US3485746A - Sulfur removal from hydrocarbons - Google Patents
Sulfur removal from hydrocarbons Download PDFInfo
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- US3485746A US3485746A US670636A US3485746DA US3485746A US 3485746 A US3485746 A US 3485746A US 670636 A US670636 A US 670636A US 3485746D A US3485746D A US 3485746DA US 3485746 A US3485746 A US 3485746A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 43
- 229910052717 sulfur Inorganic materials 0.000 title description 43
- 239000011593 sulfur Substances 0.000 title description 43
- 229930195733 hydrocarbon Natural products 0.000 title description 24
- 150000002430 hydrocarbons Chemical class 0.000 title description 24
- 239000000446 fuel Substances 0.000 description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 31
- 238000000034 method Methods 0.000 description 23
- 239000004215 Carbon black (E152) Substances 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 18
- 239000003463 adsorbent Substances 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 229930192474 thiophene Natural products 0.000 description 14
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- 150000002898 organic sulfur compounds Chemical class 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 150000003577 thiophenes Chemical class 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- -1 aromatic sulfur compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
- C10G45/26—Steam or water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to an improved process for desulfurizing hydrocarbon fuels. It finds particular application in those systems, such as fuel cells, wherein even trace amounts of sulfur and sulfur-containing cornpounds may cause a serious degradation in either the performance or endurance of the system.
- a fuel such as JP-4 or natural gas
- a typical process is hydrodesulfurization, wherein the hydrocarbon fuel is treated catalytically in the presence of hydrogen to effect a conversion of the organic sulfur compounds into an inorganic, easily-removed form, such as hydrogen sulfide, which is then removed in a subsequent refining operation.
- organic sulfur compounds including the thiophenes (Cid-14S) can be removed in this process provided conversion to hydrogen sulfide is first made and sufficient additional treatment is undertaken to substantially remove the hydrogen sulfide.
- the present invention teaches a desulfurizing technique whereby the sulfur is removed in a single step. Accordingly, it satisfies the primary object of the invention which is to strip the residual sulfur from the as-supplied hydrocarbon fuels in a process which neither seriously affects the compactness or weight of the overall power system nor adds significantly to the parasitic power requirements thereof.
- the basic technique involved provides desulfurization by reaction and/or adsorption of the sulfur-containing hydrocarbon in a bed of finely-divided nickel with the fuel in the vapor state and exposed to steam at an elevated temperature.
- reaction-adsorbent is effected at a temperature in excess of 500 F. but below that at which cracking of the fuel occurs.
- desulfurization is effected at 50G-900 F.
- a small hydrogen addition is made to increase durability of the system.
- the techniques described herein are used to process those fuels having a sulfur content less than about 1000 parts per million sulfur or, even more preferably, less than about 500 parts per million sulfur although, as hereinafter dis cussed in greater detail, the more preferred utilization is not made because of any substantial reduction in the efficiency of sulfur removal with the higher sulfur contents.
- the present process is primarily adapted to supplement and not replace the currently-existing processes directed to the removal of sulfur in gross amounts.
- FIG. l is an abbreviated schematic of a fuel cell system adapted to the practice of the instant process.
- FIG. 2 is a graph illustrating the effect of temperature on the desulfurization performance of a typical system utilizing a hydrocarbon fuel doped with thiophene to 419 parts per million sulfur.
- FIG. 3 is a graph plotting the effect of pressure on desulfurization performance with doped fuel.
- FIG. 4 illustrates the effect of a hydrogen addition on the desulfurization process.
- FIG. 5 illustrates the effect of varying thiophene percentages at a constant total sulfur level.
- FIG. 6 plots sulfur loading of the reactant-adsorbent bed as a function of bed length.
- mercaptans and disulfides are much less stable than the other organic sulfur compounds and, hence, much more amenable to removal.
- these compounds have been removed at the refinery prior to distribution of the fuel.
- the primary concern therefore, has been the removal of the more stable forms of sulfur compounds, namely the sulfides and, particularly, the thiophenes, which are both usually present in the as-supplied fuels.
