CN1726082A - 将甲烷直接转化为乙酸的催化剂和方法 - Google Patents
将甲烷直接转化为乙酸的催化剂和方法 Download PDFInfo
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- CN1726082A CN1726082A CN200380106111.0A CN200380106111A CN1726082A CN 1726082 A CN1726082 A CN 1726082A CN 200380106111 A CN200380106111 A CN 200380106111A CN 1726082 A CN1726082 A CN 1726082A
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- methane
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 19
- 230000008569 process Effects 0.000 title claims description 17
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- LIPRKYKMVQPYPG-UHFFFAOYSA-N 3-Hydroxy-2H-pyran-2-one Chemical class OC1=CC=COC1=O LIPRKYKMVQPYPG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005385 peroxodisulfate group Chemical group 0.000 claims abstract description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000005580 one pot reaction Methods 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052500 inorganic mineral Chemical class 0.000 claims description 2
- 239000011707 mineral Chemical class 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 229910002567 K2S2O8 Inorganic materials 0.000 abstract description 7
- GFMLEKMTZRGYMQ-UHFFFAOYSA-N carboxy(hydroxy)carbamic acid Chemical class OC(=O)N(O)C(O)=O GFMLEKMTZRGYMQ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001414 amino alcohols Chemical class 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 235000019394 potassium persulphate Nutrition 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 10
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 9
- 230000006315 carbonylation Effects 0.000 description 8
- 238000005810 carbonylation reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- KJVYZWGBSKNRTK-SYJLBKBESA-J (2S)-2-[[(1S)-1-carboxylatoethyl]-hydroxyamino]propanoate vanadium(4+) Chemical compound [V+4].C[C@H](N(O)[C@@H](C)C([O-])=O)C([O-])=O.C[C@H](N(O)[C@@H](C)C([O-])=O)C([O-])=O KJVYZWGBSKNRTK-SYJLBKBESA-J 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 5
