November 1950

(9) Gollmar, (10) (11) (12) (13) (14) (16) (16)

INDUSTRIAL AND ENGINEERING CHEMISTRY

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H. A., Chap. 25 of Chemistry o f Coal Utilization, New York, edited by H. H. Lowry, John Wiley & Sons, 1946. Gollmar, H. A., private communication. G o b a r , H. A., U. 8. Patent 1,719,762 (1929). Ibid.. 2,379,076 (1945). Zbid., 2,464,804 (1945). Hutchinson, A. J. L., Ibid.. 2,177,068 (1939). Jacobson, D. L., Zbid., 1,719,180 (1929). Mann, M. D., Jr., and Lebo, R. B., Ibid., 1,525,140 (Feb. 3,

1926). (17) Marshall, J. R.. Uas World (Coking Seotion), 129, 106 (1948). (18) Morgan, R. A., et al., U. 6.Patent 1,732,905 (1929). (19) Mullen, J. M., Refiner Natural Gasoline Mfr., 18, No. 4, 159 (1939). (20) Powell, A. R., IND. ENQ. CHEM., 31,789-95 (1939). (21) Powell, A. R., U. 9.Patent 2,242,323 (1941). (22) Reed, R.M., Oil d Qas J . , 44, 219-26 (1946).

(23) Reed, R. M., Petroleum Processing, 2, 907 (1947). (24) Reed, R. M., U. 8.Patent 2,399,142 (1945). (25) Read, R. M., and Wood, W. R., Trans. Am. Inst. Chem. Engrs., 37,363 (1941). (26) Reitmeier, R. E., U. 8. Patent 2,405,672 (Aug. 13, 1946). (27) Rombaugh, T. W., Proc. Am. Petroleum Inst.. 8th Mid-Year Meeting, Sect. IZI, 19, 47 (1938). (28) Rosenatein, L., and Kramer, G. A., U. 8 .Patent 1,945,163 11934). and Sohmidt, L. D., IND. ENG.CHEM., 42, 2277 (29) Sanda, A. E., (1950). (30) Shaw, J. A., U. S .Patent 2,098,124 (1936). (31) Shoeld, Mark, Ibid., 1,971,798 (1934). (32) Spew, F. W . , Jr., Proc. Am. Qae Aasoc., 1921, 282-364. (33) Technicel Oil Mimion Film, Reel 132. (34) Wood, W. R., and Storrs, B. D., Proc. Am. PefroleumInat., 8th Mid-Year Meeting, Sect. IZZ, 19,34-6 (1938). R B ~ c ~ Msroh v~~D 27, 1950.

RECOVERY OF SULFUR
FROM SYNTHESIS GAS
A. E. SANDS AND L. D.SCHMIDT
U. 8. Bureau of Mines, Synthesis Gar, Production Branch, Morgantown, W. Va.

The United States Bureau of Mines at ita Morgentown, W. Va., station, in cooperation with West Virginia University, is conducting reaearch and development work on a laboratory and pilot plant Male on the problem of producing synthesis gae directly from raw coal by a continuous, low cost process. An essential part of this work is the atudy of the g a m purification neceaary to meet the rigorous .tandads (23)required to render the gas suitable for the synthesis of liquid fuels by the Fischer-Tropsch process.

Although the purification of synthesi. gas may result in the removal of several different impurities, the complete removal of sulfur is generally considered to be the most important problem. While this involves removal of both organic sulfur and hydrogen sulfide, this paper ie largely devoted to discussion of the removal of hydrogen sulfide, with special reference to sulfur recovery. For a more extensive review of sulfur compounds in gas and their removal, refer to the excellent work of Gollmar (221.

HE recovery of sulfur from synthesis gas made from coal is a matter of interest not only to the large synthetic liquid fuel plants of the future but to present and future plants that are built to produce ammonia, alcohols, and other chemicals from coal through the medium of synthesis gas. This paper discusaaa the factors that differentiate synthesis gas purification from other gas purification practice. The relation between sulfur content of the coal used for synthesis gas production f synthesis gas purification is explored through cost and the cost o estimates for gas purification and sulfur recovery. These estimates, which are not to be considered accurate and final, were p r e p d as a baeis for discueaion and for future revised cost estimates of a m o r e aaourate nature. It is believed that the recovery of sulfur in connection with the purification of synthesis gas will yield important credits to the f gas purification. C o s t estimatw indicate that the cost of cost o removing sulfur doea not increase in proportion to the concentration of sulfur in the gre. On the other hand, the net credits resulting from sulfur r e m e r y do increase in proportion to the sulh i s relationship between gas purification costs fur content. If t and sulfur credits is validated by further experimental work, it would mean that the use of higher sulfur coals for synthesis gas production; rather than being objectionable, would be dasirable. Growing concern has been expressed with respect to the extent o f the nations sulfur reserves. At the current rate of consumption the amount of natural sulfur known to exist in the United States would last for only 30 years (19). I n 1947, production of sulfur amounted to 4,441,214 long tons (18). Because sulfur is so essnntial to the national welfare, in peace or in WW, a means of

supplying thw importpnt commodity, when natural reserves become exhausted, is of the highest importance. The recovery of sulfur from manufactured gas in any plant is not entirely a matter of economics. Several plants have found it necessary to reduce the amount of air pollution which results from purification procesaes that vent hydrogen sulfide to the a t m o s phere. These plants have turned to sulfur recovery as a means of disposal of hydrogen sulfide.

PROCESSES FOR HYDROGEN SULFIDE REMOVAL AND SULFUR RECOVERY Processes for the removal of hydrogen sulfide from gas may be classified as wet and dry processes and may be further described according to their ability to permit sulfur recovery in one form or another. The wet processes-wherein hydrogen sulfide is removed by scrubbing-are described in another paper in this symposium (88). The principal dry processes are the dry box (iron oxide) process and the activated carbon catalytic proceea. Both these processes offer possibility of sulfur recovery.
DRY BOX (IRON OXIDD

Hydrated iron oxide, coated on shavings and supported on trays in rectangular boxes, is used in most small plants that manufacture gas for city use-that is, for distribution by h i s proceaa is also used in large plants for public utilities. T h a 1 clean-up of the last 10 to 25 grains of hydrogen sulfide per 100 cubic feet of gas following such liquid purification processes aa the Seaboard (N), Thylox, or vacuum carbonate proceeaes. It is geserally lesa expensive to remove these remain-

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ing amounts of hydrogen sulfide by iron oxide than it is to operate the liquid purification process to effect complete removal. Air is generally added to the gas before the dry boxes to provide a concentration of 0.6 to 1.0% oxygen; this oxygen serves simuitaneously to revivify the ferric sulfide, yielding iron oxide and elemental sulfur. In spite of this simultaneous revivification, it is generally necessary to dump the material and revivify it in the open air, one or more times, before it is finally discarded. The material is discarded when the total sulfur content reaches 50 to 60%. When used for final clean-up in catch boxes, the total sulfur may reach only about 30% before it is discarded as it is difficult to reach high sulfur concentrations in the oxide when the hydrogen sulfide concentration of the gas is low. A t least one large company formerly sold its spent material for use in manufacture of sulfur dioxide for sulfuric acid production. Granulated blast-furnace slag was substituted for shavings in the oxide. After combustion of the sulfur the iron oxide residue was worthless for further gas purification. A t present, this company has no market for its discarded oxide, and its disposal has become a problem. Frequently, disposal of the discarded material becomes difficult as it may be necessary to ship the material some distance to a suitable dump or to the ocean. In Great Britain spent oxide has been sold for its sulfur content or new iron oxide has been furnished to gas companies free of charge in exchange for spent material. In Germany spent oxide was extracted with carbon disulfide to recover sulfur; usually one central extraction plant handled the spent oxide from several gas plantsa Some years ago one of the authors carried out a laboratory investigation of sulfur extraction using inexpensive solvents: substantially complete separation of sulfur from oxides containing over 50% elemental sulfur was obtained (26). Later, unpublished work by the author dealt with sulfur extraction in a batchoperated pilot plant having a capacity of 2 tons of spent oxide. Incomplete work on this scale indicated commercial possibilities, especially if the oxide could be used again for gas purification. Laboratory fouling tests on the extracted oxide showed that the material had some value for gas purification but that the activity was considerably less than that of new material. It was believed that the activity could be increased by use of lower temperatures during extraction and by treatment of the extracted oxide. Recent investigations in Great Britain ( 6 , 3 3 , 8 4 )deal with the use of iron oxide in a fluidized bed. This work, although on a laboratory scale, appears to have been carried out in a very thorough manner and offers promise for the application of the fluidized technique to commercial dry box purification. Extraction of sulfur from the spent material by carbon disulfide was successful and, surprisingly, the extracted material was even more reactive for hydrogen sulfide removal than was the original oxide. In plants operated a t about atmospheric pressure the additional pressure drop required in fluidization would be a factor for consideration, but the pressure drop would be negligible in synthesis plants where the gas is to be used at pressures of 300 pounds per square inch gage or higher. Not much information appears to be available from Germany on the advantageous use of elevated pressures in dry box purification, but private information obtained by the authors indicates that increasing the pressure to 500 pounds per square inch gage greatly increases the activity and capacity of the iron oxide. Even 8 moderate pressure increase (up to 50 pounds per square inch gage) is said to be beneficial. All this experimentation in the field of dry box purification should be of interest to the gas industry because in spite of the disadvantages of dry box purification, in large plants, as a single process for the removal of hydrogen sulfide, the process has certain distinctive advantages to compensate for the amount of space and labor required and, ordinarily, for the lack of sulfur recovery features. Fluidization and the use of elevated pressures, together with sulfur extraction, might eliminate these objections. Moreover, dry box purification has always offered the advantage of the greatest selectivity of absorption of hydrogen sulfide in the

