/(hfta)] of coil surface. All hot-oil systems use forced circulation because of the absence of gravity-head differences between heated and cooled oil. Centrif-

9-81

ugal pumps are usually supplied with exterior lubrication of the shaft bearings to prevent lubricating oil from entering the system. The pump should have sufficient capacity to provide a velocity through the heater of not less than I.2 m/s (4 ft/s) for oil temperaures up to 204C (400F) and about 3.05 m/s (10 ft/s) for 204Y (600F). A thermostat maintains the desired temperature in the process vessel and acts to cut out burners or electric current in the heaters when oil temperatures rise too high. To prevent constant on-off switching of the heaters a relief valve is supplied to act as a bypass and maintain a constant flow of oil through the pump and heater when the thermostat reduces the Bow of hot oil to the processing vessel. Reuse of aromatic mineral oils is continuous, with losses from the system being replaced by identical oil added to expansion tank or pump suction, Periodic analysis and comparison with initial properties will determine service life. Therminol Fluids Two basic heater designs for Therminol fluids are available: the liquid-tube types and the fire-tube types. In the former, the Therminol is pumped through the tubes at a definite Bow rate as it is heated. In fire-tube types, the fluid flows through the shell. When operating temperatures above 260C (5CPF) are required, a liquid-tube-type heater is preferable unless a specific design is devised to force a steady flow over the heat-source surface. The fluid should be pumped over the heating surface so that no areas of stagnant fluid which might present hot spots occur. The fluid velocities over the heat-sour. e surface should be in in the range of 1.2 to 3.05 m/s (4 to 10 ft/s). When electric heating is used, maximum energy density should not exceed 1.6 W/m* (10 W/in*) at the minimum velocity, although 3.2 W/m* (20 W/in) can be used with proper design and sufficiently high velocity. For large how rates, the iluid circulating pump should generally be the centrifugal type. When gear pumps are used, care should be taken to select a capacity that will give adequate Bow through the heater even after wear. If expansion loops are used in the pump suction piping, they should be arranged to prevent trapping air or noncondensables. Like most organic liquids, Therminols expand in volume by about 4 percent per 37.8OC (lOOoF) temperature rise.Thus, in heating from room temperature to 3IfYC (66VF), the tluid in the system expands by about 20 percent. The expansion tank must therefore accommodate this increase in total tluid volume; doubling the minimum size is recommended It should be on the pump suction side, above the highest point in the system, and should be connected to the system by a sufficiently small line to avoid thermal recirculation. Major venting can be done from the expansion tank. The vent should be outdoors, away from working areas. The entry of atmospheric moisture on breathing should be prevented by use of an air dryer, such as a calcium chloride pot or other desiccant. An alternative would be to blanket the expansion tank with nitrogen, but this system must be thoroughly dried. In systems using Therminol above 316OC (600F), some provision must be made to vent any HCI gas formed in the system and to assure that the system remains dry. It is advisable to provide a pipe to feed a small sidestream of hot Therminol from near the pump discharge to the vented expansion tank, above the highest liquid level. It is advisable to trace and insulate the expansion tank and vent so that any moisture accidentally entering the system will remain as yapor and not condense. COGENERATION Cogeneration is an energyDefinition and General Description production process involving the simultaneous generation of thermal (e.g., process-steam) and electric energy by using a single primary heat source. It can be employed whenever there is a need for the two energy forms and whenever on-site electric power generation is justified or when thermal-energy users are in close proximity to an electric-power-generation site. Industrial use of cogeneration leads to small, dispersed electricpower-generation installations-an alternative to complete reliance on large central power plants. Because of the relatively short distances over which thermal energy can be transported, process-heat

P, pressure

gage

T, thermometer

FtG. 9-87

Typical hot-oil circulating system. (Mobil oil Corp.)

9-82

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION Furthermore, cogeneration systems will usually not match the varying power and heat demands at all times for most applications. Thus, a cogeneration systems output frequently must be supplemented by the separate on-site generation of heat or the purchase of utility-supplied electric power. Another option is the sale of excess locally generated electric power to the local utility grid-a situation which can occur when the cogeneration system is matched to the heat load and on-site electric power demand is low. These options for on-site power and heat use are also illustrated by Fig. Q-88. Fuel-use options for cogeneration systems are determined by the primary heat-engine cycle. Closed-cycle power systems which are externally fired, such as the steam turbine, the indirectly fired opencycle gas turbine, and the closed-cycle gas-turbine power system, can use virtually any fuel which can be burned in a safe and environmentally acceptable manner; fuels such as coal, municipal solid waste, biomass, and industrial waste are burnable with closed power systems. Internal-combustion engines, such as diesel engines and open-cycle (combustion) gas turbines, are restricted to fuels which have combustion characteristics compatible with the engine type and which yield combustion products clean enough to pass through the engine without damaging it; refined liquid and gaseous fuels derived
from petroleum, shale, coal, or biomass are included in this category. These heat engines and fuel options are illustrated in Fig. 9-89.

