KR20050088206A - Multicomponent sorption bed for the desulfurization of hydrocarbons - Google Patents
Multicomponent sorption bed for the desulfurization of hydrocarbons Download PDFInfo
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- KR20050088206A KR20050088206A KR1020057011746A KR20057011746A KR20050088206A KR 20050088206 A KR20050088206 A KR 20050088206A KR 1020057011746 A KR1020057011746 A KR 1020057011746A KR 20057011746 A KR20057011746 A KR 20057011746A KR 20050088206 A KR20050088206 A KR 20050088206A
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- catalyst
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- nickel
- copper
- alumina
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 50
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 50
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 9
- 230000023556 desulfurization Effects 0.000 title abstract description 9
- 238000001179 sorption measurement Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 151
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 48
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 29
- 239000011593 sulfur Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003463 adsorbent Substances 0.000 claims description 61
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052759 nickel Inorganic materials 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 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000356 contaminant Substances 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 239000011787 zinc oxide Substances 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-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
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 abstract description 8
- 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
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- JJWKPURADFRFRB-UHFFFAOYSA-N carbon oxide sulfide Natural products O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- 238000001311 chemical methods and process Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical class CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 3
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- -1 but not limited to Chemical compound 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 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
- 230000035484 reaction time Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UQVIDDDPRSSYNJ-UHFFFAOYSA-N [S].C1CCSC1 Chemical class [S].C1CCSC1 UQVIDDDPRSSYNJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 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
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
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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
Description
본 발명은 탄화수소 원료스트림의 탈황용 촉매 베드(bed)에 관한 것이다. 이러한 촉매 베드는 각각 함황 화합물에 대한 친화성을 보유한 2종 이상의 촉매를 함유하는 것이다. 이와 같이 복합물로 사용되었을 때, 촉매 베드는 원료스트림의 황 농도를 유의적으로 감소시키는 것으로 확인되었다. 또한, 본 발명은 탄화수소 원료스트림의 황 화합물 농도를 약 500ppb 미만 수준으로 감소시키는 방법도 개시한다.The present invention relates to a catalyst bed for desulfurization of a hydrocarbon feed stream. These catalyst beds contain two or more catalysts each having an affinity for sulfur-containing compounds. When used in this composite, the catalyst bed was found to significantly reduce the sulfur concentration in the feed stream. The present invention also discloses a method for reducing the sulfur compound concentration in a hydrocarbon feed stream to levels below about 500 ppb.
천연 가스(NG), 액화석유가스(LPG) 및 가솔린과 같은 탄화수소 원료스트림은, 대부분 1 이상의 반응 단계에서 촉매를 이용하고 있는 여러 화학 공정의 출발 물질로서 사용된다. 하지만, 이와 같은 탄화수소 원료스트림이 황화합물도 함유한다면 화학 공정 중에 종종 문제를 일으키곤 한다. 이러한 황화합물은 반응 촉매를 피독시켜 촉매 베드를 실활시킨다. 일반적으로 수소화 반응에 유용한 니켈 촉매는 특히 이의 활성 표면에 피독된 황에 민감하다. 이와 마찬가지로, 다양한 촉매에 사용되는 많은 귀금속은 황에 민감하고 황 화합물이나 함황 화합물의 존재로 인해 쉽게 피독될 수 있다. 촉매의 피독(poisoning)은 바람직한 반응 시간 보다 오랜 반응시간, 불필요한 부반응 산물의 형성, 니켈 촉매의 유효수명 감소, 및 몇몇 경우에는 최종 산물의 품질 불량을 초래한다. 따라서, 화학 공정의 촉매 베드에 도달하기에 앞서서 탄화수소 원료스트림 중의 황 함량은 감소시키는 것이 유리하다.Hydrocarbon feed streams, such as natural gas (NG), liquefied petroleum gas (LPG) and gasoline, are mostly used as starting materials for many chemical processes that utilize catalysts in one or more reaction stages. However, if such hydrocarbon feed streams also contain sulfur compounds, they are often problematic during chemical processes. These sulfur compounds inactivate the catalyst bed by poisoning the reaction catalyst. Nickel catalysts, which are generally useful for hydrogenation reactions, are particularly sensitive to sulfur poisoning on their active surface. Likewise, many precious metals used in various catalysts are susceptible to sulfur and can be easily poisoned due to the presence of sulfur compounds or sulfur compounds. Poisoning of the catalyst leads to longer reaction times than the desired reaction time, formation of unnecessary side reaction products, reduction in the useful life of the nickel catalyst, and in some cases poor quality of the final product. Therefore, it is advantageous to reduce the sulfur content in the hydrocarbon feedstream prior to reaching the catalyst bed of the chemical process.
