CN101600678B - Process for carbonylation of aliphatic alcohols and/or reactive derivatives thereof - Google Patents
Process for carbonylation of aliphatic alcohols and/or reactive derivatives thereof Download PDFInfo
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- CN101600678B CN101600678B CN2006800566291A CN200680056629A CN101600678B CN 101600678 B CN101600678 B CN 101600678B CN 2006800566291 A CN2006800566291 A CN 2006800566291A CN 200680056629 A CN200680056629 A CN 200680056629A CN 101600678 B CN101600678 B CN 101600678B
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- zeolite
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- 238000000034 method Methods 0.000 title claims abstract description 82
- 238000005810 carbonylation reaction Methods 0.000 title claims description 41
- 230000006315 carbonylation Effects 0.000 title claims description 35
- -1 aliphatic alcohols Chemical class 0.000 title description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 99
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 94
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 94
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000002148 esters Chemical class 0.000 claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000203 mixture Chemical group 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004411 aluminium Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 10
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001657 ferrierite group Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 70
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 63
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 claims description 24
- 229940099204 ritalin Drugs 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 16
- 229960001866 silicon dioxide Drugs 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 241001597008 Nomeidae Species 0.000 claims description 8
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 238000010931 ester hydrolysis Methods 0.000 claims description 2
- 229960005363 aluminium oxide Drugs 0.000 claims 1
- 238000010923 batch production Methods 0.000 claims 1
- 229910001723 mesolite Inorganic materials 0.000 claims 1
- 238000012797 qualification Methods 0.000 claims 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract 1
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052676 chabazite Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KMNWCNNLFBCDJR-UHFFFAOYSA-N [Si].[K] Chemical compound [Si].[K] KMNWCNNLFBCDJR-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A product comprising a C1-C3 aliphatic carbbxylic acid or corresponding ester is produced by a process comprising reacting a C1-C3 aliphatic alcohol or a reactive derivative thereof with carbon monoxide in the presence of a zeolite catalyst having an 8-member ring channel which is interconnected with a channel defined by a ring with greater than or equal to 8 members, the 8-member ring having a window size of at least 2.5 Angstroms x at least 3.6 Angstroms and at least one Br nsted acid site and the zeolite having a silica : X2O3 ratio of at least 5, wherein X is selected from aluminium, boron, iron, gallium and mixtures thereof with the proviso that the zeolite is not mordenite or ferrierite.
Description
Background of invention
The present invention relates to a kind of through carbonylation by corresponding lower aliphatic alcohols and/or its ester or ether derivant; Selectivity prepares the method for lower alphatic carboxylic acid and/or its corresponding esters, is especially prepared the method for acetic acid and/or ritalin by methyl alcohol and/or its ester or ether derivant carbonylation selectivity.The invention still further relates to and a kind ofly more generally relate to carbonylation from the improving one's methods of dimethyl ether production ritalin, the alkyl ester of preparation aliphatic carboxylic acid by alkyl oxide.In another aspect of this invention, relate to through at first preparing alkyl ester by lower alkyl ether, then this ester is hydrolyzed into acid, thus the preparation lower alphatic carboxylic acid.A preparation that embodiment is an acetic acid like this, it forms ritalin through the dme carbonylation, and then the ester hydrolysis prepares acetic acid.
Preparation acetic acid the most widely used commercial run is carbonylation of methanol, and it for example is generally described in, English Patent 1,185,453,1,277,242 with US patent 3,689,533 in.In the method for the sort of type, methyl alcohol and carbon monoxide or contain the gas of carbon monoxide, in the presence of the catalyzer of rhodium-containing or iridium, reaction under the promotor that also has halogen-containing (normally iodine).Though be widely used, because the existence of iodide, these methods need be used expensive CRA, and cause producing be difficult on a small quantity to utilize that conventional distillation removes contains the iodine by product from acetic acid.After deliberation some be used for the catalystsystem based on non-halogen thing of this reaction, but it is not by commercialization, mainly is because its catalytic life and selective problems.
In the method that a large amount of patents are described, the mixture of methyl alcohol or methyl alcohol and dme carries out carbonylation in the presence of catalyzer.Usually this product is the mixture of acetic acid and ritalin, also comprises acetic anhydride sometimes.In these patents, disclose a reaction that can take place, promptly the dme carbonylation forms ritalin.
EP-A-0596632 disclose through in load copper, nickel, iridium, rhodium or cobalt mordenite catalyst in the presence of, Fatty Alcohol(C12-C14 and C12-C18) or its reactive derivatives contacted under high temperature and high pressure with carbon monoxide, thereby prepare the method for aliphatic carboxylic acid.
WO2005/105720 disclose through in load copper, nickel, iridium, rhodium or cobalt with silicon, aluminium and one or more gallium, boron and iron as in the presence of the mordenite catalyst of backbone element; Fatty Alcohol(C12-C14 and C12-C18) and/or its reactive derivatives are contacted with carbon monoxide, thereby prepare the method for aliphatic carboxylic acid, its ester or acid anhydrides.
US6; 387; 842 disclose through in the presence of the catalyzer that contains solid superacid, clay, zeolite or molecular sieve, the charging and the carbon monoxide of alcohol, ether and/or ether alcohol reacted under certain temperature and pressure, thereby convert the method and the catalyzer of OXO products into.