generation is characteristically an on-site process, with or without cogeneration. Fuel saving is the major incentive for the use of cogeneration. Since all heat-enginebased electric power systems reject heat to the environment, that rejected heat can frequently be used to meet all or part of the on-site or local thermal-energy needs. Use of rejected heat usually has no effect on the amount of primary fuel used, yet it leads to a saving in all or part of the fuel that would otherwise be used for the thermal-energy process. Heat engines also require a high-temperature thermal input and in some situations can obtain the input thermal energy as the rejected heat from a higher-temperature thermal-energy process. In the former case, the cogeneration process employs a heat-engine topping cycle; in the latter case, a bottoming cycle is used. The fuel-savings benefits in a topping-cycle configuration are illustrated in Fig. Q-88. &generation systems can be designed from at least two perspectives: they can be sired to meet the process-heat needs of industrial or institutional users, so that the electric power produced is treated as a by-product which must either be used on site or sold to the local utility; or cogeneration systems can be sired to meet electric power demand, and the rejected heat is then used to supply process-heat needs at or near the site. The latter approach is the likely one if utility ownership is involved.

Conventional approach

Energy demand

Fuel, OFP =OE/'lP) ---'--7 (0, -Q,,,)'q,

-.-.-.L .__._

e%-+--7

Utility power plant lheot engine) (n.1

OE -.--.-.-.._ '\

EkCiflCpower demand.

! 1

I ~ OE
I
Key
I)= energy convewon efficiency 0 = energy flow

Off-site
On-site

waste

heat*-

Ro=

/
O,I!/?)e-1)

> ,-~>(OH-OHE)X I ,A (1+,-l)

, Process zoce demand. OH OHE Recoverable waste heat J

power-to-heat ratlo for the load demand (R,= OE/O"l power-to-heat ratio for the heot engine tRHE =OEE/%EI

RHE=

Supplemental energy flows: Case 1' heotenoine matched to elec&ic demand. Of, ond R,,>R,:I~X> / Cose2: heotenglne matched toheot demandLOu, and R,E< R,:_.:'X

-.---7

*Includes combustion stock losses.

.____________---/ \ \- t ~+GiGt3
Parameter Totol fuel used. OF

Ke%tt -

Useful relotlons Cogenerotion (~IOE~~=OE;RHE>R~; opprooch (210,E=0,;R,~<Ro

Convention01 opprooch

Ro. 9-U

Illustrative fuelsavings with cogeneration.

COGENERATION

9-83

Heat-rejection alternotwes

There are at least three broad classes of application for toppingcycle cogeneration systems: . Utilities or municipal power systems supplying electric power and low-grade heat (e.g., 149C, or 300F) for local-district heating systems . Large residential, commercial, or institutional complexes requiring space heat, hot water, and electricity * Large industrial operations with on-site needs for electricity and heat in the form of process steam, direct heat, and/or space heat Typical Systems All cogeneration systems involve the operation of a heat engine for the production of mechanical work which, in nearly all cases, is used to drive an electric generator. The most common heat-engine types appropriate for topping-cycle cogeneration systems are: - Steam turbines (back-pressure and extraction configurations) - Open-cycle (combustion) gas turbines . Indirectly fired gas turbines: open cycles and closed cycles . Diesel engines Each heat-engine type has unique characteristics making it better suited for some cogeneration applications than for others. For example, engine types can be characterized by: . Power-to-heat ratio at design point . Efficiency at design point * Capacity range
for Heat Engines

. Power-to-heat-ratio variability . Off -design (part-load) efficiency . Multifuel capability The major heat-engine types are described in terms of these characteristics in Table 9-55. Representative cogeneration systems appropriate for each engine type are described in the following paragraphs. Steam-Turbine Systems Both back-pressure and extractioncondensing steam-turbine systems can be used in cogeneration applications. Typical configurations are illustrated in Figs. 9-90 and 9-91. The back-pressure configuration is better suited for applications in which the power-to-heat ratio is low and relatively fixed. Extractioncondensing steam turbines offer greater variability of power-to-heat ratio (through changes in the amount of extracted steam) and a higher power-to-heat ratio (when extracted steam is minimized). The extraction-condensing cycle must always condense the steam Bow which passes through the full-pressure ratio of the turbine; the extracted steam may or may not need to pass through the condenser, depending on the temperature limits of the heat load and whether or not it condenses the steam Row. For the back-pressure configuration, the need for a condenser, separate from the heat load, depends, first, on whether the spent steam is available for recycling to the steam generator, and second, on whether the heat load itself condenses the steam flow.

