KR100798183B1 - 탄화수소의 카복실산 및 탈수소 산물로의 기체상 촉매 산화 방법 - Google Patents
탄화수소의 카복실산 및 탈수소 산물로의 기체상 촉매 산화 방법 Download PDFInfo
- Publication number
- KR100798183B1 KR100798183B1 KR1020027003490A KR20027003490A KR100798183B1 KR 100798183 B1 KR100798183 B1 KR 100798183B1 KR 1020027003490 A KR1020027003490 A KR 1020027003490A KR 20027003490 A KR20027003490 A KR 20027003490A KR 100798183 B1 KR100798183 B1 KR 100798183B1
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- oxygen
- feed mixture
- sulfur
- ethylene
- Prior art date
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title description 7
- 150000001735 carboxylic acids Chemical class 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 40
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 14
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- -1 C 4 alkanes Chemical class 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 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 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 5
- 229910039444 MoC Inorganic materials 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910003465 moissanite Inorganic materials 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
본 발명의 방법은 공급물 중의 수소 설파이드, 황 이산화물 또는 카보닐 설파이드와 같은 황-함유 화합물 소량을 사용하는 저급 탄화수소의 증기상 산화에 의한 산화/옥시탈수소 산물의 저온 촉매 생성방법이다. 본 방법은 복합-성분의 혼합된 금속 산화 환원 반응 촉매의 존재하에 수행된다. 공급물 중의 황 화합물을 사용하는 본 발명은 또한 프로판/프로필렌의 산화/가암모니아산화 및 에탄의 에틸렌으로의 전환에 이은 에틸렌의 아세트산으로의 산화로부터의 비닐 아세테이트 단량체의 직접적인 생성에도 이용될 수 있다.
Claims (17)
- C2, C3 및 C4 알칸 및 알켄 및 이들의 혼합물로 이루어진 그룹 중에서 선택된 탄화수소, 산소, 희석제, 및 황-함유 화합물을 포함하는 공급 혼합물과 혼합된 금속 산화물 촉매를 기체상 산화를 위한 조건하 150℃ 내지 400℃의 온도에서 접촉시키는 단계를 포함하는, 탄화수소의 카복실산 및 탈수소 산물로의 기체상 변환 방법으로서, 상기 혼합된 금속 산화물 촉매가 하기의 (i) 내지 (vi) 그룹 중에서 선택되는 방법:(i) MoaVbNbcXd를 포함하는 소성 조성물(X는 P, B, Hf, Te, As 또는 이들의 혼합물에 해당하고,수치 a, b, c 및 d는 촉매 중 각 원소 Mo, V, Nb 및 X의 상대 그램-원자비를 나타내는 것으로서,a는 1 내지 5이고,b는 >0 내지 0.1이고,c는 0.01 내지 0.5이며,d가 >0 내지 0.1임);(ii) MoaVbNbcPdd를 포함하는 소성 조성물(수치 a, b, c 및 d는 촉매 중 각 원소 Mo, V, Nb 및 Pd의 상대 그램-원자비를 나타내는 것으로서,a는 1 내지 5이고,b는 0 내지 0.5이고,c는 0.01 내지 0.5이며,d는 0 내지 0.045임);(iii) MoaVbLacPddNbeXf의 소성 조성물(X가 Al, Ga, Ge, Si 중 적어도 하나의 원소에 해당하고,수치 a, b, c, d, e 및 f는 촉매 중 각 원소 Mo, V, La, Pd, Nb 및 X의 상대 그램-원자비를 나타내는 것으로서,a는 1이고,b는 0.01 내지 0.9이고,c는 >0 내지 0.2이고,d는 >0 내지 0.2이고,e는 >0 내지 0.2이며,f는 >0 내지 0.3임);(iv) MoaVbPdcLad를 포함하는 소성 조성물(a가 1 내지 5이고,b가 0.01 내지 0.9이며,c가 >0 내지 0.5이며,d가 >0 내지 0.045임);(v) MoaVbGacPddNbeXf를 포함하는 소성 조성물(원소는 산화물 형태로 산소와 배합되어 존재하고,X는 La, Te, Ge, Zn, Si, In, W, Bi, W, Mn, Sb, Sn, Fe, Co, Ni, Re, Rh, Pb, Cu, Au, Ti, Na, K, Rb, Mg, Ca, B 중 적어도 하나에 해당하고,수치 a, b, c, d, e 및 f는 촉매 중 각 원소 Mo, V, Ga, Pd, Nb 및 X의 상대 그램-원자비를 나타내는 것으로서,a는 1이고,b는 0.01 내지 0.9이고,c는 >0 내지 0.2이고,d는 >0 내지 0.2이고,e가 >0 내지 0.2이며,f가 >0 내지 0.5임); 또는(vi) MoaVbLacPddNbeXf를 포함하는 소성 조성물(수치 a, b, c, d, e 및 f는 촉매 중 각 원소 Mo, V, La, Pd, Nb 및 X의 상대 그램-원자비를 나타내고,a는 1이고,b는 0.01 내지 0.9이고,c는 >0 내지 0.2이고,d는 0.0000001 내지 0.2이고,e는 0 내지 0.2이며,f가 0 내지 0.2임).