Cheung etc. (Angew.Chem.Int.Ed 2006,45, (10), 1617) carry out carbonylation at dme with mordenite, ferrierite and ZSM-5, BEA with under the USY zeolite contacts.The three kinds of zeolites in back do not contain 8 membered ring channels.
Summary of the invention
The present invention includes selectivity and prepare C
1-C
3Aliphatic carboxylic acid, for example acetic acid and/or corresponding C
1-C
3Ester, like the method for ritalin, it is through making corresponding C
1-C
3Fatty Alcohol(C12-C14 and C12-C18); Methyl alcohol for example, and/or its ester or ether derivant, for example dme; Containing carbonylation in the presence of the catalyzer of zeolite with carbon monoxide; This zeolite has at least one 8 membered ring channel, said 8 membered ring channels with interconnect having the duct that limits more than or equal to 8 yuan ring, said 8 yuan of rings have at least 2.5
* at least 3.6
Window size and at least one Bronsted acidity position, and wherein this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
The present invention also comprises and contains C
1-C
3The C of aliphatic carboxylic acid
1-C
3The product of alkyl ester, ritalin for example, the preparation method, it comprises makes C
1-C
3Alkyl oxide; For example dme and carbon monoxide are under anhydrous basically environment; In the presence of the catalyzer that contains zeolite, carry out carbonylation with at least one 8 membered ring channel; Said 8 membered ring channels with interconnect having the duct that limits more than or equal to 8 yuan ring, said 8 yuan of rings have at least 2.5
* at least 3.6
Window size and at least one Bronsted acidity position, and wherein this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
Detailed Description Of The Invention
The present invention includes selectivity and prepare C
1-C
3Aliphatic carboxylic acid, for example acetic acid and/or ester accordingly, like the method for ritalin, it is through making corresponding C
1-C
3Fatty Alcohol(C12-C14 and C12-C18); For example methyl alcohol and/or its ester or ether derivant; Dme for example; With carbon monoxide carbonylation in the presence of the catalyzer that contains zeolite with at least one 8 membered ring channel, said 8 membered ring channels with interconnect having the duct that limits more than or equal to 8 yuan ring, said 8 yuan of rings have at least 2.5
* at least 3.6
Window size and at least one Bronsted acidity position, and wherein this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
The present invention also comprises and contains C
1-C
3The C of aliphatic carboxylic acid
1-C
3The product of alkyl ester such as the preparation method of ritalin, it comprises makes C
1-C
3Alkyl oxide; Dme and carbon monoxide carbonylation in the presence of the catalyzer that is containing zeolite under the anhydrous basically environment for example with at least one 8 membered ring channel; Said 8 membered ring channels with interconnect having the duct that limits more than or equal to 8 yuan ring, said 8 yuan of rings have at least 2.5
* at least 3.6
Window size and at least one Bronsted acidity position, and wherein this zeolite has silicon-dioxide: X
2O
3Ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
In a mode of the present invention, a component in this method charging can be C
1-C
3Fatty Alcohol(C12-C14 and C12-C18).This method is particularly useful for alcohol, for example methyl alcohol, ethanol and n-propyl alcohol.Preferred alcohol is methyl alcohol.Can or be additional to pure pure reactive derivatives as pure surrogate and comprise ester and the C that this is pure
1-C
3The ether derivant of alcohol.Suitable reactive derivatives of methanol comprises ritalin and dme.Can also use the mixture of pure and mild its reactive derivatives, for example the mixture of methyl alcohol and ritalin.
When using alcohol as the charging of this method, product depends on the transformation efficiency that this is pure.If transformation efficiency is 100%, product is exactly a corresponding carboxylic acid.Therefore, when methyl alcohol was pure charging, this product comprised acetic acid.If transformation efficiency is less than 100%, then alcohol is converted into the mixture of corresponding carboxylic acid and carboxylicesters.If as the ester of charging is symmetrical ester, ritalin for example, then the primary product of this carbonylation method is corresponding carboxylic acid (in this example, being acetic acid).If this ester is asymmetric, then product comprises the mixture of carboxylic acids from each alkyl formation of this ester.
In the other mode of the present invention, a component in this method charging comprises C
1-C
3Alkyl oxide, promptly have the compound of following formula:
R
1-O-R
2
Wherein, R
1And R
2Be C independently
1-C
3Alkyl.At R
1And R
2If the sum of carbon atom in the group is R
1And R
2Being alkyl, is 2-6.Preferred R
1And R
2Be straight chained alkyl, most preferably have the straight chained alkyl of 1-3 carbon atom respectively, for example methyl, ethyl and n-propyl.
If this ether is symmetrical ether, dme for example, then primary product is the corresponding alkyl ester of aliphatic carboxylic acid (in this example, being ritalin).If ether is asymmetric, then product comprises these two kinds of possible carboxylicesterss one or both of, and this depends on that in reaction which is ruptured in two C-O keys.For example, if charging is methyl ethyl ether (R
1=methyl, R
2=ethyl), then product comprises vinyl acetic monomer and/methyl propionate.
