WO2004060840A2 - Multicomponent sorption bed for the desulfurization of hydrocarbons - Google Patents
Multicomponent sorption bed for the desulfurization of hydrocarbons Download PDFInfo
- Publication number
- WO2004060840A2 WO2004060840A2 PCT/US2003/038297 US0338297W WO2004060840A2 WO 2004060840 A2 WO2004060840 A2 WO 2004060840A2 US 0338297 W US0338297 W US 0338297W WO 2004060840 A2 WO2004060840 A2 WO 2004060840A2
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- catalyst bed
- nickel
- copper
- zinc
- Prior art date
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 47
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 47
- 238000001179 sorption measurement Methods 0.000 title claims description 5
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 9
- 230000023556 desulfurization Effects 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 153
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 41
- 239000011593 sulfur Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000356 contaminant Substances 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- -1 nickel silicates Chemical class 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 21
- 239000007788 liquid Substances 0.000 abstract description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical class CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
Definitions
- the present invention relates to a catalyst bed for the desulfurization of a hydrocarbon feedstream.
- the catalyst bed comprises at least two catalysts, each having an affinity for sulfur-containing compounds. When used in combination, the catalyst bed demonstrates significant reductions in the sulfur concentration in the feedstream.
- a process for reducing the concentration of sulfur compounds in a hydrocarbon feedstream to a level of less than about 500 ppb is also disclosed.
- Hydrocarbon feed streams such as natural gas (NG), liquified petroleum gas (LPG) and gasoline, are used as the starting materials for several chemical processes, many of which utilize catalysts in one or more reaction steps.
- NG natural gas
- LPG liquified petroleum gas
- gasoline gasoline
- Nickel catalysts, which are generally useful for in hydrogenation reactions, are especially sensitive to sulfur poisoning on their active surfaces.
- precious metals which are used in a variety of catalysts, are sensitive to sulfur and can be easily poisoned by the presence of sulfur or sulfur- containing compounds.
- activated carbon has a high capacity for ethyl mercaptans
- manganese oxide is effective for dimethyl sulfoxide removal
- zinc oxide can be used to remove hydrogen sulfide.
- catalysts known to be effective in desulfurization processes include carbon, copper / zinc oxides, nickel-based sorbents, nickel oxides, zeolites, molecular sieves and faujasites, among others.
- different methods have been used to reduce the sulfur level in feedstreams. The most commonly used procedure involves the application of a hydrogen recycle stage to convert the sulfur-containing compounds to H 2 S, and then the removal of the sulfur compounds in a separate step. This can be an arduous and time- consuming procedure. Thus, a better method for removal of sulfur-containing compounds is needed.
- the present invention is for a novel hydrocarbon feedstream catalyst bed for the desulfurization of a gas or a liquid hydrocarbon feedstream.
- the bed comprises at least two catalysts having different sulfur compound affinities and / or specificities thereby improving the overall amount of sulfur compound removal.
- the catalyst bed is configured such that the feed stream has initial contact with a first catalyst that is more selective or that has the greater affinity for the sulfur compound that is present in relatively high concentration within the feedstream. As the feedstream passes over the first catalyst, the targeted sulfur compounds are removed generating a cleaner stream for reaction with a second catalyst.
- the catalysts are mixed within the catalyst bed. As the feedstream passes over the catalyst bed, the sulfur compounds are adsorbed by the catalyst having the highest affinity for the particular sulfur compound.
- the present development further describes a process comprising passing a hydrocarbon feedstream over a catalyst bed comprising at least two catalysts having different sulfur compound affinities and / or specificities thereby improving the overall amount of sulfur compound removal.
- the process reduces the sulfur content in a gas hydrocarbon feedstream from up to about 300 ppm to less than about 500 ppb, and in a liquid hydrocarbon feedstream from up to about 3 % to less than about 500 ppb.
- Figure 1 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present invention and the selective adsorbent section is positioned near the inlet port and the general adsorbent section is positioned near the exit port;
- Figure 2 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present invention and the general adsorbent section is positioned near the inlet port and the selective adsorbent section is positioned near the exit port; and
- Figure 3 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present invention and the general adsorbent is intermixed with the selective adsorbent to form the filter bed.
- the present invention is for a catalyst bed that is intended to be used to remove contaminants from a gas or liquid hydrocarbon feedstream.
- sulfur-containing compounds such as, but not limited to, hydrogen sulfide, carbonyl sulfide, sulfides, mercaptans, thiophenes, tert-butyl mercaptan, di-sulfides, dimethyl sulfide, tetrahydrothiophene, ethyl mercaptan, and benzothiophene.