- 삭제
- 삭제
- 제 1 항에 있어서, 촉매가 분자체, SiC, MoC, 티타니아, 지르코니아, 실리카 또는 알루미나를 포함하는 다공성 물질 상에 지지되는 방법.
- 제 1 항에 있어서, 공급 혼합물이 산소 분자를 공급 혼합물의 0.1 내지 50 부피%의 양으로 포함하는 방법.
- 제 1 항에 있어서, 공급 혼합물의 희석제가 N2, He 또는 Ar을 포함하는 불활성 기체를 5 부피% 내지 90 부피%의 양으로 포함하는 방법.
- 제 1 항에 있어서, 공급 혼합물의 희석제가 증기를 40 부피% 이하의 양으로 포함하는 방법.
- 제 1 항에 있어서, 공급 혼합물이 촉진체로서 황 함유 화합물을 공급 혼합물의 0.05 내지 5 부피%의 양으로 포함하는 방법.
- 제 8 항에 있어서, 황 함유 화합물이 SO2, SO3, H2S, COS, 아황산 및 설폰산으로 이루어진 그룹 중에서 선택되는 방법.
- 제 1 항에 있어서, 공급 혼합물이 에탄, 에틸렌, 프로판, 프로필렌, 부탄, 부틸렌 및 이들의 혼합물로 이루어진 그룹 중에서 선택되는 저급 탄화수소 5 부피% 내지 95 부피%를 포함하는 방법.
- 제 1 항에 있어서, 기체상 산화를 위한 조건이 15 psi 내지 500 psi의 압력과, 0.1초 내지 60초의 공급 혼합물과 촉매 간의 접촉 시간을 포함하는 방법.
- 삭제
- 제 1 항에 있어서, 에탄과 증기, 황-함유 화합물 및 산소 또는 산소-제공 화합물을 제 1 반응 지역에서 혼합된 금속 산화물 촉매의 존재하에 반응시켜 에틸렌, 산소, 증기 및 아세트산을 포함하는 화학량론적 제 1 산물 혼합물을 생성하고, 비닐 아세테이트 단량체 생성 촉매의 존재하에 에틸렌과 아세트산이 반응하여 비닐 아세테이트가 형성되는 제 2 반응 지역에 상기 제 1 산물 혼합물을 공급하는 단계를 포함하는 방법.
- 제 13 항에 있어서, 제 1 산물 혼합물이 부가의 성분의 첨가없이 제 2 반응 지역에 직접 공급되는 방법.
- 제 13 항에 있어서, 제 1 산물 혼합물이 일정량의 에틸렌 또는 아세트산 또는 산소 첨가 또는 조정과 함께 제 2 반응 지역에 공급되는 방법.
- 제 13 항에 있어서, 혼합물이 제 2 반응 지역에 공급되기 전에 온도 및/또는 압력 조정에 가해지는 방법.