Second component of this method is the charging that comprises carbon monoxide.This charging can comprise pure basically carbon monoxide (CO); For example; Carbon monoxide is normally provided by the supplier of industrial gas, or this charging can comprise and can not hinder alkyl oxide to be converted into the impurity of required ester, for example hydrogen, nitrogen, helium, argon, methane and/or carbonic acid gas.For example, charging can comprise common utilization from synthetic gas via low temperature separation process and/or use film to remove method and the carbon monoxide of commercialization preparation of hydrogen.
The carbon monoxide charging can comprise a large amount of hydrogen.For example, this charging can be known synthetic gas, promptly is used for any of a large amount of gaseous mixture of synthetic various organic or inorganic compound, especially ammonia synthesiss.Synthetic gas obtains by the carbonaceous material of richness and steam (in being called as the method for steam reformation) or with the reaction (method of partially oxidation) of steam and oxygen usually.These gases mainly comprise and contain carbon monoxide and hydrogen, can also comprise more a spot of carbonic acid gas and nitrogen.Carbon monoxide: the suitable molar ratio of hydrogen can be 1: 3-15: 1, for example 1: 1-10: 1.Use the ability of synthetic gas another advantage to be provided, promptly select to utilize not have so expensive carbon monoxide charging than the method for preparing acetic acid from methyl alcohol.In the method for methyl alcohol-acetic acid, comprise hydrogen in the charging and possibly cause producing unwanted hydrogenation.
The catalyzer that uses in the inventive method is a zeolite, mordenite and ferrierite.Zeolite is natural or synthetic all is to have the microporosity crystal type alumino-silicate materials of being measured by X-ray diffraction that definite crystalline structure is arranged.The compound composition of zeolite can alter a great deal, but they are usually by SiO
2Form, wherein the part Siliciumatom can be by quadrivalent atom, like Ti or Ge, and triad, like Al, B, Ga, Fe, or bivalent atom, replace like Be or its combination.Zeolite by can with other channel system or for example the system in the interconnected duct, hole of side pocket or cage form.This channel system has uniform-dimension in specific zeolite inside, and can be three-dimensional, but not necessarily, also can be two dimension or one dimension.The channel system of zeolite arrives via 12 yuan of rings, 10 yuan of rings or 8 yuan of rings usually.The zeolite that uses among the present invention comprises the duct that at least one 8 yuan rings limit.Preferred zeolite is those zeolites that do not have side pocket or cage in zeolite structured inside.Atlas of Zeolite Framework Types (C.Baerlocher, W.M.Meier, D.H.Olson, the 5th edition, Elsevier, Amsterdam, 2001) together with based on the version of webpage (
Http:// www.iza-structure.org/ databases/) be about the topology of zeolite framework and the summary of CONSTRUCTED SPECIFICATION, comprise type that is present in ring structure in the zeolite and the duct size that is limited by each annular.For the purposes of the present invention, term " zeolite " also comprises the material with zeolite type structure, and for example layered porous crystal type oxide material and column layering oxide material are like ITQ-36.
The zeolite that uses in the inventive method has at least one 8 yuan of duct that ring limits in tetrahedral coordination atom (tetrahedron); And the minimum size that has of window size of ring be 2.5
* 3.6
duct of these 8 yuan of rings and at least one be equal to or greater than 8 yuan by having, interconnect like the duct that ring limited of 10 yuan and/or 12 yuan.8,10 and 12 membered ring channels of interconnection provide the inlet that leads to the Bronsted acidity position that is contained in 8 membered ring channels, make C
1-C
3Pure or derivatives thereof for example methyl alcohol and dme can carry out carbonylation under acceptable ratio.
The zeolite that uses among the present invention can be by interconnection, and the ducts that only limited by 8 yuan of rings are formed, and the zeolite of CHA type skeleton for example is like the zeolite of chabazite and ITE type skeleton, like ITQ-3.Yet preferably this zeolite has at least one by 8 yuan of ducts of forming of ring and at least one interconnection, by having greater than 8 yuan, and 10 and/or 12 yuan the duct that ring limited for example.Not restrictive example with zeolite of 8 membered ring channels and interconnective bigger annular distance road system comprises the zeolite of OFF type skeleton, offretite for example, GME type, for example sarcolite; The MFS type, ZSM-57 for example, EON type; Like ECR-1 and ETR type, like ECR-34.The zeolite that uses in preferred the inventive method has at least one and at least one interconnective 8 membered ring channels of 12 membered ring channels, and the zeolite of those OFF and GME type skeleton for example is like offretite and sarcolite.
Yet in order to develop a kind of effective carbonylation method, it is not enough in zeolite, only having 8 membered ring channels of interconnection.The window size of this channel system also must be controlled, and makes reactant molecule can freely spread and leave this zeolite framework.If find now the minimum size of hole (hole width) of 8 membered ring channels of zeolite be 2.5 * 3.6
time, can realize effective carbonylation.The duct size of zeolite framework type can for example found among the Atlas of Zeolite Framework Types.In addition; M.D.Foster; I.Rivin; M.M.J.Treacy and O.Delgado Friedrichs are in " A geometric solution to thelargest-free-sphere problem in zeolite frameworks " Microporous and MesoporousMaterials 90 (2006) 32-38; Used the Delaunay trigonometry to be applied on the known zeolite framework, and-spherical diameter free along the maximum of three that are used for 165 zeolite framework that are listed in the Atlas of Zeolite Framework Types at present main crystallization directions diffusions processed form.The window size of ring can be changed by the atomic substitutions that is fit to, and it changes the bond distance and the bond angle of tetrahedral coordination atom and bridge joint oxygen.
