Hydrogen Sulfide in West Texas W. A. CUNNINGHAM The University of Texas, Austin, Tex. Concurrent production of hydrogen sulfide in the natural gas destined for pipe-line distribution from, and carbon black manufacture and recycling in, the Permian Basin area of West Texas and southeastern New Mexico is equivalent to almost 400 long tons of sulfur per day. About 60% of this is removed from the gas before the latter
is injected into the pipe lines; most of the hydrogen sulfide thus removed is disposed of in open flares. Production is widely scattered over the entire area and only two plants on which data are available handle a sulfur equivalent of more than 50 tons per day. Reserves in the different areas are sufficient for 10 to 25 years’ production at current rates.
I
t
1
Figure 1. Oil Fields of Permian Basin
2238
November 1950
INDUSTRIAL A N D ENGINEERING CHEMISTRY
2239
T
HE Permian Basin area of West Texas and southeastern New Mexico (Figure 1) covers between 30,000and 35,000 square
miles with oil and/or gaa production from some 28,000 wells in over 400 separate fields and subfields. Many of the fields produce several different grades of crude oil from as many as eight or ten different geologic horizons. Though most of these productive horizons are in the Permian System, some production is obtained from one or more formations ranging in age from Cretaceous to Ordovician (Figure 2). Hydrogen sulfide is available only as a by-product of oil and gas production, Exact data on oil and gas production in the Permian Basin for 1949 are not available, but estimates place such production at about 350,000,000barrels of oil and over 800 billion cubic feet of gas. Reported total sulfur contents of the crude oil range from zero in many fields to 4.2% in the Fihrman Mascho field in Andrews County. Data on the sulfur content of the gas (customarily reported as hydrogen sulfide) are rather scarce, but hydrogen sulfide is known to range from negligible in many fields to about 7 mole yoin gas from the McElroy field in Crane and Upton Counties. About 16 years ago gas from a, well in the HowardGlasscock field was reported to contaih over 30% hydrogen sulfide, but confirmation is lacking. With the exception of the Yaks field in Crockett County, no hydrocarbon gases are now being burned in flares in any of the major fields of West Texas. Forty natural gasoline plants are now operating in the Permian Basin (Figure 1); at least eight others are either proposed or under construction. When these latter plants are placed in operation, total processing capacity will be- in excess oi 2 billion cubic feet per day, and yessly operating rate probably will average about 60% of installed capacity. Each plant processes gas produced by from 60 to nearly 2200 wells located in from one to fifteen different fields. After the condensable gases are removed,
O R GROUP
u)
ELLENBURGER (371
UNNAMED CONQLOMERATIC
Figure 2. Correlation Chart for Producing Formations of Permian Basin in West Texasand Southeastern New Mexico
Table I. Major Natural Gasoline Plants in the Permian Basin
Plant Operator
Plant Name and County
El Paso Natl. Gas Gulf Oil Co. Phillips Petroleum Co. Skelly Oil Co. Warren Petroleum Co.
Monument
Chief Supply Field
Daily Ca acit M &et
8u.
NEW Mnxrco (ALLLEA COUNTY) Langlie-Mattix 50,000 Cooper-Jal 120,000 Langlie-Mattlx 60,000 Eunice 60,000 Eunice 130,000 PenroseSkelly 82,000 Drinkard Monument 60,000
Barnhsrt Hydrocarbon Co. Csbot Carbon Co.
Barnhart (Reagan) Estes (Ward Keystone
TEXAB Block 31 Univ. North Ward Keystone Kermit
Cities Service (Stanolind) El Paso Natl. Cas
Odessa (Eotor) Sealy-Smith (Ward)
North Cowden Monahans
20,000
Gulf Oil Corp.
Monahans (Ward) Waddell Crane) Odessa (Actor) Crane (Crane) Fullerton (Andrews)
North Ward Sand Hills Foster McElroy Fullerton
Goldsmith (Eotor) Bid Richardson Gasoline Co.
Judkina (Ector) Seminole (Gaines) Keystone (Winkler)
Shell-Coltexo Shell Oil Co. and Texas Co.
Wasaon (Winkler) TXL (Ector)
Wasaon TXL
Stanolind Oil Co.
Slaughter (Hockley)
Odessa Natl. Cas Co. Phillips Petroleum Co.