presence of carbon dioxide. No known liquid purification process completely removes hydrogen sulfide with as little interference by carbon dioxide. Dry box purification, under pressure and with fluidization, employing American oxides is on the program for investigation by the Bureau of Mines at these laboratories.
ACTIVATED CARBON CATALYST

Several plants in Germany-especially in Upper Silesia-removed hydrogen sulfide from gas by oxidation on an activated carbon catalyst (28). To accomplish this 10 to 15 grains of ammonia were added for each 100 cubic feet of gas treated; air or oxygen was added in about the stoichiometrical amount.

I. G. Farbenindustrie, at the Leuna Works, purified PintschBrassert water gas by this method for over 20 years. Gas containing 130 to 175 grains of hydrogen sulfide per 100 cubic feet was treated to yield a gas containing 0.04 to 0.08 grain of hydrof the hydrogen sulfide content gen sulfide per 100 cubic feet. I was too high this process could not be used because of the high temperatures resulting from the heat of reaction. As far as heat effects are concerned even 10 to 20 grains of hydrogen sulfide per 100 cubic feet (at atmospheric pressure) would be equivalent to 300 to 600 grains a t a pressure of 30 atmospheres. The activated carbon used was produced by treating brown coal at a high temperature with steam. After the carbon was in use for 10 days, it was taken off stream and extracted with ammonium sulfide a t a temperature of 40" C. in the absence of air. The polysulfide extract was then distilled a t a pressure of 2 atmospheres and a top temperature of 111" C. Molten sulfur and water were separated in two layers at the bottom of the still; vapors of solvent were condensed and returned to the extraction unit.
This process was unsuccessful on coal gas at Huls, Germany, because the gas contained gum-forming compounds which were deposited on the carbon. The activated carbon used was made from coal and should be relatively inexpensive. Two carbons investigated a t Morgantown for application to the adsorption of organic sulfur compounds are available a t 15 and 35 cents per pound; the cheaper of these f more extwo carbons was about equal in performance to that o pensive carbons for the purpose studied. When the program permits, activated carbon will be included in the catalysts for hydrogen sulfide removal being investigated at Morgantown.

SYNTHESIS GAS PURIFICATION When gas made directly from coal is to be used for synthesis purposes, special requirements make the problem of sulfur removal unique when compared to the usual plant experience with manufactured, natural, or refinery gas. Primarily for this reasou the Bureau of Mines is giving major attention to the problem.
COMPLETENESS OF REMOVAL

It is generally recognized that the total sulfur content of synthesis gas should not exceed 0.1 grain per 100 cubic feet, and a t times a lower limit may be desirable. Work in Great Britain (4), with nickel catalysts, for synthesis of methane from synthesis gas indicates the desirability of limiting the sulfur content to 0.002 grain per 100 cubic feet. Such low limits not only demand a much more complete removal of hydrogen sulfide than is usually attained in the purification of the industrial gases but necessitate the removal of organic sulfur compounds as well.
EFFECT OF CARBON DIOXIDE ON HYDROGEN SUEFIDE REMOVAL

Modern processes now being developed employing pulverized coal, steam, and oxygen may produce gas containing 8 to 20% carbon dioxide. Some processes for hydrogen sulfide removal are adversely affected by high carbon dioxide concentrations. Thus, the phenolate process, which works well on gases substantially free of carbon dioxide, is not recommended by the originators of the process for gases having high carbon dioxide content. The Thylox process, which is sensitive to pH changes of the absorbing

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solution, w o r b better on gases of lower carbon dioxide content. Although this process is in use for the purification of synthesis gas (blow run water gas) containing 7 to 8% carbon dioxide, difficulties might be expected if the carbon dioxide content were increased too far above these values. Aside from possible interference with the removal of hydrogen sulfide or with the chemistry of the process in question, higher carbon dioxide concentrations in the gas result in larger quantities of carbon dioxide absorbed by the hydrogen sulfide absorbant. This is a disadvantage, aa has been shown in the discussion of selective absorption presented in other papers in this symposium
(8, 89).

Selectivity is not so important with refinery or natural gas; the former has little or no carbon dioxide whereaa in the latter the hydrogen sulfide content generally exceeds the carbon dioxide content.
ELEVATED PREBSURES

distance, natural gas pipe line companies rather than that of the present manufactured-gas enterprise. He gives several reasons for this prediction, including the belief that economy of operation of auxiliary equipment, such as oxygen plant and coal conveying equipment from mine to plant, improves with size. Another reason is the cost reduction afforded by transporting gas by pipe lines of large diameter. As an illustration of pipe-line size and economic gas load, he states that a 22-inch diameter pipe line should carry approximately 250,000,000 cubic feet of gas per day. The communication concludes with a statement that production of this much gas by synthesis would mean a daily output of synthesis gas amounting to 800,000,000to 1,000,000,000 cubic feet and would require about 6,000,000 tons of coal per year. One conclusion resulting from the study of hypothetical plants of these magnitudes is the absolute necessity for the recovery of sulfur from the gas. This necessity results from two factors:
1. I f the sulfur content of the coal used in gas production ranges from 1 to 5%, it is estimated that the recoverable sulfur would amount to 32 to 184 long tons per day in a plant producin 336,000,000 cubic feet of gas. I t is unthinkable that this mucf sulfur would be vented to the atmosphere-either as hydrogen sulfide or sulfur dioxide-in view of the current trend of public thinking with respect to air pollution. Plants removing much less sulfur have been forced to incorporate sulfur recovery in their process even after years of operation without it, 2. Sulfur recover in amounts indicated by Breck becomes attractive economica$y. Also, if by the time large plants (presently hypothetical) are realized, the natural sulfur reserves are depleted, the need for sulfur recovery will be emphasized.