Select from The Atlas of Zeolite Framework Types have at least one minimum size be 2.5 * 3.6
the part form of zeolite framework type of interconnection 8 membered ring channels list following:
Zeolite can obtain from commercial source.They can also use known technology synthetic.Usually, synthetic zeolite is from comprising the aqueous reaction mixture preparation in suitable oxidizing thing source.In order to influence prepare zeolite, in reaction mixture, can also comprise organic directed agents with desired structure.After the component of reaction mixture suitably is mixed with each other, reaction mixture is placed suitable crystallization condition.After the complete crystallization of reaction mixture, can from remaining reaction mixture, reclaim crystallized product.This recovery can comprise filters this crystallization, calcination processing at high temperature after the washing.The synthetic of zeolite is described in a large amount of reference.For example, Y zeolite and the synthetic US 3,130 that is described in thereof, in 007, the ZSM-23 zeolite is described in US 4,076, and 842 and J.Phys.Chem.B, 109,652-661 (2005), Zones, S.I.Darton, R.J., Morris, R and Hwany are among the S-J; ECR-18 is described in Microporous Mesoporous Mat., and 28,233-239 (1999), Vaughan D.E.W.&Strohmaier is among the K.G.; θ-1 zeolite is described in Nature, and 312,533-534 (1984) .Barri, S.A.I., Smith W.G., White, D and Young is among the D.; Mazzite is described in Microporous MesoporousMat., and 63,33-42 (2003), Martucci, A, Alberti, A, Guzmar-Castillo, M.D., Di Renzo, F and Fajula are among the F.; The L zeolite is described in Microporous Mesoporous Mat., and 76,81-99 (2004), Bhat, S.D., Niphadkair; P.S., Gaydharker, TR., Awate, S.V., Belhekar; A.A.and Joshi among the P.N, also is described in J.Ind.Eng.Chem.Vol.10, No.4 (2004), 636-644; Ko YS, among the Ahn W.S, silicon potassium aluminium zeolite is described in Zeolites 255-264, and Vol.7 is among the 1987 Howden M.G..
The zeolite catalyst that uses in the inventive method uses with the acid form, is commonly referred to ' H ' type zeolite, for example, the H-offretite.The zeolite of other form, for example NH
4The type zeolite can be converted into the H type, for example, and through at high temperature calcining NH
4Type.The acid zeolite has Br (H
+) position, it is distributed in the various channel system of zeolite.For example, the H of H-offretite
+The position is arranged in 12 membered ring channels and 8 membered ring channels.Be arranged in the H of any special channel system
+The quantity of material or concentration can confirm through prior art, and is for example infrared, NMR spectrum is technological.Come quantitative Bronsted acidity through FTIR and NMR spectrum, for example, be described in Makarova; M.A., Wilson, A.E., van Liemt, BJ., Mesters, C.de Winter, A.W., Williams, C.Journal of Catalysis 1997,172, (1) is in 170.This duct of two types in the H-offretite (being limited with 8 yuan of rings on 12 yuan of rings) can produce at least two keys that link to each other with the hydroxyl zone of H-offretite; One corresponding to the vibration in the bigger hole, another with lower frequency vibration in less hole.The inventor's work shows the H that is arranged in 8 membered ring channels
+Have dependency between the quantity at position and the carbonylation speed, and do not observe this dependency for 12 membered ring channels.Have been found that the increase of carbonylation speed and H in 8 membered ring channels
+The quantity at position parallels.Comparatively speaking, there are not evidence demonstration and the H in 12 membered ring channels
+The dependency of the quantity at position.H in 8 membered ring channels
+The quantity at position can be passed through for example Na of metallic cation
+Or Co
2+Use known ion exchange technique to substitute H
+Control.
The chemical constitution of zeolite can be expressed as and relate to following molar relationship:
SiO
2∶X
2O
3
Wherein X is a trivalent element, for example aluminium, boron, iron and/or gallium, preferably aluminium.The SiO of given zeolite
2: X
2O
3Ratio is normally variable.For example, can synthesize as everyone knows and have SiO
2: Al
2O
3Than for 6-90 or bigger offretite, Y zeolite, it is about 6 to have about 1-, the about 2-2000 of chabazite, and can synthesize and have SiO
2: Al
2O
3Sarcolite greater than 4.Common SiO
2: X
2O
3The upper limit of ratio is unconfined, for example the ZSM-5 zeolite.The SiO of the zeolite that the present invention uses
2: X
2O
3Mol ratio is at least 5, preferred 7-40, for example 10-30.Preferred SiO
2: X
2O
3Mol ratio is less than or equal to 100.For many zeolites, special SiO
2: X
2O
3Than obtaining (wherein X is Al), through utilizing the standard technique of high-temperature steam processing or pickling through dealuminzation.