- the organic sulfides can be represented by the general formula R-S-R, Where R and R are organic groups, either aliphatic or aromatic, and the molecule itself can also occur as a saturated ring structure.
- R and R are organic groups, either aliphatic or aromatic, and the molecule itself can also occur as a saturated ring structure.
- the thiophenes are aromatic sulfur compounds based on thiophene (Gli-14S).
- the basic reactant-adsorbent of the present invention is finely divided nickel, including the high nickel content alloys.
- the most preferred form of the reactant-adsorbent comprises 50 percent nickel supported on kieselguhr, such as Girdler G-49B nickel catalyst.
- the reactant-adsorbent is usually ground to 1%6 mesh, as the best balance between the desired high surface area and low pressure drop factors considered.
- Desulfurization was, in general, practiced at temperatures between about 500-900 F., and pressures were varied between about 40-250 p.s.i.a., the effects of varying temperature and pressure in a specific system being set forth in FIGS. 2 and 3, respectively.
- the thiophenes are considered the most difficult organic sulfur compounds to remove in the fuel processing sequence.
- nickel base materials were effective in the single stage removal of sulfur in varying degrees of efiiciency, the nickel-tungsten material, for example, being most effective at 700 F.
- an existing system was adapted to incorporate the reactant-adsorbent desulfurizer described with the G-49B material.
- the reformer was operated without any loss in output for 200 hours using JP-4 fuel modified with a 50-50 mixture of thiophene and diphenyl sulfide to a total sulfur content of 470 parts per million by weight.
- Two 1GO-hour replaceable cartridges were utilized at an hourly space velocity, grams sulfur fed/ hr.)/ (gram of reactant-adsorbent), and a pressure of 240 p.s.i.a. Temperatures in the bed varied from 500 to 800 F., depending on location.
- the method of stripping residual sulfur from the hydrocarbon to prevent poisoning of the reformer catalyst while avoiding substantial cracking of the hydrocarbon with the formation of coke in the sulfur-removal process which comprises the steps of:
- hydrogen is added to the vaporized hydrocarbon-steam a 6 mixture admitted to the reactant-adsorbent bed in a FOREIGN PATENTS ratio of about CD2-0.1 pounds of hydrogen per 511398 8/1939 Great Britain ⁇ pound of hydrocarbon.
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Description
Dec. 23, 1969 Filed Sept. 26, 1967 Dec. 23, 1969 H J, SETZER ET AL 3,485,746
SULFUR REMOVAL FROM HYDROCARBONS Filed Sept. 26, 1967 3 Sheets-Sheet 2 United States Patent O ILS. Cl. 208-244 2 Claims ABSTRACT OF THE DISCLOSURE A process is described wherein residual sulfur is removed from hydrocarbon fuels in a single step by contact with finely divided nickel at an elevated temperature in the presence of steam.
BACKGROUND OF THE INVENTION The present invention relates to an improved process for desulfurizing hydrocarbon fuels. It finds particular application in those systems, such as fuel cells, wherein even trace amounts of sulfur and sulfur-containing cornpounds may cause a serious degradation in either the performance or endurance of the system.
One of the more promising fuel cell concepts currently envisioned contemplates a hydrocarbon-air reaction, using a fuel such as JP-4 or natural gas, in an indirect system wherein hydrogen is first generated by steam reformation of the hydrocarbon fuel. Unfortunately, the reform catalyst and the palladium-silver membrane purifier of the reformer, as well as the typical fuel cell catalyst, are all susceptible to parasitic poisoning when the fuels utilized contain sulfur at the concentrations usually found in as-supplied JP-4, for example, typically in the range of 20D-500 parts per million sulfur. The necessity for removal of the sulfur is, accordingly, quite evident.