Synthesis gas, after purification, is ordinarily employed in the synthesis at elevated pressures. Therefore it is economical to compress the gas before removal of sulfur compounds. Although such purification under pressure is common in the treatment of natural or refinery gas, elevated pressures are not used in the purification system in the manufacture of city gas. City-gas distribution systems are generally under relatively low pressures, measured in inches of water. Some parts of manufactured-gas distribution systems may operate at higher pressures (perhaps 50 pounds per square inch gage), but the gas is made and purified at ordinary pressures. G a s compression costa would make it prohibitive to employ pressures of 300 to 450 pounds per square inch gage in gas purification if the gas were to be used or distributed at low preasures. Because pressure is advantageous in absorption and adsorption, the possibility of employing pressure is an important consideration in removing sulfur from synthesis gas. In comparing processes that have been employed a t only normal pressures, consideration should be given to the possibility that at elevated pressures such processes may give different relative performances than at lower pressures. Relative comparisons of processes at substantially atmospheric pressure and at, for example, 20 atmospheres, will depend on the extent of changes in equilibrium for the hydrogen sulfide-absorbant solution system in question. This can be determined reliably only by experimentation. Investigation of the effect of pressure on hydrogen sulfide absorp tion by various absorbanta will be undertaken by the Bureau of Mines in its gas purification pilot plant a t Morgantown. The bureaus demonstration plant at Louisiana, Mo., should soon be in a position to furnish actual operating data on the purification of gas under pressure by the processes employed in that plant.
U R G E PLANTS

SULFUR RECOVERY
In processes that yield elemental sulfur directly, recovery involves only separation-in the Ferrox, nickel, and Thylox processes by flotation and in the dry box and activated carbon processes by extraction from the purifying mass. In the absorption-desorption processes hydrogen sulfide is separated from the solution by stripping with steam. The following section describes methods for the commercial utilization of this hydrogen sulfide.
UTILIZATION AS HYDROGEN SULFIDE

Although current uses for hydrogen sulfide are limited mainly to laboratory work and chemical reduction on a small scale, it is possible that chemical technology may develop new uses for the gas, if available in pure quality and large quantities. Also solutions of sodium hydrosulfide are prepared easily by absorption in caustic soda. Sodium hydrosulfide is used in the textile, dye, and tanning industries.
UTILIZATION AS SULFUR DIOXIDE

Another distinctive feature of synthesis gas purification is the employment of large gas capacities. Present-day synthesis gas purification is restricted to synthetic ammonia and alcohol plants having capacities of the order of 60,000,000 to 90,000,OOO cubic feet per day. These capacities are large compared with most plants manufacturing gas for city use. However, plants built in the future to produce synthetic liquid fuels or pipe line gaa are expected to be even larger. Most of the bureaus cost studies for hypothetical synthetic liquid fuel plants are baaed on plants producing a t least 10,OOObarrels of product per day. This minimum plant would require in the neighborhood of 336,000,000 cubic feet of raw synthesis gas per day. In a communication to the authors ( 8 ) Breck states that when the synthesis of gas comparable in heating value with natural gas becomes a commercial reality the order of magnitude of an individual operation will probably be much closer to that of the long

Hydrogen sulfide can be burned to yield sulfur dioxide, which can be used to produce sulfuria acid. In the a6tual production of sulfur dioxide it i s claimed that combustion of hydrogen sulfide is less troublesome than is the operation of brimstone burners (16). Gollmar (11) indicates some of the necessary steps to be taken : Because ammonia and hydrogen cyanide will yield nitrogen compounds in the sulfuric acid, it is desirable to treat the hydroen sulfide to remove the nitrogen compounds when present. k m o n i a and hydro en cyanide are said to be easily removed by washing with water fg4). Experimental work in pulverized coal gasification at Morgantown indicates that only extremely low concentrations of ammonia and hydrogen cyanide will be encountered. Difficulties caused by the water formed by combustion of hydrogen sulfide can be avoided by cooling and dehydrating the combustion gases before passing them through the converter ( 14 ) or by using a water-insensitive catalyst and fractional condensation of the sulfuric acid in specially designed equipment (IO,16). Difficulties due to acid mist, which persists in gases leaving the condensers when water is present, can be minimized by using electrical precipitators.

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Val. 42, No. 11

PASS

LEGEND

F I FLOW UJDICATOR RFC-RATIO FLOW CONTROLLER PC- PRESSURE CONTROLLER

SW- COOLING WATER

AIR BLOWER

COM BU S T IO N
CHAMBER

Figure 1.

PUMPS Girdler SuIfur Recovery Plant

recovery plant of the Claus type. problem as follows: Gollmar (IS) analyzes the

In a private communication the authors have been advised that one company, which is exploring the possibility of sulfuric acid manufacture from hydrogen sulfide, is concerned over possible excessive corrosion in the acid plant due to presence of water. This company believes that such corrosion would require exteneive use of stainless steel and that, for this reason, it is moye economical to convert the hydrogen sulfide to brimstone in a Claus kiln, using the brimstone for acid manufacture. The Seaboard plant of Koppers Company a t Kearny, N. J., however, burns hydrogen sulfide recovered from its vacuum carbonate plant and utilizes the sulfur dioxide for acid manufacture. This plant has a capacity of 15,000pounds of sulfur per day from 48,000,O cubic feet of coke-oven gas (18). The authors have been advised that in this plant brimstone or hydrogen sulfide is used interchangeably and that the choice of either is immaterial, rn far as operating difficulties are concerned ($1). Hydrogen sulfide from the vacuum carbonate process is similarly utilized at the Neville Island plant a t Pittsburgh, Pa., which has a capacity equivalent to 12,000 pounds of sulfur per day from 20,000,000 cubic feet of coke-oven gas. If a sulfuric acid plant is to be operated in conjunction with a gas purification plant, it would appear advantageous to burn the hydrogen sulfide to sulfur dioxide rather than t o operate a sulfur

Although a sulfuric acid plant utilizing hydrogen sulfide costs more to build because it requires a lead-lined cooler and electrical precipitator, maintenance and operating costs for this additional equipment are a minor item per ton of sulfur in comparison with capital and operating costs for Claus kiln operation. Sulfuric acid plants utilizing brimstone and those using hydrogen sulfide both employ dryers, the former for drying air before combustion and the latter for drying the cooled products of combustion leaving the electrical precipitator. Both dryers are of ordinary steel construction, and neither type is troublesome to operate. The chief advantage of the Claus kiln in plants is its sulfur storage capacity; it is preferable to store sulfur rather than sulfuric acid. On the other hand, a real advantage of burnin the hydrogen sulfide to sulfur dioxide is that less sulfur is vente$ to the atmosphere. Sulfuric acid plants can keep the sulfur content of their effluent gases at a much lower level than Claus kilns, but, of course, if both an acid plant and a Claus kiln are operated, the situation will be that much worse. In addition to its use in sulfuric acid manufacture sulfur dioxide is easily liquefied and, if dehydrated, presumably could be shipped in cylinders or tank cas.

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OXIDATION OF HYDROGEN SULFIDE TO BRIMSTONE

Clam Kilns in Germany. Elemental sulfur can be produced by reaction of 2 molecules of hydrogen sulfide with 1 molecule of oxygen. The reaction is carried out in equipment known as a Claus kiln ( 3 ) . The original Claus kiln was developed in Germany around 1880; it consisted of a single chamber containing bauxite or iron oxide catalyst. The chief difficulty i~ the operation of old type kilns was temperature control. Thermodynamically, the most favorable temperature for the production of sulfur by this reaction is 320" to 360" C. The heat of the reaction is sufficient to heat the reaction mixture far above this temperature. In the old type kilns heat was removed by natural radiation only; this required oversized kilns when the amount of hydrogen sulfide treated was large. In kilns of the new type, developed during World War I1 by I. G. Farbenindustrie, the obvious modification consisted of burning part of the hydrogen sulfide separately and cooling the gas to about 300" C. by generation of steam in the boiler. These kilns also employed a new bauxite catalyst, said to have 10 times the capacity of the old. Cain (3) stated that no pilot plant or commercial plant data were available for use in the design of a plant. Specificationsfor the catalyst were also lacking. All this information was believed to be at the Leuna plant of I. G. Farbenindustrie in the Russian Zone. A patent application found among captured German documenta ($99) mentions a catalyst which does not disintegrate at elevated temperatures. This catalyst consisted of pulverised bauxite pressed into granules or tiny tubes; binders were admixed and sintered under the influence of temperature. The new type kiln WM said to produce 2 tons of steam per ton of sulfur. Recovery of sulfur was 90% of theoretical. Sulfur Recovery Plants in United States. Sulfur recovery plants in the United States, either in operation or under construction, have a total design capacity of over 600 tons of elemental sulfur per day. A recent report (91) gives the following:
Loostion McKamis, Ark. Operator Mathieson Chemiaal Corp. Mathieson Chemical Corp Hanaock Chemical Co. Type Gaa Natural Natural Refinery Sulfur/Day,

oven gae by the vacuum carbonate process and from coke water gaa by the phosphate process.
GIXDLER SULFUR RECOVERY PWLNTS

An h e r i c a n development of the Claus kiln, similar to the new German type, is the Girdler Corporation process. In the company's description of the plant (9), recovery of 90% of the hydrogen sulfide ia the minimum guarantee for a two-stage plant; up to 95% may be expected. In a single-stage plant (one converter) 80 to 85% may be recovered. It is stated that any mixture of hydrogen sulfide and carbon dioxide can be procesead, although if the hydrogen sulfide falls below 30% special techniques may be required to promote the reactions. Steam produced is said to vary from 1 to 2 pounds of steam per pound of sulfur recovered, depending on the concentration of the hydrogen sulfide in the gas mixture, pressure of steam desired, and boiler efficiency. A flow diagram of the process is shown in Figure 1. One Girdlerengineered sulfur recovery plant is the Westville, N. J., plant of the Freeport Sulfur Company.