그러나, 탄화수소 원료스트림은 공급원의 근원지가 다양하다. 이는 각 원료스트림마다 독특한 황화합물 오염물질과 다른 농도의 오염물질을 함유한다는 것을 의미한다. 예를 들어, 표 1은 천연 가스, LPG 및 가솔린 스트림에서 흔히 발견되는 일부 황 화합물 종을 정리한 것이다. 더욱이, 황 화합물 종은 원료스트림의 종류 뿐만 아니라 공급원의 근원지에 따라 달라지기도 한다. 즉, 알라스카에서 생산된 천연 가스 원료스트림 조성물은 북러시아에서 생산된 천연 가스 원료 스트림 조성물과 크게 다를 수 있다.However, hydrocarbon feedstreams vary in source of origin. This means that each feed stream contains unique sulfur compounds and different concentrations of pollutants. For example, Table 1 lists some of the sulfur compound species commonly found in natural gas, LPG and gasoline streams. Moreover, the sulfur compound species may depend on the type of source stream as well as the source of the source. In other words, the natural gas feedstream composition produced in Alaska may differ significantly from the natural gas feedstream composition produced in North Russia.
황화합물 제거에 효과적인 다수의 다른 촉매는 당해기술분야에 공지되어 있다. 예를 들어, 활성화된 탄소는 에틸 머캅탄에 대해 높은 활성이 있고, 산화망간은 설폭시화디메틸 제거에 효과적이며, 산화아연은 황화수소 제거에 사용될 수 있다.Many other catalysts effective for the removal of sulfur compounds are known in the art. For example, activated carbon has high activity against ethyl mercaptan, manganese oxide is effective for removing dimethyl sulfoxide, and zinc oxide can be used for hydrogen sulfide removal.
탈황 공정에 효과적인 것으로 알려진 기타 다른 촉매에는 특히 탄소, 구리/산화아연, 니켈계 흡착제, 니켈 산화물, 제올라이트류, 분자체 및 포자사이트(faujasite)류가 포함된다. 또한, 원료스트림 중의 황 농도를 감소시키는 방법에도 여러 가지 방법이 사용되고 있다. 가장 일반적으로 사용되는 절차는 수소 재생 단계를 적용하여 함황 화합물을 H2S로 전환시킨 뒤, 이 황 화합물을 별도의 단계로 제거하는 것을 수반한다. 하지만, 이러한 절차는 힘들고 시간소모적인 절차일 수 있다. 따라서, 함황 화합물을 제거하는 보다 양호한 방법이 필요로 되고 있다. 하지만, 원료 스트림에 존재하는 구체적인 황 화합물 종의 다양성과 황 화합물의 농도 때문에 기체 및 액체 탄화수소 스트림으로부터 거의 모든 황화합물을 제거하는데 보편적으로 효과적인 단일 촉매 조성물을 찾아내기는 어려울 것이다.Other catalysts known to be effective in the desulfurization process include carbon, copper / zinc oxide, nickel-based adsorbents, nickel oxides, zeolites, molecular sieves and faujasites. In addition, various methods are used to reduce the sulfur concentration in the feed stream. The most commonly used procedure involves applying a hydrogen regeneration step to convert the sulfur compound to H 2 S and then removing the sulfur compound in a separate step. However, this can be a difficult and time consuming process. Therefore, there is a need for a better method for removing sulfur-containing compounds. However, it will be difficult to find a single catalyst composition that is universally effective in removing almost all sulfur compounds from gas and liquid hydrocarbon streams due to the diversity of specific sulfur compound species present in the feed stream and the concentration of sulfur compounds.