(dinkier)
Equiv. Sulfur a t 60% Cap Long Geologic T ~ ~ / D ~ System Y
No. of Connected Wells
Hi8 Moie
I
360 233 613 526
0.3 0.2 0.4 0.80 0.8 0.60
3.6 5.8 4.8 9.50 24.8 9.S0
Permian Permian
485
0.2"
2.99
Permian
66
io1
%
Permian Permian Permian
25,000 30,000 64,000
468 810
0.1' 0.5" 2.09
0.Bo 3.W 26.00
60.000
666
2.50 0.4
36.0"
20,000 40 000 30:000 30,000 90,000
323 290 836 678 669
0.1 1.4 2.5" 0.2
0.5 13.5 18.00 61.0 4.3
Goldsmith
110,000
1273
2.0
53.0
Penwell Seminole Keystone
30 000 30'000 6d,OOO
6J 5 321 506
2.1 2.0 0.6
16.1 14.4 7.8
120,000 90,000
1462 423
0. 1.0
8.6 21.6
Permian Devonian Ordovician Permian Ordovician Permian Permian Permian >o Ordovician Permian Devonian Ordovician
90,000
2143
1.5
32.4
Permian
Slaughter Total Texas New Mexico Permian Basin
934,000 542 000 1,476:OOO
7
7.1
1.9
307 61 368
Estimates based on amount of hydrogen sulfide i n gas being produced from near-by fields and corresponding geologic horizons.
Ordovician Permian Permian t o Permian Ordovician Permian and Ordovician Permian Permian Permian
INDUSTRIAL AND ENGINEERING CHEMISTRY
2240
Table 11. Sulfur Content of Crude Oil from Various Geologic Horizons Field6 of This Age
Total
No. of Fields on Whioh Sulfur Content Datahe Avadable
57
34
1.14
26 57
28
7
1.04 1.48
96
28
1.43
51
10
No. of
Geologio Age I. Permian Bystem Yatea Seven Rivera
11. 111. IV. V. VI.
8Kgurg San Andrea San AngeloGlorietta Clear Fork Wiohita Wolfaamp Penqey!vapian Mississippian Devpnian Sdunan Ordpvician Simpson Ellenburger
17 37
SUlfUtr
1.68
No data
9 28 1 19 11
Avera e %
1 3
0.1
No data
0.6 0.2
Datauncertain Data unaertain 8
About 0 . 3 0.2
the tail gases m used for repressuring, are sent to carbon black plants, or are delivered to gas transmission lines for ultimate use. as fuel. Gas for the last outlet must be stripped of hydrogen sulfide by one or a combination of several processes before injection into the line. The hydrogen sulfide thus removed is herein considered as being “produced” or available, though it is now being burned in flares near the scrubbing plant. Becauae most of the producing organizations and gasoline plant operators consider hydrogen sulfide as nuisance material of no potential value, and hence, until recent years, have made very little effort to determine the actual amount present in the gas, it is obvioue that in an area so large as this even the existing data must be examined critically. For example, for many years the analytical procedure in common use involved scrubbing the gas sample with sodium hydroxide and reporting the volume decrease as hydrogen sulfide. Little consideration was given to the fact that this procedure also removed other acidic gases-e.g., carbon dioxide-present in the gas. It is now recognized that in the gas from many areas the amount of carbon dioxide is equal to, or greater than, the amount of hydrogen sulfide present; analytical procedures have been modified accordingly. Data that can be considered reliable have been obtained from approximately half of the gasoline plants now operating, In several instances, however, the average hydrogen sulfide content of the inlet plant gas is reported, with very scarce information as to the rate of intake from the various fields to which the plant is connected. It must be assumed that, because hydrogen sulfide removal costs money, the sweet gas fields will be drawn from in the maximum amounts permitted by existing state laws and railroad commission rules. Hence, if the life of the fields connected to the plant i a estimated a t 20 years plus a t current production rates, it is possible that the hydrogen sulfide content of the intake gas will increase in the future and that hydrogen sulfide reserves are actually greater than would be indicated by present analytical data.