Several processes for sulfur removal from hydrocarbons are known in the petroleum industry, as evidenced by the patents to Houdry 2,259,469 and Watson 2,064,- 999. A typical process is hydrodesulfurization, wherein the hydrocarbon fuel is treated catalytically in the presence of hydrogen to effect a conversion of the organic sulfur compounds into an inorganic, easily-removed form, such as hydrogen sulfide, which is then removed in a subsequent refining operation. It is known that all types of organic sulfur compounds, including the thiophenes (Cid-14S) can be removed in this process provided conversion to hydrogen sulfide is first made and sufficient additional treatment is undertaken to substantially remove the hydrogen sulfide.
SUMMARY OF THE INVENTION Briefiy described, the present invention teaches a desulfurizing technique whereby the sulfur is removed in a single step. Accordingly, it satisfies the primary object of the invention which is to strip the residual sulfur from the as-supplied hydrocarbon fuels in a process which neither seriously affects the compactness or weight of the overall power system nor adds significantly to the parasitic power requirements thereof.
The basic technique involved provides desulfurization by reaction and/or adsorption of the sulfur-containing hydrocarbon in a bed of finely-divided nickel with the fuel in the vapor state and exposed to steam at an elevated temperature.
In the more preferred embodiment the reaction-adsorbent is effected at a temperature in excess of 500 F. but below that at which cracking of the fuel occurs. Hence, the desulfurization is effected at 50G-900 F. In the most preferred embodiment a small hydrogen addition is made to increase durability of the system.
ICC
It is another object of the present invention to provide a desulfurization process for hydrocarbon fuels which is essentially completely efficient in the sulfur removal sense.
In its more preferred manner of utilization, the techniques described herein are used to process those fuels having a sulfur content less than about 1000 parts per million sulfur or, even more preferably, less than about 500 parts per million sulfur although, as hereinafter dis cussed in greater detail, the more preferred utilization is not made because of any substantial reduction in the efficiency of sulfur removal with the higher sulfur contents. Hence, the present process is primarily adapted to supplement and not replace the currently-existing processes directed to the removal of sulfur in gross amounts.
BRiEF DESCRIPTION OF THE DRAWINGS FIG. l is an abbreviated schematic of a fuel cell system adapted to the practice of the instant process.
FIG. 2 is a graph illustrating the effect of temperature on the desulfurization performance of a typical system utilizing a hydrocarbon fuel doped with thiophene to 419 parts per million sulfur.
FIG. 3 is a graph plotting the effect of pressure on desulfurization performance with doped fuel.
FIG. 4 illustrates the effect of a hydrogen addition on the desulfurization process.
FIG. 5 illustrates the effect of varying thiophene percentages at a constant total sulfur level.
FIG. 6 plots sulfur loading of the reactant-adsorbent bed as a function of bed length.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The various types of organic sulfur compounds usually found in the hydrocarbon fuels can generally be Classified as:
(a) mercaptans (b) sulfides (c) disulfides, and (d) thiophenes The mercaptans and disulfides are much less stable than the other organic sulfur compounds and, hence, much more amenable to removal. Generally, in fuels such as JP-4, these compounds have been removed at the refinery prior to distribution of the fuel. The primary concern, therefore, has been the removal of the more stable forms of sulfur compounds, namely the sulfides and, particularly, the thiophenes, which are both usually present in the as-supplied fuels. The organic sulfides can be represented by the general formula R-S-R, Where R and R are organic groups, either aliphatic or aromatic, and the molecule itself can also occur as a saturated ring structure. The thiophenes are aromatic sulfur compounds based on thiophene (Gli-14S).
In general, the detailed tests performed were directed toward fuels doped with thiophene since it represents the most diicult type of sulfur compound to remove. To insure controlled conditions with respect to the sulfur level in the various fuels, sulfur compounds were mixed with a sulfur-free hydrocarbon to bring the total sulfur level to about 400 parts per million, this level being chosen since it is representative of the average sulfur level of JP-4 marketed by the various manufacturers.