TABLE9-55

&generation

Characteristics Size range, MWe/unit

Engine type
Steam turbine Extraction-condensing type

Efficiency at design point

0.2-0.30 0.20-0.25 0.25-0.30 0.25-0.30 0.25-0.30 0.35-0.40

Part-load
efficiency

Multifuel
capability

Maximum temperature of recoverable heat,

OF(C)

Recuverable
he&fltu 0

Typical power-to-heat ratio

30-300 20-200 lo-loo lo-85 5-350 0.05-2.5

Fair Fair PGlX PO01 Excellent Good

Excellent Excellent PO01 Good Good Fair to poor

200 @!3)-600

(315H

Back-pressure type Combustion gas turbines Indirectly fired gas turbines Open-cycle turbines Clued-cvcle turbines Diesel en&es 1 Btu = tsaturated l&5]. steam

200 (93)~Mx) (315H 1000 (538-1200 (649) 700 (371)~900 700 (371)~900 500 (260-700 (482) (482) (371)

ll,OOO35.000 17,Oca70,000 3090-11,000 35wa500 35Ow35a 4000-6000

0.1-0.3 0.05-0.2 0.3-0.45 0.4-1.0 0.4-1.0 Ox-O.85

9-84

ENERGY UTIUZATION,
STOCk

CONVERSION,

AND RESOURCE CONSERVATION

5 CB

tw

--,

Electric power

&

Combustion-gas-turbine FIG. 9-93 = combo&or; T = turbine.

$ir?i! I
C T Recuperator

tieot load

cogeneration

cycle. C = compressor; CB

Pump

power
Extraction-wndensing-steam-turbine cogeneration combustor; P = pump; T = turbine; --= cycle options.

FIG. 9-90

cycle. CB

Gas-Turbine modynamic

Systems cycle: adiabatic

Gas turbines

operate

on the Brayton

ther

compression, isobaric heating, adiabatit expansion, and isobaric cooling. Gas turbines may be either of thl combustion or the indirectly fired type. In a combustion turbine : clean fuel is burned directly in the compressed-air working fluid and the combustion products are then expanded through the turbin and exhausted to the atmosphere. Indirectly fired turbines receiw their thermal input via an external combustor and a heat exchanger so that none of the combustion products pass through the turbine The combustion turbine must be an open cycle; that is, one in whicl the working fluid (in this case, air mixed with combustion product in the turbine) is not recycled and compressor inlet and turbin exhaust are at atmospheric pressure. Indirectly fired gas turbines dc not contaminate their working fluid with combustion products ant can therefore recycle the working &rid, allowing the cycle to b either open (to the atmospheric intake and exhaust) or closed. Closet gas-turbine cycles offer distinct advantages in terms of choice o working fluid and system pressure level. The two classes of gas-tur bine co eneration systems are illustrated in Figs. 9-92 and 9-93. Corn Ls tton gas turbines. The combustion-gas-turbine systen
(Fig. 9-92) provides a higher power-to-heat ratio than typical steam

Usually a gas or light liquid with virtually no ash, sulfur, or heavy metal present.

turbine configurations (see Table 9-55). Of all systems considered, the combustion gas turbine also provides rejected heat at the highest temperature [up to 650% (12OOF)j However, the waste heat in the turbine exhaust cannot generally be used directly, because of the presence of combustion products, and must be removed by means of a heat exchanger or a boiler. While low in capital cost, combustion gas turbines have the drawbacks of poor part-load efficiency and the requirement for clean fuel to avoid erosive or corrosive damage to the turbine. Indirectly fired gas turbines avoid Indtwctly fired gas turbines. the problems of fuel sensitivity of combustion gas turbines. Otherwise, the major advantage of indirect firing is the possibility of using a closed- (pressurized-) cycle configuration. Closed-cycle gas turbines, as illustrated in Fig. 9-93, can be coupled to a gas-management system which adjusts the working-tluid inventory (hence, mean pressure level) so that load tluctuations can be accommodated with little or no loss in efficiency. This latter feature is a consequence of the fact that load variations are met by changes in density without the need to change temperature, pressure ratios, or relative velocities in the turbomachinery. Power-to-heat-ratio variations over a relatively wide range (see Table 9-55) are accommodated by varying the recuperator-bypassRow fraction. With no recuperator bypass, a maximum power-toheat ratio is obtained. Combustion gas turbines may similarly be recuperated (see Fig. 9-92). Diesel Engines Diesel engines have long been used in smallscale (e.g., l- to lO-MWe) cogeneration applications. They are characterized (see Table 9-55) by high engine efficiency, good part-load

Electric

Heat load

*-------;_ c 3-i
steam use r--1 Back-presure-steam-turbine cageneration cycle. CB = cumbu!

Open-cycle
OptIon *For closedcycle Only

FIG. 9-91 tor; P =

pump; T = turbine; --- = cycle options.

Indirectly-fired-gas-turbine cogeneration cycle (closed-cycle FIG. 9-93 figuration shown). C = compressor; CB = combustor; T = turbine.