Depend on feed properties, water can produce on the spot.For example, when alcohol is used as charging, utilize pure dimerization reaction to ether to generate water, the esterification that water also can pass through alcohol and carboxylic acid product produces.Water can be introduced separately or introduce with alcohol or ester feed component or its mixture.Water can exist with liquid state or gasiform form.Method of the present invention is carried out under aqueous conditions, and charging is when being Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ester, and the product of carbonylation reaction is corresponding carboxylic acid and/or ester.For example, when charging was methyl alcohol or ritalin, reaction product was an acetic acid and/ritalin.In charging is C
1-C
3During alkyl oxide, dme for example, carbonylation reaction preferably carries out under anhydrous condition.Under anhydrous basically condition, the carbonylation selectivity of dme generates the ritalin product.
This is reflected at when implementing under the anhydrous basically condition, and catalyzer should carry out drying with preferred feed component before beginning operation, for example, and through being preheating to 400-500 ℃.
Usually, be ether in charging, for example during dme, this method is equal to or less than under about 250 ℃ in temperature carries out, that is and, temperature is about 250 ℃ of about 100-, about 180 ℃ of preferably about 150-.When charging is alcohol or ester, for example methyl alcohol or ritalin, this method is carried out under greater than 250 ℃ temperature, and promptly temperature is about 400 ℃ of about 250-, about 350 ℃ of preferably about 275-.
Usually total working pressure is the about 100bar of about 1bar-, and the pressure that preferably has a carbon monoxide is lower than 5bar greater than the pressure of 10bar and reactant.
This method can be continuously or batch operation, usually preferred operate continuously.Basically, this method is operated in gas phase, and the reactant that is introduced into can be liquid state or gasiform, and product is as gas recovery.As desired, reaction product can be cooled and condensation subsequently.Catalyzer can use with suitable form, also can be with fixed bed or fluidized-bed.In the operation of this method, unreacted starting raw material can reclaim and be recycled in the reactor drum.When product is ritalin, can reclaims also and can former state sell, or, can be transported in other chemical process unit as desired.If desired, all reaction product can be sent into conversion and other optional component of being used for ritalin or acetic acid in the chemical process unit and be converted into other useful product.
In a preferred embodiment of the present invention, when product was methyl acetate, it can reclaim from product and contact via hydrolysis formation acetic acid with water.In addition, all products can pass through hydrolysing step, then and acetic acid separated.This hydrolysing step can carry out in the presence of acid catalyst, can adopt the mode of active distillation method known in the art.
After separation, any alcohol that in reaction, obtains can be sent into and prepare ether in the dehydration reactor, and it can separate from water and be recycled in the carbonylation unit as the fresh feed of carbonylation reactor.
In another embodiment, in case when preparing a large amount of ester, then accomplish the hydrolysis of ester products to alcohol and carboxylic acid through on one or more points of catalyst bed, injecting water through carbonylation.Inject water with this mode and for example stopped dme basically, and eliminated the needs of the hydrolysis reactor that separates to this conversion of ritalin.
The following embodiment that provides is used to explain the present invention.Yet they have no intention to limit scope of the present invention.
General method
1) Preparation of catalysts
The catalyst sample of ammonia formula or acid utilizes Specac Press, compresses in the mould of 33mm with 12 tons pressure, crushes then and sieves into granularity grades 212-335 micron.Then, (in the furnace volume=30L), calcining is with NH in the still air normal atmosphere at retort furnace for this catalyzer (normally 1g)
4 +Form is converted into H
+Form.Temperature is raised to 450 ℃ with the soaring speed of 5 ℃/min from room temperature, keeps this temperature then 12 hours.The details of zeolite is described in the following table 1
Table 1
Through in the 1 volumetric molar concentration ammonium nitrate solution of 10ml, stirring the 1g raw material three hours, filtering solution then, the zeolite A of na form is converted into NH
4 +Form.Repeat this operation three times, and before compressing and sieving, solid is dry down in 100 ℃ in air.NH before using
4 +The NaA of exchange is calcining not.
Dimethyl ether carbonylation reaction
Dimethyl ether carbonylation reaction is operated in the pressure current reactor unit that the parallel isothermal identical by 60 and flow tubular reactor are formed.Each the pipe in, with the 50ml catalyst cupport to having on the metal sintering thing that hole size is 20 μ m.All catalyst samples are with the soaring speed of 5 ℃/min, under atmospheric pressure, and at N
2In, flow velocity is 3.33ml/h, be heated to 100 ℃, and kept this temperature 1 hour.So this reactor drum is by N
2Be pressurized to 70barg, and this condition of this system held 1 hour.The nitrogen feed subsequent transformation is that gas flow rate is the mixture that contains 64mol% carbon monoxide, 16mol% hydrogen and 20mol% nitrogen of 3.33ml/h, and this system is heated to 300 ℃ with the soaring speed of 3 ℃/min.This condition of this system held is 3 hours then.After this, temperature is reduced to 180 ℃ and also stablize 10min.Think that at that point catalyst activation accomplishes, gas feed is converted into the mixture that contains 64mol% carbon monoxide, 16mol% hydrogen, 15mol% nitrogen and 5mol% dme that gas flow rate is 3.33ml/h.Reaction continues 27.8 hours, and temperature is elevated to 250 ℃ then.The materials flow of from reactor drum, coming out is through having three pillar (molecular sieve 5A;
Q and CP-Wax-52), each pillar is furnished with Varian 4900 little gas chromatographs of thermal conductivity detector; And have two pillars (CP-Sil 5 with CP-Wax 52), each pillar is furnished with flame ionization detector, Interscience Trace gas chromatograph.The result of carbonylation reaction provides in table 2.