The basic reactant-adsorbent of the present invention is finely divided nickel, including the high nickel content alloys. The most preferred form of the reactant-adsorbent comprises 50 percent nickel supported on kieselguhr, such as Girdler G-49B nickel catalyst. The reactant-adsorbent is usually ground to 1%6 mesh, as the best balance between the desired high surface area and low pressure drop factors considered.
Desulfurization was, in general, practiced at temperatures between about 500-900 F., and pressures were varied between about 40-250 p.s.i.a., the effects of varying temperature and pressure in a specific system being set forth in FIGS. 2 and 3, respectively.
During the development process it was found that a small hydrogen addition to the reactant chamber, typically about 0.03 pound of hydrogen per pound of fuel, is advantageous. The experimental results clearly demonstrated that, although desulfurization could be accomplished without the addition of hydrogen to the fuelwater feed mixture, the breakthrough time for a given bed was 40 percent shorter without the hydrogen addition. Breakthrough was considered to have occurred when detectable sulfur in the fuel condensate was found, usually at about parts per million sulfur. The effect of a hydrogen addition on breakthrough time with varying quantities of hydrogen is illustrated graphically in FIG. 4.
As mentioned previously, the thiophenes are considered the most difficult organic sulfur compounds to remove in the fuel processing sequence. Tests with fuels containing 50-50 mixtures of diphenyl sulfide and benzothiophene indicated that the sulfide removal can be accomplished 5 or 7 times as readily as the thiophene removal when calculated in terms of sulfur retention in the reactant bed. It is thought that in the former case the sulfur is stripped from the organic molecule and retained at the bed as nickel sulfiide, while the thiophene molecule is adsorbed intact in the bed. The sulfur retention in a typical bed as a function of the thiophene fraction in the fuel is plotted in FIG. 5.
Exploratory tests were run with a variety of reactantadsorbents under a number of feed conditions. Tests run with fuel alone (no water or hydrogen feed) at 600 F. had to be terminated within ten minutes due to a plugged reactor resulting from coke formation in the bed.
` While the exact mechanism is not known, it is felt that the addition of steam provides an oxygen monolayer on the individual nickel particles which prevents catalytic cracking of the fuel and the consequent undesirable coke formation in the bed and presence of hydrogen sulfide in the eiuent from the bed. However, the monolayered oxygen does not interfere with the chemisorption of the sulfide and thiophene, probably through an oxygen displacement mechanism. On the other hand, a substantial conversion of the reactant-adsorbent to nickel oxide is to be avoided since nickel oxide is ineffective in providing the desired sulfur removal as clearly indicated with tests on nickel oxide reactant.
As suggested, a balance must be effected within the reactant chamber or bed in order to attain the desulfurization objective. It appears that the presence of hydrogen prevents the undesirable oxide buildup without destroying the desired blanketing monolayer on the nickel, thereby achieving the balance whereby catalytic fuel cracking is virtually prevented and yet the reactant remains sufiiciently active with respect to sulfur and the various sulfur corresponds to effect their complete removal.
It should be reiterated, however, that the hydrogen addition, while preferable, is yet only optional. Tests without the hydrogen addition indicated satisfactory sulfur removal, although the breakthrough time was measurably shortened. It is thought that a small amount of hydrogen is generated in the early stages of the reaction, this selfgenerated hydrogen serving to at least partially prevent the oxide buildup as previously mentioned.
1n the initial screening tests, fuel and water were fed to a small electrically heated boiler by positive displacement pumps, and hydrogen was supplied, as appropriate, from a pressurized cylinder. The mixture was introduced to a reactor containing the nickel reactant-adsorbent, the temperature of the reactor being maintained by external electrical heaters. A series of condensers downstream of `the reactor were used to collect the efiluent from the reactor for the purposes of analysis.