Vd. 42, No. 11
No reliable data are available concerning the hydrogen sulfide content of the gas burned in the thirteen carbon black plants in the Permian Basin area. The locations of the gasoline plants are shown in Figure 1. The gasoline plants on which reliable hydrogen sulfide data (indicated by full black circles) are available are well scattered over the producing area. Because, with few exceptions, the plants on which full information is lacking draw gases from the same 01 adjoining fields as do those on which data are available, at least a reasonable estimate of the hydrogen sulfide production and reserves can be obtained.
CURRENT HYDROGEN SULFIDE PRODUCTION Strictly speaking, the only hydrogen sulfide actually being produced a t the present time is that removed at the various gasoline plants which furnish sweet gas to the transmission lines. Though daily production will vary, the twelve or fifteen plants in this service produce and dispose of hydrogen sulfide equivalent to about 225 long tons per day. A complete listing of all the gasoline plants operating and under construction appears unnecessary; hence an abridged list is presented in Table I, which shows data on the most important plants now operating in the Permian Basin. On the assump tion that the planta operate at 60% of installed capacity, the 24 plants listed are processing approximately one billion cubic feet of gas containing hydrogen sulfide equivalent to somewhat less than 400 long tons of sulfur per day. At an assumed gas input rate of 60% of installed capacity, only two of them, the Phillips Petroleum Company Crane plant in Crane County and the Phillips Petroleum Company Goldsmith plant in Ector County, handle a sulfur equivalent of more than 50 tons per day. The plants now proposed or under construction will have combined capacities of approximately 500,000,000 cubic feet of gas per day, an increase of about 25% of present gasoline plant capacity. However, they will not increase the equivalent sulfur production by a corresponding amount, because most of the gm they will process will be drawn from producing formations older than Permian which have an appreciably smaller sulfur content.
HYDROGEN SULFIDE RESERVES The potentially available hydrogen sulfide is, of course, a direct function of the oil and gas reserves; estimates of the latter vary, not only with the individuals making the estimate, but also with the amount of information the estimator has available to him at the time. Perhaps estimates as to the potential production from a particular field should be labeled more correctly m intelligent guesses. In general, many more data me available concerning the sulfur content of the oil produced than exist on the hydrogen sulfide in the gas concurrently produced with the crude. However, it can be assumed that, qualitatively a t least, the two ara related. Because reservoirs or pools existing in the geologically younger formations yield oil with higher total sulfur content, one would expect that the gas coming from the Permian Series would contain greater amounts of hydrogen sulfide than would the gas coming from older horizons. A comparison of the data in Table I1 showing the average Table 111. Number and Dates of Oil and Oaa Discoveries in Permian Basin sulfur content of the crude Geologia Age of Major Produotion Horizons from the different formations Permian with those in Table I will show 8an Andres, the proximity of correlation. San ClearYaks Angelo- fork Ordovician It is evident that the fields of kved Gray- Glori- Wich: Wolf- Pennsyl- DevSgSimp- EllenYeara Rivera Queen burg etta ita aamp vanian onian urian eon burger Permian age are of primary im1028-1930 23 6 16 21 1 .. *1. 1 portance in so far as hydrogen 1981-1985 7 1 6 10 ..63 1 .. 1 sulfide reserves are concerned. 1 .. .. 2 10 20 * . 14 13 1086-1940 1 0 9 25 21 13 6 1041-1946 *. 2 4 14 However, though the hy7 10 9 12 20 8 19 16 1946-1080 8 1 drogen sulfide content of the
....
....
