ABSTRACT

This project is about the development & design of Refinery gas sweetening system of CPCL-plant 12. Refinery gas sweetening is the process used to remove the so called Acid Gases which are hydrogen sulphide and carbon dioxide from the refinery gas streams. These acid gas removal processes used in the refinery are required either to purify a gas stream for further use in a process or for environmental reasons. Though there are various processes meant for the sour gas removal the Chemical reaction type is selected and adopted on grounds that it can selectively remove H2S from all the sour gas components. For serving this purpose, the newly developed MDEA solution of 35 % mol is used in a mole ratio of 2.2. The factors that are all considered for the selection of MDEA over MEA, DEA and DGA are also discussed. For the entire flow sheet the material and energy balances are developed and the corresponding equipment are designed. Plant layout, cost estimation and safety measures are going to be carried out.

TABLE OF CONTENTS CHAPTER TITLE ACKNOWLEDGEMENT

DEFINED.

PAGE NO. ERROR! BOOKMARK NOT I II VI VII VIII

ABSTRACT TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES LIST OF SYMBOLS AND ABBREVIATIONS 1 INTRODUCTION
1.1 ORGANISATION PROFILE 1.2 CRUDE OIL 1.3 CRUDE OIL REFINERY 1.4 REFINERY OPERATIONS

1 2 3 4

PROPERTIES
2.1 PHYSICAL PROPERTIES OF MDEA 2.2 PHYSICAL COMPARISION OF MEA AND MDEA 2.3 CHEMICAL PROPERTIES OF MDEA 6 7 8

TYPES OF PROCESSES
3.1 VARIOUS PROCESSES FOR THE REFINERY GAS TREATING 3.2 REACTION TYPE GAS TREATING 3.3 PHYSICAL SOLVENT GAS TREATING 3.4 PHYSICAL/CHEMICAL TYPE 3.5 CARBONATE TYPE 9 9 10 11 12

SELECTION OF PROCESS
4.1SELECTION PROCEDURE FOR THE CHEMICAL REACTION
TYPE FOR GAS SWEETENING 4.2 PROCESS PARAMETERS AND DESCRIPTION OF VARIOUS AMINE SOLVENTS 4.3 FACTORS THAT ARE CONSIDRED FOR THE SELECTION OF MDEA OVER MEA, DEA & DGA

13 14 19

PROCESS FLOW DIAGRAM

II

20

PROCESS DEVELOPMENT AND DESCRIPTION

6.1 ABOUT REFINERY GAS SWEETENING 6.2 PROCESS DESCRIPTION 6.3 PROCESS CHEMISTRY 6.4 THERMODYNAMIC PRINCIPLES 21 22 22 23

MATERIAL BALANCE
7.1 FLOW RATE OF COMPONENTS OF SOUR GAS THAT DISTILLED OUT FROM THE CDU-2 24 7.2 MATERIAL BALANCE ACROSS ABSORBER 25 7.3 MATERIAL BALANCE ACROSS STRIPPER 26

ENERGY BALANCE
8.1 HEAT CAPACITY CONSTANTS FOR THE COMPONENTS OF
SOUR GAS 29 8.2 ENERGY BALANCE ACROSS THE ABSORBER 30 8.3 ENERGY BALANCE ACROSS THE SOLUTION INTERCHANGER 33 8.4 ENERGY BALANCE ACROSS THE COOLER 35 8.5 ENERGY BALANCE ACROSS THE STRIPPER 36 8.6 CONDENSER DUTY 39

HEAT EXCHANGER DESIGN

9.1 PLANT DATA 9.2 PROPERTIES OF THE FLUID 9.3 CALCULATION OF P & R 9.4 FILM COEFFICIENT - TUBE SIDE-LEAN AMINE 9.5 FILM COEFFICIENT - SHELL SIDE-COOLING WATER 9.6 TUBE WALL RESISTANCE 9.7 OVERALL HEAT TRANSFER COEFFICIENT 9.8 HEAT TRANSFER AREA REQUIRED 9.9 PRESSURE DROP TUBE SIDE 9.10 PRESSURE DROP SHELL SIDE 9.11 DESIGN SUMMARY 41 42 43 45 46 47 47 48 48 49 50

III

10

STRIPPER DESIGN
10.1 FINDING THE NUMBER OF TRAYS (FROM KREMSERS CORRELLATION GRAPH) 10.2 FINDING THE EQUILIBRIUM DISTRIBUTION 51 51 52 52 53 54 59 60

RATIO FOR INDIVIDUAL COMPONENTS 10.3 CALCULATING THE IDEAL NUMBER OF TRAYS 10.4 CALCULATING THE ACTUAL NUMBER OF TRAYS 10.5 KREMSERS CORRELATION GRAPH 10.6 THE INTERNAL DIAMETER OF THE STRIPPING COLUMN 10.7 CALCULATION OF COLUMN HEIGHT 10.8 DESIGN SUMMARY

11

COST ESTIMATION
11.1 INTRODUCTION 11.2 TOTAL CAPITAL INVESTMENT 11.3 CALCULATION OF DIRECT COST FACTOR 11.4 CALCULATION OF INDIRECT COST FACTOR 11.5 ESTIMATION OF THE CAPITAL INVESTMENT IN THE AUXILIARY SERVICE, IA 11.6 ESTIMATION OF THE CAPITAL INVESTMENT AS WORKING CAPITAL, IW 11.7 ESTIMATION OF TOTAL CAPITAL INVESTMENT 61 61 62 63 64 65 65

12

PLANT LOCATION AND LAY OUT

12.1 PLANT LAYOUT 12.2 FACTORS IN PLANNING LAY-OUT 12.3 METHODS OF LAY-OUT PLANNING 12.4 SCALE MODELS 12.5 EQUIPMENT LAYOUT 12.6 PLANT LOCATION 66 66 66 66 68 69

13

HAZARDS AND SAFETY

13.1SAFETY 13.2 HAZARDS IN REFINERIES 13.3DESIGN SAFETY 13.4 LAYOUT 13.5 OPERATING PROCEDURES 13.6 STATIC EQUIPMENT 13.7 FIRE 13.8 HEALTH HAZARD IV 72 72 72 73 73 73 73 74

13.9IMPORTANT SAFETY RULES TO PREVENT HIGH PRESSURE HAZARDS 13.10 ENVIRONMENTAL CONTROL

74 75

14

CONCLUSION REERENCES

76 77

LIST OF TABLES
Table 1. 1Composition of Crude Oil Table 1. 2 Composition of Hydrocarbons Table 1. 3 Physical comparision of MEA and MDEA 2 3 7

Table 7. 1 Flow rate of components of sour gas thats distilled out from the CDU.2 Table 7. 2 The total liquid and vapour flow rates

24 56

Table 8. 1Heat capacity constants for the components of sour gas Table 8. 2 Enthalpy of sour gas entering at 314k Table 8. 3 Enthalpy of sweetened gas leaving absorber at 311k Table 8. 4 Enthalpy of strip out gases at 380 k Table 8. 5 Enthalpy of Acid gas to SRU at 313K:

29 30 31 38 39

Table 11. 1 Estimation of fixed capital investment Table 11. 2 Calculation of direct cost factor Table 11. 3 Calculation of indirect cost factor Table 11. 4 Estimation of the capital investment in the auxiliary service

62 63 63 64

VI

LIST OF FIGURES
Figure 6. 1 Process flow diagram 20

Figure 7. 1 Material balance across absorber Figure 7. 2 Material balance across the stripper

25 26

Figure 8. 1 Energy balance across the absorber Figure 8. 2 Energy balance across the solution interchanger Figure 8. 3 Energy balance across the cooler Figure 8. 4 Energy balance across the stripper Figure 8. 5 Condenser duty

30 33 35 36 39

Figure 9. 1 Hot amine cooler Figure 9. 2 Graph for finding the correction factor Figure 10. 1Kremsers correlation graph Figure 10. 2 Graph for finding the Brown and Souders flood constant

42 43

53 58

Figure 12. 1 Plant layout

67

VII

LIST OF SYMBOLS AND ABBREVIATIONS

LIST OF SYMBOLS Symbols T TLMTD Tt Ft Di do L PT De Db Ds B ut us Cp T To Ti Name Difference In Temperature Logarithmic Mean Temperature Differenc True Mean Temperature Difference Temperature Correction Factor Degree Inlet Diameter Inlet Diameter Length of Tube Square Pitch Equivalent Diameter Bundle Diameter Shell Diameter Baffle Spacing Tube Velocity Shell Velocity Viscosity Specific heat capacity Temperature Temperature - Out Temperature In m m m m m m m m m/s m/s kg/m s kJ /kg oC C or K C or K C or K Units C C C

VIII

QH QC U H D L A m k NTU LP LW DP b AP As Xm Nt NP Re Pr Nu

Heat Transfer duty Hot fluid Heat Transfer duty Cold fluid Overall Heat Transfer Coefficient Heat Transfer Coefficient Diameter Length Area Mass flow rate Thermal Conductivity Density Number of Transfer Unit Length of the plate Width of the plate Diameter of the plate Thickness of the plate Area of single plate Effective area of Shell Thickness of Material Total number of tubes Number of passes Reynolds Number Prandtl Number NussultNumber

kcal/h kcal/h W / m2 K W / m2 K m m m2 kg / h W / m oC kg / m3 m m m m m m2 m2 m

IX

LIST OF ABBREVIATIONS

CPCL - Chennai Petroleum Corporation Limited MRL - Madras Refinery Limited GoI - Government of India AMOCO - American Oil Company NIOC - National Iranian Oil Company IOC - Indian Oil Corporation Limited EIL - Engineers India Limited MMTPA - Million Metric Tonnes Per Annum WHO - World Health Organization FAO - Food and Agriculture Organization UNISEF - United Nations Childrens Fund LSRG - Light Straight Run Gasoline NMP - Normal Methyl Pyrrolidone MEA - Mono Ethanol Amine MDEA Methyl di ethanol Amine DEA Di ethanol Amine DGA Di glycol Amine SRC - Solvent Recovery Column IBP - Initial Boiling Point TBP - Total Boiling Point MP - Medium Pressure LP - Light Pressure HP - High Pressure SHE - Spiral Heat Exchanger LEL - Lower Explosive Limit

CHAPTER 1 INTRODUCTION

1.1

Organisation profile
Chennai Petroleum Corporation Limited (CPCL), formerly known as Madras Refineries

Limited (MRL) was formed as a joint venture in 1965 between the Government of India (GOI), AMOCO and National Iranian Oil Company (NIOC) having a shareholding in the ratio 74%:13%:13% respectively. Originally, CPCL Refinery was set up with an installed capacity of 2.5 Million Tonnes Per Annum (MMTPA).