Various reactant-adsorbents were tested in addition to the G-49B mentioned above, including those identified as follows: two high nickel content hydrogenation types: one moderate nickel and one nickel-tungsten material, usually utilized as hydrogenation catalysts, and identified as G-60RS and Ni-4301, respectively; one nickel oxide sample; and one cobalt-molybdenum hydrodesulfurization catalyst: G-35. Both the nickel oxide bed and the cobalt-molybdenum materials were completely ineffective as reactant-adsorbents in the context of the present invention. It is not to be expected, therefore, that the usual desulfurization catalysts will necessarily work in the present process, emphasizing the 'basic difference between the reaction and/ or adsorption process herein described and the catalytic processes conventionally employed. The nickel base materials were effective in the single stage removal of sulfur in varying degrees of efiiciency, the nickel-tungsten material, for example, being most effective at 700 F.
In one demonstration, an existing system was adapted to incorporate the reactant-adsorbent desulfurizer described with the G-49B material. The reformer was operated without any loss in output for 200 hours using JP-4 fuel modified with a 50-50 mixture of thiophene and diphenyl sulfide to a total sulfur content of 470 parts per million by weight. Two 1GO-hour replaceable cartridges were utilized at an hourly space velocity, grams sulfur fed/ hr.)/ (gram of reactant-adsorbent), and a pressure of 240 p.s.i.a. Temperatures in the bed varied from 500 to 800 F., depending on location.
The efficiency of the sulfur removal was demonstrated during the course of a program designed to provide a means for detecting an incipient breakthrough. Prior to the actual breakthrough sulfur contents in the effluent stream were generally below those amounts detectable by all but the -more refined methods. Moreover, in the work with the supported nickel reactant-adsorbents, no hydrogen sulfide was eveer found in the effluent, even at periods well after breakthrough While this invention has been described in connection with several preferred embodiments and particular examples, these will be understood to be illustrative only, no limitation being intended thereby. The invention in its true `scope and spirit will be measured by the appended claims.
What is claimed is:
1. In a fuel cell system utilizing a low-boiling, hydrocarbon fuel feed having a residual sulfur content of up to 500 parts per million by weight wherein the hydrocarbon is passed through a catalystic reformer to convert a substantial portion of the hydrocarbon to hydro-gen and carbon oxides prior to admission of the fuel to the fuel cell, the method of stripping residual sulfur from the hydrocarbon to prevent poisoning of the reformer catalyst while avoiding substantial cracking of the hydrocarbon with the formation of coke in the sulfur-removal process, which comprises the steps of:
prior to admission of the hydrocarbon to the reformer,
vaporizing the hydrocarbon and mixing it `with steam in a ratio of about 2-5 moles of steam per mole of carbon in the hydrocarbon,
and passing the steam-hydrocarbon mixture through a reactant-adsorbent granular bed consisting of elemental nickel or alloy of high nickel content supported on an inert carrier at a temperature of 500- 900 F., and adsorbing the sulfur and sulfur-containing compounds thereon while preventing substantial cracking of the hydrocarbon;
recovering the desulfurized hydrocarbon from the reactant-adsorbent bed;
and feeding the efliuent to the reformer.
2. The method according to claim 1 in which:
hydrogen is added to the vaporized hydrocarbon-steam a 6 mixture admitted to the reactant-adsorbent bed in a FOREIGN PATENTS ratio of about CD2-0.1 pounds of hydrogen per 511398 8/1939 Great Britain` pound of hydrocarbon.