Tons

Magnolia, Ark.

100 (total both plants)

LOBAngeles, Calif.

60

(enlarging

It is believed that the plant at McKamis, Ark., is the oldest Claus-type sulfur recovery plant in this country; it was completed in November 1943. This plant originally purchased acid gases from the McKamis Gas Cleaning Company, paying a royalty, according to a 1947 report, amounting to a / ~of ~ the market value of sulfur recovered. A second plant a t Magnolia, Ark., was reported to have contracted for acid gases a t a royalty of 7/82 of the market value of sulfur recovered (90). The Hancock plant at Los Angeles, Calif., takes foul diethanolamine solution from four nearby refineries, actifies the solution by stripping a t the sulfur recovery plant, and returns the actified solution to 4he four refineries on a pro rata basis (31). The Wyoming plant of the Texns Gulf Sulfur Company operates with hydrogen sulfide stripped from monoethanolamine solution. The New Jersey plant of the Freeport 8ulfur Company will operate on hydrogen sulfide recovered from three Girbotol plants operated by the Eagle Point Refinery of the Texas Company. One of thew plmts is said to be a liquid-treating plant employing diethanolamine (87). The sulfur recovery plant of the Morgantown Ordnance Works is designed to operate on hydrogen sulfide recovered from coke-

RELATION OF SULFUR RECOVERY TO SYNTHESIS GAS PURIFICATION With growing public reaction against air pollution, sulfur recovery in large syathetic fuel plants in the future will be a necessity. The authors believe, moreover, that sulfur recovery, in many plants, will constitute a significant credit toward the cost of synthesis gas purification. The credit resulting from sulfur recovery is of great importance in planning for future synthetic liquid fuel plants utilizing coal because of its bearing on plank location. Although other factors are Importancfor example, the availability of adequate waterthe availability of sufficient tonnages af coal is even more important. Coals of widely varying sulfur contents are available, ranging from as low as 0.5 to over 5.0% sulfur. Coals of high sulfur content may have low ash fusion points, but this is not necessarily a disadvantage; lower ash fusion points are desirable in gasifiers where the ash is removed as slag. Coals of higher sulfur content may be available at lower cost, especially when they can be used without washing. Much research and process development must be completed in the production of synthesis gas directly from coal, but work already accomplished by the bureau a t Morgantown indicates that any coal from lignite to anthracite can be gasified successfully. However the importance of the sulfur content of coal and its relation to gas purification costs is not yet known, and purification costs cannot be considered together with coal costs in comparing possible sources of coal for synthesis gas. Estimation of purification costs-especially with coals of varying sulfur contents-must include the possible credits accruing to gas purification for the sulfur recovered therefrom. Communications from various sources reveal a wide difference in opinion as to the magnitude of these credits. The royalty paid in 1947 for hydrogen sulfide by the first American sulfur recovery plant (a/,@ of the market value of sulfur recovered) without processing costs for conversion to elemental sulfur, was proposed as a criterion by one gas purification plmt. This royalty would amount to $3.35 per long ton at the present market price of sulfur, $18.00. The fallacy in using this royalty 8 s a basis for estimating the value of hydrogen sulfide as a credit to gas purification costs is obvious as it does not account for the profit of the company converting the hydrogen sulfide to elemental sulfur. Large plants producing synthetic liquid fuels or other chemicals, such as ammonia and alcohols, from synthesis gas might be expected to add sulfur or chemicals requiriig sulfur M a raw material to its other chemical products. No data are available on royalty arrangements between companies purifying gas and companies stripping hydrogen sulfide and converting it to elemental sulfur. In such instances, if a

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royalty is paid the crrdit accruing to gas purification will exceed the royalty by an amount equivalent to the cost of the stripping operation. In absorption-desorption processes the stripping cost is normally the greater part of the total cost of removing hydrogen sulfide; if this stripping operation is performed by another company free of charge, the reduction in gas purification cost thus effected is in addition to the price paid, if any, for the hydrogen sulfide. In the opinion of the authors the logical credit to gas purification for sulfur (or hydrogen sulfide equivalent to sulfur) is the value of such sulfur less the cost of conversion of hydrogen sulfide to brimstone or less the additional incidental costs encountered when hydrogen sulfide is burned directly.
VALUE OF SULFUR

The authors believe that the value of either sulfur, or hydrogen sulfide equivalent in terms of sulfur, should be equal to that of natural sulfur. The purity of sulfur recovered by the Claus process usually is equal to the mined product. It has already been stated that the management of one plant considers hydrogen sulfid~ of utility equal to sulfur in the production of sulfuric acid. It follows then that the prirc obtained for recovered sulfur (or equivalent hydrogen sulfide) should be equal to the price of natural sulfur at the plant location, assuming a market exists a t that location or a t a point more remote from the sulfur mines. This price, of course, is the price of sulfur a t the mines plus the freight charges to the plant.

Table I. Delivered Prices of Sulfur at Typical Coal Centers

Total Delivered Freight Price per Via Charges Long Ton Rail-barge-rail $ 9 64 $29.14a All-rail 9.68 27.68 Rail-barge-rail 12.15 30.15 All-rail 1 1 .44 29.44 Port-to-port 7.32 26.8Za barge All-rail 11.44 29.44 Plaquemine, La. Morgantown, W. Va. Rail-barge 11.26 29,26 Boling, Tex. Morgantovrn, W. \'a. All-rail 13.64 31.64 Boling, Tex. Morgantown, W. Va. 9.20 28.70" Barge-rail Plaquemine La. Island, Ky. 9.02 27.02 All-rail Plaquemine: La. Island, KY. 29.71 Rail-barge-rail 11.71 Boling. Tex. Island, Ky. All-rail 11.66 29.66 Boling, Tex. Island. Icy. a Delivered prices based on $19.50 per ton, f.0.b. in barge: other prices based on $18. 0 per ton at point of orlgln. To Plaquemine La, Terre Haute, Ind. Plaquemine: La. Terre Haute Ind. Boling, Tex. Terre Hauti, Ind. Boling, Tex. Terre Haute, Ind. Plaauemine, La. Morgantown, W. Va
From

Table I gives delivered prices for unground, unrefined sulfur a t three typical coal centers. (It is assumed that large synthesis plants will be located in coal fields.) Freight rates from two sulfur shipping points are included ($0). Minimum barge shipments are 500 long tons. Minimum rail shipments that involve both rail and barge vary; these minima are 40,000, 60,000, and 80,000 pounds, Minimum quantities for all-rail shipments are 100,000 pounds. (It is presumed that small consumers cannot take advantage of the lower freights by barge.) The lowest delivered price of natural sulfur a t any of these coal centers is $26.82 per ton. However, in order to provide for adjustment of credits, for some cost items that may have been omitted, and for other economic considerations, the price of sulfur a t the recovery plant is assumed to be $18.00. For elemental sulfur conversion costs arc deducted from that figure to determine the credit to gas purification.
CREDIT FOR HYDROGEN SULFIDE