- 삭제
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/399,275 | 1999-09-17 | ||
US09/399,275 US6258992B1 (en) | 1999-09-17 | 1999-09-17 | Gas phase catalytic oxidation of hydrocarbons to carboxylic acids and dehydrogenated products |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20020029132A KR20020029132A (ko) | 2002-04-17 |
KR100798183B1 true KR100798183B1 (ko) | 2008-01-24 |
Family
ID=23578911
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020027003490A KR100798183B1 (ko) | 1999-09-17 | 2000-09-11 | 탄화수소의 카복실산 및 탈수소 산물로의 기체상 촉매 산화 방법 |
Country Status (10)
Country | Link |
---|---|
US (1) | US6258992B1 (ko) |
EP (1) | EP1212276B1 (ko) |
JP (1) | JP4711582B2 (ko) |
KR (1) | KR100798183B1 (ko) |
CN (1) | CN1213983C (ko) |
AT (1) | ATE261925T1 (ko) |
DE (1) | DE60009092T2 (ko) |
ES (1) | ES2215724T3 (ko) |
SA (1) | SA00201005B1 (ko) |
WO (1) | WO2001021570A1 (ko) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6841699B2 (en) * | 2001-04-25 | 2005-01-11 | Rohm And Haas Company | Recalcined catalyst |
US6642173B2 (en) * | 2001-04-25 | 2003-11-04 | Rohm And Haas Company | Catalyst |
JP2002322116A (ja) | 2001-04-25 | 2002-11-08 | Nippon Shokubai Co Ltd | (メタ)アクリル酸の製造方法 |
TW574071B (en) * | 2001-06-14 | 2004-02-01 | Rohm & Haas | Mixed metal oxide catalyst |
DE10132526A1 (de) * | 2001-07-09 | 2003-01-30 | Ruhrgas Ag | Verfahren zum Herstellen eines Alkanderivats |
US20040158112A1 (en) * | 2003-02-10 | 2004-08-12 | Conocophillips Company | Silicon carbide-supported catalysts for oxidative dehydrogenation of hydrocarbons |
JP5301110B2 (ja) * | 2007-05-15 | 2013-09-25 | 三菱レイヨン株式会社 | メタクロレインの製造方法 |
JP2009051816A (ja) * | 2007-08-23 | 2009-03-12 | Rohm & Haas Co | 不飽和カルボン酸およびニトリルの製造方法 |
US20100030002A1 (en) * | 2008-07-31 | 2010-02-04 | Johnston Victor J | Ethylene production from acetic acid utilizing dual reaction zone process |
US20100030001A1 (en) * | 2008-07-31 | 2010-02-04 | Laiyuan Chen | Process for catalytically producing ethylene directly from acetic acid in a single reaction zone |
CN103861619A (zh) * | 2012-12-11 | 2014-06-18 | 江苏省海洋石化股份有限公司 | 一种烷烃脱氢硫化物催化剂及烷烃脱氢的方法 |
CN105142780A (zh) * | 2013-04-24 | 2015-12-09 | 沙特基础工业公司 | 用于从烷烃产生不饱和羧酸的负载型催化剂 |
US20200238259A1 (en) * | 2017-08-01 | 2020-07-30 | Purdue Research Foundation | Nickel alloy catalysts for light alkane dehydrogenation |
US11986805B2 (en) | 2019-03-26 | 2024-05-21 | Sabic Global Technologies B.V. | Method of reactivating catalyst |
CN109939688B (zh) * | 2019-04-03 | 2021-12-14 | 华东理工大学 | 铁镓基丙烷脱氢催化剂及其制备方法 |
CN110504108A (zh) * | 2019-08-22 | 2019-11-26 | 杭州求实新材料科技有限公司 | 一种超级电容器用多孔超薄碳膜负载碳化钼量子点的制备方法 |
EP4342873A1 (de) | 2022-09-26 | 2024-03-27 | Linde GmbH | Verfahren und anlage zur herstellung von ethylen und essigsäure, verfahren und anlage zur herstellung einer zielverbindung unter verwendung von ethylen und essigsäure |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4899003A (en) * | 1985-07-11 | 1990-02-06 | Union Carbide Chemicals And Plastics Company Inc. | Process for oxydehydrogenation of ethane to ethylene |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2423418A (en) | 1943-08-14 | 1947-07-01 | Texas Co | Process for producing alkadienes by dehydrogenating alkenes |
US2720550A (en) | 1952-08-09 | 1955-10-11 | Trustees Of Iowa College | Dehydrogenation of naphthenes by means of sulfur dioxide |
US2867677A (en) | 1956-05-15 | 1959-01-06 | Sun Oil Co | Dehydrogenation of hydrocarbons |