CPCL has two refineries with a combined refining capacity of 11.5 Million Tonnes Per Annum (MMTPA). The Manali Refinery has a capacity of 10.5 MMTPA. CPCL's second refinery is located at Cauvery Basin at Nagapattinam. The Manali Refinery located at Chennai is one of the most complex and integrated refineries with three crude distillation units, Diesel Hydro De-sulphurisation unit, Fluid Catalytic Cracking unit, Furfural Extraction unit, Lube Hydrofinishing unit, NMP Extraction unit, Hydro-Cracker unit, Propylene unit and Petrochemical Feedstock unit.

The main products of the company are LPG, Motor Spirit, Superior Kerosene, Aviation Turbine Fuel, High Speed Diesel, Naphtha, Bitumen, Lube Base Stocks, Paraffin Wax, Fuel Oil, Hexane and Petrochemical feed stocks. CPCL, ever since its inception, has been methodically planning and implementing several environmental conservation measures. A dedicated Environment Management Team functions exclusively to plan, implement, operate and monitor all environment-related activities.

CPCL Manali Refinery has obtained ISO 9001, ISO 14001 and OHSAS-18001 certifications.

1.2 Crude oil

Crude Oil is a naturally occurring flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds, that are found in geologic formations beneath the Earth's surface. Petroleum is recovered mostly through oil drilling. The use of fossil fuels such as petroleum can have a negative impact on Earth's biosphere, releasing pollutants and greenhouse gases into the air and damaging ecosystems through events such as oil spills. Concern over the depletion of the earth's finite reserves of oil, and the effect this would have on a society dependent on it, is a field known as peak oil.

Composition of Crude Oil

In its strictest sense, petroleum includes only crude oil, but in common usage it includes all liquid, gaseous, and solid hydrocarbons. The exact molecular composition varies widely from formation to formation but the proportion of chemical elements vary over fairly narrow limits.

Elements Carbon Hydrogen Nitrogen Sulphur Oxygen Metals

Composition (%) 83 to 87 10 to 14 0.1 to 2 0.05 to 6 0.05 to 1.5 Traces

Table 1- 1Composition of Crude Oil

Four different types of hydrocarbon molecules appear in crude oil. They are Paraffins, Napthalenes, Aromatics and Asphaltics.

Hydrocarbon

Average Composition (%)

Paraffins Napthalenes Aromatics Asphaltics

30 49 15 6

Table 1- 2 Composition of Hydrocarbons

Crude oil varies greatly in appearance depending on its composition. It is usually black or dark brown. In the reservoir it is usually found in association with natural gas, which being lighter forms a gas cap over the petroleum, and saline water which, being heavier than most forms of crude oil, generally sinks beneath it. Crude oil may also be found in semi-solid form mixed with sand and water, as in the Athabasca oil sands in Canada, where it is usually referred to as crude bitumen.

1.3

Crude oil refinery

An oil refinery or is an industrial process plant where crude oil is processed and refined

into

more

useful and

products liquefied

such

as petroleum

naphtha, gasoline, diesel refineries are

fuel, asphalt large

base, kerosene,

petroleum

gas. Oil

typically

industrial complexes with extensive piping running throughout, carrying streams of fluids between large chemical processing units. The process is very complex and involves both chemical reactions and physical separations.

1.4

Refinery operations Crude Oil Distillation

Crude oil distillation is used to separate the hydrocarbons in crude oil into fractions based

on their boiling points. The separation is done in a large tower that is operated at atmospheric pressure. The tower contains a number of trays where hydrocarbon gases and liquids interact. The liquids flow down the tower and the gases up. The lighter materials such as butane and naphtha are removed in the upper section of the tower and the heavier materials such as distillate and residual fuel oil are withdrawn from the lower section.

Catalytic Reforming
Catalytic reforming is a chemical process used to convert petroleum refinery naphthas, typically having low octane ratings, into high-octane liquid products called reformates which are components of high-octane gasoline. Basically, the process re-arranges or re-structures

the hydrocarbon molecules in the naphtha feedstocks as well as breaking some of the molecules into smaller molecules.

Catalytic Cracking
Fluid catalytic cracking (FCC) is the most important conversion process used in petroleum refineries. It is widely used to convert the high-boiling, high-molecular weight hydrocarbon fractions of petroleum crude oils to more valuable gasoline, olefinic gases, and other products. Cracking of petroleum hydrocarbons was originally done by thermal cracking, which has been almost completely replaced by catalytic cracking because it produces more gasoline with a higher octane rating. It also produces byproduct gases that are more olefinic, and hence more valuable, than those produced by thermal cracking.

Alkylation and Isomerisation

In the alkylation process, isobutane is reacted with either isobutylene or propylene to form complex paraffin isomers. The reactions take place in the presence of hydrofluoric or sulfuric acid catalysts. By combing these molecules the octane level of the paraffin isomer or 4

alkylate is increased to around 93-96 octane. Refiners use this process to improve the octane level of the gasoline pool. Light naphtha can have its octane number improved by the use of an isomerization process to convert normal paraffins into their isomers. This results in an increase in octane number as evidenced by increase in normal pentane to iso-pentane. The process uses a platinum catalyst. Like alkylation, this process improves the octane quality of the gasoline pool.

Hydrotreating
Hydrotreating is a process where a petroleum fraction is reacted with hydrogen for the purpose of removing impurities. The process is usually used to remove sulfur. Hydrotreating processes use hydrogen from the catalytic reformer or a hydrogen plant.

Product Blending
Product blending is where the different petroleum fractions are combined together to make the final product. The fractions are mixed so they meet the specifications discussed earlier. Each product has a specific recipe that calls for the proper mix of petroleum fractions. For example, in order to make gasoline, the refiner would mix naphtha, reformate, catalytic gasoline, alkylate and butane so that the mixture had the required octane number, vapor pressure, sulfur level and aromatics content. The process requires knowing these values for all of the components going into the blend.

CHAPTER 2 PROPERTIES

2.1 Physical properties of MDEA

Structure

CH3 N (C2H4OH) 2 119 g/mol

Molecular weight

Strength of solution used

35%mol

Boiling point

at 760 mm hg - 247.3c at 50 mm hg - 163.5 c at 10 mm hg- 128.6c

Refractive index

at 20C -1.4694

Heat of combustion

at 25c -12,200 btu/lb

Flash point

Pensky-martens closed cup (ASTM D93), 138 C

Freezing point

-21C

Vapor pressure

at 20c, mm hg <0.01

Specific gravity

1.03
6

2.2

Physical comparision of MEA and MDEA

Previously in the refinery the MEA solvent had been used since the inception of this

plant. Later on due to the following advantages that MDEA is possessing over MEA the MDEA has been adopted. The following table gives the physical comparision of MEA over MDEA.

S.No

Monoethanolamine (MEA)

Methyldiethanolamine (MDEA) Higher solvent cost relative to Monoethanolamine, Diethanolamine and Diglycolamine agent. Low vapor pressure which results in potentially lower solvent losses. Methyldiethanolamine is less corrosive. Non-reclaimable by conventional reclaiming techniques, and Minimal COS, CS2 removal. Efficient energy utilization. Selectivity of H2 S over CO2 in mixed gas system. High resistance to degradation. Molecular weight of Methyldiethanolamine is 119.21 g/mol Lower comparative reactivity. Complete H2S removal while only a portion of CO2 is removed. The most significant application of MDEA solvent was in tail gas treating units.

1.

Low solvent cost compared to other solvents. High solvent vapor pressure which results in higher solvent losses than the other alkanolamines. Higher corrosion potential than other alkanolamines. Partial removal of COS and CS2, which requires a reclaimer. High energy requirements due to the high heat of reaction. Nonselective removal in a mixed acid gas system. Formation of irreversible degradation products with CO2, COS and CS2 which requires continuous reclaiming. Molecular weight of Monoethanolamine is 61.1 g/mol High reactivity due to its primary amine character. Gas is treated at low pressures, and maximum removal of H2S and CO2 is required. More efficient solvents particularly for the treatment of high pressure natural gas are rapidly replacing MEA.

2. 3. 4. 5. 6. 7. 8. 10. 11. 12.

Table 1- 3 Physical comparision of MEA and MDEA

2.3 Chemical properties of MDEA Reaction of MDEA with H2S

2RNH2 + H2S (RNH3)2S + H2S (RNH3)2S 2 RNH3HS

2RNH2 + H2S

(RNH3)2S

The above equations mention the chemistry of the reaction between MDEA and H2S. It can be seen that stoichiometrically 1 mol of MDEA can absorbs 1 mol of H2S from the sour gas.