I n estimating these credits no deduction was made from the sulfur value for additional expense in operating the acid plant since Gollmar (IS) indicates that these costs may be a minor item; it is believed that the freight differential of over $8.00 per ton of sulfur more than covers this. In assuming the market price of sulfur from future plants to be the current price of 818.00 per long ton, not much consideration has been given to the relation between supply and demand of sulfur during a period in the future when all the nation's oil requirements will be supplied from coal. On the basis that a 10,000-barrel-per-day synthetic fuel plant, operating on 3% sulfur coal, would yield 105 long tons of sulfur per day, only 115 such plants would be required to produce as much sulfur as was produced in the United States during 1947. This number of synthetic fuel plants would produce 1,150,000 barrels of oil per day as compared with a daily consumption of crude petroleum in 1947 of over 5,000,000 barrels. Although not all liquid fuel plants are expected to be FischerTropsch plants (many, if not most, will be coal hydrogenation plants requiring no sulfur removal from the gas), when the nation's oil requirements are met by synthesis from coal as a basic raw material, more sulfur can be produced in such plants than was required in 1947. On the other hand, use of lower sulfur coalsfor example, western lignites and subbituminous coals-would yield less sulfur, and the requirements for sulfur may increase by the time crude oil from petroleum is replaced by synthesis. Other complicating factors in making long-range predictions of the sulfur market situation are the possibilities of sulfur recovery from sour natural gas; eventual replacement of natural gas by synthesis from coal, which would result in additional sulfur production; the competitive situation of pyrites; and other sources of sulfur. These are problems that must be considered when an actual plant is to be built. It is likely that when oil and natural gas are replaced by synthesis from coal the market price of sulfur used in this paper as a basis for calculating credits may be greatly changed. If, instead of looking forward to the time when the last synthesis plant is built, costs are projected for the situation which will exist when the first few plants are built then the current market price of sulfur is a proper basis for estimates. Even more realistic is consideration of sulfur recovery from the synthesis plants which are already producing ammonia, alcohols, and other chemicals. However, in the data presented here different values for sulfur credit may be assumed without much difficulty. Even with a greatly reduced value for sulfur credits, the use of higher sulfur coals does not appear to be a disadvantage, especially when lower coal costs and conservation of premium coals for metallurgical purposes may become economic factors.
CREDIT FOR ELEMENTAL SULFUR

Hydrogen sulfide, in plants burning it for sulfuric acid manufacture, is credited at $18.00 per long ton of equivalent sulfur. Heat recovered as high pressure steam is credited at 30 cents per 1000 pounds; it was assumed that two thirds of the heat of combustion of the hydrogen sulfide was recovered as steam. This results in credits per 1000 cubic feet of gas for hydrogen sulfide and steam of 0.240, 0.633, and 1.061 cent for the gas containing 167, 500, and 833 grains of hydrogen sulfide (1,3,and 5% sulfur coals), respectively.

In estimating t,he credit to gas purification costs for elemental sulfur, the cost of conversion must be deducted frem the value of the sulfur. Allowance also must be made for the fact that recovery will be only 90% of the amount equivalent to the hydrogen sulfide. The construction cost of a sulfur recovery plant in a new location, according to Wilcoxon ( 3 2 ) in 1943 amounted to $7.00 per ton of yearly capacity. Operating costs, according to Weber ( S I ) , amount to $6.00 per ton of sulfur produced. This is believed to represent both overhead and operating costs. If a sulfur recovery plant is constructed as an adjunct to a large existing plant, plant cost estimates will include costs of sewers, utility lines, and other services only to the plant boundary, but if the plant is to be a separate establishment, services and other facilities, such as office building and laboratory, must be included. Table I1 gives the requirements for sulfur recovery plants in sizes necessary to convert the hydrogen sulfide from the three

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2283

principal sizes of Girbotol plants. The data were furnished by the Girdler Corporation (I). These requirements were used in es1 1 . timating the costs of plant operation given in Table 1 In these estimates overhead is equal to 19% of the investment per year. Depreciation is at a rate of lo%, which is believed to be conservative in view of the rather long life of some Claw kilns in Germany and depreciation rates used for comparable equjpment in sulfuric acid plants. Fairlee (7) suggests about 5% of the depreciable fixed assets per year as depreciation for a chamber acid plant and about 7% for a contact acid plant. This reference is somewhat old (1936), but, presumably, useful life of equipment in modern plants should be as great. Interest was computed a t 4% of the original investment per year without allowance for a yearly decrease in the amount of investment due to depreciation. Some accountants, engineers, business managers, and owners hold that interest on plant investment is not chargeable to production cost (l7),whereas others believe that it is so chargeable. (It is not permitted as a deduction for federal income tax purposes.) Maintenance a t 5% without actual plant data available is admittedly a matter of conjecture; Girdler suggests 3%, inasmuch as the plant was designed to reduce maintenance cost-alloy tubes are provided in the waste-heat boiler, for example. Girdler states that more operating experience is necessary to predict the 3% rate with surety, so the conservative rate of 5% was used. The maintenance charge in the smallest plant (32 tons per day) amounts to $20.75 per day. This amount should aover costs of repairs; replacement of entire units of equipment is provided for by depreciation. The initial charge of bauxite catalyst is included in the plant cost as it is expected to have indefinite life. Poor operational control could conceivably result in stoppages with sulfur or with carbon if the hydrogen sulfide contains carbonaceous gases. These troubles could be corrected by reworking the catalyst. Replacement is covered by depreciation. The rate of $2.00 per hour was charged for the labor of one operator per shift; supervision and the services of a chemist are furnished by Girbotol plant personnel. No charges for make-up water for the boiler were included in costs as it was assumed that eventually the steam would be condensed and returned for use as feed water. Steam from the boiler (2 pounds per pound of sulfur) is sufficient to supply the power requirements for the pumps and combustion air blower, and if exhausted at 50 pounds per square inch gage, it is available for other uses-for example, the steam requirements for heating the reboiler of the stripping columns in the gas purification plant. Although exhaust steam would be an appreciable credit in larger plants, it is not included in these estimates. In the net credits for elemental sulfur, the conversion costs shown in Table I11 were deducted from the established value of $18.00 per ton, giving $13.33, $14.81, and $16.25 for the 32- , 105- , and 184ton-per-day plants, respectively. The net credit per ton of sulfur increases with recovery plant capacity (with increasing hydrogen sulfide content of the gas.) These credits, on the basis of lo00 cubic feet of gas purified, are 0.13, 0.46, and 0.83 cent, respectively.

Table 11. Estimated Requirements for a Girdler Recovery Plant

Coal sulfur content % 1 3 5 HtS content, grainshoo stand. cu. ft. 167 500 833 Recoverable sulfur, long tons/day 32 105 184 Plant cost, dollars 186,000 525.000 830,000 Cooling water, gal./min. 150 480 840 Labor: 1 operator/ahift, all lants Supervisor and chemist: Girgotol plant personnel handle this as extra duty. without charge to sulfur recovery Power for combustion air blower and liquid sulfur pumping furnished by recovered steam.

Table 111. Estimated Daily Costs of Sulfur Recovery

Capacity, long tons sulfur/day Overhead Cooling water Labor Total cost/day Total cost/ton Net credit available/ton Net credit available/day Net credit available/1000 cu. ft. gas

32 96.80 4.32 48,OO $149.12 4.67 13.33 427.00 I 0.13

$

105 $273.00 13.82 48.00 $334.82 3.19 14.81 1556.00 $ 0.46

--_

184 $432.00 25.92 48.00 $495.92 2.75 15,25 2765.00 $ 0.83

also assumed that both hydrogen sulfide and organic sulfur concentrations would vary in proportion to the sulfur content of the coal. The cost estimates given here are a revision of the preliminary estimates in the work just cited. Also, a coal containing 0.5% sulfur has been added to the other three considered in that work. Basis of Estimates. It is important to remember that all estimates of costs and credits made in this paper are derived from certain concentrations of sulfur in the gas. The relationship between the sulfur content of the gas and of the coal may, s;nd probably will, differ from the assumed relationship. The true relationship will depend on the amount of sulfur retained by the ash and the yield of gas per unit weight of coal. Sulfur retained by the ash is lost, whereas higher yields of gas per unit weight of coal serve to dilute the sulfur concentrations in the gas. In the cost of gas purification per se, the relation between sulfur in gas and sulfur in coal is unimportant, but the relation is important in considering Eoals for gasification with respect to purification costs. For such purposes, data currently being acquired in the bureaus gasification pilot plant a t Morgantown with coals of different sulfur content will be helpful. These data are not now sufficient to predict reliably the relation between the concentration of sulfur in the coal and the concentrations of hydrogen sulfide and organic sulfur in the gas.