- DJQJFMSHHYAZJD-UHFFFAOYSA-N lidofenin Chemical compound CC1=CC=CC(C)=C1NC(=O)CN(CC(O)=O)CC(O)=O DJQJFMSHHYAZJD-UHFFFAOYSA-N 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- LIRCFGBNQPWVRY-UHFFFAOYSA-K aluminum;2-methyl-4-oxopyran-3-olate Chemical compound [Al+3].CC=1OC=CC(=O)C=1[O-].CC=1OC=CC(=O)C=1[O-].CC=1OC=CC(=O)C=1[O-] LIRCFGBNQPWVRY-UHFFFAOYSA-K 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical class O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 3
- OXXDGKNPRNPMLS-UHFFFAOYSA-N 2-Hydroxy-3-methyl-4H-pyran-4-one Natural products CC1=C(O)OC=CC1=O OXXDGKNPRNPMLS-UHFFFAOYSA-N 0.000 description 2
- DWNWGHRHQSAJBT-UHFFFAOYSA-N 2-[1-carboxyethyl(hydroxy)amino]propanoic acid Chemical compound OC(=O)C(C)N(O)C(C)C(O)=O DWNWGHRHQSAJBT-UHFFFAOYSA-N 0.000 description 2
- JAGQEJXPXPGNJB-UHFFFAOYSA-N 2-[carboxymethyl(hydroxy)amino]acetic acid Chemical compound OC(=O)CN(O)CC(O)=O JAGQEJXPXPGNJB-UHFFFAOYSA-N 0.000 description 2
- -1 2-hydroxyethylyl Chemical group 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229940043353 maltol Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YOIAWAIKYVEKMF-UHFFFAOYSA-N trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F YOIAWAIKYVEKMF-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 125000005287 vanadyl group Chemical group 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000208173 Apiaceae Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- 229910019501 NaVO3 Inorganic materials 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007998 bicine buffer Substances 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- 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
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/46—C-H or C-C activation
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Abstract
本发明包括在温和的条件下，有或者没有一氧化碳存在，根据反应通式(I)，在过氧焦硫酸盐(K2S2O8)存在条件下，在三氟乙酸(CF3COOH)中利用催化剂络合物将甲烷直接一锅法转化为乙酸，所述络合物为钒(处于+4或+5氧化态)和通过氮和氧(N，O)或氧和氧(O，O)原子配位的两个或多个配位基配体络合的，配体来自氨基乙醇、(肟基)二羧酸、羟基吡喃酮、三氟乙酸、三氟甲磺酸或无机酸。
Description
(a)背景技术，发明目的和有益效果
将甲烷转化为有价值官能团化合物一直是现代化工业面临的巨大挑战，特别是近年来，在催化下，将该气体与一氧化碳合成乙酸的操作又引起人们对这方面的关注。针对该操作，最近发现了几个以钒氧化物和杂多酸为基础的催化剂[1]，同时也发现其他催化体系：Pd(OAc)2/Cu(OAc)2[2]，CaCl2[3]，NaVO3[4]，RhCl3[5，6]，(在O2存在下[6]，同时还有蚁酸和甲醇)，镧盐[7]，K2S2O8[8]和超酸[9]的催化能力和选择性是很低的。此外，在不存在有毒的一氧化碳的情况下合成羰基化产品的操作也引起了人们的兴趣，最近以钒杂多酸[10]或Cu(OAc)2[11]为催化剂，成功的将甲烷转化为三氟乙酸甲酯或乙酸甲酯。另外已知的将甲烷转化为乙酸的方法是在100-500℃的温度范围内，在不同种催化剂催化下利用二氧化碳将前者羰基化。催化剂包括Pd[12]，Rh[13]，Ir[13]，Ru[13]或Cu/Co[14，15]。这些操作过程分为两个明显的阶段，以甲醇为中间体[16]。