Table 2
| Embodiment | Catalyzer | Temperature of reaction/℃ | Time/hrs in the materials flow | ?STY MeOAcgl -1h -1 |
| 1. | NH4-silicon potassium aluminium zeolite-10 | 180 | ?19.6 | ?55 |
| 2. | 250 | 48.8 | 21 | |
| 3. | The NH4-chabazite | 180 | 19.7 | 13 |
| 4. | 250 | 49.0 | 0 | |
| 5. | NH4-ZSM-23 | 180 | 21.2 | 1 |
| 6. | 250 | 50.4 | 4 | |
| 7. | NH4-ECR-18 | 180 | 16.0 | 25 |
| 8. | 250 | 50.8 | 1 | |
| 9. | NH4-θ-1 | 180 | 17.3 | 0 |
| 10. | 250 | 52.1 | 1 | |
| 11. | Na-zeolite A | 180 | 21.4 | 0 |
| 12. | 250 | 50.6 | 0 | |
| 13. | The NH4-zeolite L | 180 | 20.3 | 0 |
| 14. | 250 | 49.5 | 0 | |
| 15. | The H-mazzite | 180 | 20.7 | 1 |
| 16. | 250 | 49.9 | 6 | |
| 17. | NH4-β-18 | 180 | 16.2 | 1 |
| 18. | 250 | 51.0 | 2 |
In above-mentioned test; The silicon-dioxide of silicon potassium aluminium zeolite, chabazite and ECR-18 zeolite: alumina molar ratio is at least 5; The window size of 8 membered ring channels be at least 2.5
* at least 3.6
have at least one Bronsted acidity position, and 8 membered ring channels interconnect with the duct that limits more than or equal to 8 yuan ring.These tests illustrate through these zeolites can obtain significant carbonylation activity.Yet, in carbonylation reaction, use zeolite, ZSM-23, θ-1, A zeolite, L zeolite, mazzite and β-18, almost do not find (if any) any carbonylation.ZSM-23, θ-1 only have 10 membered ring channels, do not have 8 membered ring channels; β-18 only has 12 membered ring channels with the L zeolite, does not have 8 membered ring channels; The A zeolite has 8 membered ring channels but the ratio of its silica/alumina is lower than 5; Existing 8 membered ring channels of mazzite also have 12 membered ring channels, but 8 membered ring channels do not interconnect with 8 membered ring channels or 12 membered ring channels.
General method B
In order to study the catalytic activity that the methanol carbonyl that is used to not have iodide changes into the zeolite of acetic acid, this zeolite can be tested in band baric flow reactor drum according to following program.With size is that the zeolite pellets of 500-1000um is loaded in the band baric flow reactor drum.Also use the catalyzer external crucible to guarantee the effective mixing/heating of reactant.External crucible is to make methyl alcohol form methyl alcohol/dme/isorrheic gama-alumina.Through at nitrogen gas stream (100cm
3/ min) in, kept 16 hours down in 350 ℃, then at carbon monoxide (200cm
3/ min) in, kept 2 hours down in 350 ℃, make this catalyst activation.Utilize back pressure regulator that this system is pressurized to 30barg then.The flow velocity of carbon monoxide is adjusted to 400cm
3/ min (GHSV=2200), methyl alcohol is introduced in this reactor drum (speed+0.15ml/min) via pump.Liquid product and unconverted reactant are collected in the cold scoop, and gaseous product and unreacted feed utilize on-line gas chromatograph to take a sample in downstream.This reaction is by frequent interval sampling, and liquid product utilizes gc to carry out off-line analysis.In above-mentioned carbonylation of methanol, use zeolite H-offretite (silicon-dioxide: alumina molar ratio is 10) as catalyzer, expect that a large amount of ritalins and acetic acid all become liquid product.Similarly be, to expect that a large amount of ritalins and acetic acid all become liquid product if use zeolite H-sarcolite (silicon-dioxide: alumina molar ratio is 8) as the catalyzer of above-mentioned carbonylation of methanol.Offretite and sarcolite all have and interconnective 8 membered ring channels of 12 membered ring channels.Comparatively speaking, (silicon-dioxide: alumina molar ratio is 23 if zeolite H-ZSM-5 is used in expection; 10 membered ring channels are only arranged) or zeolite H-Y (silicon-dioxide: alumina molar ratio is 12; 12 membered ring channels are only arranged) as catalyzer, only there is the acetic acid of trace can become liquid product.
All publications and the patented claim of quoting in this manual are hereby incorporated by, just as each independent publication or patented claim by clear and definite with point out to be incorporated herein by reference separately.
Although in order clearly to understand goal of the invention; Foregoing invention has been carried out some detailed descriptions through setting forth with embodiment, however those do not break away from according to instruction of the present invention accompanying claims spirit or scope some variation and revise apparent to those skilled in the art.