Table IV. Assumed Conditions for Gas Purification Cost Estimates

Sulfur content of coal, % 0.5 Has grains/100 stand. cu. ft. Raw as 83 25 Sarub%ed as H i s ,purifiecfgas 0 O r anic sulfur, grains/100 atand. cu. ft. 3.3 fiaw gas 0.10 Purified gas Gas treated/hr., stand. cu. ft. 14,000,000 Coo, raw gas, % 10
~~ ~

1.0
167 25

3.0 500 25 0

5.0 833 25 0
33.3

6.7 20 0.10 0.10 All cases All cases

0.10

HYDROGEN SULFIDE SCRUBBING-COST ESTIMATES

a A 8 PURIFICATION COST ESTIMATES

In connection with a study of coals available for synthetic liquid fuels made by the bureau (6) a rough preliminary estimate of the cost of sulfur removal was prepared to obtain some idea of the importance of sulfur content in comparing coals avai!able. Three cases were considered-that is, coals containing 1, 3, and 5 % sulfur. It waa arbitrarily assumed that coal containing 3% sulfur would yield gas containing 500 grains of hydrogen sulfide and 20 grains of organic sulfur per 100 standard cubic feet. It was

Table IV gives the conditions assumed for estimating purposes in the present study. Hydrogen sulfide left in the scrubbed gas is shown as 25 grains, instead of 10 grains, the value used in the preliminary estimates. The estimates include capital charges (depreciation, 6.7%; interest, 4%; and maintenance, 4% per year) ag well as operating costs for labor, materials, and utilities. The Girbotol process employing triethanolamine was selected for hydrogen sulfide remoyal not because it is necessarily cheaper than competing processes but because it is the process to be used in the bureaus demonstration plant a t Louisiana, Mo., where

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facilities acquired from the Army Ordnance Department included a Girbotol plant, formerly designed for the purification of natural gw. In all the calculations it was neceasary to make several arbitrary aasumptions because of the lack of pilot or commercial plant operating data. Since cost trends for changing sulfur content,, rather than absolute costs, were the first purpose of making the estimates, this lack of data wtlfi not serious.

NET COST OF HYDROGEN SULFIDE REMOVAL BY SCRUBBING

RELLTDN OF W D R O G M SULFIOL COST TO SULFUR CONTONTW C O 4 USED WITH CREDITS FOR UIDRObLN

muneiua

Figure 2 is a plot of the gross and net costs of hydrogen sulfide removal by scrubbing with triethanolamine solution, together with credits for hydrogen sulfide and steam, which have been previously described. The removal costs used were the highest of the two estimates-that is, the Girdler estimates for 167 and 500 grains and the Morgantown estimates for 833 grains of hydrogen sulfide per 100 cubic feet. An additional point at 83 grains of hydrogen sulfide per 100 cubic feet has been added by extrapolation. These curves show that the net cost of hydrogen sulfide removal by scrubbing at first increased, then at about 134 grains per 100 cubic feet of hydrogen sulfide in the coal (0.8% sulfur) decreased, and reached zero cost at about 651 grains of hydrogen sulfide per 100 cubic feet in the coal (3.9% sulfur). Figure 3 is a similar plot of the cost of hydrogen sulfide removal by scrubbing, but with credits based on elemental sulfur at the previousIy determined rates. There is an increase in the net cost of hydrogen sulfide removal as the sulfur content of the coal increases from 0 . 5 to 1.0%; with a continued increase in sulfur content, the net cost decremes, becoming zero between 5 and 6%.
COST OF COMPLETE SULFUR
REMOVAL FROM SYNTHESIS GAS

SULFIOT AND STEAM

__

Thus far only the cost of hydrogen sulfide removal by scrubbing h a s been considered, and the net credits resulting from hydrogen
0 1 2 3 4 5 SULFUR IN COAL, % 6 7 8

Figure 2

Results of Estimates. The results of the cost calculations were compared with estimates which were later submitted by the Girdler Corporation, gas processes division (1). The Girdler estimates gave plant costs and quantities of utilities and labor required. By applying the same rates for interest, depreciation, and maintenance to the plant costs cited by Girdler and using Girdler's data for operating requirements for labor, materials, and utilities, charged at the same unit cost rates used in the Morgantown estimates, the following comparison is obtained :
1 Coal sulfur oontent, % HnS raw gas, grains/100 stand. cu. ft. 167 Estimated plant cost (turnkey) $1,510,000 H& rernovrtl eost/1000 cu. ft. 0 19 (Morgantown) H t S removal cost/1000 cu. ft. 0.61 (Girdlerj Vo Deviation. based on Girdler -19.7

51,900,000
0.71

3 500

5 833 $2,wO,oo(r 0.90

0.77

0.88

-7.8

+2.3

The only important difference between the two estimates is in the figures for coal containing 1% sulfur. As a matter of fact, the Girdler estimates emphasize the conclusion reached from the Morgantown estimates-that the cost of hydrogen sulfide removal by scrubbing does not increase in proportion to the increase in coal sulfur or, in other words, to the increase in hydrogen sulfide content of the gas. Actually, the Girdler estimates show less proportional increase in cost of hydrogen sulfide removal with increasing sulfur content than do the Morgantown estimates. The reason for the less-than-proportional increase i n removal cost for increasing hydrogen sulfide concentrations is not difficult to see. As the hydrogen sulfide concentration in the gas increases, the carrying power of the absorbant solution also increases, although usually not in direct proportion. Increasing carrying power of the solution means that the solution circulation rates and/or tower heights do not need to increase in proportion to changes i n concentration of hydrogen sulfide. T h i s $so means that pumping, steam, and capital costs do not increaae in proportion to changes in hydrogen sulfide concentration.

sulfide or elemental sulfur have been applied to this cost. After a critical pointis reached, thenet cost of hydrogen sulfide removal decreases with increasing concentrations of that impurity in the gas. If this were the only sulfur removal process to be used, the higher the sulfur content in the coal, the more desirable the coal would be for synthesis gas production. Before proceeding to such a surprising conclusion, however, other sulfur-removal costs must be considered as indicated by the assumed conditions given in Table IV. There me still 25 grains of hydrogen sulfide and 3.3 to 33.3 grains of sulfur m organic sulfur compounds to be rerlloved from each 100 cubic feet of gas. The final total sulfur content must not exceed 0.1 grain of suIfur per 100 cubic feet, of gas at standard conditions (eo", 30 inches, dry.) Dry Box Puri5cation Cost. The dry box plant was assumed to consist of eight towers in operation and one spare. Equip ment cost was assumed to be $1,300,000. Overhead charges at 14.67% amount to $525 per day. Labor for changing oxide is estimated at $80 per day, and with oxide consumption of 400 bushels per day at 65 cents per bushel amounts to $260 per day. The total cost of dry box operation is thus $865 per day; based on 336,000,000 cubic feet of gas per day, this amounts to 0.26 oent per IO00 cubic feet. In making this estimate the dry box plant design was based on reported removal e5ciencies under elevated premres. Actually, in consideringstrictly relative costs for sulfur removal from gases with different hydrogen sulfide contents, the cost of dry box operation is unimportant since scrubbing plant design caloulations were based on the same concentration of hydrogen sulfide in the gas leaving the scrubbers in all instances. Organic Sulfur Removal Cost. At the present stage in the art of gas purification the removal of organic sulfur is more expensive per pound of sulfur than is the removal of hydrogen sulfide. For this reason, investigations are being carried out in the Morgantown laboratories with the object of lowering this cost. The work ineludes the study of catalysts for simultaneous removal of hydrogen sulfide and organic aulfur, Girdler catalysh for the conversion of organic sulfur in the presence of large amounts of hydrogen sulfide, alkalized iron oxide catsly& for oxidation of organic sulfur, miscellaneous other catalysts for conversion of organic sulfur, and activated carbon for adsorption o f organic sulfur. Removal of Organic Sulfur by Alkalized Iron. Hot alkalized