本发明的目的是选择催化剂并且找到一种在温和或者适中温度和压力下将甲烷一锅法直接转化为乙酸的方法，尤其是不使用一氧化碳作为羰基化剂。
与目前工业上采用的操作方法相比，使用这些催化体系的优点主要是简单和节约能量。目前工业方法包括三个明显的复杂且耗能阶段，也就是(i)甲烷重整(高度吸热过程，由金属催化剂催化)形成“合成气体”，(ii)该气体在高温下催化转化为甲醇，然后(iii)该醇与一氧化碳作用实现羰基化，生成乙酸。该反应通过Monsanto方法完成。此方法需要一种昂贵的催化剂(以铑或铱为基础的BP-Amoco改良方法)本发明使用钒做催化剂，它比上述提到的金属要便宜的多。
(b)创新特征
本发明涉及一种新的催化体系的建立。与上面提到的甲烷羰基化体系相比，这些催化剂在温和或适中的操作条件下即表现出活性，用在一锅法(one-pot conversion)将甲烷转化为乙酸的操作中，收率较高。尤其是该操作不需要使用一氧化碳。
一些催化剂的组成成份在生物学上的应用前景也是具有创新性的。，特别是采用Amavadine模型，这是一种存在于某种伞形毒菌中的天然的钒络合物，其生物功能还不清楚。当涉及到甲烷羰基化时，本发明增大了Amavadine的催化活性范围。已经发现Amavadine在烷烃和芳烃的过氧化物卤化，羟基化或氧化反应中显示出卤化过氧化酶或过氧化酶类的活性[17]，并且可能在硫醇催化氧化中起到电子转移中间体的作用。[18，19]。
(c)技术说明
本发明涉及到利用由钒(+4或+5氧化态)与氮和氧(N，O)原子或氧和氧(O，O)原子配位的二或多配位基的配体形成络合物的催化剂系统，该配体来自氨基乙醇、(肟基)二羧酸、羟基吡喃酮、三氟乙酸、三氟甲磺酸(triflic acid)或无机酸，有或者没有一氧化碳存在，在过氧焦硫酸盐(K2S2O8)和三氟乙酸(CF3COOH)存在的情况下，根据反应通式(I)将甲烷直接一锅法(single-pot conversion)转化为乙酸。
催化剂从下列三种主要类型中选择：(i)[VO(N，O-L)]类型的氧化钒(V)络合物，[N，O-L＝三乙醇胺N(CH2CH2O-)3或N，N-双(2-羟乙烷基)甘氨酸(N-二(羟乙基)甘氨酸)N(CH2CH2O-)2(CH2COO-)的基本形式，(ii)合成的Amavadine和它的模型，即钒(IV)和N，O配体的络合物的Ca2+盐，配体有[V(HIDPA)2]2-、[HIDPA 2，2′-(羟基亚氨基)二丙酸，-ON{CH(CH3)COO-}2的基本形式]和[HIDA＝2，2′-(羟基亚氨基)二乙酸，-ON(CH2COO-)2的基本形式]，以及(iii)钒和钒氧基及O，O-配体的络合物。O，O-配体为[VO(O，O-L)2]，其中，[O，O-L＝(maltolate)麦芽酚(3-羟基-2-甲基-4-吡喃酮的基本形式)；(heida)双-2-羟基乙基亚氨基二乙酸，N(CH2CH2OH)(CH2COO-)2的基本形式；三氟醋酸盐(CF3COO-)；三氟甲磺酸盐(CF3SO2O-))和VOSO4。
表格显示的数值是在典型的试验条件下即：在CF3COOH中，温度为80℃，CH4：钒催化剂和K2S2O8：钒催化剂摩尔比率分别是46∶1(对应于5大气压的CH4)和200∶1，反应的转换数(TON，每摩尔金属催化剂的乙酸摩尔数)和产量(以甲烷为基础)。这些数值通常是在反应20小时后获得的，但是如果反应时间缩短，所得到的产量与反应20小时所得的接近。(例如，第一栏所示的为反应2小时后所得的产量，该产量是反应20小时后所得产量的92％)。
-表格-
活性最好的催化剂(以甲烷为基础，产量超过50％，TONs接近30)如下所示：类型(i)中的三乙醇胺(基本形式))络合物[VO{N(CH2CH2O)3}]，Amavadine模型(类型ii)和类型(iii)中的[VO(O，O-L)2](O，O-L＝maltolate，CF3COO-或CF3SO2O-)。与之相反，[VO(N，O-L)](N，O-L＝N-二(羟乙基)甘氨酸或heida)和更简单的VOSO4盐表现出很低的活性。
虽然一氧化碳气体也可以作为羰基化剂，但甲烷的羰基化不需要该气体(如下所示)。
利用13C浓化(enrich)甲烷，通过13C-{1H}和13C NMR光谱对生成的13CH3COOH进行分析可以知道，生成的乙酸中甲基来源为甲烷。因为没有用CO，生成的乙酸中羰基来源应为溶剂CF3COOH。根据文献[20]，三氟乙酸可以与K2S2O8衍生物产生剧烈反应。该乙酸形成过程不会发生甲烷到游离态甲醇的转化，因为在实验条件下，该醇没有转化为相应的酸。在足够低压下CO可以促进乙酸的形成，这表明它可以用作羰基化剂，但是根据对[VO{N(CH2CH2O)3}]的观察，在该催化剂的作用下，CO显示的催化作用效果变得次要少。如果所用CO压力增大(例如对于该催化剂压力超过ca.8atm同时甲烷的压力5atm)，则会对反应产生抑制。