con-

COGENERATION
Stock qos (exhaust) ,Electric Dower Heat

9-85

the power-toheat ship is given by

ratio R supplied by the heat engine. This relation-

(h@

Heat load (low temp.) FIG. 9.94

Diesal-engine cogenerntion cycle

and is plotted as a function of A, for fixed values of vs. in Fig. 9-95. For large values of Ii, nw approaches nx, as the useful-heat portion of the engine output goes to xero and the engine reverts to a conventional, noncogenerating operating mode. For low values of R, 7, rises to unity as the power-to-heat ratio drops to the minimum value Rmi,when all the rejected heat from the engine is fully utilized. R,, is given by &II - Ix/(1 - 9x) (9-48)

characteristics, a relatively low rejected-heat temperature, and a high power-toheat ratio. As an internal-combustion engine (the working iluid is, in part, made up of the combustion products), the diesel offers only a limited tolerance for fuel variability. Diesels supply heat in two forms: low-temperature (93 to 121C, or 200 to 25OF) engine coolant; and higher-temperature (260 to 371C, or 500 to 7OPF) exhaust gas. The diesel engine as a cogeneration system is illustrated in Fig. 9-94. EnergySaving Potential The energy-saving potential of an onsite cogeneration system can be analyzed in the manner illustrated by Fig. 9-88. An on-site energy demand for electricity and process heat is conventionally met through the purchase of electric power, generated by an off-site heat engine (usually a steam-turbine cycle) at a central utility, and the burning of fossil fuel in an on-site boilersteam generator. When cogenerating, an on-site heat engine supplies all or a portion of the electricity demand, while the heat demand can be supplied, at least in part, by the rejected heat from the heat The fuel-saving potential for a heat engine having an efficiency [from fuel (HHV) input-to-shaft power output1 nx can best be estimated by the overall efhciency [fuel (HHV) to-useful work and power] nm of the cogeneration cycle, which is, in turn, a function of High heating value.

Equation (9-48) applies to an internal-combustion engine, such as a combustion gas turbine or a diesel engine, or to an external-combustion (i.e., indirectly fired) engine in which all rejected thermal energy, relative to the ambient reference, can be removed, including the energy in the stack gases from an external combustor. In most cases it is not practical to extract 100 percent of the available thermal energy, especially from the combustion-product stream of a dirtyfuel combustor. If that combustor has an efficiency [fuel (HHV) to heat delivered to cycle working fluid] ns, then the maximum overall efficiency is ~)a, not unity, and the minimum value for the power-toheat ratio R,, for such an external combustion cycle is given by ILL,, = tlE/(% - I)E) (949)

For the cam of a heat-engine efficiency of 30 percent, including combustor losses as defined by a value of ns = 0.85, values for A,,. and A& are illustrated in Fig. 9-95. Figure 9-95 is useful as a means for estimating overall-fuel-use efficiency and its dependence on the delivered power-to-heat ratio for a given heat-engine efficiency. It is not intended as a substitute for a cogeneration-performance prediction for a particular cogeneration system. The limitation of Fig. 9-95, in this regard, is due to the fact that for most of the heat-engine cycles considered here (the diesel engine being the exception) the efficiency of the heat engine nx is a function of the power-to-heat ratio R. For instance, the engine effi-

r)~=

Heat-enqlne
(HHV)to

effnency, shaft power efflclency

fuel

~~=Combustor

I
I
I I
I

I
I I It, 0.5 I 1.0 Power-to-heat ratio, 13 I 1.5

2.0

~0.9-95

overall efficiency of a heat engine in cogeneration mode.

9-86

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION 8, the zeropower throttle-tlow fraction representing leakage and recirculation losses within the turbine To use such a performance map, the value of the extraction-flow fraction r is first determined so that the heat demand is satisfied (r cannot exceed 1.0; if the heat demand requires T to be >l.O, then supplemental heat must be supplied). For the defined extraction-flow fraction r, the throttle flow ff is set to deliver the required power, subject to the constraints on maximum and minimum turbine power output for a given value of r. The performance of an extraction-condensing steam turbine in a typical cogeneration application is illustrated in Fig. 9-97. Zndirectly Fired Gas Turbine The performance of an indirectly fired gas turbine with variable recuperator bypass as a means for matching a power-to-heat-ratio variation is illustrated in Fig. 9 98. The illustrated cycle schematic is for a closed cycle gas turbine. However, the performance envelope is applicable also to open cycles (which would have no cooler or cooling heat load Q.) with the same cycle parameters (temperatures, pressure ratio, component e5cienties, etc.). Since the assumed combustor efficiency is 0.85, this value marks the upper limit on overall efficiency (refer to the discussion for Fig. $95). Overall efficiency is determined as a function of the power-t* heat ratio A, recuperator-bypass fraction A, and gas temperature T, at the exit of the heater supplying the useful heat load Qw. In a partitular cogeneration application, the power-to-heat demand ratio can be supplied by a range of combinations of recuperator bypass fraction A and heater exit temperature T,. However, the desired operating parameters are given by that combination of A and T, which