References Cited PAUL M. COUGHLAN, JR., Primary Examiner UNITED STATES PATENTS D J. M. NELSON, Assistant Examiner 3,379,505 4/1968 Holmes et a1. 23--212 8,367,862 2/1968 Mason et a1. 208-244 U-S- C1- X-R- 2,516,876 8/1950 Home et a1. 208417 136-86? 208-217
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US67063667A | 1967-09-26 | 1967-09-26 |
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US (1) | US3485746A (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4336130A (en) * | 1980-11-28 | 1982-06-22 | Union Oil Company Of California | Desulfurization of hydrocarbons |
US4419224A (en) * | 1980-11-28 | 1983-12-06 | Union Oil Company Of California | Desulfurization of hydrocarbons |
US4806232A (en) * | 1984-10-09 | 1989-02-21 | Environment Protection Engineers Inc. | Method for the desulphurization of sulphur-containing fuels and fuel desulphurized by said method |
EP0435724A2 (en) * | 1989-12-27 | 1991-07-03 | Petroleum Energy Center | Improvement in fuel cell electricity generation process |
US5284717A (en) * | 1989-12-27 | 1994-02-08 | Petroleum Energy Center | Method for producing raw materials for a reformer by cracking and desulfurizing petroleum fuels |
WO2000039252A1 (en) * | 1998-12-28 | 2000-07-06 | International Fuel Cells, Llc | System and method for desulfurizing gasoline or diesel fuel to produce a low sulfur-content fuel for use in an internal combustion engine |
WO2001046341A1 (en) * | 1999-12-22 | 2001-06-28 | International Fuel Cells, Llc | Method for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
WO2001062871A1 (en) * | 2000-02-24 | 2001-08-30 | International Fuel Cells, Llc | Method for desulfurizing gasoline or diesel fuel for use in an internal combustion engine |
US20020071976A1 (en) * | 2000-11-03 | 2002-06-13 | Edlund David J. | Sulfur-absorbent bed and fuel processing assembly incorporating the same |
US6497856B1 (en) | 2000-08-21 | 2002-12-24 | H2Gen Innovations, Inc. | System for hydrogen generation through steam reforming of hydrocarbons and integrated chemical reactor for hydrogen production from hydrocarbons |
US20030106841A1 (en) * | 2001-08-16 | 2003-06-12 | China Petroleum & Chemical Corporation | Process for adsorptive desulfurization of light oil distillates |
US6726836B1 (en) * | 2000-09-01 | 2004-04-27 | Utc Fuel Cells, Llc | Method for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
US6736961B2 (en) | 2001-01-30 | 2004-05-18 | Marathon Oil Company | Removal of sulfur from a hydrocarbon through a selective membrane |
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GB511398A (en) * | 1938-08-11 | 1939-08-17 | Heliodor Rostin | Process for purifying hydrocarbon oils |
US2516876A (en) * | 1946-09-27 | 1950-08-01 | Gulf Research Development Co | Desulfurization of light petroleum hydrocarbons |
US3367862A (en) * | 1965-10-18 | 1968-02-06 | Exxon Research Engineering Co | Process for desulfurization by hydrolysis with metals on charcoal base catalysts |
US3379505A (en) * | 1964-05-12 | 1968-04-23 | British Petroleum Co | Process for reforming hydrocarbons employing a nickel-sepiolite catalyst composition |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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GB511398A (en) * | 1938-08-11 | 1939-08-17 | Heliodor Rostin | Process for purifying hydrocarbon oils |
US2516876A (en) * | 1946-09-27 | 1950-08-01 | Gulf Research Development Co | Desulfurization of light petroleum hydrocarbons |
US3379505A (en) * | 1964-05-12 | 1968-04-23 | British Petroleum Co | Process for reforming hydrocarbons employing a nickel-sepiolite catalyst composition |
US3367862A (en) * | 1965-10-18 | 1968-02-06 | Exxon Research Engineering Co | Process for desulfurization by hydrolysis with metals on charcoal base catalysts |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4336130A (en) * | 1980-11-28 | 1982-06-22 | Union Oil Company Of California | Desulfurization of hydrocarbons |
US4419224A (en) * | 1980-11-28 | 1983-12-06 | Union Oil Company Of California | Desulfurization of hydrocarbons |