甲烷压力的变化可以显著地影响TON，例如在使用[VO{N(CH2CH2O)3}]催化剂的情况下，甲烷压力从3个大气压增加到12个大气压，TON从5增加到28。当达到最大值后再增加甲烷的压力时，产量趋向于减少。
可以使用下述方法获得更高的产量(i)在同样的压力下减少甲烷的数量，例如在使用Ca[V(HIDPA)2]的情况下将甲烷数量降低2.8个点，产量则会从从17％增加到54％，或者(ii)增大催化剂用量。例如在CO和CH45个大气压下将[VO{N(CH2CH2O)3}]浓度增加五倍，产量则从24增加到43％。
在研究的任何一个实例中，如果没有钒催化剂存在，反应就不能进行。
实施例
为了便于解释，以下是对一个典型实验的说明。该实验可以较容易进行变化而适应其它反应条件。
将钒催化剂(0.0625mmol)和K2S2O8(3.38g，12.5mmol)加入到39cm3盛有CF3COOH(23cm3)的不锈钢高压灭菌锅中，高压灭菌锅密闭。通过二氮气流和真空将锅中的空气排除，然后在要求的压力下(例如5个大气压，2.86mmol)导入甲烷。搅拌下对该高压锅灭菌锅油浴加热，在要求的时间内加热到要求的温度。冷却高压灭菌锅，排出残气后，打开，过滤最终混合物溶液。向溶液中加入二乙醚使过量的K2S2O8沉淀析出，过滤除去。通过气相色谱(GC)或气相色谱-质谱(GC-MS)对得到的溶液进行分析。
如果有CO存在，则在导入甲烷后再将该气体导入到高压灭菌锅中，根据相似的操作程序进行实验。对于不同的试剂摩尔比、不同溶剂体积或不同高压灭菌锅容积的反应来说，操作都是类似的。
根据文献方法制备下述络合物：[VO{N(CH2CH2O)3}][21]，Ca[V(HIDPA)2][22]，Ca[V(HIDA)2][22]，[VO(maltolate)2][23]和[VO(CF3SO2O)2][24]。新的络合物[VO{N(CH2CH2O)2(CH2COO)}]，[VO{N(CH2CH2OH)(CH2COO)2}(H2O)]和[VO(CF3COO)2]分别根据参考文献[25]中的[VO{N(CH2CH2O)3}]或[VO(CF3SO2O)2]的方法制备，但是要使用相应的的配体。化合物VOSO4、K2S2O8和CF3COOH可以从Merck和Aldrich购买。
参考文献
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表格.由甲烷转化为乙酸(典型例子)a
| 催化剂类型(i)[VO{N(CH2CH2O)3}]e[VO{N(CH2CH2O)2(CH2COO)}]h类型(ii)Ca[V(HIDA)2]Ca[V(HIDA)2]类型(iii)[VO(maltolate)2]j[VO{N(CH2CH2OH)(CH2COO)2}(H2O)]k[VO(CF3COO)2]l[VO(CF3SO2O)2]lVOSO4 m | P(CH4)b(atm)555553812555555585551255555555555 | P(CO)b(atm)--51520151515155---5151515-1515-15--520-520-20 | 时间(h)220202020202020202020220202020202020202020202020202020202020 | TONc910111065252810f4g27131081012i10102878221197101212 | 产量d(％)202124221319342635f43g5152921171654i212125151854231915222925 |
a除非特别指出，在试验部分提到的典型条件下和80℃。
b在25℃时测定的压力。
c转换数：每摩尔金属催化剂的乙酸摩尔数。
d相对于甲烷的摩尔产量(％)，例如每100摩尔甲烷的乙酸摩尔数。
eN，O-配体＝三乙醇胺的基本形态。
f相对于a，使用较大体积的CF3COOH(28cm3)，和较小量的CH4(1.84mmol)。
g相对于a，使用五倍量的金属催化剂(0.312mmol)。
hN，O-配合基＝N，N-双(2-羟基乙烷基)甘氨酸(N-二(羟乙基)甘氨酸)的基本形态。
i相对于a，在较小的反应器(23.5cm3)中使用较少量的甲烷(1.02cm3)：金属催化剂(0.046mmol)，K2S2O8(9.2mmol，如：200∶1催化剂)，CF3COOH(17cm3)。
JMaltolate＝麦芽酚(3-羟基-2-甲基-4-吡喃酮)的基本形态。
KN，O-配合基(heida)＝双(2-羟基乙基亚氨基二乙酸)的基本形式(络合物分子带有1个结晶H2O)。
L每个络合物分子带有2个结晶H2O。
m每个络合物分子带有5个H2O。
权利要求书
(按照条约第19条的修改)