ciency of an extraction-condensing steam turbine (Fig. 9-91) is a strong function of how much steam is extracted and at what pressure level. A similar argument applies to gas-turbine cycles in which the recuperator-bypass-flow fraction is varied to accommodate a chang ing power-to-heat demand. Typically, heat-engine efficiency vE decreases as the demand for heat rises (R decreases), and heat-engine performance must be compromised to meet it. Such a characteristic is illustrated in Fig. 9-95. Cogeneration Performance of Representative Systems The engineer designing a cogeneration system for a particular application must analyze the performance capabilities of the most appropriate heat-engine types, selected on fhe basis of the characteristics listed in Table 9-55. Examples for two-engine types, an extraction-condensing steam turbine and an indirectly-fired-gas-turbine cycle, both chosen because of their compatibility with coal firing, are presented in the following paragraphs, Extraction-Condensing Steam Turbine The performance of a representative extraction-condensing steam turbine, allowing for variable extraction to permit variation in the delivered power-tc+heat ratio, is illustrated in Fig. 9-96. The performance envelope is seen to be specified by: fa the full-throttle flow for no extraction 7, the ratio of maximum-extraction Bow to full-throttle flow, f0 IM and 7~. the efficiencies for the high- and low-pressure portions of the turbine hl, hb, hb,, the isentropic enthalpies defined by the steam-supply conditions (state l), the extraction conditions (state 2). and the condensing conditions (state 3)

r-_-_____

_____

--_--_____________

_____

_______-__

________

W, = f,(h,-h3) 3fO[(h,-h~,l~~+(h~,-h3,)~J W,=f.[(h,-hz,)rl~l Where T=temperature

I I

Ii= enthalpy s= entropy v= turbine efficiency

I

I fo

I I I I I
1

f, =I' f, Throttle Ro. 9-96

1.5 f,

flow,f,

fo(l+ f,

Performance envelope for a typical steam extraction-condensing turbine. (Derfced from Elliott Multivalve Turbines, BuK H-87, Gmfer &rpomtti, 1973.)

. Elliott
l

turbine

model 600 psia (4137 800F (427C) 103 psio (710 330F IlG6Cl 1 in Hg (3.5 kPo) kPo)

Throttle Extraction

conditions: conditions:

Condensmg Efficiencies.

condations:

kPo)

ir=1.0

combustor, 0.85; turbine, 0.7 (high pressure), 0.8 (low pressurel, pumps, 0.7

$$y

.
Throttle

ii
flow,

I fx = r. r=

fe;

fe = 0.8 fo; p = 0.05 fraction

extroctlon-flow

fT I 0.5 Power-to-heat ratio, I 1.0 (W-W, l/OS I 1.5

Ro.

9-97

Steam extraction-condensing

cogenerationsycle

performance

characteristics

L ?

2
< I 3 T z n ;

1sI?

0.53-

Woste-heatergas exit, T, =80F

(27C)

l 0.t

0.;

1 B p 0.c >0 6 I 0.: j-

2 % ; 0.4 if I 0.: iI 5 LO.2 i E .t E c, = ? s 0 0.1

Assumptaons:
COmPreSSOr Inlet, T, = 80F (27*C) Turbine inlet, T, = 1500F (816oC) Recuperator effectiveness, e = 0.90

Combustor Compressor Turbine Compression Pressure-loss

efficiency. efficiency, ratio, ratio,

7e = 0.85 vc = 0.88 7r = 0.91

efficiency,

rc= 4 pL = 0.05

0 Power-to-heot ratio, R-

(WT

- WC IlOw

Typical performance envelope for an indirectly fired, open- or closed-cycle gas-turbine cogenerstion system: air-working fluid; recuperation with variable bypass.
FlG. 9-91

1.0

no.9

2 : 0.0

c 0.7 2
7

Indirectly-fired, open- or closed-cycle --

0.6----

P
1. >

= 05I 4 ? 0.4 Svstem z .; u 0.3Steam

l

Steam data turbine turbine conditions: 600 psia kPo); 9OOF(482Cl Gas turbine . Recuperator 0.90 effectweness with variable bypass . .
l

turbine

Both
l

Extractton-condensing Throttle (4137

0 p 0.2 0
0.1 / 0

Compression Turbine inlet,

ratio.

4 .
l

Process neat suppllea as sream at 103 ps,a (710 kPa) and 33OF (166C) Combustor Pressure-loss efficiency. ratio, 0.85

Turbine efficiencies: high pressure. 0.70; low pressure, 0.80

15OOOF (816Cl inlet, 8OF (27CI 0.86;

Compressor Efficiencies: turbine: Working

Aplp: 0.05

Condenser

pressure 12 InHg (3.5kPa)

compressor, 0.91 ow pinch

flud.

I
0.5

9 ST;;:,enerotor 0

50F

I
1.0 ratio, fired) Ri

I
1.5

Power-to-heat RQ. 9-W Compamtive performance of steam-turbine and gas-turbine (indirectly

mgeneration

cycles supplying

16PC (330F) steam and electric power.

- - ---

Process-steam

demand demand ratlo - 500

:I,

-EElectr~c-power I L__ ----.-Power-to-heat

:-> I

- 400 r 3 ; 300 0 -. P % ;, 1.0

;200

E al ;,

0 : 0.5 _ _ ; : & & B

100

1:
M 1

3 4

LO 91011 Hour N of the 12 day 3 4 5 67 8 9101

20

Ro. 9-100 Typical power end heat demand for P typical fall weekday in P large institutional complex. l@ Btu/ h = 1.055 X ld J/h; 14 kWh/h = 3.143 X 10e Btu/h thermal equivalent.