Selective removal of H2S over CO2 by MDEA

The biggest advantage that MDEA possess over other amine solvents such as DGA, MEA, DEA is that it can selectively remove the H2S from the sour gas over the presence of CO2.

Non formation of corrosive heat stable compounds in the presence of COS, CS2
The MDEA solution doesnt yield a corrosive nature unlike the formation of heat stable compounds by DGA and MEA in the presence of COS, CS2. This gives an advantage not to operate a reclaimer to regenerate the amine solution thereby equipment cost that would be spent is prevented.

CHAPTER 3 TYPES OF PROCESSES 3.1 Various processes for the refinery gas treating

The selected popular processes for the refinery gas treating are grouped as follows:

1. Reaction type: MEA, DEA, MDEA, DGA, Stretford

2. Physical solvent type: Fluor solvents (propylene carbonate)

3. Physical chemical type: Sulfinol

4. Carbonate type: Potassium carbonate

3.2

Reaction type gas treating

The amines (MEA, DEA, MDEA, DGA) are the most popular treating solutions. At one time MEA, and later MEA and DEA, dominated the market. Amines in general should be considered for: Low acid gas partial pressures (product of system pressure and concentration of acid gases-H2S and CO2 in the feed) of roughly 50 psi and below. Low acid gas concentrations in the gas product of roughly 4-8 ppm. Heavier hydrocarbons present ( provide better filtration for DGA) For CO removal with no H2S, a CO2 partial pressure of 10-15 psi.

Application of various amine solvents and their respective cases:

Among the amines, 1. MEA is preferred for low contactor pressures and stringent acid gas specifications such as H2S well below 0.25grains/ l00scf, and C02 as low as 100 ppmv. MEA is degraded by COS and CS2 with the reactions only partially reversible with a reclaimer.

2. DEA is preferred when system pressure is above 500psi. The 0.25 grains/ l00scf is more difficult to produce with DEA. COS and CS2 have few detrimental effects on DEA. This, and high solution loadings, provide advantages over MEA. DEA will typically be used for refinery and manufactured gas streams that have COS and CS2. 3. MDEA is preferred for selective H2S removal and lack of degradation from COS and CS2. 4. DGA is preferred for cold climates and high (50-70 wt %) solution strength for economy. By comparison, solution strength for MEA is 15-25 wt%, and for DEA, 25-35 wt %. Provide good filtration for DGA because it has a greater affinity for heavy hydrocarbons than other amines. The feed gas must have at least 1% acid gas for DGA to provide savings over MEA.

3.3

Physical solvent gas treating

The physical solvent types of gas treatment are generally preferred when acid gases in the feed are above 50- 60psi. This indicates a combination of high pressure and high acid gas concentration.

10

Heavy hydrocarbons in the feed discourage physical solvents, but not COS and CS2, which do not degrade the solvents.

Usually, physical solvents can remove COS, CS2, and mercaptans. Physical solvents are economical because regeneration occurs by flashing or stripping which require little energy.

Selexol, licensed by the Norton Company, uses the dimethyl ether of polyethylene glycol. A Selexol plant can be designed to provide some selectivity for H2S. For example, the plant can be designed to provide pipeline quality gas while slipping 85% of the CO.

The Fluor solvent, propylene carbonate, is used primarily for removal of CO, from high pressure gas streams. The CO, off gas stream was used for enhanced oil recovery.

3.4

Physical/chemical type

The Sulfinol process from Shell Development Company is a good example of the physical/chemical type of process. It blends a physical solvent and an amine to obtain the advantages of both. The physical solvent is Sulfolane (tetra hydro thiophene dioxide) and the amine is usually DIPA (di isopropanol amine). The flow scheme is the same as for an amine plant.

Advantages of the Sulfinol Process

The physical solvent Sulfolane like other physical solvents, has higher capacity for acid gas at higher acid gas partial pressures. At these higher partial pressures the Sulfinol B process has lower circulation rates (higher solution loading) and better economy than MEA. Sulfinol is demonstratively advantageous against

11

MEA when the H2S/CO2 ratio is greater than 1 : 1 while at high acid gas partial pressures. In the solution, the amine DIPA is meanwhile able to achieve pipeline quality gas. COS, CS2 and mercaptans are removed. CO2 slightly degrades DIPA, but reclaiming is easy. Low corrosion/carbon steel. Low foaming.

Low vapor losses. 3.5 Carbonate type

Hot (230-240F) potassium carbonate treating was patented in Germany in 1904 and perfected into modern commercial requirements by the U.S. Bureau of Mines.

The U.S. Bureau of Mines was working on Fischer-Tropsch synthesis gas at the time.

Potassium carbonate treating requires high partial pressures of CO2. It therefore cannot successfully treat gas containing only H2S.

12

CHAPTER 4 SELECTION OF PROCESS

4.1

Selection procedure for the Chemical Reaction type for gas sweetening

Of the gas treating methods mentioned above, the Chemical reaction type has been selected on basis of the following reasons:

Potassium carbonate treating requires high partial pressures of CO2. It therefore

cannot successfully treat gas containing only H2S.

The physical/ chemical type, the SULFINOL process possess high priced
chemicals and process royalty and the licensee requires many engineering services.

The physical solvent types of gas treatment are generally preferred when acid
gases in the feed are above 50- 60 psi. Usually, physical solvents can remove COS, CS2, and mercaptans. But the gas that has to be treated has no presence of mercaptans and else.

Thus the amine solvents- the chemical reaction type can selectively remove H2S and do not show any degradation by COS, CS2 and so it is selected for the sour gas sweeteing.

13

4.2

Process parameters and description of various amine solvents Mono ethanol amine
This is the most common acid gas absorption process. Normally 1520 wt% MEA in

water is circulated down through a trayed absorber to provide intimate contact with the sour gas. The rich solution is routed to a steam stripping column where it is heated to about 250 F at 10 psig to strip out the acid gases. The lean MEA solution is then returned to the absorber.

MEA is the most basic (and thus reactive) of the ethanol amines. MEA will completely sweeten sour gases removing nearly all acid gases if desired. The process is well proven in refinery operations.

Like all of the amine solvents used for acid gas removal MEA depends upon its amino nitrogen group to react with the acidic CO2 and H2S in performing its absorption. The particular amines are selected with a hydroxyl group which increases their molecular weight and lowers their vapor pressures yielding minimum solvent losses to the gas stream. MEA is considered a chemically stable compound. If there are no other chemicals present it will not suffer degradation or decomposition at temperatures up to its normal boiling point.
The process reactions are given below:
HOCH2CH2NH2 = RNH2 = MEA

Low temp

2 RNH2 + H2S
High temp

(RNH3)2S

Low temp

(RNH3)2S + H2S
High temp

2RNH3HS

14

Some of the degradation products formed in these systems are highly corrosive. They are usually removed by filtration or reclaimer operations.

Filtration will remove corrosive by products such as iron sulfide. Reclaiming is designed to remove heat stable salts formed by the irreversible reaction of MEA with COS, CS2 (carbonyl sulfide and carbon disulfide). The reclaimer operates on a side stream of 13% of the total MEA circulation. It is operated as a stream stripping kettle to boil water and MEA overhead while retaining the higher boiling point heat stable salts.

When the kettle liquids become saturated at a constant boiling point with the degradation products it is shut in and dumped to the drain. Union Carbide has developed a well proven corrosion inhibitor system for MEA that allows solution strengths of 2832%. The inhibitor requires payment of a royalty. The inhibitor chemicals are both expensive and hazardous for personnel to handle. The system does reduce corrosion problems to nearly zero and allows much higher system capacity for the same size equipment.

In addition to the chemical degradation mentioned above, MEA oxidizes when exposed to air. Storage and surge tanks must be provided with inert blanket gases such as N2 or sweet natural gas to avoid this degradation.

Amine systems foam rather easily resulting in excessive amine carryover in the contactor. Foaming can be caused by solids such as carbon or iron sulfide; condensed hydrocarbon liquids from the gas stream; degradation products; almost any foreign material introduced to the system such as valve grease, excess corrosion inhibitor, etc. Some of these items such as iron sulfide or carbon particles are removed by cartridge filters. Hydrocarbon liquids are usually removed by the use of a carbon bed filter on a lean amine side stream (about 10% of total flow). Corrosion byproducts are removed by reclaiming as noted above.

15

High skin temperatures on the reboiler / reclaimer tubes promote amine degradation. Steam or hot oil used for the reboiler should be limited to a maximum of 285F (140C) to avoid excessive temperatures. The reclaimer should not see hot oil or steam above 415F (213C).

MEA is nonselective in absorbing acid gases. It will absorb H2S faster than CO2 but the difference is not significant enough to allow its use to separate them. With the lowest molecular weight of the common amines, it has a greater carrying capacity for acid gases on a unit weight or volume basis. This generally means less pure amine circulation to remove a given amount of acid gases. Because the solvent is in solution with water, the gas with which it comes in intimate contact will leave the cotactor at its water saturation point. If dehydration is necessary it must be done after the MEA system.

Diethanol amine
DEA does not degrade when contacted with CS2, COS, and mercaptans as does MEA. However for product gas streams which must meet lower than 1 grain per scf of H2S, MEA must be used. Because of this, DEA has been developed as a preferred solvent when these chemicals are present in the stream to be treated.

The reaction with acid gas for any of the amines is a mole to mole reaction. The molecular weight of DEA is 1.7 times that of MEA. Even after correcting for density it requires 1.6 lb of DEA to react with the same amount of acid gas as 1 lb of MEA.

DEA is a weaker base (less reactive) than MEA. This has allowed DEA to be circulated at about twice the solution strength of MEA without corrosion problems. DEA systems are commonly operated at strengths up to 30 wt% in water and it is not unusual to see them as high as 35 wt%. This results in the DEA solution circulation rate usually being a little less than MEA for the same system design parameters.