도 1은 촉매 베드가 본 발명에 따라 제조되고 선택적 흡착제 구역이 유입구 부근에 위치하고 보편적 흡착제 구역이 배출구 부근에 위치한 탄화수소 원료스트림 탈황 시스템의 촉매 베드에 대한 투시도이다;1 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system in which a catalyst bed is prepared in accordance with the present invention and a selective adsorbent zone is near the inlet and a universal adsorbent zone is near the outlet;
도 2는 촉매 베드가 본 발명에 따라 제조되고 보편적 흡착제 구역이 유입구 부근에 위치하고 선택적 흡착제 구역이 배출구 부근에 위치한 탄화수소 원료스트림 탈황 시스템의 촉매 베드에 대한 투시도이다;2 is a perspective view of a catalyst bed of a hydrocarbon feedstream desulfurization system in which a catalyst bed is prepared in accordance with the present invention and a universal adsorbent zone is near the inlet and a selective adsorbent zone is near the outlet;
도 3은 촉매 베드가 본 발명에 따라 제조되고 보편적 흡착제가 선택적 흡착제와 혼합되어 필터 베드를 형성하고 있는 탄화수소 원료스트림 탈황 시스템의 촉매 베드에 대한 투시도이다.3 is a perspective view of a catalyst bed of a hydrocarbon feed stream desulfurization system in which a catalyst bed is prepared according to the present invention and a universal adsorbent is mixed with a selective adsorbent to form a filter bed.
상세한 설명details
본 발명은 기체 또는 액체 탄화수소 원료스트림의 오염물을 제거하는데 사용하기 위한 촉매 베드를 제공한다. 당업계에 공지된 바와 같이, 이러한 원료스트림의 가장 보편적 오염물 중 몇 가지는 황화수소, 황화카르보닐, 황화물류, 머캅탄류, 티오펜류, tert-부틸 머캅탄, 이황화물류, 황화디메틸, 테트라하이드로티오펜, 에틸 머캅탄 및 벤조티오펜(이에 국한되지 않음)과 같은 함황 화합물이다. 이러한 황 오염물은 대부분 강한 악취를 풍겨 원료스트림을 이용하는 공정 주위에서의 작업을 어렵게 하며, 뿐만 아니라 황은 탄화수소 출발 물질을 이용하는 다수의 촉매들에게 유독하다.The present invention provides a catalyst bed for use in removing contaminants in a gas or liquid hydrocarbon feedstream. As is known in the art, some of the most common contaminants of these feed streams are hydrogen sulfide, carbonyl sulfide, sulfides, mercaptans, thiophenes, tert-butyl mercaptans, disulfides, dimethyl sulfide, tetrahydrothiophene Sulfur compounds such as, but not limited to, ethyl mercaptan and benzothiophene. Most of these sulfur contaminants have a strong odor, making it difficult to work around processes using feed streams, as well as sulfur being toxic to many catalysts using hydrocarbon starting materials.
도 1에 도시한 바와 같이, 탄화수소 원료스트림 탈황 시스템(10)은 유입구(14)와 배출구(16)를 보유한 촉매 베드 반응기(12)를 포함한다. 이러한 촉매 베드 반응기(12)는 촉매 베드(20)를 수용한다. 탄화수소 원료스트림 F는 유입구(14)에서 반응기(12)로 유입된다. 이러한 탄화수소 원료스트림은 베드(20)의 크기와 원료스트림의 유속에 따라 결정되는 소정의 잔류 시간 동안 촉매 베드(20)와 접촉되게 된다.As shown in FIG. 1, the hydrocarbon feedstream desulfurization system 10 includes a catalyst bed reactor 12 having an inlet 14 and an outlet 16. This catalyst bed reactor 12 houses a catalyst bed 20. Hydrocarbon feedstream F enters reactor 12 at inlet 14. This hydrocarbon feed stream is brought into contact with the catalyst bed 20 for a predetermined residence time which is determined by the size of the bed 20 and the flow rate of the feed stream.
당업계에 공지된 바와 같이, 촉매 베드(20)는 제어된 온도와 압력 하에 놓일 수 있다. 원료스트림 F는 그 다음 배출구(16)를 통해 촉매 베드(20)에서 배출되어진다. 원료스트림 F가 베드(20)를 통해 통과할 때, 오염물은 원료스트림으로부터 제거된다.As is known in the art, catalyst bed 20 may be placed under controlled temperature and pressure. Feedstream F is then discharged from catalyst bed 20 through outlet 16. As feedstream F passes through bed 20, contaminants are removed from the feedstream.