- a hydrocarbon feedstream desulfurization system 10 includes a catalyst bed reactor 12 having an inlet port 14 and an exit port 16.
- the catalyst bed reactor 12 houses a catalyst bed 20.
- a hydrocarbon feedstream, F enters the reactor 12 at the inlet port 14.
- the hydrocarbon feedstream is in contact with the catalyst bed 20 for a predetermined residence time, determined by the dimensions of the bed 20 and the rate of flow of the feedstream.
- the catalyst bed 20 can have a controlled temperature and pressure.
- the feedstream F then exits the catalyst bed 20 through the exit port 16. As the feedstream F passes over the bed 20, contaminants are removed from the feedstream.
- the hydrocarbon feedstream may be supplied as a gas or as a liquid.
- the typical sulfur concentration of the raw gas-phase hydrocarbon feedstream can have a sulfur concentration of up to about 300 ppm and the liquid-phase feedstream can have a sulfur concentration of up to about 3 %.
- the process of the present invention reduces the sulfur concentration to less than about 500 ppb.
- the catalyst bed 20 comprises a first catalyst or a general adsorbent catalyst 22, and a second catalyst or a selective adsorbent catalyst 24, each having an affinity for sulfur-containing compounds.
- the first catalyst 24 is positioned near the inlet port 14 of the bed 20.
- the second catalyst 22 is positioned near the exit port 16 of the bed 20.
- the first or selective adsorbent catalyst 24 is preferably selected based on the material's 24 specificity for a predetermined class of chemical compounds.
- a non-limiting list of some selective catalyst materials 24 would include copper/zinc catalysts, zinc oxide catalysts, copper/zinc/molybdenum oxide catalsyts, nickel aluminas, nickel silicas or combinations thereof.
- a "selective adsorbent catalyst” is a material that fails to adsorb at least one of the sulfur compounds - ethyl mercaptan, tert- butyl mercaptan, tetrahydrothiophene and dimethyl sulfide - at a temperature of about 38°C, a pressure of about 15 psig, and a feedstream space velocity of not less than about 3000 hr '1 . If desired, the relative degrees of specificity for a series of adsorbents can be graded by increasing the reaction temperature and / or decreasing the space velocity.
- the second or general adsorbent catalyst 22 is preferably selected from a group of relatively materials which are capable of adsorbing sulfur constituents without a high degree of specificity.
- a non-limiting list of some general adsorbent catalysts would include activated carbon, magnesium oxide, copper/manganese, silver on alumina, nickel silicates, nickel silica/magnesia/alumina, zeolites, molecular sieves, faujasites and combinations thereof, have been shown to be.
- a "general adsorbent catalyst” is a material that adsorbs ethyl mercaptan, tert-butyl mercaptan, tetrahydrothiophene and dimethyl sulfide at a temperature of about 38°C, a pressure of about 15 psig, and a feedstream space velocity of not less than about 3000 hi '1 .
- the hydrocarbons when the hydrocarbon feedstream passes over the catalyst bed 20, the hydrocarbons initially passes over the selective adsorbent 24 where the targeted sulfur-containing components are adsorbed by selective adsorbent material 24. The remaining hydrocarbons then pass over the general adsorbent 22 where other sulfur-containing components may be retained by the adsorbent material 22. The remaining hydrocarbons then exit the catalyst bed 20.
- a catalyst bed 120 comprises a general adsorbent catalyst 122 positioned near an inlet port 114 and a selective adsorbent catalyst 124 positioned near an exit port 1 16.
- the hydrocarbon feedstream first passes over the general catalyst 122, and then over the selective catalyst 124. If the selective adsorbent catalyst 124 is highly selective, it will be relatively unaffected by the presence of other sulfur-containing compounds.
- FIG. 3 shows a second alternative embodiment for a catalyst bed 220.
- a general adsorbent catalyst 222 is intermixed with a selective adsorbent catalyst 224 throughout the length of the catalyst bed 220.
- selected sulfur-containing compounds are adsorbed preferentially onto the selective catalyst 224 leaving the general catalyst 222 available to adsorb other sulfur-containing compounds.
- the bed 220 with the catalysts intermixed is most effective when each catalyst 222, 224 has an affinity for a particular class of sulfur- containing compounds.
- each catalyst 222, 224 has an affinity for a particular class of sulfur- containing compounds.