US3403192A (en) * | 1965-03-29 | 1968-09-24 | Exxon Research Engineering Co | Sulfur-promoted oxidative dehydrogenation process |
US3456026A (en) * | 1967-11-01 | 1969-07-15 | Exxon Research Engineering Co | Sulfur dehydrogenation of organic compounds |
US3585249A (en) * | 1968-12-02 | 1971-06-15 | Exxon Research Engineering Co | Sulfur promoted oxidative dehydrogenation of organic compounds |
US3585248A (en) * | 1968-12-02 | 1971-06-15 | Exxon Research Engineering Co | Sulfur oxide dehydrogenation of organic compounds |
US3585250A (en) * | 1968-12-02 | 1971-06-15 | Exxon Research Engineering Co | Sulfur promoted dehydrogenation of organic compounds |
BE755817A (fr) * | 1969-09-19 | 1971-03-08 | Petro Tex Chem Corp | Procede de deshydrogenation oxydante favorisee par le soufre |
US3970697A (en) | 1974-07-01 | 1976-07-20 | National Distillers And Chemical Corporation | Oxidation of ethylene to acetic acid |
US4339355A (en) | 1975-10-09 | 1982-07-13 | Union Carbide Corporation | Catalytic oxide of molybdenum, vanadium, niobium and optional 4th metal |
US4188490A (en) | 1977-05-27 | 1980-02-12 | National Distillers And Chemical Corporation | Catalytic oxidation of ethylene to mixtures of acetic acid and vinyl acetate |
US4148757A (en) | 1977-08-10 | 1979-04-10 | The Standard Oil Company | Process for forming multi-component oxide complex catalysts |
DE2811115A1 (de) | 1978-03-15 | 1979-09-27 | Hoechst Ag | Traeger-katalysator fuer die herstellung von vinylacetat aus ethylen, essigsaeure und sauerstoff in der gasphase |
US4250346A (en) | 1980-04-14 | 1981-02-10 | Union Carbide Corporation | Low temperature oxydehydrogenation of ethane to ethylene |
US4568790A (en) | 1984-06-28 | 1986-02-04 | Union Carbide Corporation | Process for oxydehydrogenation of ethane to ethylene |
US4524236A (en) | 1984-06-28 | 1985-06-18 | Union Carbide Corporation | Process for oxydehydrogenation of ethane to ethylene |
US4596787A (en) | 1985-04-11 | 1986-06-24 | Union Carbide Corporation | Process for preparing a supported catalyst for the oxydehydrogenation of ethane to ethylene |
DE3803900A1 (de) | 1988-02-09 | 1989-08-17 | Hoechst Ag | Verfahren zur herstellung von vinylacetat |
US5185308A (en) | 1991-05-06 | 1993-02-09 | Bp Chemicals Limited | Catalysts and processes for the manufacture of vinyl acetate |
TW295579B (ko) * | 1993-04-06 | 1997-01-11 | Showa Denko Kk | |
FR2705668B1 (fr) | 1993-05-28 | 1995-08-25 | Rhone Poulenc Chimie | Procédé de préparation d'acide acétique par oxydation ménagée de l'éthane. |
GB9616573D0 (en) * | 1996-08-07 | 1996-09-25 | Bp Chem Int Ltd | Process |
US6013597A (en) | 1997-09-17 | 2000-01-11 | Saudi Basic Industries Corporation | Catalysts for the oxidation of ethane to acetic acid processes of making same and, processes of using same |
US6028221A (en) * | 1998-06-29 | 2000-02-22 | Saudi Basic Industries Corporation | Catalyst systems for the one step gas phase production of acetic acid from ethylene and methods of making and using the same |
US6087297A (en) * | 1998-06-29 | 2000-07-11 | Saudi Basic Industries Corporation | Catalysts for gas phase production of acetic acid from ethane, processes of making the same and methods of using same |
US6060421A (en) * | 1998-12-23 | 2000-05-09 | Saudi Basic Industries Corporation | Catalysts for the oxidation of ethane to acetic acid, methods of making and using the same |