탄화수소 원료스트림은 기체 또는 액체로서 공급될 수 있다. 미가공 기체상 탄화수소 원료스트림의 일반적인 황 농도는 최고 약 300ppm 일 수 있고, 액체상 원료스트림의 황 농도는 최고 약 3% 일 수 있다. 본 발명의 방법은 황 농도를 약 500ppb 미만으로 감소시킨다.The hydrocarbon feedstream can be supplied as a gas or a liquid. Typical sulfur concentrations in the crude gaseous hydrocarbon feedstream may be up to about 300 ppm and sulfur concentrations in the liquid feedstream may be up to about 3%. The method of the present invention reduces the sulfur concentration to less than about 500 ppb.
다시 도 1에 대해 설명하면, 본 발명의 촉매 베드(20)는 각각 함황 화합물에 대해 친화성을 보유하는 제1 촉매 또는 보편적 흡착제 촉매(22)와 제2 촉매 또는 선택적 흡착제 촉매(24)를 함유하는 것이다. 제1 촉매(24)는 베드(20)의 유입구(14) 부근에 위치하고 있다. 제2 촉매(22)는 베드(20)의 배출구(16) 부근에 위치하고 있다. Referring again to FIG. 1, the catalyst bed 20 of the present invention contains a first catalyst or universal adsorbent catalyst 22 and a second catalyst or selective adsorbent catalyst 24, each of which has an affinity for sulfur-containing compounds. It is. The first catalyst 24 is located near the inlet 14 of the bed 20. The second catalyst 22 is located near the outlet 16 of the bed 20.
제1 또는 선택적 흡착제 촉매(24)는 소정 클래스의 화학적 화합물에 대한 촉매 물질(24)의 특이성에 근거하여 선택되는 것이 바람직하다. 예를 들어, 일부 선택적 촉매 물질(24)의 비제한적 예에는 구리/아연 촉매, 산화아연 촉매, 구리/아연/몰리브덴 산화물 촉매, 니켈 알루미나, 니켈 실리카 또는 이의 혼합물이 포함될 수 있다. 본 명세서에 사용된 "선택적 흡착제 촉매"는 약 38℃의 온도, 약 15psig의 압력 및 약 3000hr-1 이상의 원료스트림 공간 속도에서 황 화합물, 예컨대 에틸 머캅탄, tert-부틸 머캅탄, 테트라하이드로티오펜 및 디메틸설파이드 중 적어도 1종을 흡착하지 못하는 물질이다. 필요한 경우에는, 반응 온도 증가 및/또는 공간 속도 감소를 통해 일련의 흡착제를 상대적 특이도에 따라 등급별로 분류할 수 있다. 제1 함황 화합물과 제2 함황 화합물의 흡착 사이의 온도 구배가 커지면 커질수록 제1 함황 화합물에 대한 선택적 흡착제의 특이성은 더욱 커진다. 이와 마찬가지로, 제1 함황 화합물과 제2 함황 화합물의 흡착 사이의 공간 속도 구배가 커지면 커질수록 제1 함황 화합물의 선택적 흡착제에 대한 특이성도 더욱 커진다.The first or selective adsorbent catalyst 24 is preferably selected based on the specificity of the catalytic material 24 for certain classes of chemical compounds. For example, non-limiting examples of some optional catalytic materials 24 may include copper / zinc catalysts, zinc oxide catalysts, copper / zinc / molybdenum oxide catalysts, nickel alumina, nickel silica, or mixtures thereof. “Selective adsorbent catalyst” as used herein refers to sulfur compounds such as ethyl mercaptan, tert-butyl mercaptan, tetrahydrothiophene at a temperature of about 38 ° C., a pressure of about 15 psig and a feedstream space velocity of at least about 3000 hr −1. And substances that do not adsorb at least one of dimethyl sulfide. If necessary, a series of adsorbents can be sorted by their relative specificity by increasing the reaction temperature and / or decreasing the space velocity. The greater the temperature gradient between the adsorption of the first sulfur compound and the second sulfur compound, the greater the specificity of the selective adsorbent for the first sulfur compound. Similarly, the larger the space velocity gradient between the adsorption of the first and second sulfur compounds, the greater the specificity of the first sulfur compound for the selective adsorbent.