16

The process reactions are shown below.

HOCH2CH2NHCH2CH2OH = R2NH = DEA
Low temp

2R2NH + H2S
High temp

(R2NH2)2S

Low temp

(R2NH2)2S + H2S
High temp

2R2NH2HS

Because the system has much fewer corrosion problems and removes acid gases to nearly pipeline specifications it has been installed as the predominant system in recent years.

Diglycol amine
This process has been developed by the Fluor Company. It originally began as a combination of 15% MEA, 80% tri ethylene glycol, 5% water. The system would both sweeten and dehydrate (to the same level as 95% TEG) the gas in a single step.

The high vapor release during regeneration (both water vapors and acid gases) causes severe erosion/corrosion problems in the amine/amine exchanger and in the regeneration column. This system has generally been abandoned.

The present system uses 2- (2-amono ethoxy) ethanol at a recommended solution strength of 60 wt% in water. DGA has almost the same molecular weight as DEA and reacts mole for mole with acid gases. DGA seams to tie up acid gases more effectively so that the higher concentration of acid gas per gallon of solution does not cause corrosion problems as experienced with the usual amine systems.

17

The system reactions are given below.

HOCH2CH2OCH2CH2NH2 = RNH2 = DGA
Low temp

2RNH2 + H2S
High temp

(RNH3)2S

Low temp

(RNH3)2S + H2S
High temp

2RNH3HS

DGA does react with COS and mercaptans similarly to MEA but forms N, N1, bis (hydroxy, ethoxy ethyl) urea, BHEEU. BHEEU can only be detected using an infrared test rather than chromatography. Normal operating levels of 24% BHEEU are carried in the DGA without corrosion problems. BHEEU is removed by the use of a reclaimer identical to that for an MEA system but operated at 385F (196C).

There has been a concern that DGA might be a good solvent for unsaturated hydrocarbons. A survey of the DGA users indicates that many of the systems are operated on gas containing concentrations of C5+ above 2% without any indication of hydrocarbon loading of the system.

Those systems near their hydrocarbon dew point are usually installed with a flash tank on the rich amine from the absorber. The flash tank is operated at a reduced pressure just high enough to get into the plant fuel gas system. It reduces the vapor load on the regenerator column. (A similar system is recommended on MEA systems operating near the hydrocarbon dew point.)

DGA allows H2S removal to less than 0.25 grain per 100 scf and removes CO2 to levels of about 200 ppm using normal absorber design parameters.

18

4.3

Factors that are considred for the selection of MDEA over MEA, DEA & DGA

1. The overall reaction of MEA gives us one mole of H2S to one mole of MEA. But this is seldom experienced in actual contactor due to the limitations in ideal contacting. A ratio of 3 moles of MEA to 1 mole of acid gas is used.

2. The usage of MEA has receded in the recent years due to its corrosive nature by forming heat stable compounds in the presence of COS & CS2. This requires the use of a reclaimer to regenerate back the amine solution. But this leads to the loss of amine and also adds up to the equipment cost.

3. MEA may degrade at higher temperatures around 160c.

4. DEA does not degrade but has lesser absorbing capacity as it is a weaker base.

5. In the case of DGA the high vapor release during regeneration (both water vapors and acid gases) causes severe erosion / corrosion problems in the amine exchanger and in the regeneration column. So this system has generally been abandoned.

19

CHAPTER 5 PROCESS FLOW DIAGRAM

Figure 6- 1 Process flow diagram

20

CHAPTER 6 PROCESS DEVELOPMENT AND DESCRIPTION

6.1

About Refinery gas sweetening

Refinery gas sweetening is the process used to remove the so called Acid Gases

which are hydrogen sulphide and carbon dioxide from the refinery gas streams. These acid gas removal processes used in the refinery are required either to purify a gas stream for further use in a process or for environmental reasons. Clean air legislation now being practiced through most industrial countries require the removal of these acid gases to very low concentrations in all atmosphere to form very diluted sulphuric acid and carbon dioxide to form carbonic acid both of which are considered injurious to personal health. These compounds also cause excessive corrosion to metals and metallic objects. The removal of sour or acid gas components such as hydrogen sulphide, carbon monoxide, carbonyl sulphide and mercaptans from gas and liquid hydrocarbon streams is a process requirement in many parts of the hydrocarbon processing industry. Typical industrial gas treating application include the production of natural gas, refinery fuel gas, high purity hydrogen and carbon monoxide, and purification of ammonia, synthesis gas, landfill gas, coke oven gas or sulphur recovery unit tail gas. For over fifty years, the alkanolamines have been utilized for acid gas removal in the natural gas and petroleum processing industries.

21

6.2

Process description
Sour gas (rich in H2S) enters the bottom of the trayed absorber (or Contactor).

Lean Amine is introduced at the top tray of the absorber section to move down the column operating at 45 MPa g. Contact between the gas and amine liquid on the trays results in the H2S in the gas being absorbed into the amine. The sweet gas is water washed to remove any entrained amine before leaving the top of the contactor. Rich amine leaves the bottom of the contactor at 340.51 k to enter a surge drum. If the contactor pressure is high enough a flash stream of H 2S can be routed from the drum to a trayed stripper. The liquid is preheated to 459.01 k before entering a stripping column on the top stripping tray that is operating at 125 kPa a. This stripper is reboiled with 10.5 bar saturated steam. The H2S is stripped off and leaves the reflux drum to the sulphur production plant 12 at 313 k. The lean amine leaves the stripper bottom at 389 k and is cooled. The cooled stream is routed to the contactor.

6.3

Process chemistry
(RNH3)2S 2 RNH3HS

2RNH2 + H2S (RNH3)2S + H2S

2RNH2 + H2S

(RNH3)2S

Though stoichiometrically, MDEA of 1 mol absorbs 1 mol of H2S, for practical cases the mole ratio is set at 2.2 mol MDEA/ mol H2S.

22

6.4

Thermodynamic principles

The process reaction for the absorption of H2S on MDEA is as follows:

CH3 N (C2H4OH) 2 = RNH2 = MDEA
Low temp

2 RNH2 + H2S
High temp

(RNH3)2S

Low temp

(RNH3)2S + H2S
High temp

2RNH3HS

The underlying thermodynamic principle for any reaction at equilibrium is Le Chatliers principle.

A simple study of the above reaction would indicate that a high pressure and low temperature is expected for thermodynamic feasibility of absorption of the acid gases.

Thus a high pressure of 45 MPa g is maintained in the absorber and the inlet sour gases are fed at a low temperature of 314 k.

Similarly, due to the inverse nature of stripping process, a low pressure of the order of 150 kPa is maintained in the stripper. Here steam at 10.5 bar is provided to strip the acid gases from the down coming amine solution. A reboiler is used to maintain the temperature profile along the column. This is limited by the boiling point of the amine solution or the point to which it is not degradable.

23

CHAPTER 7 MATERIAL BALANCE 7.1 Flow rate of components of sour gas that distilled out from the CDU-2

Component of sour gas H2 S H2 C1 C2 C3 iC4 n-C4 n-C5 C6 TOTAL

kmol/h 27.21 36.32 59 35.7 46.6 18.9 20.4 1.3 1.6 247.03

Table 7- 1 Flow rate of components of sour gas thats distilled out from the CDU-2

24

7.2

Material balance across absorber

Figure 7- 1 Material balance across absorber

Total sour gas into the absorber = 247.03 kmol/h As a mole ratio of 2.2 kmol MDEA/ kmol H2S is set and a solution of strength 35 % mol has been used, Total Lean Amine circulation rate for the absorption of 27.21 kmol H2S Rich Amine rate which has absorbed 27.21 kmol H2S

= 170.97 kmol/h

= 170.97 +27.21 = 198.18 kmol/h = 219.82 kmol/h

Sweetened gas flow rate

25

Overall material balance:

Input = Output Sour gas + Lean Amine = Sweetened gas + Rich Amine 247.03 + 170.97 = 219.82 + 198.18 kmol/h

7.3

Material balance across stripper

Figure 7- 2 Material balance across the stripper

Rich Ammine entering the stripper = 198.18 kmol/h = 500 * 10-6 *170.97 = 0.085 kmol/h

500 ppm loading of H2S in Lean Amine

Stripped gas contains H2S & water thats condensed and returned as Reflux. In the accumulator , the H2S leaves at 40C with moisture in it. 26

 H2S in the stripped gas

= 27.21- 0.085 = 27.125 kmol/h

Reflux flow rate

= 27.125 kmol/h (Since reflux ratio =1)

H2O (entrapped moisture) in the H2S leaving the accumulator:

This can be found by making use of partial & vapour pressure data. This gives the makeup H2O rate. Considering the contact of Reflux water thats condensed & H2S in the accumulator. As H2O is pure the vapour pressure @ 40C = Partial pressure of H2O in H2S leaving accumulator

Now we can obtain the mole fraction of H2O in H2S, using Raoults law.
Pa = ya P ; where Pa= partial pressure of the component a in vapour. P = Total pressure of the gas stream =150-25 = 125 kPa. Assuming 25 kPa pressure drop in condenser. ya= 7.375/125 = 0.059

Using the mole fraction obtaining the specific moisture content.

Specific moisture content = M.F. of H2O / M.F. of H2S = 0.0626 kmol H2O/ kmol dry gas

27

The amount of H2O leaving with H2S from the Accumulator

= 0.0626 * 27.125 kmol/h = 1.70 kmol/h This is the amount that lost from the reflux water. Thats the make up for reflux. So a total of 28.90 kmol/h of acid gas is sent to SRU plant 9.