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iron oxide was used in the German synthetic fuel plants to remove organic sulfur compounds from synthesis gaa. The German practice in using this material-sometimes referred to as sodairon-was reviewed in a previous paper ($3). It frequently was necessary to pretreat the gas, using activated carbon, to remove thiophene and gum-forming constituents. Thiophene (CIHIS) is not removed by alkalized iron, and gum-forming constituents poison the catalyst. Fortunately, synthesis gas made from coal, steam, and oxygen by the Morgantown process contains no thiophene and, it is believed, no gum formers. Activated carbon is to be used prior to the alkalized iron oxide at the bureaus demonstration plant at Louisiana, Mo., because cost cilculations, based on laboratory experiments a t Morgantown, show that it will be cheaper to remove organic sulfur by activated carbon than by alkalized iron. In a secondary position the alkalized iron oxide will serve mainly as a safety factor. The game vessel and heat exchangers used for alkalized iron can later be used for another hot catalytic process if present experimentation at Morgantown proves successful. The cost of removing organic sulfur from gas by alkalized iron oxide waa calculated from estimate, prepared by the technical Organization at the bureaus demonstration plant at Louisiana, Mo.,based on gas containing 10 grains of organic sulfur per 100 cubic feet of gas; accordingly, that cost had to be adjusted to the basis of the different concentrations used for this paper. The basic estimate assumed a plant investment of $1,OOO,OOO, a catalyst cost of $60.00 per ton, and a removal capacity for the catalyst such that the spent catalyst would contain 7% sulfur; the daily cost for the removal of organic sulfur was $3600. For the adjustments to different concentrations of organic sulfur, capital cost w& assumed to be constant since the same vessels and heat exchangers could be used, but costs of catalyst and labor for dumping and filling were assumed to be in proportion to the concentrations removed. This method of adjustment is not strictly accurate because optimum conditions probably would require a variation in space velocity, necessitating a change in number of vessels and hence a change in plant investment. This would, however, probably not be in direct proportion to concentration. For the present purpose, the method of adjustment is sufficiently accurate. The cost of removing 6.7, 20, and 33.5 grains of organic sulfur per 100 cubic feet amounted to 0.79, 2.10, and 3.43 cents per thousand cubic feet of ga3, respectively. The cost of temoving 3.3 grains per 100 cubic feet was determined by extrapolation. In Figure 4 these organic sulfur removal costs, together with costs of purification by iron oxide, have been added to the costs previously presented in Figure 2 to give the total cost of complcte removal of sulfur by the three processes in question-triethanolamine scrubbing, iron ouide, and alkalized iron oxide. Net costs of complete removal, after taking credits for hydrogen sulfide, are also shorn. Figure 5 shows similar data with net credits for elemental sulfur recovered. These curves show t,hat the cost of complete removal of sulfur from syuthesis gas increases with increasing sulfur content of the gas (or coal) hut not in dirert proportion.
REMOVAL OF ORQANIO SULFUR BY ACTIVATED CARBON

compounds such as carbon disulfide and especially thiophene. Although no thiophene is found in gas made by the Morgantown process, carbon disulfide unquestionably is resent. An important conclusion reached from t\e laboratory experimenta was that the amount of sulfur (as carbonyl sulfide) adsorbed by the carbon under the test conditions is proportional to the concentration of sulfur (as carbonyl sulfide) in the gas, between the limits of 10 and 30 grains of sulfur per 100 cubic feet, providing the carbon dioxide concentration is held approximately constant.

-0.PL 0

--I II
1

II
P

II
3
SULFUR

II
4

II II II II
5 6 1 8

II
9

IN OOAL, 96 Figure 3

Thus (with 10% carbon dioxide in the gas), when the carbonyl sulfide concentration is equivalent to 10 pains of sulfur per 100 cubic feet, the carbonyl sulfide adsorbed is equivalent to 0.00325 gram of sulfur per gram of carbon; when the concentration in the gas is equivalent to a0 grains per 100 cubic feet, the sulfur adsorbed is 0.00650 gram per gram of carbon; and when the concentration in the gaa fa equivalent to 30 grains, the sulfur adsorbed is 0.00975 gram per gram of carbon. These are all saturation values-that is, capacities for the carbon up to the time when 75% of the inlet organic sulfur concentration passes through the carbon. &otually, the saturation point occurs soon after the break point. It is assumed that a t least two beds would be used in series when the break point occurs. No experimental data were found in the literature concerning the adsorption of carbonyl sulfide, but statements (35) concerning the technique of adsorption, in general, confirm the observation of identical time periods for the adsorption part of the cycle for different concentrations of adsorbate over a limited range. The fact that the adsorption period is of the same duration for concentrations ranging from 10 to 30 grains of sulfur (as COS) per 100 cubic feet is important, since it means that the cost of organic sulfur removal by adsorption remains constant for the concentrations that have been assumed to result from gasification of coals containing from 1 to 5% sulfur. (Strictly speaking, the range of organic sulfur of concentrations corresponding to these coals should be 6.7 to 33.5 grains per 100 cubic feet, but assumption of a constant adsorption period to include this increased range makes little difference.) Regeneration of spent carbons by steam is about 90% complete when the carbon is heated to the temperature of saturated steam. Regeneration i s completed during drying, which is accomplished by inert gas a t 600F. No differences in steaming or drying time were noted regardless of the amount of carbonyl sulfide adsorbed by the carbon. With the operating cycle, steam, and drying requirements remaining constant for the concentrations of organic sulfur in question, it follows that equipment and operating costs will be constant for the adsorption procass. One important cost factor in adsorption processm is the charge for replacement of activated carbon. The life of an original charge of carbon is often expressed in terms of percentage loss per cycle. It is known that in solvent recovery as many as 2000 cycles have been used; this experience, however, was with more expensive carbons, which might suffer less degradation. In the laboratory

Tests were made of various samples of activated carbon in the LMorgantownlaboratory. Among the carbons tested was a sample of GW carbon supplied by the Pittsburgh Coke & Chemical Company. This carbon, made from coal, costa about 15 cents per pound. Testa were conducted a t 300 pounds per Bquare inch gage, using various concentrations of carbonyl sulfide (COS) ran ng from 10 to 25 grains of sulfur per 100 standard cubic feet. %e carrier gas was hydrogen containing controlled concentrations of carbon dioxide; carbon dioxide decreaaea the capacity of activated carbon for carbonyl sulfide adsorption. Carbonyl sulfide is not so readily adsorbed aa are the less volatile organic sulfur

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experiments with carbonyl sulfide adsorption the ultimate life of the carbons tested could not be determined because only some 30 cycles of adsorption and regeneration were carried out. X o difference in performance was noted between the first and last cycles.

content of the caal. A similar trend for the nebcost curve is shown in Figure 5.

INTERPRETATION OF COST ESTIMATES The authors believe that the preparation of cost estimates during the various stages of process development serve not only to evaluate results already accomplished but are an important aid in guiding the future course of experimental work. In work such t l b is being carried out at Morgantown, where the major effort ie directed toward the development of new low cost processes for the production of synthesis gas (the cost of which represents over60% of the final product), it is important that the entire organization be cost-conscious.