제2 또는 보편적 흡착제 촉매(22)는 고도의 특이성 없이 황 성분을 흡착할 수 있는 상대적 물질의 그룹 중에서 선택되는 것이 바람직하다. 예를 들어, 몇 가지 보편적 흡착제 촉매의 비제한적 목록에는 활성화된 탄소, 산화마그네슘, 구리/망간, 알루미나 상의 은, 니켈 실리케이트, 니켈 실리카/마그네시아/알루미나, 제올라이트, 분자체, 포자사이트 및 이의 혼합물이 포함될 수 있으며, 제시된 바 있다. 본 명세서에 사용된, "보편적 흡착제 촉매"는 약 38℃의 온도, 약 15psig의 압력 및 약 3000hr-1 이상의 원료스트림 공간 속도에서 에틸 머캅탄, tert-부틸 머캅탄, 테트라하이드로티오펜 및 디메틸설파이드를 흡착하는 물질이다.The second or universal adsorbent catalyst 22 is preferably selected from the group of relative materials capable of adsorbing sulfur components without high specificity. For example, a non-limiting list of some universal adsorbent catalysts includes activated carbon, magnesium oxide, copper / manganese, silver on alumina, nickel silicate, nickel silica / magnesia / alumina, zeolites, molecular sieves, spores, and mixtures thereof. It may be included and has been suggested. As used herein, “universal adsorbent catalyst” refers to ethyl mercaptan, tert-butyl mercaptan, tetrahydrothiophene and dimethylsulfide at a temperature of about 38 ° C., a pressure of about 15 psig and a feedstream space velocity of at least about 3000 hr −1. It is a substance that adsorbs.
도 1의 구체예에서, 탄화수소 원료스트림이 촉매 베드(20)를 통해 통과할 때, 탄화수소는 먼저 표적의 함황 성분이 선택적 흡착제 물질(24)에 의해 흡착되는 선택적 흡착제(24) 상으로 통과한다. 나머지 탄화수소는 그 다음 기타 다른 함황 성분이 흡착제 물질(22)에 의해 보유될 수 있는 보편적 흡착제(22) 상으로 통과한다. 그 다음, 남은 탄화수소는 촉매 베드(20)에서 배출된다.In the embodiment of FIG. 1, when the hydrocarbon feed stream passes through catalyst bed 20, the hydrocarbon first passes over selective adsorbent 24 where the sulfur-containing component of the target is adsorbed by selective adsorbent material 24. The remaining hydrocarbons then pass onto the universal adsorbent 22 where other sulfur-containing components can be retained by the adsorbent material 22. The remaining hydrocarbon is then discharged from the catalyst bed 20.
도 2의 구체예에 도시된 바와 같이, 촉매 베드(120)은 유입구(114) 부근에 위치한 보편적 흡착제 촉매(122)와 배출구(116) 부근에 위치한 선택적 흡착제 촉매(124)를 함유한다. 이러한 대안적인 보편적 촉매(122)와 선택적 촉매(124)의 상대적 위치에 따라, 탄화수소 원료스트림은 먼저 보편적 촉매(122) 상으로 통과한 뒤, 선택적 촉매(124) 상으로 통과하기도 한다. 선택적 흡착제 촉매(124)가 고도로 선택적이라면, 이 촉매는 다른 함황 화합물의 존재에 의해서는 비교적 영향을 받지 않을 것이다. 하지만, 선택적 흡착제 촉매(124)가 이 촉매(124)의 표적 화합물 외의 다른 함황 화합물에 대하여 친화성이 있다면, 이러한 배열은 선택적 촉매(124)를 몇가지 측면에서 보편적 흡착제로서 작용할 수 있게 할 위험이 있어서, 촉매 베드(120)의 총 효능을 감소시킬 수 있다.As shown in the embodiment of FIG. 2, catalyst bed 120 contains a universal adsorbent catalyst 122 located near inlet 114 and a selective adsorbent catalyst 124 located near outlet 116. Depending on the relative position of this alternative universal catalyst 122 and the selective catalyst 124, the hydrocarbon feedstream may first pass over the universal catalyst 122 and then over the selective catalyst 124. If the selective adsorbent catalyst 124 is highly selective, this catalyst will be relatively unaffected by the presence of other sulfur compounds. However, if the selective adsorbent catalyst 124 is affinity for sulfur-containing compounds other than the target compound of the catalyst 124, this arrangement risks making the selective catalyst 124 act as a universal adsorbent in some respects. As a result, the total efficacy of the catalyst bed 120 may be reduced.