28

CHAPTER 8 ENERGY BALANCE 8.1 Heat capacity constants for the components of sour gas

Feed gas composition H2S H2 C1 C2 C3 i- C4 n- C4 n-C5 C6 Total

kmol/h 27.21 36.32 59 35.7 46.6 18.9 20.4 1.3 1.6 247.03

A 34.523 28.6105 19.249 4.1261 -4.222 -8.9133 -2.451 -3.6266 -4.4152

B*103 -17.64 1.0194 52.113 155.021 306.26 419.53 391.82 487.4859 581.9223

C*106 67.66 -0.1476 11.973 -81.545 -158.63 233.633 -202.98 -258.0312 -311.8584

D*109 -53.24 0.769 -11.317 16.975 32.145 51.043 40.793 53.0488 64.9193

Table 8- 1Heat capacity constants for the components of sour gas

29

8.2

Energy balance across the absorber

Figure 8- 1 Energy balance across the absorber

Enthalpy of sour gas entering at 314k:

Feed gas composition H2S H2 C1 C2 C3 i- C4 n- C4 n-C5 C6 Total ni kmol/h 27.21 36.32 59 35.7 46.6 18.9 20.4 1.3 1.6 247.03 ni *a*101 939.38 1039.13 1135.71 193.24 -196.98 -166.94 -50 -4.71 -7.06 2881.77 ni *b*103 -480.20 37.02 3074.7 6357.71 14271.90 7929.19 7993.28 398.14 931.08 40512.82 ni *c*106 1841.20 -5.36 706.41 -2405.28 -7392.23 4415.67 -4140.96 -206.22 -498.97 -7685.74 ni *d*109 -1448.81 27.93 -667.72 311.11 2472.07 964.72 832.17 41.79 103.87 2637.13

Table 8- 2 Enthalpy of sour gas entering at 314k

30

Q= 298314 (2881.77 + 40512.82*10-3T - 7685.74*10-6 T 2 + 2637.13*10-9 T 3 )dT Q= 65.04 KW

Enthalpy of sweetened gas leaving absorber at 311k:

Feed gas composition H2S H2 C1 C2 C3 i- C4 n- C4 n-C5 C6 Total ni kmol/h Nil 36.32 59 35.7 46.6 18.9 20.4 1.3 1.6 219.82 ni *a*101 ni *b*103 ni *c*106 ni *d*109 nil 27.93 -667.72 311.11 2472.07 964.72 832.17 41.79 103.87 4085.94

nil 1039.13 1135.71 193.24 -196.98 -166.94 -50 -4.71 -7.06 1942.39

Nil 37.02 3074.7 6357.71 14271.90 7929.19 7993.28 398.14 931.08 40993.02

nil -5.36 706.41 -2405.28 -7392.23 4415.67 -4140.96 -206.22 -498.97 -9526.94

Table 8- 3 Enthalpy of sweetened gas leaving absorber at 311k

Q= 298 311 (1942.39 + 40993*10-3T - 9526.94*10-6 T 2 + 4085.94*10-9 T 3 ) dT Q= 49.32 KW

31

 Heat generated due to absorption:

The exothermic heat of reaction @ 298.15 k for the absorption of H2S is Therefore, heat generated due to absorption = (27.21*34)*1047 = 269.06 KW--------- (1) 1047 kJ / kg.

Heat given up in the absorber by the gas mixture:

= Enthalpy of (sour gas-sweet gas) = 52.65 - 49.32 = 15.72 KW---------- (2)

Enthalpy of Lean Amine

= (170.97 * 53.35) * 3.77 * (316-298)

=171.94 KW--------- (3)

Enthalpy of Rich Amine

= (1) + (2) + (3)

= 456.72 KW

Overall energy balance:

Enthalpy of sour gas in + Heat generated due to absorption + Heat given off by the sour gas mixture + Enthalpy of Lean Amine = Enthalpy of sweetened gas+ Enthalpy of Rich Amine

65.04 + 269.06 + 15.72 + 171.94 = 456.72 + 49.32 KW

32

8.3

Energy balance across the solution interchanger

459.01 k

353 k

Lean Amine 389 k 9121.25 Kg/h Tube side in

Rich Amine 340.51 k 9121.25 Kg/h Shell side in

Figure 8- 2 Energy balance across the solution interchanger

In this exchanger, Lean amine cools down from 389 k to 353 k.

Enthalpy of Rich Amine- shell side in

= 456.72 KW

Heat given up as the solution cools down = 9121.25 * 3.77 * (389 - 353)
= 1299.07 KW This much heat would be picked up by the Rich Amine entering at 340.51 k with 2% radiation loss. Thus heat absorbed by Rich Amine = 1299.07 * 0.98 = 1273.09 KW

Enthalpy of Rich Amine- shell side out

= 1273.09 + 456.72 = 1729.08 KW

Enthalpy of Lean Amine- Tube side in

= 869.23 KW

Enthalpy of Lean Amine- Tube side out = 525.36 KW 33

Overall energy balance across the Heat Exchanger:

Q in = Q out Enthalpy of ( Lean Amine-in + Rich Amine-in)+ Heat released + Heat lost due to radiation = Enthalpy of ( Lean Amine-out + rich Amine-out) 456.72 + 869.23 + 1299.07 + 54 = 525.36 + 1729.08 KW

Finding the temperature of Rich Amine leaving the solution interchanger.

Q = m Cp dt 1273.09 KW*3600 = 10046 * 3.85 *(T-340.51) Thus temperature of Rich Amine is 340.51 k

34

8.4

Energy balance across the cooler

Figure 8- 3 Energy balance across the cooler

In this cooler, the Lean Amine is cooled down to 316 K from 353 K and then it enters the absorber. Heat transfer duty = 9121.25 * 3.77 * (353-316) Q = 353.42 KW

Cooling water requirement:

Q = m Cp dt fixing dt = 10k 353.42 * 3600 = m *4.1868 *10 m = 3038.89 kg/h m = 3.038 m3/h

35

8.5

Energy balance across the stripper

Figure 8- 4 Energy balance across the stripper

Finding the temperature of the stripped out gas from stripper:

Applying Raoults law for this purpose : ya=Pa/P and also xa=Pa/Pa Combining the above two expressions, xa Pa = Pa =ya P where Pa Pa xa ya = Partial pressure of the component A in gas = Vapour pressure of component A in liquid = Mole fraction of water vapour in the gas leaving stripper = Mole fraction of water in the total liquid in the stripper

36

Finding ya = = (27.125+1.70) / (27.125+1.70+27.125) = 0.52 Therefore, Pa = 0.52*150 kPa = 77.28 kPa Now finding Xa = = (1.70+ 170.97*0.65)/(170.97+27.125) = 0.57 And now Pa = Pa/ xa = 77.28/0.52 = 148.62 kPa From the vapour pressures table, Temperature of gas stream leaving the stripper=107.13C = 380k

Enthalpy of Heat in streams:

1) Enthalpy of rich amine stream =10046*3.85*(459.01-298) = 1729.83 KW-------------- (1) 2) Enthalpy of Reflux + Make up H20 @40c = (27.125+1.70)* 18 * (h@40C-h@25C) = 518.85 * (168.771 - 104.77) = 9.22 KW-------------- (2) 3) Heat supplied by the reboiler @ 2% radiation loss = (x*0.98) KW-------------- (3) 37

Enthalpy of heat out streams:

4) Heat generated due to desorption 5) Enthalpy of Lean Amine stream = 269.06 KW-------------- (4) = 9121.25 * 3.77 * (389-298) = 869.23 KW-------------- (5) 6) Enthalpy of strip out gases at 380 k Feed gas composition H2S H2O Total ni kmol/h 27.21 28.91 56.12 ni *a*101 939.38 1469.93 2409.31 ni *b*103 -480.20 6160.14 56810 ni *c*106 1841.20 -16412.52 -16412.52 ni *d*109 -1448.81 18347.20 18347.20

Table 8- 4 Enthalpy of strip out gases at 380 k

Q = 298380 (2409.31 + 56810*10-3T - 16412.52*10-6 T 2 + 18347.20*10-9 T 3 ) dT Q = 72.09 KW-------------- (6)

Overall energy balance across the stripper:

(1)+ (2) + (3) = (4) + (5) + (6) 1729.83 + 9.22 + (x*0.98) = 269.06 + 869.23 + 72.09 x = -539.46 KW i.e. 539.46 KW has to be supplied by Reboiler. For serving this purpose, a saturated steam @ 10.5 bar supplied of latent heat = 2006 kJ/kg

Therefore , steam requirement in reboiler = 539.46 / 2006

= 0.27 kg/s = 968.12 kg/h 38

8.6

Condenser duty

Figure 8- 5 Condenser duty

Condenser duty at 2%radiation loss = Enthalpy of (Stripped gas- acid gas to SRU Reflux)

Enthalpy of Acid gas to SRU at 313K:

Feed gas composition H2S H2O Total ni kmol/h 27.21 1.70 28.90 ni *a*101 939.38 86.44 1025.82 ni *b*103 -480.20 362.24 -117.96 ni *c*106 1841.20 -1073.38 767.82 ni *d*109 -1448.81 1164.09 -284.72

Table 8- 5 Enthalpy of Acid gas to SRU at 313K:

Q= 298313 (1025.82 - 117.96*10-3T + 767.82*10-6 T 2 - 284.72*10-9 T 3 )dT Q= 4.40 KW

Enthalpy of Reflux:
= (27.21*18) ( h at40C- h at25C) =27.21*18 (168.771-104.771) = 8.71 KW 39

Therefore condenser duty at 2%radiation loss = (72.09 - 4.40 - 8.71) / 0.98 = 60.18 KW