Claims (42)
1. one kind prepares C
1-C
3The method of aliphatic carboxylic acid and/or corresponding esters is through with corresponding C
1-C
3Fatty Alcohol(C12-C14 and C12-C18) and/or its ester or ether derivant and carbon monoxide be carbonylation in the presence of the catalyzer that contains the zeolite with at least one duct that is limited on 8 yuan of rings of tetrahedral coordination atom, and said ether derivant has general formula R
1-O-R
2, R wherein
1And R
2Be C independently
1-C
3Alkyl, described 8 membered ring channels with interconnect in the duct that ring limited more than or equal to 8 yuan, described 8 membered ring channels have at least
* at least
Window size and at least one Br position, and the silicon-dioxide of zeolite: X
2O
3Mol ratio be at least 5, wherein X is selected from aluminium, boron, iron, gallium and composition thereof, its condition is that this zeolite is not mordenite or ferrierite.
2. according to the process of claim 1 wherein C
1-C
3Carboxylic acid is an acetic acid.
3. according to the process of claim 1 wherein C
1-C
3The ester of carboxylic acid is a ritalin.
4. according to the process of claim 1 wherein C
1-C
3Alcohol is methyl alcohol or ethanol.
5. according to the method for claim 4, wherein alcohol is methyl alcohol.
6. has general formula R according to the process of claim 1 wherein
1-O-R
2Ether, R wherein
1And R
2Be C independently
1-C
3Alkyl, by carbonylation.
7. according to the method for claim 6, wherein has general formula R
1-O-R
2Ether, R wherein
1And R
2Be C independently
1-C
3Alkyl, be dme.
8. has general formula R according to the process of claim 1 wherein
1-O-R
2Ether, R wherein
1And R
2Be C independently
1-C
3Alkyl, under about 100 ℃-Yue 250 ℃ by carbonylation.
9. has general formula R according to the process of claim 1 wherein
1-O-R
2Ether, R wherein
1And R
2Be C independently
1-C
3Alkyl, under about 150 ℃-Yue 180 ℃ by carbonylation.
10. according to Claim 8 or 9 method, wherein has general formula R
1-O-R
2Ether, R wherein
1And R
2Be C independently
1-C
3Alkyl, be dme.
11. according to the process of claim 1 wherein C
1-C
3Fatty Alcohol(C12-C14 and C12-C18) or its ester derivative under about 250 ℃-Yue 400 ℃ by carbonylation.
12. according to the process of claim 1 wherein C
1-C
3Fatty Alcohol(C12-C14 and C12-C18) or its ester derivative under about 275 ℃-Yue 350 ℃ by carbonylation.
13. according to the method for claim 11 or 12, wherein C
1-C
3Fatty Alcohol(C12-C14 and C12-C18) is a methyl alcohol, and ester derivative is a ritalin.
14. according to the process of claim 1 wherein that catalyzer is used for fixing bed.
15. according to the process of claim 1 wherein that catalyzer is used for fluidized-bed.
16. continuation method according to claim 1.
17. batch process according to claim 1.
18. according to the process of claim 1 wherein that the charging that contains carbon monoxide further comprises hydrogen.
19. according to the method for claim 18, the charging that wherein contains carbon monoxide comprises synthetic gas.
20. according to the process of claim 1 wherein said ether derivant by carbonylation, and wherein this method is carried out under anhydrous basically condition, product is corresponding ester.
21. according to the method for claim 20, wherein ether is dme, and this method carries out under anhydrous basically condition, product is a ritalin.
22., comprise that further ester hydrolysis is with the preparation corresponding carboxylic acid according to the method for claim 20.
23., comprise that further hydrolysis ritalin is with preparation acetic acid according to the method for claim 21.
24. according to the method for claim 22 or 23, wherein hydrolysis is implemented in the reactor drum that separates with the ester preparation feedback.
25. according to the method for claim 22 or 23, wherein hydrolysis is implemented in the reactor drum identical with the ester preparation feedback.
26. according to the process of claim 1 wherein that zeolite catalyst is selected from the zeolite that framework types is OFF, CHA, ITE, GME, ETR, EON and MFS.
27. according to the method for claim 26, wherein catalyzer is selected from offretite, sarcolite, ZSM-57 and ECR-18.
28. according to the method for claim 27, its mesolite is an offretite.
29. according to the process of claim 1 wherein that catalyzer is by only being made up of the duct of 8 yuan of ring qualifications.
30. interconnect having the duct that limits greater than 8 yuan ring 8 yuan of ducts of limiting of ring and at least one according to the process of claim 1 wherein.
31. according to the method for claim 30, wherein, at least one is limited on 10 or 12 yuan of rings in the duct that limits greater than 8 yuan ring.
32. according to the method for claim 31, wherein, at least one is limited on 12 yuan of rings in the duct that limits greater than 8 yuan ring.
33. according to the process of claim 1 wherein that this method carries out under aqueous conditions.
34. according to the method for claim 33, wherein water is introduced separately, or is introduced into alcohol and/or its ester.
35. according to the process of claim 1 wherein silicon-dioxide: X
2O
3Ratio be less than or equal to 100.
36. according to the process of claim 1 wherein silicon-dioxide: X
2O
3Ratio be 7-40.
37. according to the process of claim 1 wherein silicon-dioxide: X
2O
3Ratio be 10-30.
38. according to the process of claim 1 wherein that X is selected from aluminium, gallium and its mixture.
39. according to the process of claim 1 wherein that X is an aluminium.
40. according to the process of claim 1 wherein that X is an aluminium, and silicon-dioxide: Al
2O
3Ratio be less than or equal to 100.