3 4 SULFUR IN COAL, %

Figure 4

In plant practice loss of carbon may result from physical breakdown of carbon particles or by loss of adsorptive capacity due to fouling by gum, elemental sulfur, or other materials. With a suitable carbon, no elemental sulfur will be formed from organic sulfur compounds, but even traces of hydrogen sulfide may, in the presence of oxygen, form enough elemental sulfur to ruin some carbons. In view of the uncertainty with respect to the carbon replacement cost in the operating plant, the authors have included in Table V costs of organic sulfur removal by activated carbon on the basis of three rates for loss of activated carbon per cycle. Rates assumed were 0.1, 0.5, and 1.0%. For comparing costa in relation to variations in the sulfur content of the coal, the rate of depletion selected is really immaterial, since the cost of removal for the different concentrations of organic sulfur are assumed to be the same, as already stated. For specific cost information the rate is, of course, important. The authors believe that loss of carbon will not exceed 0.1% per cycle, and this value has been used in the present study. The true rate of carbon loss can be determined when operations have been carried out in the Morgantown gas purification pilot plant and in the demonstratian plant. Figure 4 shows that, when activated carbon is used for removal of organic sulfur, the net cost of complete sulfur removal by the three processes is approximately constant for coals containing 0.5 to 1.0% sulfur; after a coal sulfur content of 1.0% is reached, the cost of complete sulfur removal decreases with increasing sulfur

3 4 SULFUR IN COAL, %

Figure 5 Although the benefits derived from preparation o f cost estimates are extremely significant, the estimates may be misinterpreted either by those preparing them or by others. To be of any value-in fact to avoid being misleading-the purpose of the estimate must be known, the basic assumptions must be understood, and finally all concerned must be aware that estimates prepared for operations as yet untried are subject to revision as new or additional operational experience becomes available. The cost estimates presented here were prepared primarily to determine the importance of the sulfur content of coals as a factor in selecting coals for synthesis gas production by the processes under investigation. An arbitrary relation between sulfur in coal and in gas was assumed; whether this relation is correct or not is not so important as is the trend of purification cost, which does c h v g e with changing sulfur content of the coal. This relation was also assumed for the hydrogen sulfide scrubbing process, although it was certainly representative of one of the possible processes. Unit costs for the various factors included in the calculations

November 19%

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Table V. Cost of Removal of Organic Sulfur by Activated Carbon

Carbon loss per cycle, % 0.1 0.5 1.0 Overhead, cost/day 5307 S307 3307 Steam cost/day 800 300 300 hotivited carbon, cost/day 118 590 1180 Total oost/da $725 $1197 81787 Total cost/l& ou. ft. gas 0.2166 0.35af 0.5320 Bask: 3.5-33 5a grains 9 &a COS) per 100 CU. ft., COI 10%;a ace velocity, 210/hr. (60; F., 300 Ib.(sq. in. gage, dry); linear velbcity, 486 ft./hr. 0 A small decreaae in coat may be expected between 3.5 and 10 grains and a small increase in cost between 30 and 33.5 grains; the differences are relatively unimportant.

(9) Gii dlei Corporation, Gas Processes Division, Louisville, Ky.. Sulfur Recovery Plant, 1948. (10) Girsewald, C. von, Piecke, W., and Wohlwill, M., U. S. Patent 2,115,091(1938). (11) Gollmar, H.A., Chemistry of Coal Utilization, pp. 947-1007. New York, N. Y., John Wiley & Sons, 1945. (12)Gollmar, H. A.,Koppers Company, Pittsburgh. Pa., private communication (1949). (13)Ibid. (1950). (14) Hechenbleikner, I., Oliver, T. C.. and Spangler, 5. F.. U. S Patent 2,002,443(1935). (15) Koolman, C.,Siecks, W., and Wohlwill, M., Ibid., 2,172,817 (1939). (16) Koppeis Company, Pittsburgh, Pa., Use o f Sodium Phenolate (17) Lang, Theodore (editor), Cost Accountanta Handbook, p 901,New York, Ronald Press Company, 1949. (18) Mafhews, A. F. (editor), Minerals Year Book 1947, p. 1123, U. 5. Dept. Interior, Bureau of Mines, Government Printing Office, Washington, D. C., 1949. (19) Meyerhoff, H.A.,Mining Eng., 187,No.1, 72 (1950). (20) Phipps, J. W., Jr., Baltimore and Ohio Railroad Company, Brtltimore, Md., private communication, 1950. (21) Powell, A. R., Koppers Company, Pittsburgh, Pa., private communication, 1949. ( 2 2 ) Reed, R. >I., and Updegraff, N. C., IND. ENQ. CHEM., 42,2269 (1 950). (23) Sands, A.E., Wainwright, H. W., and Schmidt, L. D.. Ibid., 40, 607-20 (1948). (24) Schwarz, S.C.,Western Gas, 3, 113-118 (1927). (25) Sperr, F. W., Jr., Proc. Am. Bas Assoc., 1921,pp. 282-:3(54. (26) Sweeney, E. L.,and Sands, A. E., Gas Age-Record, 77, 657-62 (1936). (27) Updegraff, N. C., The Girdler Corporation, Gas Processes Division, Louisville, Ky., private communication, 1950. (28) U. S. Bur. Mines, Inform. Circ. 7370 (1946). (29) U. S. Dept. Commerce, OTS, Technical Oil Mission, Reel 312, item 27. (30) Weber, George, Oil and Gas J . , 45, No. 44,58-9, 84-7 (1947). (31)Ibid., 48, No. 34,38 (1949). (32) Wilcoxon, B. H., Process Equipment Cost Estimates, p. 8, New York, McGraw-Hill Publishing Co., 1948. (33) Williamson, R. H., and Garside, J. E., Inst. Gas Enu. Comm.. 345 (1948). (34)Ibid., 357 (1949). (35) Zabor, J. W., Pittsburgh Coke and Chemical Company, Pittsburgh, Pa., General Characteristics of Beds of Granular and Activated Carbon, p. 5, 1947.
R E F E I V EMarch ~ 27, 1950.

for Hydrogen Sulfide Removal.

were assumed a t what were believed to be reasonable rates, but these are subject to variation in different localities and under different conditions. Use of a particular interest rate does not imply that the rate is established; interest is a controversial item in cost estimates and is subject to determination under conditions governing a particular enterprise. The estimates show that in one scheme of sulfur removal, high sulfur coals, far from being objectionable, may even be preferred. The authors believe this hypothesis has not been proposed prior to publication of this paper. The absolute accuracy of the statement is less important than is comprehension of the fact that if certain costs and credits for the various processes can be achieved, there is a possibility that high sulfur coals can be wed without appreciably higher gas purification costs, and such coals cannot be discounted as a source for production of synthesis
ws.

Obviously, more accurate estimates will be possible as pilot plant and demonstration plant operating results become available; then, there will be further appreciable changes for plants producing 336,000,000 or 1,OOO,OOO,OOO cubic feet of gas per day. Even in a full scale commercial plant many costs can not be established with absolute accuracy until after some years of operation. The cost study contained in this paper should therefore be considered as one of a series of basic studies; the preparation of each of these studies can be facilitated by the groundwork contained in the previous report.

ACKNOWLEDGMENT
The authors gratefully acknowledge the assistance rendered by the many technical men in the preparation of this paper. Some of these contributions involved as much time and effort aa is frequently expended in the preparation of a technical pa er. The authors also wish especiallyto t h a n k 2 W. Wainwright, G. C. Egelson, C. M. Brock, and J. P. McGee of the Bureau of Mines, Morgantown W. Va.; R. G. Dressler and H. R. Batchelder, bureau of Mines, Louisiana, Mo.; 0. E. Auer, N. C. W degraff, and R. E. Reitmeier of the Girdler 8or oration, huisville, Ky.; and H. A. Gollmar, ! C o p pers Company, Pittsburgh, Pa.

LITERATURE CITED
(1) Auer, 0. E., The Girdler Corporation, Gas

Processes Division, Louisville, Ky., private communication (1960). (2)Breck, C. R., Southern Natural Gas Company, New York, N. Y., private communication
(1960). (3) Cain, G. A., U. S. Dept. Commerce, FIAT Find Rept. 1015 (1947). (4) Dent, F. J., and Hebden, D., Gus Research Board Pub. GRB 51 (1949). (6) Dent, F. J., and Moignard, M. H., Ibid., Comm. GRB 52 (1949). (6) Doherty, J. D., Minino Transactions, pp. .. 116-124 (1949). (7)Fairlee, A. M., Sulfuric Acid Manufacture, p. 569, New York, Reinhold Publishing Corp., 1936. ( 8 ) Frszier, H. D., and Kohl, A. L., IND. ENG. CHEM., 42,2288 (1960).