Cooling water requirement:

Q = m Cp dt 60.18*3600 = m*4.1886*10 m =5.172 tonnes /h

40

CHAPTER 9 HEAT EXCHANGER DESIGN 9.1 Plant data:

= 32C 42C = 80C 43C = 0.37 W/ mC = 0.519 W/ mC

Shell side temperature (cooling water) Tube side temperature (lean amine) Thermal Conductivity of lean amine Thermal Conductivity of cooling water

Lean amine flow rate from stripper to absorber (tube side) = 9121.25 kg/h Cooling water flow rate (shell side) Shell side fluid: Cooling water Tube side fluid: Hot lean Amine Heat load (Q) = 9121.25 * 3.77 * (80-43) / 3600 = 353.42 KW = 3038.89 kg/h

TLMTD

= ( 38-11) / ln (38/11) = 21.78 0 C

41

Picturistic description:

Figure 9- 1 Hot amine cooler

9.2

Properties of the fluid Tube Side

1003 kg/m 4.18 kJ/kg K 0.00033 kg/ms 0.37 W/mk

Properties
Density Specific Heat Capacity Viscosity Thermal Conductivity

Shell Side
995 kg/m 3.77 kJ/kg K 0.00095 kg/ms 0.519 W/mk

Heat profile:
hot amine 80C 42C cold water 43C 32C

42

9.3

Calculation of P & R
P = dTh / (Th1- Tc1) =10 / 48 = 0.2083 R = dTh / dTc = 37/10 = 3.7 R= 1/R = 0.27 P= R*P = 0.77

Graph for finding the correction factor :

Figure 9- 2 Graph for finding the correction factor

43

To find Correction Factor, consider 1 Shell and even even Tube pass Ft = 0.87 Tm = Ft * TLMTD Tm = 0.87 * 21.78 Tm = 18.95 C Assuming an Overall heat transfer coefficient of U = 500 W/m2 0 C

Provisional Area:
A = Q/U Tm A = 353.42*103 / 500*18.95 A = 37.3 m2

Tube description:
Outer Diameter Bwg Internal Diameter Length = 20 mm = 14 = 15.8 mm = 4880 mm

Allowing for tube sheet thickness take Le = 4830 mm Pitch = 25 mm

44

Area of one tube

= * Do * Le = * 0.02*4.83 =0.3033 m2 = 0.3630 m2

Number of tubes (Nt )

= provisional area / area of one tube Nt = 37.3 / 0.3033 Nt = 123 tubes

Therefore, number of tube passes is 4.

Shell description:
Inner Diameter Number of shell side passes = 387.35 mm = 1 as theres a temperature approach only.

9.4

Film coefficient - tube side-lean amine

hi Di/ k = 0.023 Re0.8 Pr0.33 (/w )0.14 Re Gt At = Gt Di / where Gt = Mass velocity of the fluid in tube side. = mh /At where At = area of tube side per pass. = /4 * Di2 * Nt/ Np = 0.0060 m2 Gt = 2.534 / 0.0060 = 422.33 kg/m2s 45

Re

= 422.33 * 0.0158/ 0.33 * 10-3 =20220.7921

Pr

= Cp / k = 3.77*103*0.33*10-3 / 0.37 = 3.362

hi

= 0.023 * 20220.79210.8 * 3.3620.33 (1)0.14 * 0.37 / 0.0158 = 2237.12 W/m2 C

hio hio hio

= hi *Di/Do = 2237.12 * 0.0158 / 0.02 = 1767.325 W/ m2 C

9.5

Film coefficient - Shell side-cooling water

ho De/ kf = 0.36 Re0.55 pr0.33 (/w )0.14 for triangular pitch De = 4/Do * ( 0.86 Pt2- /4 Do2 ) = 4/*0.02 * ( 0.86 0.0252- /4 0.022 ) = 0.0127 m

Gs As

= mc/ As = B c D / Pt The baffle cut is kept to be 40 % of the shell ID. = (0.4 * 0.387) *0.005 * 0.387 / 0.025 = 0.0120 m2 46

Gs

= 0.8441 / 0.0120 = 70.3417 kg/ m2s

Re

= Gs De/ = 70.3417 * 0.0127 / 0.95 * 10-3 = 940.3575

Pr

= Cp / k = 0.95*10-3 * 4.18*103 / 0.519 = 6.7305

ho ho

= 0.36 *940.35750.55 * 6.73050.33 (1)0.14 * 0.519 / 0.0127 = 1354.93 W/m2 C

9.6
Rw Rw

Tube wall resistance

= Do ln (Do/Di ) / 2 Kw = 1*10-6 W/m2 C

Considering a combined dirt factor of 0.0006 m2 C / W

9.7
Uo Uo

Overall heat transfer coefficient

= = 524.97 W/m2 C )-1

47

9.8
Ar Ar Ar

Heat transfer area required

= Q / Ua Tm = 353.42*103/ 524.97*18.95 = 35.53 m2

% excess % excess % excess

= Aa-Ar/Ar * 100 = 37.3-35.53/ 35.53 *100 = 5% so the design is safe.

9.9
Pt

Pressure drop tube side

+ 2.5 Np v2 s

= = 0.72 Re-0.33 = 0.0273

= Gt/ = 422.33/ 1030 = 0.4100 m/s

L Np Di

= 4.88 m =4 = 0.0158 m =1

48

s Pt Pt

= 1.03 = 1.460+0.8657 = 2.3258 kPa

9.10
Ps

Pressure drop shell side

= = 1.87 Re-0.2 = 1.87 * 940.3572-0.2 = 0.4755

Gs De Nb

= 70.3417 kg/m2s = 0.0127 m = = 4.8 / 0.01548 = 31

= 0.995 =1

Ps

= 1.147 kPa.

49

9.11 Design summary

The cooler is designed to be consisting of tubes of 20mm OD * 15.8 mm ID * 4880 mm long and a shell ID of 387.35 mm of passes 4 and 1 respectively. The overall heat transfer coefficient for the respective duty is found to be 524.97 W/m2 C. A pressure drop of 2.3258 kPa is achieved in tube side and a drop of 1.147 kPa in shell side.

50

CHAPTER 10 STRIPPER DESIGN 10.1 Finding the number of trays (from Kremsers Correllation Graph):
In order to find the number of trays of the stripper where the H2S is stripped off from the rich amine by making use of the stipping steam thats used as a heating medium the stripping factor has to be calculated. Stripping factor = VK/L where, L is the number of moles of liquid V is the number of moles of vapour K is the equilibrium distribution ratio

10.2 Finding the equilibrium distribution ratio for individual components:

The equilibrium distribution ratio for the individual components is found by Vapour pressure data which in turn found by making use of the Antoinnes equation for the respective components. For calculation purpose an average temperature of column of about 111.5 C is used.

The Antoinnes equation for H2O:

log10 P = Where pressure is in mmHg and temperature is in C. As calculated, the Vapour pressure of H2O is 1129.966 mmHg. So K = = = 0.743 51

The Antoinnes equation for H2S:

log10 P = Where pressure is in bar and temperature is in k. As calculated, the Vapour pressure of H2S is 107.720 bar. So K = = = 53.860 The average K values of the components at the stripper operating pressure of 2 bar are given in the following table. An average vapour to liquid ratio of about 0.05 is taken. Components H2S H2O Avg.K 53.860 0.743 S.F= VK/L 2.69 0.037

10.3 Calculating the ideal number of trays:

The ideal number of trays can be calculated from the following Kremser equation correlation graph for a stripping factor of 2.69 and 100% stripping. So the ideal number of trays = 4

10.4 Calculating the actual number of trays

As stripping has a very low efficiency due to desorption of gases by steam stripping from a liquid, that too in larger sized column. Due to this, the tray efficiency varies from 12 % to 18%. Assuming an average efficiency of 13%, The actual number of trays = 4 /0.13 = 30 trays 52

10.5 Kremsers correlation graph

Figure 10- 1Kremsers correlation graph

53

10.6 The Internal Diameter of the stripping column

For finding the Internal Diameter of the column, the cross sectional area has to be calculated.

The cross sectional area of the tower will be based on the vapour and liquid flow rates at the bottom tray.

Finding the total amount of vapour to the bottom tray:

The total vapour to the tray =27.125 + 27.125 + 1.70

= 55.95 kmol/hr Finding the volume occupied by the vapour thats stripped out of the column at the prevailing conditions: At standard Temperature and pressure P1 =101.325 k Pa T1 =273 k As we know that at NTP ( thats P=101.325 kPa and T=273 k) 1 kmol of gas occupies 22.414 m3. V1 = 55.95 * 22.414 =1254.06 m3/h

And now the prevailing conditions of pressure and temperature in the stripper are as follows :

P2 = 148.62 kPa T2 = 380 k

54

By volumetric law thats by the combination of Boyles law and Charles law,

V2 =

V2 =

V2 = 1190.08 m3/h Finding the total vapour flow rate in terms of mass flow rate:

Mass flow rate = (27.125+1.70) * 18 + 27.125 *34

= 518.85 + 922.25

= 1441.1 kg/h

Finding the total amount of liquid from the bottom tray:

Total liquid from the bottom tray i.e. the lean amine flow rate = 198.18 kmol/h

= 10046 kg/h = 10.046 m3/h

55

The following tabular column shows the total liquid and vapour flow rates to and from the bottom tray respectively: kmol/h liquid flow rate vapour flow rate 198.18 55.95 kg/h 10046 1441.1 m3/h 10.046 1190.08

Table 7- 2 The total liquid and vapour flow rates

Finding the vapour density and liquid density:

vapour density =

= 1.21 kg/m3 liquid density =

= 1000 kg/m3

Finding the Brown and Souder flood constant :

For the assumed tray spacing of 15 inches or 38.1 cm, of sieve trays the K factor is found from the below given graph as K= 111 m/s ( 600 ft./s from graph) Loading at flood =K = 111 = 3858 kg/h m2 The design loading is to be 80 % of the loading at flooding. Therefore, design loading = 0.8 * 3858 kg/h m2 = 3086 kg/h m2

56

The cross sectional area of the column = = = 0.1085 m2

57

Graph for finding the Brown and Souders flood constant:

Figure 10- 2 Graph for finding the Brown and Souders flood constant

58

Finding the Internal Diameter of the column:

Therefore Internal Diameter of the column ID = = 0.38 m = 1.2 ft. 2 ft.