- the "general" catalyst preferentially adsorbs thiophenes
- the "selective" catalyst preferentially adsorbs mercaptans
- Figures 1 - 3 have been presented and described in terms of only two catalysts or adsorbents. However, more than one catalyst can be combined to form the "general adsorbent catalyst" and / or more than one catalyst can be combined to form the "selective adsorbent catalyst".
- the catalyst bed may vary in design and equipment from what is illustrated herein.
- the general adsorbent catalyst and the selective adsorbent catalyst may be optimized to a particular hydrocarbon feedstream or contamination mixture.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A novel hydrocarbon feedstream catalyst bed for the desulfurization of a gas or a liquid hydrocarbon feedstream and a process comprising passing a hydrocarbon feedstream over the catalyst bed is descrived. The bed comprises a least two catalysts having different sulfur compound affinities and / or specificities thereby improving the overall amount of sulfur compound removal. The process reduces the sulfur content in a gas hydrocarbon feedstream from up to about 300 ppm to less than about 500 ppb, and in a liquid hydrocarbon feedstream from up to about 3% to less than about 500 ppb.
Description
BACKGROUND
The present invention relates to a catalyst bed for the desulfurization of a hydrocarbon feedstream. The catalyst bed comprises at least two catalysts, each having an affinity for sulfur-containing compounds. When used in combination, the catalyst bed demonstrates significant reductions in the sulfur concentration in the feedstream. A process for reducing the concentration of sulfur compounds in a hydrocarbon feedstream to a level of less than about 500 ppb is also disclosed.
Hydrocarbon feed streams, such as natural gas (NG), liquified petroleum gas (LPG) and gasoline, are used as the starting materials for several chemical processes, many of which utilize catalysts in one or more reaction steps. However, problems frequently arise during the chemical processing if the hydrocarbon feed stream also contains sulfur compounds. These sulfur compounds can poison the reaction catalysts rendering the catalyst bed ineffective. Nickel catalysts, which are generally useful for in hydrogenation reactions, are especially sensitive to sulfur poisoning on their active surfaces. Similarly, many precious metals which are used in a variety of catalysts, are sensitive to sulfur and can be easily poisoned by the presence of sulfur or sulfur- containing compounds. Poisoning of the catalysts results in longer then desired reaction times, formation of undesired side reaction products, reduction in the life expectancy of the nickel catalyst, and, in some instances, poor quality of the finished product. Thus, it is beneficial to reduce the sulfur content in the hydrocarbon feed stream before it reaches the chemical processing catalyst bed.
However, hydrocarbon feed streams have different sources of origin. This means that each feed stream has unique sulfur compound contaminants and contaminants present at different concentrations. For example, Table I shows some sulfur species commonly found in natural gas, LPG and gasoline streams. Moreover, the sulfur species vary not only by type of feed stream but also by source of origin. In other words, the natural gas feed stream composition originating in Alaska can vary significantly from the natural gas feed stream composition originating in northern Russia.
TABLE 1. Some sulfur species commonly found in hydrocarbon feedstocks
Species Natural Gas LPG Gasoline
H2S X X
Carbonyl Sulfide (COS) X — t-Butyl Mercaptan X X
Di-sulfides X X X
Dimethyl Sulfide (DMS) X —
Tetrahydrothiophene (THT) i X " X
C2-C3 mercaptans X X X thiophene — ~ X
C4+ mercaptans — — X benzothiophenes — " X subs.- benzothiophenes — — X sulfides _.- ._. X
X indicates present in the feedstream; ~ indicates absent in the feedstream
A number of different catalysts that are effective for removing sulfur compounds are known in the art. For example, activated carbon has a high capacity for ethyl
mercaptans, manganese oxide is effective for dimethyl sulfoxide removal, and zinc oxide can be used to remove hydrogen sulfide.
Other catalysts known to be effective in desulfurization processes include carbon, copper / zinc oxides, nickel-based sorbents, nickel oxides, zeolites, molecular sieves and faujasites, among others. In addition, different methods have been used to reduce the sulfur level in feedstreams. The most commonly used procedure involves the application of a hydrogen recycle stage to convert the sulfur-containing compounds to H2S, and then the removal of the sulfur compounds in a separate step. This can be an arduous and time- consuming procedure. Thus, a better method for removal of sulfur-containing compounds is needed. However, because of the variations in the specific sulfur compound species and the concentration of the sulfur compounds in the feed streams, it can be difficult to find a single catalyst composition that is universally effective for the removal of essentially all sulfur compounds from gas and liquid hydrocarbon streams.