HEAT RRGENERATION
just satisfies the requirement that the heat Qw be supplied with no less than a specified minimum temperature difference (called the pinch) between the gas-turbine working tluid, which is being cooled, and the heat-supply-system fluid (usually water or steam), which is being heated.

9-89

Comparative Performance of Steam and Indirectly Fired Gas-Turbine System As noted in Table 9-55, gas-turbine systems
can be expected to operate at higher overall efficiency for a given power-to-heat ratio than will a steam-turbine system; conversely, for a given overall efficiency, a gas turbine will yield a higher delivered power-to-heat ratio than will a steam-turbine cogeneration system. This comparison is illustrated in Fig. 9-99, in which the two cycles described by Figs. g-969-97, and 9-98 have been compared as they supply electric power and 166C (330OF) steam in varying proportions. For a given power-to-heat ratio, the gas turbine yields an overall efficiency 15 to 18 points higher than that of the assumed steam cycle. Similarly, to achieve an overall efficiency of 0.60 or greater, the steam turbine is restricted to power-to-heat ratios of less than 0.375, whereas for the same efficiency limit the indirectly fired gas turbine can realize power-to-heat ratios as high as 1.0. Thus, the major determinant in whether a gas or a steam turbine is the more appropriate is not the efficiency but rather the power-to-heat ratio which the system must supply. In addition, if the gas-turbine cycle is a closed (pressurized) cycle, it offers the additional very valuable feature of accommodating large load swings (down to I5 to 20 percent of design power level) with no significant effect on efficiency. As noted earlier, this benefit is achieved by virtue of the ability to change working-fluid inventory (and, hence, pressure level) in the system. Finally, closed-cycle gas turbines also offer the benefit of selection of working fluids (other than air) which may yield enhanced turbine and heat-exchanger performance. Operational Issues

20

R=0.8.IE 0.3, =

56%

Fuel-cost

sownqs for CR = 6

Varying, Noncoincident Load Demands for Power and Heat For most practical cogeneration applications, the demand for heat and power varies considerably during the course of a typical day. Such a variation for a typical large institutional complex is illustrated in Fig. 9-100. For a cogeneration system to meet the entire power and heat demand for the typical day shown, it would have to have the following performance range capability: . Power-to-heat ratio R, 0.31 to 0.84 * Power level, 38 MWe (at R = 0.31) to 79 MWe (at R = 0.84) If an extraction-condensing steam-turbine system were chosen for this application, it could not efficiently meet the high power-to-heat demand portion to the daily load; either the system would be designed to meet the steam demand, in which case large quantities of electric power would have to be purchased during the middle of the day, or the system would be designed to meet the electrical load, in which case system efficiency would be greatly reduced during the high-power-to-heat-ratio portion of the day. On the other hand, an indirectly fired gas turbine could efficiently meet (at >60 percent overall efficiency) all the heat and power demand except, possibly, in the early morning hours, when the power-to-heat ratio dips below 0.35. In this case, the system can be designed to meet either the steam demand, while selling excess power to the utility during the period from 1 to 5 A.M. (when the utility is least likely to want it), or the power demand, while supplying the small unsatisfied steam demand with a separate fired boiler. Cost Considerations Ultimately, cost saving is the oblective in most cogeneration installations. The exceptions are those applications which are remote from utility power grids or which have special reli-

1
Power-to-heat mt10. R(I

FIG. 9-101

Fuel-cost savings for heat-engin&s.sed

cogeneration systems.

ability or security concerns (e.g., military installations, hospitals, etc.). Cogeneration involves additional fixed costs associated with buying and maintaining a larger, generally more complex, on-site physical plant. Against this added hxed cost can be traded the reduction in total fuel costs when purchased electricity is considered a high-grade fuel for on-site use. The reduction in total fuel costs must be greater than the increased annualized fixed cost associated with the cogeneration plant in order to justify the facility economically. While a treatment of capital costs for various cogeneration alternatives is beyond the scope of this subsection, an analysis of fuel-cost savings, as a function of fuel-price ratios and cogeneration-system parameters can be useful. Figure 9-101 presents the fractional reduction in total fuel costs (purchased electricity plus fossil fuel burned on site) as a function of power-to-heat ratio, heat-engine efficiency, and the ratio of electricity to fossil-fuel cost on a thermal equivalent ($/Btu or $/J) basis. By way of illustration, a cogeneration application with a power-to-heat ratio of 0.8, using a heat engine at 30 percent efficiency, with a fuel-cost ratio of 6, would realize a fuel-costsaving fraction of 0.56. or 56 percent.