US4806232A (en) * | 1984-10-09 | 1989-02-21 | Environment Protection Engineers Inc. | Method for the desulphurization of sulphur-containing fuels and fuel desulphurized by said method |
EP0435724A2 (en) * | 1989-12-27 | 1991-07-03 | Petroleum Energy Center | Improvement in fuel cell electricity generation process |
EP0435724A3 (en) * | 1989-12-27 | 1992-06-10 | Petroleum Energy Center | Improvement in fuel cell electricity generation process |
US5284717A (en) * | 1989-12-27 | 1994-02-08 | Petroleum Energy Center | Method for producing raw materials for a reformer by cracking and desulfurizing petroleum fuels |
WO2000039252A1 (en) * | 1998-12-28 | 2000-07-06 | International Fuel Cells, Llc | System and method for desulfurizing gasoline or diesel fuel to produce a low sulfur-content fuel for use in an internal combustion engine |
US6129835A (en) * | 1998-12-28 | 2000-10-10 | International Fuel Cells, Llc | System and method for desulfurizing gasoline or diesel fuel to produce a low sulfur-content fuel for use in an internal combustion engine |
EP1252257A1 (en) * | 1999-12-22 | 2002-10-30 | International Fuel Cells, LLC | Method for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
CN100422293C (en) * | 1999-12-22 | 2008-10-01 | Utc电力公司 | Method for desulfurizing gasoline or diesel fuel for use in fuel cell power plant |
US6454935B1 (en) * | 1999-12-22 | 2002-09-24 | Utc Fuel Cells, Llc | Method for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
WO2001046341A1 (en) * | 1999-12-22 | 2001-06-28 | International Fuel Cells, Llc | Method for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
EP1252257A4 (en) * | 1999-12-22 | 2004-03-24 | Int Fuel Cells Llc | Method for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
US20020104781A1 (en) * | 2000-02-24 | 2002-08-08 | Lesieur Roger R. | Method for desulfurizing gasoline or diesel fuel for use in an internal combustion engine |
WO2001062871A1 (en) * | 2000-02-24 | 2001-08-30 | International Fuel Cells, Llc | Method for desulfurizing gasoline or diesel fuel for use in an internal combustion engine |
US6533924B1 (en) * | 2000-02-24 | 2003-03-18 | Utc Fuel Cells, Llc | Method for desulfurizing gasoline or diesel fuel for use in an internal combustion engine |
US6623719B2 (en) | 2000-08-21 | 2003-09-23 | H2Gen Innovations | System for hydrogen generation through steam reforming of hydrocarbons and integrated chemical reactor for hydrogen production from hydrocarbons |
US6497856B1 (en) | 2000-08-21 | 2002-12-24 | H2Gen Innovations, Inc. | System for hydrogen generation through steam reforming of hydrocarbons and integrated chemical reactor for hydrogen production from hydrocarbons |
US6726836B1 (en) * | 2000-09-01 | 2004-04-27 | Utc Fuel Cells, Llc | Method for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
US20040124125A1 (en) * | 2000-09-01 | 2004-07-01 | Lesieur Roger R. | Method for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
GB2384447A (en) * | 2000-11-03 | 2003-07-30 | Idatech Llc | Sulfur-absorbent bed and fuel processing assembly incorporating the same |
WO2002049128A3 (en) * | 2000-11-03 | 2002-08-29 | Idatech Llc | Sulfur-absorbent bed and fuel processing assembly incorporating the same |
GB2384447B (en) * | 2000-11-03 | 2004-12-22 | Idatech Llc | Sulfur-absorbent bed and fuel processing assembly incorporating the same |
US20020071976A1 (en) * | 2000-11-03 | 2002-06-13 | Edlund David J. | Sulfur-absorbent bed and fuel processing assembly incorporating the same |
US6736961B2 (en) | 2001-01-30 | 2004-05-18 | Marathon Oil Company | Removal of sulfur from a hydrocarbon through a selective membrane |
US20030106841A1 (en) * | 2001-08-16 | 2003-06-12 | China Petroleum & Chemical Corporation | Process for adsorptive desulfurization of light oil distillates |
US6875340B2 (en) * | 2001-08-16 | 2005-04-05 | China Petroleum & Chemical Corporation | Process for adsorptive desulfurization of light oil distillates |
DE10297118B4 (en) * | 2001-08-16 | 2014-07-10 | China Petroleum & Chemical Corp. | Process for the adsorptive desulphurisation of light oil distillates |
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