SUMMARY
The present invention is for a novel hydrocarbon feedstream catalyst bed for the desulfurization of a gas or a liquid hydrocarbon feedstream. The bed comprises at least two catalysts having different sulfur compound affinities and / or specificities thereby improving the overall amount of sulfur compound removal. In one embodiment, the catalyst bed is configured such that the feed stream has initial contact with a first catalyst
that is more selective or that has the greater affinity for the sulfur compound that is present in relatively high concentration within the feedstream. As the feedstream passes over the first catalyst, the targeted sulfur compounds are removed generating a cleaner stream for reaction with a second catalyst.
Because the stream is cleaner when it reaches the second catalyst, the efficiency of the second catalyst is enhanced. In an alternative embodiment, the catalysts are mixed within the catalyst bed. As the feedstream passes over the catalyst bed, the sulfur compounds are adsorbed by the catalyst having the highest affinity for the particular sulfur compound.
The present development further describes a process comprising passing a hydrocarbon feedstream over a catalyst bed comprising at least two catalysts having different sulfur compound affinities and / or specificities thereby improving the overall amount of sulfur compound removal. The process reduces the sulfur content in a gas hydrocarbon feedstream from up to about 300 ppm to less than about 500 ppb, and in a liquid hydrocarbon feedstream from up to about 3 % to less than about 500 ppb.
SUMMARY OF THE FIGURES
Figure 1 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present
invention and the selective adsorbent section is positioned near the inlet port and the general adsorbent section is positioned near the exit port;
Figure 2 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present invention and the general adsorbent section is positioned near the inlet port and the selective adsorbent section is positioned near the exit port; and
Figure 3 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system wherein the catalyst bed is made in accordance with the present invention and the general adsorbent is intermixed with the selective adsorbent to form the filter bed.
DETAILED DESCRIPTION
The present invention is for a catalyst bed that is intended to be used to remove contaminants from a gas or liquid hydrocarbon feedstream. As is known in the art, some of the most pervasive contaminants in these feedstreams are sulfur-containing compounds, such as, but not limited to, hydrogen sulfide, carbonyl sulfide, sulfides, mercaptans, thiophenes, tert-butyl mercaptan, di-sulfides, dimethyl sulfide, tetrahydrothiophene, ethyl mercaptan, and benzothiophene. Many of these sulfur contaminants not only have strong odors, making it unpleasant to work around processes utilizing the feedstreams, but the sulfur is also poisonous for many catalysts that use hydrocarbon starting materials.
As shown in Figure 1 , a hydrocarbon feedstream desulfurization system 10 includes a catalyst bed reactor 12 having an inlet port 14 and an exit port 16. The catalyst bed reactor 12 houses a catalyst bed 20. A hydrocarbon feedstream, F, enters the reactor 12 at the inlet port 14. The hydrocarbon feedstream is in contact with the catalyst bed 20 for a predetermined residence time, determined by the dimensions of the bed 20 and the rate of flow of the feedstream.
As is known in the art, the catalyst bed 20 can have a controlled temperature and pressure. The feedstream F then exits the catalyst bed 20 through the exit port 16. As the feedstream F passes over the bed 20, contaminants are removed from the feedstream.
The hydrocarbon feedstream may be supplied as a gas or as a liquid. The typical sulfur concentration of the raw gas-phase hydrocarbon feedstream can have a sulfur concentration of up to about 300 ppm and the liquid-phase feedstream can have a sulfur concentration of up to about 3 %. The process of the present invention reduces the sulfur concentration to less than about 500 ppb.
Referring again to Figure 1, in the present invention, the catalyst bed 20 comprises a first catalyst or a general adsorbent catalyst 22, and a second catalyst or a selective adsorbent catalyst 24, each having an affinity for sulfur-containing compounds. The first catalyst 24 is positioned near the inlet port 14 of the bed 20. The second catalyst 22 is positioned near the exit port 16 of the bed 20.
The first or selective adsorbent catalyst 24 is preferably selected based on the material's 24 specificity for a predetermined class of chemical compounds. For example,
a non-limiting list of some selective catalyst materials 24 would include copper/zinc catalysts, zinc oxide catalysts, copper/zinc/molybdenum oxide catalsyts, nickel aluminas, nickel silicas or combinations thereof. As used herein, a "selective adsorbent catalyst" is a material that fails to adsorb at least one of the sulfur compounds - ethyl mercaptan, tert- butyl mercaptan, tetrahydrothiophene and dimethyl sulfide - at a temperature of about 38°C, a pressure of about 15 psig, and a feedstream space velocity of not less than about 3000 hr'1. If desired, the relative degrees of specificity for a series of adsorbents can be graded by increasing the reaction temperature and / or decreasing the space velocity. The greater the temperature gradient between the adsorption of a first sulfur-containing compound and a second sulfur-containing compound, the greater the specificity of the selective adsorbent for the first sulfur-containing compound. Similarly, the greater the space velocity gradient between the adsorption of a first sulfur-containing compound and a second sulfur-containing compound, the greater the specificity of the selective adsorbent for the first sulfur-containing compound.