HEAT REGENERATION
Storage of heat is a temporary operation since perfect thermal insulators are unknown; thus heat is temporarily absorbed in solids or liquids as sensible or latent heat to be released later at designated times and conditions. Examples of collecting and releasing heat on a

9-90

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

tended to confine regenerator design to the readily available and less expensive standard refractories. Blast-Furnace Stoves A typical blast furnace, producing 1650 tons of pig iron per day, will be blown with 47 m3/s (lCCt,OOO standard fts/min) of atmospheric air, preheated to temperatures ranging in normal practice from 482 to 649OC (900 to 1200F) with 538C (1000F) close to an average. To preheat this blast volume, a set of four stoves is usually provided. A vertical and horizontal section of one such stove is shown in Fig. 9-103. Each stove consists of a vertical steel cylinder 7.3 m (24 ft) in diameter, 33m (110 ft) high, topped with a spherical dome. A side combustion chamber is separated by a bridgewall with a lens-shaped horizontal cross section. The remaining volume is filled with heat-absorbing checkerwork. The heat-exchanging surface in each stove is just under 11,506 m* (124,096 ft*). In operation, each stove is carried through a twostep 4-h cycle. In one 3-h on-gas step, the checkers are heated by the combustion of blast-furnace gas. In the alternating on-wind lh step, the checkers are cooled by the passage of cold air through the stove. At any given time, three stoves are simultaneously on gas, while a single stove is on wind. After 3 h on gas, an on-wind step is initiated. At the start, about one-half of the air, entering at 93C (2WF), passes through the checkers, the other half being bypassed around the stove through the cold-blast mixer valve. The gas passing through the stove exhausts initially at 1093OC (2000F). Mixing this with the unheated air produces a blast temperature of 538OC (lOOOF). The temperature of the heated air from the stove falls rapidly, minute by minute, throughout the on-wind step. The fraction of total air volume bypassed through the mixer valve is continually decreased by progressive closing of this valve, its operation being automatically regulated under control of a thermocouple and potentiometer. At the end of 60 min of on-wind operation, in usual practice the cold-blast mixer valve is practically closed, the entire blast then passing through the checkers. Satisfactory approach to uniform blast temperature can readily be realized by this automatic control of the mixer valve, provided that the uniform blast temperature does not greatly exceed one-half of the combustion temperature in the preceding on-gas step. The rapid decrease in temperature exhibited by the air discharging from the checkers is a characteristic feature of classical checkerwork heat transfer. The thickness of the refractory flue walls retards the flow of heat by thermal diffusion into the central portions of the brick. Although the heat removed in an on-wind step is less than 5 percent of the total sensible heat stored in the stove refractories, the intro duction and removal of heat from such large-dimensioned refractory elements is sluggish, with the result that the in-and-out movement of heat is largely a skin effect confined closely to the refractory surface. Open-Hearth and Glass-Tank Regenerators Because of the higher working temperatures, more drastic thermal shock, and dirtier gases encountered in open-hearth and glass-tank regenerators, checkerwork construction in these furnace units, while somewhat similar to that employed in blast-furnace stoves, requires considerable modification. The vertical height of the flues is limited by the elevation of the furnace above plant level. Short flues from 3 to 4.9 m (10 to 16 ft) are common in contrast to the 26- to 29-m (85- to 95ft) flue lengths in blast-furnace stoves. Larger brick shapes (Fig. 9IO2b) form flue cross sections 5 times as large as the stove flues, and the percentage of voids in the checkerwork is 51 percent, in contrast with the stove 32 percent voids. In a typical open hearth (Fig. g-104), a checker volume of 210 ms (7500 ft ) contains 810 flues. As a result of the larger dimensions of flues and the restricted surface per unit gas passed, regenerators employed with this type of reverberatory furnace exhibit much lower efficiency than would be realised with smaller flue dimensions. In view, however, of the large amount of iron oxide contained in the open-hearth exhaust gas and the alkali fume present in glass-tank stack gases, resort to smaller checker dimensions has appeared impractical. Coke-Oven Regenerators In the by-product coke oven, wasteheat recovery is effected in the standard Siemens manner, although, as seen in Fig. 9-105, the dimensions of the upstream and down-

Cc)

FIG. q-102

Checkerworkdesigns.

batch or continuous basis are the checkerwork regenerator for blast furnaces as a batch operation or the Ljungstrom type as a continuous operation. Recuperators are covered in the discussion on heat-transfer equipment (Sec. 11). Checkerbrick Regenerators Preheating combustion air in openhearth furnaces, ingot-soaking pits, glass-melting tanks, by-productcoke ovens, heat-treating furnaces, and the like has been universally carried out in regenerators constructed of fireclay, chrome, or silica brick shapes. Although many geometric arrangements have been used in practice, the so-called basketweave design shown in Fig. 9102~ and b has been adopted in many applications. In blast-furnace stove construction, standard 22.9- by 11.4- by 6.4cm (9- by 4.5- by 2.5-in) firebrick, assembled in basketweave design, forms square flues 8.3 by 8.3 cm (32.5 by 3.25 in) (Fig. 9-102n). In open-hearth regenerators, 46 by 15- by 7-cm (la- by 6 by 3-m) tiles form flues 19 by 19 cm (7.5 by 7.5 in) (Fig. 9-102b). Special shapes have been devised for more complicated, if frequently less rugged, heat-absorbing elements, e.g., coke-oven tiles (Fig. 9-102c). Standard firebricks are cheaper than special shapes, and this fact has

Checker

work

Combustion chamber

Hbter -Hot

cooled blast

wtve

iif=
A* H Burner

To chimney Ro. 9-103

%-

Gas

Blast-furnace stove.