10.7 Calculation of column height

Height between bottom tray and top tray:

Height between bottom tray and top tray = Tray spacing (No.of trays - 1)

= 38.1 * ( 30-1)

= 11.05 m

Height between top tray and top tan:

The top tray to top tan distance is generally fixed at around 1m.

Height between bottom tray and bottom tan:

The resident time of the liquid hold up is based on the pumping capacity. Assuming a hold up time of 2 minutes.

59

Therefore, Volume resident

*2

*2

= 0.32 m3.

Height of the liquid level = = 2.95 m say 3 m. As an allowance of 1 m has to be given so the bottom tray to bottom tan is 4m. So, the tan-to-tan distance = 16 m. And now, a skirting of 5 m is also provided which makes the entire structure to rise to a height of 21 m or 69 ft. 10.8

Design summary
Thus a stripper of ID 2 ft., height 69 ft., and with 30 trays each of 15 inch spacing is designed for the purpose.

60

CHAPTER 11 COST ESTIMATION

11.1 Introduction
Cost estimation is the approximation of the cost of a program, project, or operation. The cost estimate is the product of the cost estimating process. The cost estimate has a single total value and may have identifiable component values. A problem with a cost overrun can be avoided with a credible, reliable, and accurate cost estimate. The cost estimation of the sour gas treating unit , plant 12 of CPCL are as follows.

11.2 Total Capital Investment

Total capital investment represents the total cash investment that shareholders and debt holders have made in a company. Total capital investment is used in several important measurements of financial performance, including return on invested capital, economic value added and free cash flow.

Estimation of Total Capital Investment

The total capital investment I involves the following: The fixed capital investment in the process area, IF. The capital investment in the auxiliary services, IA. The capital investment as working capital, IW. i.e., I = IF + IA + IW

Estimation of Fixed Capital Investment in the process area, IF:

This is the investment in all processing equipment within the processing area. Fixed capital investment in the process area, IF = Direct plant cost + Indirect plant cost The approximate delivered cost of major equipments used in the sour gas treating plant12 of CPCL are furnished below:

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S.No.

Equipment

Units

Cost in lakhs/unit

Cost in lakhs

Absorption column

150

150

2 3

Stripping column Exchanger and cooler

1 2

150 50

150 100

Filter Pumps, accumulator etc.,

1 2+1

15 25+50

15 75

5 tanks,etc Total

490 lakhs

Table 11- 1 Estimation of fixed capital investment

11.3 Calculation of direct cost factor

A price that can be completely attributed to the production of specific goods or services. Direct costs refer to materials, labour and expenses related to the production of a product. S.No 1 2 3 4 Items Delivered cost of major equipments Equipment installation Insulation Instrumentation Direct Cost Factor (%) 100 25 15 20 Cost in Lakhs 490.00 122.5 73.5 98

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5 6 7 8 9

Piping Land and building Foundation Electrical Clean up Total

75 30 10 20 5 300

367.5 147 49 98 24.5 1470

Table 11- 2 Calculation of direct cost factor

Direct plant cost = [(Delivered cost of major equipments) x (Total direct cost factor) / 100] Direct plant cost = [(490 x 300) / 100] = 1470 lakhs

11.4 Calculation of Indirect Cost factor

Costs, such as depreciation or administrative expenses, are more difficult to assign to a specific product, and therefore are considered indirect costs.

S.No 1 2 3

Item Overhead Contactor Engineering fee Contingency Total

Indirect Cost Factor 30 13 13 56

Cost in Lakhs 441 191.1 191.1 823.2

Table 11- 3 Calculation of indirect cost factor

Indirect plant cost

= [(Direct plant cost) x (Total indirect cost factor))/100] = [(1470 x 56)/100)] = 823.2 lakhs

Fixed capital investment in the process area, IF = Direct plant cost + Indirect plant cost = 1470+823.2 = 2293.2 lakhs

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11.5 Estimation of the capital investment in the auxiliary service, IA

Such items as steam generators, fuel stations and fire protection facilities are commonly stationed outside the process area and serve the system under consideration.

S.No 1 2 3 4 5 6 7 8 9 10

Items Auxiliary buildings Water supply Electric Main Sub station Process waste system Raw material storage Fire protection system Roads Sanitary and waste disposal Communication Yard and fence lighting Total

Auxiliary services cost 5 2 2 1 2 1.5 1.0 0.5 0.5 0.5 16

Cost in Lakhs 114.66 45.864 45.864 22.932 45.864 34.398 22.932 11.466 11.466 11.466 366.912

Table 11- 4 Estimation of the capital investment in the auxiliary service

Capital investment in the auxillary services = [(Fixed capital investment in the process area) x (Auxiliary services cost factor) / 100] = 366.912 lakhs Installed cost = Fixed capital investment in the process area + Capital investment in the auxiliary service = 2293.2 + 366.912 = 2660.112 lakhs

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11.6 Estimation of the capital investment as working capital, IW

This is the capital invested in the form of cash to meet day-to-day operational expenses, inventories of raw materials and products. The working capital may be assumed as 15% of the total capital investment made in plant.

Capital investment as working capital, IW

= [(2660.112) x 15) / 85] = 39901.68/ 85 = 469.43 lakhs

11.7 Estimation of total capital investment

Total capital investment, I = IF+ IA+ IW = 2293.2+366.912+469.43 = 3129.54 lakhs

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CHAPTER 12 PLANT LOCATION AND LAY OUT 12.1 Plant layout

The arrangements of equipment and facilities specified from process flow sheet considerations is a necessary requirement for accurate preconstruction cost estimation or for future detailed design involving piping, structural and electrical facilities. Careful attention to the development of plot and elevation plans will point out unusual plant requirements and therefore give reliable information on building and site costs required for precise preconstruction cost accounting.

12.2 Factors in planning lay-out

Rational design must include arrangement of processing areas and handing areas in efficient coordination and with regard to such factors as, 1. New site development or addition to a previously developed site. 2. Future expansion. 3. Economic distribution of services water, process steam, power and gas. 4. Weather conditions are they amenable to outdoor construction. 5. Safety consideration possible hazards of fire explosion and fumes. 6. Building code requirements. 7. Waste disposal problems. 8. Sensible use of floor and elevation space.

12.3 Methods of lay-out planning

To start a detailed planning study, space requirements must be known for various products, by-products and raw-materials as well as for process equipment. A starting or reference point, together with a directional schematic slow pattern will enable the design engineers to make a trial plot as shown in the figure. A number of such studies will be required before a suitable plot and elevation plan is chosen. The various methods of Lay-out are as follows:

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Unit area concept

The basic blocks with which to build an arrangement for plot plans are often used in the unit area concept. This method is particularly well adopted to large plan Lay-outs. Unit areas are often delineated by means of distinct process phases and operational procedures, by reason of contamination and by safety requirements.

Two-dimensional Lay-out
To visualize the layout problem, two dimensional scaled templates or small cutouts of unit areas and equipment within each areas are shifted about on crosshatched scale paper.

Figure 12- 1 Plant layout

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12.4 Scale Models

Recent developments in the use of scale models have shown the advantage of this method over the detailed two-dimensional method. The method is used to develop plot and elevation plans and can also be used for piping and utilities layout with a good dimensional accuracy. The advantage of three-dimensional models can be summarized as, 1) Optimum design selection. 2) Effective construction planning. 3) Savings in engineering design, construction, operating and maintenance cost 4) More rapid and safer training of personnel.

12.5 Equipment Layout

In making a layout, ample space is assigned to each piece of equipment. Accessibility is an important factor of maintenance. It is extremely poor economy to fit the equipment layout too closely into a building. A slightly large building than appears necessary will cost little more than one this is crowded. The extra cost will indeed be small in comparison with the penalties that will be extracted if, in order to iron out the kinds, the building must be expanded. The operations that constitute a process are essentially a series of unit operations that may be carried on simultaneously. These include filtration, crystallization, separation, and drying. Since these operations are repeated several times in the flow of materials it should be possible to arrange the necessary equipments into groups of the same kinds. This sort of layout will make possible a division of operating labour so that the one or two operators can be detailed to tend all equipment of a like nature. The relative levels of the several pieces of equipment and their accessories determine their placement. Although gravity flow is usually preferable it is not altogether necessary because liquids can be transported by blowing or by pumping and solids can be moved by mechanical means. Access for initial construction and maintenance is a necessary part to planning. For example, overhead equipment must have space for lowering into place, and heat exchange equipment should be located near access areas where trucks and hoists can be placed for pulling and replacing tube bundles. Thus space should be provided for repair and replacement 68

of equipment and also for access way around doors and underground hatches. But a little regard should be given for proper placement of each of these services, practicing good design, aids in ease of operation, orderliness, and reduction in costs of maintenance.

Building
After a complete study of qualitative factors, the selection of the building or buildings must be considered. A complete architect should be consulted to design a building around the process. It is fundamental chemical engineering industries that the buildings should be built around the process, instead of the process being made to fit buildings of conventional design.