도 3은 촉매 베드(220)의 또 다른 대안적 구체예를 도시한 것이다. 이 베드(220)에서는, 보편적 흡착제 촉매(222)가 촉매 베드(220)의 길이 전체에서 선택적 흡착제 촉매와 혼합되어 존재한다. 이러한 촉매 베드(220) 상으로 탄화수소 원료스트림이 통과하면, 보편적 촉매(222)가 다른 함황 화합물을 흡착할 수 있게 방치한 채, 선택된 함황 화합물이 선택적 촉매(224) 상에 주로 흡착되어진다. 이와 같이 촉매가 혼합되어 있는 베드(220)는 각 촉매(222, 224)가 특정 클래스의 함황 화합물에 대해 친화성이 있는 것인 경우에 가장 효과적이다. 예를 들어, "보편적" 촉매가 주로 티오펜류를 흡착하고, "선택적" 촉매가 주로 머캅탄류를 흡착한다면, 이러한 두 클래스의 황 화합물은 원료스트림이 혼합 베드 상을 통과할 때 제거될 수 있다.3 illustrates another alternative embodiment of catalyst bed 220. In this bed 220, a universal adsorbent catalyst 222 is present in admixture with the selective adsorbent catalyst throughout the length of the catalyst bed 220. As the hydrocarbon feed stream passes over the catalyst bed 220, the selected sulfur-containing compound is mainly adsorbed onto the selective catalyst 224 while the universal catalyst 222 is allowed to adsorb other sulfur-containing compounds. The bed 220 in which the catalysts are mixed is most effective when the catalysts 222 and 224 are affinity for a specific class of sulfur-containing compounds. For example, if the "universal" catalyst mainly adsorbs thiophenes and the "selective" catalyst mainly adsorbs mercaptans, these two classes of sulfur compounds can be removed as the feedstream passes through the mixed bed phase. .
도 1 내지 3의 구체예들은 단지 2종의 촉매 또는 흡착제를 사용하여 예시하고 설명하였다. 하지만, 1종 보다 많은 촉매를 혼합하여 "보편적 흡착제 촉매"를 구성할 수 있고(있거나) 1종 보다 많은 촉매를 혼합하여 "선택적 흡착제 촉매"를 구성할 수도 있다.The embodiments of FIGS. 1-3 are illustrated and described using only two catalysts or adsorbents. However, more than one type of catalyst may be mixed to form a "universal adsorbent catalyst" and / or more than one type of catalyst may be mixed to form a "selective adsorbent catalyst".
또한, 도 1 내지 3의 구체예들은 탄화수소 원료스트림으로부터 함황 화합물을 제거하는 것과 관련하여 예시 및 설명한 것이다. 하지만, 촉매 물질의 선택은 변화될 수 있으며, 이러한 선택은 원료스트림으로부터 제거되어야 하는 특정 오염물에 따라 달라질 수 있다.Also, the embodiments of FIGS. 1-3 are illustrated and described in connection with removing sulfur-containing compounds from hydrocarbon feed streams. However, the choice of catalyst material may vary and this choice may depend on the particular contaminant to be removed from the feedstream.
이상의 설명으로부터 당업자는 본 발명의 특징에 대한 변형을 고안할 수 있을 것이다. 예를 들어, 촉매 베드는 본 명세서에 예시된 것과 다른 디자인 및 장치로 변형될 수 있다. 또한, 보편적 흡착제 촉매와 선택적 흡착제 촉매는 특정 탄화수소 원료스트림 또는 오염 혼합물에 따라 최적화될 수 있다. 이러한 변형 및 기타 다른 변형은 첨부되는 청구 범위의 취지와 영역에 속하는 것으로 간주되어야 한다.From the above description, those skilled in the art will be able to devise variations on the features of the present invention. For example, the catalyst bed can be modified with other designs and devices than those illustrated herein. In addition, universal adsorbent catalysts and selective adsorbent catalysts can be optimized depending on the particular hydrocarbon feedstream or contamination mixture. Such and other variations are to be regarded as belonging to the spirit and scope of the appended claims.