2
November 1950
INDUSTRIAL A N D ENGINEERING CHEMISTRY
gas from the Simpson and the Ellenburger formations of the Ordovician System.is low, the estimated gas reserves are high; any gasoline plant processing such gas in large quantities will make available a considerable tonnage of hydrogen sulfide. For example, a plant which processes 1OO,O0O,OOO cubic feet perday of Ellenburger gas with an average of 0.2 mole %of hydrogen sulfide will produce the equivalent of about 8 long tons of sulfur per day. Oil and gas reserves, and hence hydrogen sulfide reserves, available for future recovery are closely related to the discovery dates of the fields concerned. Though the oil production in the Permian Basin dates back tQ about 1923,the data in Table I11 show that new discoveries have moved forward steadily since that time. The total number of field discoveries in Table 111 does not necessarily agree with the data of Figure 2, for some fields may have more than one major producing horizon. Even though most discoveries prior to 1940 were in the normally high-sulfur Permian Series, over one hundred fields of that age have been discovered since that date. Because fields may vary in proved production area from 40 to as much as 75,000 acres, a mere tabulation of the number of fields is of little value. However, it is of vital interest to note that of the 961,000acres of oil fields in the Permian Basin 896,000
2241
acres have production from horizons of Permian age. Of the gasoline plants proposed, under construction, or in operation, twenty-five have source production of Permian age only, seven of Permian and non-Permian age combined, and ten of exclusive non-Permian age. Although the newer plants are being built to process gaa from the older horizons, i t is evident that the operators of the plants do not anticipate any serious depletion of the higher-sulfur-bearing gases of Permian age in the near future. Hydrogen sulfide is now available in sizable quantities in the Permian Basin of West Texas and New Mexico; but the area is large, and hence the availability in any one region is limited by the amount of gas that is processed in that vicinity. Although reserves are known to be large, they will vary so widely from one area to the other that they can be estimated only aa from as low as 10 to as high aa 25 or more years a t c u m n t rates of production. ACKNOWLEDGMENT Among the primary sources of information on which this paper is based were V. E. Cottingham, chairman, North Basin Pools En ' eering Committee. W. J. Murray, chairman, Texas RailroayCommission; R. k,. Purvin and associates, Dallas; and D. H. Tucker, El Paso Natural Gas Company. REOBIVED ~ p r i li a , 1960.
Economic Utilization of Sulfur Dioxide from Metallurgical Gases R. A. KING The Consolidated Mining and Smelting Company of Canada, Limited, Trail, B. C. T h e peculiar conditions regarding the dispersion of smelter smoke a t Trail are outlined, and the development of the various sulfur-recovery processes employed is traced, with mention of the technical and economic considerations involved. The Trail smelter i s located in a mountainous area where topographical and meteorological conditions are unfavorable for adequate dispersion of the sulfur dioxide contained in metallurgical waste gases. Expansion of the smelter output in the middle 1920's resulted in some atmospheric pollution, and proximity to the United States border lent International complications. Many of the developments were based on integration of new plants with existing ones and utilimtion of by-product materials from established operations. The availability of ammonia made possible i t s employment as an absorbant for sulfur dioxide. The acidification process for releasing sulfur dioxide from the absorbing solution was practical because a supply of sulfuric acid was at hand and the company was already producing and marketing ammonium sulfate. By-product oxygen made possible operation of the sulfur dioxide reduction process, and later the availability of by-product oxygen and substantially pure sulfur dioxide made possible the development of the cyclic process of sulfuric acid manufacture. The IS years prior to 1943 witneesod the development of processes and installation of fertilizer plants a t Trail, with the reault that sulfur dioxide has changed from a waste material to a valuable raw material in ehort supply. To meet the demand for acid for fertilizer production, roasting of iron ooncentratu for a d d reaovery h a m e necessary In 1943. At present all master and dntering
plant gas is treated for sulfur recovery, and iron concentrate is roasted intermittently, depending on the demand for acid and the availability of customs zinc concentrates. Total current loss to the atmosphere from Trail operations is less than 9% of the sulfur charged. The sulfur released to the atmosphere annually in 1947 and 1948 was less than in any other year since 1904.
T
RAIL'S problem of dilution of the sulfur dioxide emitted from the smelter originated in 1894,when August Heinse's copper plant commenced operation on Rossland copper-gold ore, In 1897 the Canadian Pacific Railway bought out Heinse to obtain his railway rights and thus became the owner of the Trail smelter. In 1901 a lead plant was added to treat the rich ores from the Slocan district, and in 1906 the present company, The Consolidated Mining and Smelting Company of Canada, Limited, was formed, still controlled by the Canadian Pacific. The Sullivan mine in East Kootenay was acquired in 1910, and all subsequent developments were based on this property. Operation of the zinc plant commenced in 1916, but the Sullivan mill was not completed until 1923, following successful solution of the problem of separating mixed lead, zinc, and irgn sulfide ores high in iron. It was not until 1926 that a claim for smoke damage was filed from the Northport, Wash., area. This date coincided both with plant expansion doubling the metal output and consequently the emission of sulfur dioxide and with the erection of two stacks 409 feet high. An International Joint Commission waa appointed in 1927 to