The second or general adsorbent catalyst 22 is preferably selected from a group of relatively materials which are capable of adsorbing sulfur constituents without a high degree of specificity. For example, a non-limiting list of some general adsorbent catalysts would include activated carbon, magnesium oxide, copper/manganese, silver on alumina, nickel silicates, nickel silica/magnesia/alumina, zeolites, molecular sieves, faujasites and combinations thereof, have been shown to be.
As used herein, a "general adsorbent catalyst" is a material that adsorbs ethyl mercaptan, tert-butyl mercaptan, tetrahydrothiophene and dimethyl sulfide at a temperature of about 38°C, a pressure of about 15 psig, and a feedstream space velocity of not less than about 3000 hi'1.
In the embodiment of Figure 1, when the hydrocarbon feedstream passes over the catalyst bed 20, the hydrocarbons initially passes over the selective adsorbent 24 where the targeted sulfur-containing components are adsorbed by selective adsorbent material 24. The remaining hydrocarbons then pass over the general adsorbent 22 where other sulfur-containing components may be retained by the adsorbent material 22. The remaining hydrocarbons then exit the catalyst bed 20.
As shown in the embodiment of Figure 2, a catalyst bed 120 comprises a general adsorbent catalyst 122 positioned near an inlet port 114 and a selective adsorbent catalyst 124 positioned near an exit port 1 16. With the alternative relative positioning of the general catalyst 122 and the selective catalyst 124, the hydrocarbon feedstream first passes over the general catalyst 122, and then over the selective catalyst 124. If the selective adsorbent catalyst 124 is highly selective, it will be relatively unaffected by the presence of other sulfur-containing compounds. However, if the selective adsorbent catalyst 124 has an affinity for sulfur-containing compounds other than its 124 target compound, this configuration risks allowing the selective catalyst 124 to function in some respects as a general adsorbent, thereby decreasing the overall efficacy of the catalyst bed 120.
Figure 3 shows a second alternative embodiment for a catalyst bed 220. In the bed 220, a general adsorbent catalyst 222 is intermixed with a selective adsorbent catalyst 224 throughout the length of the catalyst bed 220. As the hydrocarbon feedstream passes over the catalyst bed 220, selected sulfur-containing compounds are adsorbed preferentially onto the selective catalyst 224 leaving the general catalyst 222 available to adsorb other sulfur-containing compounds. The bed 220 with the catalysts intermixed is most effective when each catalyst 222, 224 has an affinity for a particular class of sulfur- containing compounds. For example, if the "general" catalyst preferentially adsorbs thiophenes and the "selective" catalyst preferentially adsorbs mercaptans, both classes of sulfur compounds can be removed as the feedstream passes over the mixed bed.
The embodiments of Figures 1 - 3 have been presented and described in terms of only two catalysts or adsorbents. However, more than one catalyst can be combined to form the "general adsorbent catalyst" and / or more than one catalyst can be combined to form the "selective adsorbent catalyst".
Further, the embodiments of Figures 1 - 3 have been presented and described in terms of removal of sulfur-containing compounds from a hydrocarbon feedstream. However, the selection of the catalyst materials can vary and the selection will be dependent on the particular contaminants that are to be removed from the feedstream.
From a reading of the above, one with ordinary skill in the art should be able to devise variations to the inventive features. For example, the catalyst bed may vary in design and equipment from what is illustrated herein.
Further, the general adsorbent catalyst and the selective adsorbent catalyst may be optimized to a particular hydrocarbon feedstream or contamination mixture. These and other variations are believed to fall within the spirit and scope of the attached claims.
Claims
1. A catalyst bed for the removal of contaminants from a hydrocarbon feedstream, said catalyst bed comprising:
(a) a selective adsorbent catalyst having an affinity for a predetermined class of chemical compounds; and
(b) a general adsorbent catalyst capable of adsorbing hydrocarbon feedstream contaminants without a high degree of specificity, said selective adsorbent catalyst and said general adsorbent catalyst being in tandem to form said catalyst bed.
2. The catalyst bed of Claim 1 wherein said selective adsorbent material is selected from the group consisting of copper/zinc catalysts, zinc oxide catalysts, copper/zinc/molybdenum oxide catalysts, nickel aluminas, nickel silicas and combinations thereof.