41. according to the method for claim 40, wherein silicon-dioxide: Al
2O
3Ratio be 7-40.
42. according to the method for claim 40, wherein silicon-dioxide: Al
2O
3Ratio be 10-30.
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| JP (1) | JP2010513270A (en) |
| KR (2) | KR20090092280A (en) |
| CN (1) | CN101600678B (en) |
| BR (1) | BRPI0622186A2 (en) |
| CA (1) | CA2671361C (en) |
| UA (1) | UA95663C2 (en) |
| WO (1) | WO2008073096A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2292578A1 (en) * | 2009-09-03 | 2011-03-09 | BP Chemicals Limited | Process for producing acetic acid and dimethyl ether using a zeolite catalyst |
| CN103012062B (en) * | 2012-12-20 | 2015-04-22 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| RU2658005C2 (en) * | 2013-03-08 | 2018-06-19 | Бп Кемикэлз Лимитед | Carbonylation method |
| CN106365992B (en) * | 2015-07-20 | 2019-01-01 | 中国科学院大连化学物理研究所 | A method of preparing acetal carbonyl compound |
| CN106365995B (en) * | 2015-07-20 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of production method of methyl acetate |
| CN106365994B (en) * | 2015-07-20 | 2019-01-01 | 中国科学院大连化学物理研究所 | A kind of production method of lower aliphatic carboxylic acid's Arrcostab |
| WO2019037766A1 (en) | 2017-08-24 | 2019-02-28 | Bp P.L.C. | Process |
| WO2019037768A1 (en) | 2017-08-24 | 2019-02-28 | Bp P.L.C. | Process |
| CN114539057B (en) * | 2020-11-18 | 2024-03-19 | 中国科学院大连化学物理研究所 | Preparation method of methyl acetate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5856588A (en) * | 1994-11-14 | 1999-01-05 | Huntsman Specialty Chemicals Corporation | Two-stage etherification of tertiary butyl alcohol using second stage zeolite catalysts for the intermediate preparation of isobutylene |
| US20060252959A1 (en) * | 2005-05-05 | 2006-11-09 | The Regents Of The University Of California | Process for carbonylation of alkyl ethers |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3130007A (en) | 1961-05-12 | 1964-04-21 | Union Carbide Corp | Crystalline zeolite y |
| GB1185453A (en) | 1967-02-20 | 1970-03-25 | Monsanto Co | Multiphase Catalysis. |
| US3717670A (en) | 1968-08-02 | 1973-02-20 | Monsanto Co | Production of carboxylic acids and esters |
| US3689533A (en) | 1971-03-15 | 1972-09-05 | Monsanto Co | Production of carboxylic acids and esters |
| CA1064890A (en) | 1975-06-10 | 1979-10-23 | Mae K. Rubin | Crystalline zeolite, synthesis and use thereof |
| US4612387A (en) | 1982-01-04 | 1986-09-16 | Air Products And Chemicals, Inc. | Production of carboxylic acids and esters |
| GB9223170D0 (en) * | 1992-11-05 | 1992-12-16 | British Petroleum Co Plc | Process for preparing carboxylic acids |
| US6127432A (en) | 1998-01-29 | 2000-10-03 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for preparing oxygenates and catalysts therefor |
| GB0409490D0 (en) | 2004-04-28 | 2004-06-02 | Bp Chem Int Ltd | Process |
-
2006
- 2006-12-15 KR KR1020097012298A patent/KR20090092280A/en active Application Filing
- 2006-12-15 KR KR1020147009999A patent/KR20140054448A/en not_active Application Discontinuation
- 2006-12-15 CA CA2671361A patent/CA2671361C/en not_active Expired - Fee Related
- 2006-12-15 CN CN2006800566291A patent/CN101600678B/en not_active Expired - Fee Related
- 2006-12-15 WO PCT/US2006/047718 patent/WO2008073096A1/en active Application Filing
- 2006-12-15 EP EP06845427A patent/EP2114850A4/en not_active Withdrawn
- 2006-12-15 BR BRPI0622186-6A patent/BRPI0622186A2/en not_active IP Right Cessation
- 2006-12-15 UA UAA200907279A patent/UA95663C2/en unknown
- 2006-12-15 JP JP2009541278A patent/JP2010513270A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5856588A (en) * | 1994-11-14 | 1999-01-05 | Huntsman Specialty Chemicals Corporation | Two-stage etherification of tertiary butyl alcohol using second stage zeolite catalysts for the intermediate preparation of isobutylene |
| US20060252959A1 (en) * | 2005-05-05 | 2006-11-09 | The Regents Of The University Of California | Process for carbonylation of alkyl ethers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20090092280A (en) | 2009-08-31 |
| CA2671361C (en) | 2014-10-21 |
| BRPI0622186A2 (en) | 2011-12-27 |
| KR20140054448A (en) | 2014-05-08 |
| UA95663C2 (en) | 2011-08-25 |
| EP2114850A1 (en) | 2009-11-11 |
| EP2114850A4 (en) | 2013-03-27 |
| CN101600678A (en) | 2009-12-09 |
| WO2008073096A1 (en) | 2008-06-19 |
| CA2671361A1 (en) | 2008-06-19 |
| JP2010513270A (en) | 2010-04-30 |
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