본 발명은 기체 또는 액체 탄화수소 원료스트림의 탈황에 효과적인 신규 탄화수소 원료스트림 촉매 베드에 관한 것이다. 이러한 베드는 상이한 황 화합물 친화성 및/또는 특이성을 보유한 2종 이상의 촉매를 함유하여 황화합물의 총 제거량을 증가시킨다. 일 구체예에서, 본 발명의 촉매 베드는 원료 스트림에 비교적 고농도로 존재하는 황 화합물에 대해 보다 큰 친화성을 갖거나 보다 선택성이 큰 제1 촉매와 1차 접촉되도록 배열된 것이다. 이와 같이 원료스트림이 상기 제1 촉매 상으로 통과하면, 표적의 황 화합물은 제거되어 제2 촉매와 반응되는 보다 깨끗한 스트림이 생성된다. The present invention relates to a novel hydrocarbon feedstream catalyst bed effective for desulfurization of gas or liquid hydrocarbon feedstreams. These beds contain two or more catalysts with different sulfur compound affinity and / or specificity to increase the total removal of sulfur compounds. In one embodiment, the catalyst bed of the present invention is arranged to be in primary contact with a first catalyst having greater affinity or greater selectivity for sulfur compounds present in relatively high concentrations in the feed stream. As this feed stream passes over the first catalyst, the sulfur compound of the target is removed to produce a cleaner stream that is reacted with the second catalyst.
이와 같이 스트림이 제2 촉매에 도달할 때 보다 깨끗해져 있기 때문에 제2 촉매의 효율은 향상된다. 대안적 구체예에서, 촉매들은 촉매 베드 내에 혼합되어 있어도 된다. 이러한 촉매 베드 상으로 원료스트림이 통과하면, 특정 황 화합물에 대해 가장 큰 친화성을 갖는 촉매에 의해 황화합물이 흡착되게 된다.Thus the efficiency of the second catalyst is improved because the stream is cleaner when it reaches the second catalyst. In alternative embodiments, the catalysts may be mixed in the catalyst bed. As the feed stream passes over the catalyst bed, the sulfur compounds are adsorbed by the catalyst having the highest affinity for a particular sulfur compound.
본 발명은 또한 다른 황 화합물 친화성 및/또는 특이성을 보유한 2종 이상의 촉매를 함유하는 촉매 베드 상으로 탄화수소 원료스트림을 통과시켜 황화합물의 총제거량을 증가시키는 방법에 관한 것이다. 이러한 방법은 기체 탄화수소 원료스트림 중의 황 함량을 최고 약 300ppm에서부터 약 500ppb 미만까지 감소시키고, 액체 탄화수소 원료스트림 중의 황 함량은 최고 약 3%에서부터 약 500ppb 미만까지 감소시킨다. The invention also relates to a process for increasing the total removal of sulfur compounds by passing a hydrocarbon feed stream onto a catalyst bed containing two or more catalysts having different sulfur compound affinity and / or specificity. This method reduces the sulfur content in the gaseous hydrocarbon feed stream from up to about 300 ppm to less than about 500 ppb, and reduces the sulfur content in the liquid hydrocarbon feedstream from up to about 3% to less than about 500 ppb.
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US10/328,809 US20040118751A1 (en) | 2002-12-24 | 2002-12-24 | Multicomponent sorption bed for the desulfurization of hydrocarbons |
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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 |
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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 |
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 |
DE202010014363U1 (en) | 2010-04-14 | 2010-12-23 | Süd-Chemie AG | Apparatus for the adsorption treatment of a fluid or fluid stream |
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 |
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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 |
US5458861A (en) * | 1992-04-15 | 1995-10-17 | Mobil Oil Corporation | Desulfurizing a gas stream |
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 |
US6193877B1 (en) * | 1996-08-23 | 2001-02-27 | Exxon Research And Engineering Company | Desulfurization of petroleum streams containing condensed ring heterocyclic organosulfur compounds |
US6267874B1 (en) * | 1997-11-18 | 2001-07-31 | Tonengeneral Sekiyu K.K. | Hydrotreating catalyst and processes for hydrotreating hydrocarbon oil with the same |
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 |
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