3. The catalyst bed of Claim 1 wherein said general adsorbent material is selected from the group consisting of activated carbon, magnesium oxide, copper/manganese, silver on alumina, nickel silicates, nickel silica/magnesia/alumina, zeolites, molecular sieves, faujasites and combinations thereof.
4. The catalyst bed of Claim 1 wherein said general adsorbent catalyst is positioned near an inlet port of said catalyst bed.
5. The catalyst bed of Claim 1 wherein said selective adsorbent catalyst is positioned near an inlet port of said catalyst bed.
6. A catalyst bed for the removal of contaminants from a hydrocarbon feedstream, said catalyst bed comprising a mixture of a selective adsorbent catalyst having an affinity for a predetermined class of chemical compounds; and a general adsorbent catalyst capable of adsorbing hydrocarbon feedstream contaminants without a high degree of specificity.
7. The catalyst bed of Claim 6 wherein said selective adsorbent material is selected from the group consisting of copper/zinc catalysts, zinc oxide catalysts, copper/zinc/molybdenum oxide catalsyts, nickel aluminas, nickel silicas and combinations thereof.
8. The catalyst bed of Claim 6 wherein said general adsorbent material is selected from the group consisting of activated carbon, magnesium oxide, copper/manganese, silver on alumina, nickel silicates, nickel silica/magnesia/alumina, zeolites, molecular sieves, faujasitesand combinations thereof.
9. A process for removing contaminants from a hydrocarbon feedstream, said process comprising the steps of:
(a) providing a catalyst bed, having an inlet port and an exit port, said catalyst bed comprising a selective adsorption catalyst and a general adsorption catalyst, and
(b) allowing said hydrocarbon feedstream to enter said catalyst bed through said inlet port and to exit said catalyst bed through said exit port, said feedstream residing in said catalyst bed for a predetermined period of time at a predetermined temperature and pressure.
10. The process of Claim 9 wherein said selective adsorbent material is selected from the group consisting of copper/zinc catalysts, zinc oxide catalysts, copper/zinc/molybdenum oxide catalsyts, nickel aluminas, nickel silicas and combinations thereof.
11. The process of Claim 9 wherein said general adsorbent material is selected from the group consisting of activated carbon, magnesium oxide, copper/manganese, silver on alumina, nickel silicates, nickel silica/magnesia/alumina, zeolites, molecular sieves, faujasites and combinations thereof.
12. A catalyst bed for the removal of sulfur-containing components from a hydrocarbon feedstream, said catalyst bed comprising:
(a) a selective adsorbent catalyst having an affinity for at least one sulfur- containing compounds; and (b) a general adsorbent catalyst capable of adsorbing sulfur-containing compounds in said hydrocarbon feedstream without a high degree of specificity, said selective adsorbent catalyst and said general adsorbent catalyst being in tandem to form said catalyst bed.
13. The catalyst bed of Claim 12 wherein said selective adsorbent material is selected from the group consisting of copper/zinc catalysts, zinc oxide catalysts, copper/zinc/molybdenum oxide catalysts, nickel aluminas, nickel silicas and combinations thereof.
14. The catalyst bed of Claim 12 wherein said general adsorbent material is selected from the group consisting of activated carbon, magnesium oxide, copper/manganese, silver on alumina, nickel silicates, nickel silica/magnesia/alumina, zeolites, molecular sieves, faujasites and combinations thereof.
15. The catalyst bed of Claim 12 wherein said general adsorbent catalyst is positioned near an inlet port of said catalyst bed.
16. The catalyst bed of Claim 12 wherein said selective adsorbent catalyst is positioned near an inlet port of said catalyst bed.
17. A catalyst bed for the removal of sulfur-containing components from a hydrocarbon feedstream, said catalyst bed comprising a mixture of a selective adsorbent catalyst having an affinity for at least one sulfur-containing compound; and a general adsorbent catalyst capable of adsorbing sulfur-containing compounds in said hydrocarbon feedstream without a high degree of specificity.
18. The catalyst bed of Claim 17 wherein said selective adsorbent material is selected from the group consisting of copper/zinc catalysts, zinc oxide catalysts, copper/zinc/molybdenum oxide catalsyts, nickel aluminas, nickel silicas and combinations thereof.