Waste-Disposal
Throughout the chemical industry much thought should be given to the disposal of waste liquor, fumes, dusts and gases. Ventilation, fume elimination and drainage may require the installation of extra equipment. In the selection and the placement in the process area, such pieces of equipment for doing the above services is also an important point. Sometimes air conditioning of the plant is called for that may require an elaborate set up.

Materials Handling Equipment

Consideration of equipment for material handling is only a minor factor in most cases of arrangement owing to the multiplicity of available material handling devices. But where this operation is paramount in a process serious thought must be given to it.

12.6 Plant Location

The various needs and conditions must be defined clearly before considering a site to locate a factory. The main factor that is to be considered for deciding the location of a site for a factory is that it should yield maximum possible benefit with minimum possible efforts. The many number of factors that are to be taken into account to satisfy the above statement are broadly divided into two groups. 1) Primary factors 2) Secondary factors 69

Primary factors
Availability of raw materials The location of the factory is influenced by the sources of raw materials. It is definitely advantageous things of the factory is located near the source of raw materials.

Availability of power, Fuel Power is an essential requirement for a factory. Therefore sufficient quantity of power should be available for the needs of the factory without failure.

Availability of water Water is important requirement for a factory. It is used for cooling the reactors. So, plant is located near the rivers.

Availability of labour Availability of required number of labour in the requisite type is also an essential consideration. Density of population is not only the consideration. The people in surrounding areas are willing to work the factory. This depends on the maturity of citizens, influence of local industries lively hood, etc.

Climatic and atmosphere conditions If the climatic and atmosphere conditions are not favourable, employees may not be willing to work. The second consideration is the precision machines get spoiled. a) If there is much fluctuation of temperature. b) If the factory is within the vicinity of the sea breeze it requires a cool atmosphere. In modern days the temperature inside the factory is regulated by scientific method. Market facilities Facilities for marketing the finished goods should be available. If the markets are near to factory, a) The cost of transportation will be less. b) The finished goods will be known in the market.

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Transport facilities Economical conveyance a quick transport facilities should always be available whenever the raw materials, etc. are to be transported to the factory or finished products to the markets. Road, rail, water or air transportation facilities are required for the plant under consideration.

Secondary Factors
The following factors are also be taken into account before selecting a site for a factory. 1. Cost of land 2. Laws governing the area 3. Fire protection 4. Availability of water for the employees and factory purposes 5. Progressive attitude of the citizens of the area towards the industry

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CHAPTER 13 HAZARDS AND SAFETY

13.1 Safety
Safety is a science which deals with aspects that keeps away the working atmosphere out of hazard. Hence safety is the prime consideration in the design of process plants. Disregard of safety is comparable to criminal negligence. The general safety code applies to all employees.

13.2 Hazards in Refineries

Indian Oil industries is about 100 years old. In 1985, a safety council composed of senior officials of the Ministry of Petroleum & Natural Gas was constituted with chief Executives of the Oil Companies & other concerned heads of statutory bodies as an Apex body. The council is assisted by a safety Directorate. All activities of refineries are under the Jurisdiction of the safety Directorate. Hydrocarbons handled in Petroleum industry are highly toxic & corrosive which are present in the crude oil & its finished products. The people working in the petroleum industry are always exposed to danger of fire, explosion, pollution & health hazards. Hazards in refineries are overcome by various means in various stages, which are discussed below.

13.3 Design Safety

Potentially hazardous situation in refinery is generally get created during Start Up, Shutdown & Emergency because of various causes like Utility failure, Instrument Failure, etc,. To handle all such situation, facilities like Relief or Disposal system, Shutdown system, Instrument with Manual/Auto system, etc, are provided & necessary procedures are followed. All these aspects are looked into right at the stage of design. Area of concern in petroleum industry is the disposal systems including routing of safety valves, discharge to atmosphere, vent stacks, condensable & non condensable blow downs to flare, flare height, location & size, remote depressurizing, insulation & fire proofing instrumentation, fail 72

safe trips for critical equipment. Static electricity has been cause of many fires in the oil industry. Refineries also deal with toxic chemicals. Health monitoring is necessary for the operating personnel who work in the areas where these toxic chemicals are handled.

13.4 Layout
Layout consideration has to be given for the inter spacing between 1) Equipment within the process block 2) Utilities 3) Tankage & Loading gantries to minimize the involvement of adjacent equipment in the event of fire. 4) The effects of radiant heat from storage tanks & the BLEVE effects from LPG storage vessels are to be given serious consideration.

13.5 Operating Procedures

In many of the worst disasters that took place all over the world, it was not the technology that was lacking rather the discipline required to follow procedures & good operating practices. Adhering to written procedures, keeping the instruments healthy & online are some of the essential items of a good operating discipline.

13.6 Static Equipment

Crude containing naphthenic acid, which affects transfer lines. Vessels & piping in MEA services are susceptible to cracking. All equipment, pressure vessels, Pipe lines, tankage are to be periodically checked for corrosion aspects for different operating conditions.

13.7 Fire
Fire in petroleum industry can breakout due to any of the following reasons, Spark by Electrical circuit, Hot work, Storage vessel not earthed, etc,. Hence a good fire protection systems like Detectors, Monitors, Sprinklers, etc, should be considered inside the plant to kill the fire if triggered. 73

13.8 Health Hazard

Health hazard for men can be caused due to air/water/thermal/noise pollution due to H 2S, SO2, etc., higher than acceptable limits flying of solid catalyst dust, solid sulphur particles Acid & Alkalis burns due to handling Leakage/Spillage of toxic chemical, such as phenol, formaldehyde, chlorine, etc.

13.9 Important Safety Rules to Prevent High Pressure Hazards

1. Pressure gauges like Bourdon type should be free of air inside the tube. The gauges should be installed above eye level. Tube should never be allowed to corrode. Too rapid rise or fall of pressure must be avoided. Root valve must be opened only to the required level & not wide open. 2. Flammable gases at HP on rubbing against wall of metallic pipes causes static electricity discharge. Good earthing is essential. 3. Bursting of rupture disc in vessels cause sudden high temperature which may ignite flammable gases. Sufficient venting height is necessary, where it can cause no harm. Discharge line must have sufficient diameter to carry the excess load release. 4. Direct fires vessels should not be emptied suddenly. The fluid running in slow velocities slowly cools them. 5. Two Safety valves, one operating at slightly lower pressure is advantageous in very high pressure equipment's. 6. HP tubing's should be anchored securely at frequent intervals to prevent whipping in case of break. 7. Welded equipment should be heat treated to relieve locked up stresses. Expert welders should be engaged. Too frequent radiography test of these equipment must be carried out for any possible cracks developed during operation. 8. Oils should never be used as lubricant when oxygen is compressed. 9. Regular inspection should be carried out with experienced staff.

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13.10 Environmental Control

Emission norms as stipulated by Central Pollution Control Board and other mandatory regulations shall be satisfied for the project. Liquid effluent shall conform to MINAS standards. All unit designers have to necessarily furnish complete effluent characteristics in the format of Exhibit-I.

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CHAPTER 14 CONCLUSION
Firstly, the organization profile has been given and followed by that the characteristics of crude oil is explained. The various refinery operations are also mentioned.

The Material and Energy balances have been developed to the whole of the process flow diagram.

The cooler is designed to be consisting of tubes of 20mm OD * 15.8 mm ID * 4880 mm long and a shell ID of 387.35 mm of passes 4 and 1 respectively. The overall heat transfer coefficient for the respective duty is found to be 524.97 W/m2 C. A pressure drop of 2.3258 k Pa is achieved in tube side and a drop of 1.147 k Pa in shell side.

A stripper of ID 2 ft., height 69 ft., and with 30 trays each of 15 inch spacing is designed for the purpose of regeneration of rich amine.

The safety and handling procedures for the refinery are elaborately studied and given and the plant location and layout are clearly depicted.

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REFERENCES

1. Bhatt .B.I., Vora .S.M., Stoichiometry, 4thEdition, McGrawHill. 2. Coulson & Richardsons, (1999), Chemical Engineering, Vol.1, Sixth Edition. 3. Coulson & Richardsons, (2002), Chemical Engineering, Vol.2, Fifth Edition. 4. Coulson & Richardsons, (2005), Chemical Engineering Design, Vol.6, Fourth Edition. 5. David M.Himmelblau, Basic Principles and Calculation in Chemical Engineering Prentic Hall of India. 6. G.K.Roy, Solved Examples in Chemical Engineering, Khanna Publishers Delhi, 6th Edition. 7. Harry Silla, Chemical Process Engineering Design and Economics 8. James G.Speight (2006), The Chemistry and Technology of petroleum(4thEdition). 9. Jullius Scherzer and A.J.Gruia Hydrocracking Science And Technology,Marcel dekker publications. 10. McCabe L. Warren, Smith C. Smith, Harriot Peter, Unit Operations in Chemical Engineering, Sixth edition, 2007, McGrawHill. 11. Peters and Klaus D. Timmerhaus, Process Economics and Plant Design, McGraw Hill International Edition. 12. Process design principles: Synthesis, analysis and evaluation by 13. Robert E Meyers ,Handbook of Petroleum Refining Processes 14. Robert E.Treyball, Mass Transfer Operations, Tata McGraw Hill Publishing Co.3rd Editon. 15. Robert H. Perry, Don W. Green, Perrys Chemical Engineers Handbook, Fifth Edition, 1978, McGrawHill Sherves Chemical Process Industries, G.T. Austin 5th edition, McGraw Hill publications 16. Stanley M.Walas, Chemical process Equipment Selection and Design, ButterworthHeinemann series. 17. Warren D. Seider, Daniel R. Lewin, J.D. Seader

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