本申请引述了Taniguchi Y.等人出版的Org.Lett.，1999，1，No.4557-559并且将其作为X类文件，为了明确的显示与其结果没有重叠对权利要求进行了修改。实际上我们的工艺不需要使用一氧化碳(CO)，而公开的工艺必须使用CO。因此，通过增加“不需要使用一氧化碳”对权利要求1进行了修改。
而且，通过将权利要求2和3合并为一个权利要求(修改后的权利要求2)并且限定催化剂的成分，我们保证我们所有的催化剂都和上述X类出版物不同，它们使用的催化剂是钒氧化物V2O3和V2O5，钒酸盐NaV2O3，2，4-戊二酮盐(acac)化合物[VO(acac)2]和各种杂多酸，例如H5PV2Mo10O40，H7PV4Mo8O40和H5SiVW11O40。本系统使用如下种类的络合物作为催化剂：(i)[VO(N，O-L)]类型的氧化钒(V)络合物，[N，O-L＝三乙醇胺N(CH2CH2O-)3或N，N-双(2-羟基乙烷基)甘氨酸(N-二(羟乙基)甘氨酸)N(CH2CH2O-)2(CH2COO-的基本形式)，(ii)合成的Amavadine和它的模型，即带有N，O配合基[V(HIDPA)2]2-和[V(HIDA)2]2-的钒(IV)络合物Ca2+盐，[HIDPA＝2，2′-(羟基亚氨基)二丙酸，-ON{CH(CH3)COO-}2的基本形式]，[HIDA＝2，2′-(羟基亚氨基)二乙酸，-ON(CH2COO-)2的基本形式]，以及(iii)[VO(O，O-L)2]类型的钒氧基络合物[O，O-L＝麦芽酚(3-羟基-2-甲基-4-吡喃酮的基本形式(maltolate)；双-2-羟基乙基亚氨基二乙酸，N(CH2CH2OH)(CH2COO-)2的基本形式(heida)；三氟醋酸盐(CF3COO-)；三氟甲磺酸盐(CF3SO2O-))。
因此相应的修改了原权利要求4(修改后的权利要求3)。虽然它提到了使用一氧化碳，但是如前段中涉及修改后的权利要求2所指出的，它关注的使用的催化剂(根据修改后的权利要求2)和上述X类出版物中的那些不同。
1.用于在相对温和的条件下将甲烷直接一锅法转化为乙酸的催化剂系统和方法，其特征在于含有钒络合物，过氧焦硫酸盐和三氟乙酸，但不需要使用一氧化碳。
2.根据权利要求1所述的催化剂系统和方法，其特征在于使用处于金属+4或+5氧化态的钒与通过氮和/或氧原子配位的二或多配位基的配体的络合物，该配体来自氨基乙醇、(肟基)二羧酸、羟基吡喃酮、三氟乙酸或三氟甲磺酸。
3.根据权利要求2所述的催化剂系统和方法，其特征在于使用一氧化碳。
Claims (4)
1.用于在相对温和的条件下将甲烷直接一锅法转化为乙酸的催化剂系统和方法，其特征在于含有钒络合物，过氧焦硫酸盐和三氟乙酸。
2.根据权利要求1所述的催化剂系统和方法，其特征在于使用的络合物是由钒与通过氮和氧(N，O)原子或氧和氧和氧(O，O)原子配位的二或多配位基配体络合的。
3.根据权利要求1或2所述的催化剂系统和方法，其特征在于使用处于+4或+5氧化态的钒与配体的络合物，该配体来自氨基乙醇、(肟基)二羧酸、羟基吡喃酮、三氟乙酸、三氟甲磺酸或无机酸。
4.根据权利要求1，2或3所述的催化剂系统和方法，其特征在于使用一氧化碳。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008006244A1 (en) * | 2006-07-04 | 2008-01-17 | Dalian Institute Of Chemical Physics Chinese Academy Of Sciences | Oxidation catalyst |
| CN101875604A (zh) * | 2009-04-30 | 2010-11-03 | 北京化工大学 | 一种液相部分氧化甲烷的方法 |
| CN101875604B (zh) * | 2009-04-30 | 2013-04-24 | 北京化工大学 | 一种液相部分氧化甲烷的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003267887A1 (en) | 2004-05-13 |
| US7238838B2 (en) | 2007-07-03 |
| WO2004037416A2 (en) | 2004-05-06 |
| CN100357026C (zh) | 2007-12-26 |
| WO2004037416B1 (en) | 2004-10-07 |
| PT102859B (pt) | 2004-10-29 |
| JP2006503693A (ja) | 2006-02-02 |
| EP1558383A2 (en) | 2005-08-03 |
| US20060155145A1 (en) | 2006-07-13 |
| AU2003267887A8 (en) | 2004-05-13 |
| PT102859A (pt) | 2004-04-30 |
| WO2004037416A3 (en) | 2004-08-12 |
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