19. The catalyst bed of Claim 17 wherein said general adsorbent material is selected from the group consisting of activated carbon, magnesium oxide, copper/manganese, silver on alumina, nickel silicates, nickel silica/magnesia/alumina, zeolites, molecular sieves, faujasitesand combinations thereof.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003293244A AU2003293244A1 (en) | 2002-12-24 | 2003-11-26 | Multicomponent sorption bed for the desulfurization of hydrocarbons |
| JP2004565165A JP2006512453A (en) | 2002-12-24 | 2003-11-26 | Multi-component adsorption bed for hydrocarbon desulfurization |
| CA002509200A CA2509200A1 (en) | 2002-12-24 | 2003-11-26 | Multicomponent sorption bed for the desulfurization of hydrocarbons |
| EP03790238A EP1575884A2 (en) | 2002-12-24 | 2003-11-26 | Multicomponent adsorption bed for the desulfurization of hydrocarbons |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/328,809 US20040118751A1 (en) | 2002-12-24 | 2002-12-24 | Multicomponent sorption bed for the desulfurization of hydrocarbons |
| US10/328,809 | 2002-12-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2004060840A2 true WO2004060840A2 (en) | 2004-07-22 |
| WO2004060840A3 WO2004060840A3 (en) | 2004-09-30 |
Family
ID=32594588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2003/038297 WO2004060840A2 (en) | 2002-12-24 | 2003-11-26 | Multicomponent sorption bed for the desulfurization of hydrocarbons |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20040118751A1 (en) |
| EP (1) | EP1575884A2 (en) |
| JP (1) | JP2006512453A (en) |
| KR (1) | KR20050088206A (en) |
| AU (1) | AU2003293244A1 (en) |
| CA (1) | CA2509200A1 (en) |
| WO (1) | WO2004060840A2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006117921A (en) * | 2004-09-22 | 2006-05-11 | Idemitsu Kosan Co Ltd | Method for removing sulfur from liquid fuel and method for producing hydrogen and fuel battery system |
| JP2008524377A (en) * | 2004-12-17 | 2008-07-10 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | System and method for reducing the sulfur content of a hydrocarbon stream |
| DE202010014363U1 (en) | 2010-04-14 | 2010-12-23 | Süd-Chemie AG | Apparatus for the adsorption treatment of a fluid or fluid stream |
| DE202010016522U1 (en) | 2010-04-14 | 2011-02-17 | Süd-Chemie AG | Apparatus for the adsorption treatment of a fluid or fluid stream |
| WO2011128363A1 (en) | 2010-04-14 | 2011-10-20 | Süd-Chemie AG | Device for adsorption treatment of a fluid or fluid stream |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7597798B2 (en) * | 2005-06-17 | 2009-10-06 | Exxonmobil Research And Engineering Company | Method for reducing the amount of high molecular weight organic sulfur picked-up by hydrocarbon streams transported through a pipeline |
| US20070000385A1 (en) * | 2005-07-01 | 2007-01-04 | Stouffer Mark R | Adsorbents for removing H2S, other odor causing compounds, and acid gases from gas streams and methods for producing and using these adsorbents |
| US9152238B2 (en) * | 2005-08-01 | 2015-10-06 | Wai-Lin Maw | Asymmetric shuffle keyboard |
| AR066574A1 (en) * | 2007-05-18 | 2009-08-26 | Shell Int Research | A REACTOR SYSTEM, A PROCESS OF OLEFINE OXIDE PRODUCTION 1,2-DIOL 1,2-DIOL ETER, 1,2-CARBONATE OR ALCANOLAMINE |
| JP5562841B2 (en) * | 2007-05-18 | 2014-07-30 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Reactor system and process for reacting feed |
| US8142646B2 (en) * | 2007-11-30 | 2012-03-27 | Saudi Arabian Oil Company | Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds |
| CA2723988A1 (en) | 2008-05-15 | 2009-11-19 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of alkylene carbonate and/or alkylene glycol |
| WO2009140318A1 (en) | 2008-05-15 | 2009-11-19 | Shell Oil Company | Process for the preparation of an alkylene carbonate and an alkylene glycol |
| JP5469470B2 (en) * | 2010-01-22 | 2014-04-16 | 東京瓦斯株式会社 | Higher-order desulfurization apparatus and higher-order desulfurization method for raw fuel supplied to a steam reformer |
| JP6607387B2 (en) * | 2015-02-02 | 2019-11-20 | パナソニックＩｐマネジメント株式会社 | Desulfurization method and desulfurizer |
| CN109331629A (en) * | 2018-11-06 | 2019-02-15 | 广州点蓝环保设备有限公司 | Arrangement for catalytic purification and its application method is concentrated in low-concentration organic exhaust gas |