HEAT REGENERATlON

9-9 1

FIG.

9-104

Cross

section of an open-hearth

steel furnace,

including

regenerators.

stream regenerators show little outward resemblance either to the blast-furnace stove or to the reverberatory-furnace regenerators. From structural necessity, the coke-oven regenerator is located under the oven itself and must assume the dimensions of an extremely narrow parallelepiped. Fortunately, the design problem is simplified because of the absence of fume and dust in the flue system. Special regenerator blocks are commonly employed, a typical design being shown in Fig. 9-102c. An oven 12 by 3.7 by 0.5 m (40 ft by 12 ft by 16 in) carbonizing 24 tons/day coal to produce 17 tons/day coke will be provided with a pair of regenerators having a horizontal cross section of 6.5 m* (70 ft*) containing 210 flues (slots) and an overall volume of 8.4 ma (300 fts). Because fuels used in underfiring are either cleaned coke-oven gas, clean blast-furnace gas, or mixtures of the two, difficulty with dirt and fume accumulation in the tlues is not encountered, and because of the lower working temperatures in coking, this intricate type of flue has been found satisfactory. Attempts to duplicate coke-oven-regenerator construction in other Siemens units have not been successful. Pebble Stove Although considerable ingenuity has been applied to the design of the Cowper checkerwork, involving variations in

FIG. 9-106

Pebble-bed regenerator.

FIG. 9-105

Regenerator system for by-product coke ovens

bricklaying patterns and special ceramic shapes, the checkerbrick regenerators still exhibit five engineering defects: (1) high initial cost of construction; (2) unsatisfactory thermal efficiency with clean heatexchanging surfaces; (3) tendency to lose efficiency with dust-and fume-coated surfaces inevitable with dirty gas; (4) inaccessibility of surface causing lost time and high labor cost in any cleaning operation; and (5) danger of fusion, slagging, and spalling when subjected to high maximum temperatures and rapid temperature changes. It is possible that one or even all of these difficulties are inherent in the Cowper checkerbrick system, as such. No serious attempt, however, to alter US construction appears to have been made prior to 1929, when the Department of Agriculture undertook to substitute the socalled pebble-bed heat-exchanging structure for the classical checkerwork in order to provide higher air preheat in the blast-furnace smelting of phosphate rock. In this departure from regenerator precedent, a mass of small refractory particles, enclosed in a brick-lined steel shell, was substituted as a functional equivalent of standard checkerwork (see Fig. 9106). In the operation of an experimental phosphate blast furnace, blast temperatures as high as 1093OC (2000F) were readily obtained. In later operation of a 25ton/day blast furnace producing pig iron, ferromanganese, ferrochromium, and ferrosilicon, air preheat temperatures of 1538OC (2800F) were attained and maintained. In connection with the process of converting air into NO [Daniels and Gilbert, hd. Eng. Gem., 40, 1719 (1948)] air was pre heated to 1980C (36OOOF) in magnesia refractory pebble stoves. Aside from the engineering value of the elevated temperatures attained with pebble-stove regenerators, extremely high thermal efficiencies are an inherent characteristic of this type of heat interchanger. Ljungstrom Heater The continuous-regenerative type of air heater or recuperator is familiarly known as the Ljungstrom heater (Fig. g-107). The heater assembly consists of a slow-moving rotor packed with closely spaced metal plates or wires. At each end of the rotor is a housing divided by partitions to confine the hot gas to one half of the rotor and the cold gas to the other. Radial and circumferential seals sliding on the rotor limit the leakage between streams. The rotor is divided into sectors and each sector packed with a filling to promote high heat transfer at low pressure drop. The packing may be divided into layers of different materials to suit the temperature and corrosion conditions. Leakage between streams comes from (1) entrainment in the rotor passages (this can be reduced by providing for a blowout section between the hot and cold zones), (2) leakage around the circumference of the rotor through the annular space between rotor shell and housing, and (3) leakage of radial seals. These heaters are available with rotors up to 6-m (29ft) diameter. Gas temperatures up to 816OC (15OOF) can be handled [a higher temperature of 982OC (18OWF) with special alloys]. and gas face velocities are usually around 2.5 m/s (500 ft/min). Thickness of rotor depends on service, efficiency, and operating conditions but usually

9-92

ENERGY UTIUZATION,

CONVERSION,

AND RESOURCE CONSERVATION

Rotor kontalnlng heat transfer surface)

FIG. 9-107

Ljungstrom air heater

ranges from 20.3 to 91.4 cm (8 to 36 in). Rotors are driven by small motors with rotor speed up to 10 to 20 r/min. The effectiveness of these heaters can be as high as 85 to QO percent. Ljungstrom-type heaters are widely used in power-plant boilers. Use in process industries is increasing for air conditioning and building heating by transferring heat between the fresh and exhaust air streams and for process-heat recovery.

Many systems have been proposed for Miscellaneous Systems transferring heat regeneratively, such as described earlier, plus the use of high-temperature liquids and tluidized beds for direct contact with gases, but other problems which limit industrial application are encountered. These systems are covered by methods described in Sec. 11.