US6143921A (en) * | 1999-05-14 | 2000-11-07 | Saudi Basic Industries Corporation | Method for producing vinyl acetate monomer from ethane or ethylene oxidation |
-
1999
- 1999-09-17 US US09/399,275 patent/US6258992B1/en not_active Expired - Lifetime
-
2000
- 2000-02-23 SA SA00201005A patent/SA00201005B1/ar unknown
- 2000-09-11 ES ES00962474T patent/ES2215724T3/es not_active Expired - Lifetime
- 2000-09-11 WO PCT/EP2000/008889 patent/WO2001021570A1/en active IP Right Grant
- 2000-09-11 DE DE60009092T patent/DE60009092T2/de not_active Expired - Lifetime
- 2000-09-11 CN CNB008130280A patent/CN1213983C/zh not_active Expired - Fee Related
- 2000-09-11 JP JP2001524951A patent/JP4711582B2/ja not_active Expired - Fee Related
- 2000-09-11 KR KR1020027003490A patent/KR100798183B1/ko not_active IP Right Cessation
- 2000-09-11 EP EP00962474A patent/EP1212276B1/en not_active Expired - Lifetime
- 2000-09-11 AT AT00962474T patent/ATE261925T1/de not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4899003A (en) * | 1985-07-11 | 1990-02-06 | Union Carbide Chemicals And Plastics Company Inc. | Process for oxydehydrogenation of ethane to ethylene |
Non-Patent Citations (1)
Title |
---|
미국특허공보 4,899,003호(1990.2.6 공고 ) |
Also Published As
Publication number | Publication date |
---|---|
DE60009092T2 (de) | 2005-01-20 |
ATE261925T1 (de) | 2004-04-15 |
JP4711582B2 (ja) | 2011-06-29 |
DE60009092D1 (de) | 2004-04-22 |
SA00201005B1 (ar) | 2006-08-01 |
ES2215724T3 (es) | 2004-10-16 |
KR20020029132A (ko) | 2002-04-17 |
CN1374936A (zh) | 2002-10-16 |
EP1212276A1 (en) | 2002-06-12 |
WO2001021570A1 (en) | 2001-03-29 |
EP1212276B1 (en) | 2004-03-17 |
CN1213983C (zh) | 2005-08-10 |
JP2003520202A (ja) | 2003-07-02 |
US6258992B1 (en) | 2001-07-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100798183B1 (ko) | 탄화수소의 카복실산 및 탈수소 산물로의 기체상 촉매 산화 방법 | |
US6143921A (en) | Method for producing vinyl acetate monomer from ethane or ethylene oxidation | |
CA2411000C (en) | Process for the production of vinyl acetate | |
JP2011116789A (ja) | アルケン分離方法 | |
JP2003520202A5 (ko) | ||
EP1089816B1 (en) | Catalyst systems for the one step gas phase production of acetic acid from ethylene | |
CA2465380C (en) | Integrated process for the manufacture of alkenyl carboxylates | |
US7256319B2 (en) | Catalysts for production of olefins by oxidative dehydrogenation, and methods of making and using the same | |
AU2001273924A1 (en) | Catalytic conversion of alkanes to alkenes | |
CA2476181C (en) | Process for the production of an alkenyl carboxylate or an alkyl carboxylate | |
JP2002537220A (ja) | エチレンからの酢酸の一段気相製造用触媒システム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
AMND | Amendment | ||
E902 | Notification of reason for refusal | ||
AMND | Amendment | ||
E601 | Decision to refuse application | ||
AMND | Amendment | ||
J201 | Request for trial against refusal decision | ||
E902 | Notification of reason for refusal | ||
B701 | Decision to grant | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20121226 Year of fee payment: 6 |
|
FPAY | Annual fee payment |
Payment date: 20140103 Year of fee payment: 7 |
|
FPAY | Annual fee payment |
Payment date: 20141230 Year of fee payment: 8 |
|
FPAY | Annual fee payment |
Payment date: 20151217 Year of fee payment: 9 |
|
FPAY | Annual fee payment |
Payment date: 20161220 Year of fee payment: 10 |
|
FPAY | Annual fee payment |
Payment date: 20171219 Year of fee payment: 11 |
|
LAPS | Lapse due to unpaid annual fee |