| US11773338B1 (en) | 2022-11-03 | 2023-10-03 | Saudi Arabian Oil Company | Methods of processing whole crude oils that include sulfur |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1319515A (en) * | 1969-07-07 | 1973-06-06 | Azote & Prod Chim | Desulphurizing agents |
| US5458861A (en) * | 1992-04-15 | 1995-10-17 | Mobil Oil Corporation | Desulfurizing a gas stream |
| US5882614A (en) * | 1998-01-23 | 1999-03-16 | Exxon Research And Engineering Company | Very low sulfur gas feeds for sulfur sensitive syngas and hydrocarbon synthesis processes |
| US6193877B1 (en) * | 1996-08-23 | 2001-02-27 | Exxon Research And Engineering Company | Desulfurization of petroleum streams containing condensed ring heterocyclic organosulfur compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657663A (en) * | 1985-04-24 | 1987-04-14 | Phillips Petroleum Company | Hydrotreating process employing a three-stage catalyst system wherein a titanium compound is employed in the second stage |
| US5439860A (en) * | 1992-04-16 | 1995-08-08 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Catalyst system for combined hydrotreating and hydrocracking and a process for upgrading hydrocarbonaceous feedstocks |
| US6267874B1 (en) * | 1997-11-18 | 2001-07-31 | Tonengeneral Sekiyu K.K. | Hydrotreating catalyst and processes for hydrotreating hydrocarbon oil with the same |
-
2002
- 2002-12-24 US US10/328,809 patent/US20040118751A1/en not_active Abandoned
-
2003
- 2003-11-26 JP JP2004565165A patent/JP2006512453A/en active Pending
- 2003-11-26 KR KR1020057011746A patent/KR20050088206A/en not_active Application Discontinuation
- 2003-11-26 WO PCT/US2003/038297 patent/WO2004060840A2/en active Application Filing
- 2003-11-26 CA CA002509200A patent/CA2509200A1/en not_active Abandoned
- 2003-11-26 AU AU2003293244A patent/AU2003293244A1/en not_active Abandoned
- 2003-11-26 EP EP03790238A patent/EP1575884A2/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1319515A (en) * | 1969-07-07 | 1973-06-06 | Azote & Prod Chim | Desulphurizing agents |
| US5458861A (en) * | 1992-04-15 | 1995-10-17 | Mobil Oil Corporation | Desulfurizing a gas stream |
| US6193877B1 (en) * | 1996-08-23 | 2001-02-27 | Exxon Research And Engineering Company | Desulfurization of petroleum streams containing condensed ring heterocyclic organosulfur compounds |
| US5882614A (en) * | 1998-01-23 | 1999-03-16 | Exxon Research And Engineering Company | Very low sulfur gas feeds for sulfur sensitive syngas and hydrocarbon synthesis processes |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006117921A (en) * | 2004-09-22 | 2006-05-11 | Idemitsu Kosan Co Ltd | Method for removing sulfur from liquid fuel and method for producing hydrogen and fuel battery system |
| JP2008524377A (en) * | 2004-12-17 | 2008-07-10 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | System and method for reducing the sulfur content of a hydrocarbon stream |
| DE202010014363U1 (en) | 2010-04-14 | 2010-12-23 | Süd-Chemie AG | Apparatus for the adsorption treatment of a fluid or fluid stream |
| DE202010016522U1 (en) | 2010-04-14 | 2011-02-17 | Süd-Chemie AG | Apparatus for the adsorption treatment of a fluid or fluid stream |
| DE102010014890A1 (en) | 2010-04-14 | 2011-10-20 | Süd-Chemie AG | Apparatus for an adsorption of a fluid or fluid stream for desulfurization of a fluid fuel e.g. natural gas, comprises a container for receiving adsorbent material, two fluid line connectors, and a thermally-activated shut-off fluid |
| WO2011128363A1 (en) | 2010-04-14 | 2011-10-20 | Süd-Chemie AG | Device for adsorption treatment of a fluid or fluid stream |
| US9149756B2 (en) | 2010-04-14 | 2015-10-06 | Clariant Produkte (Deutschland) Gmbh | Device for the adsorption treatment of a fluid or fluid stream |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1575884A2 (en) | 2005-09-21 |
| AU2003293244A1 (en) | 2004-07-29 |
| US20040118751A1 (en) | 2004-06-24 |
| JP2006512453A (en) | 2006-04-13 |
| KR20050088206A (en) | 2005-09-02 |
| CA2509200A1 (en) | 2004-07-22 |
| AU2003293244A8 (en) | 2004-07-29 |
| WO2004060840A3 (en) | 2004-09-30 |
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