CN106694049B - 一种醋酸甲酯催化剂体系及应用 - Google Patents
一种醋酸甲酯催化剂体系及应用 Download PDFInfo
- Publication number
- CN106694049B CN106694049B CN201611070791.0A CN201611070791A CN106694049B CN 106694049 B CN106694049 B CN 106694049B CN 201611070791 A CN201611070791 A CN 201611070791A CN 106694049 B CN106694049 B CN 106694049B
- Authority
- CN
- China
- Prior art keywords
- rhodium
- iodide
- catalyst
- methyl acetate
- catalysis agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 43
- 239000010948 rhodium Substances 0.000 claims abstract description 43
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- GMLREHXYJDLZOU-LEPYJNQMSA-N 3-Acetylmorphine Chemical class O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GMLREHXYJDLZOU-LEPYJNQMSA-N 0.000 claims abstract description 15
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- QZJVWTNHFOMVHX-UHFFFAOYSA-N methanol;methyl acetate Chemical compound OC.COC(C)=O QZJVWTNHFOMVHX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 9
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000011135 tin Substances 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims abstract description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 235000009518 sodium iodide Nutrition 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- GPMUMMNTAZMBEC-UHFFFAOYSA-N bis(oxomethylidene)rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-] GPMUMMNTAZMBEC-UHFFFAOYSA-N 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- DOXGZURQPFRNFH-UHFFFAOYSA-N [Rh].C(C)(=O)OC.CO Chemical compound [Rh].C(C)(=O)OC.CO DOXGZURQPFRNFH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003426 co-catalyst Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RXANXOVTOLTSID-UHFFFAOYSA-N ClB(B(B(CC)Cl)Cl)Cl Chemical compound ClB(B(B(CC)Cl)Cl)Cl RXANXOVTOLTSID-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- AOZUYISQWWJMJC-UHFFFAOYSA-N acetic acid;methanol;hydrate Chemical compound O.OC.CC(O)=O AOZUYISQWWJMJC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical class O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- 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
- B01J2231/49—Esterification or transesterification
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- 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
-
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明属于化工技术领域，特别涉及一种甲醇制醋酸甲酯的催化剂体系及应用。该催化剂体系以羰基铑‑乙酰吗啉‑金属三者共同组成的络合物为催化剂，钌、锇、镍、钴、铂、钯、锌、镉、汞、锰、钒、钛、镓、铟、铊、钨、铜、铝、锡、锑中的任意一种或多种金属盐作为稳定剂；碘甲烷、氢碘酸、碘化锂、碘化钠、碘化钾、碘化铯和碘化镍中的至少一种碘化物为助催化剂。本发明通过在铑催化剂体系中加入乙酰吗啉类有机配体和金属稳定剂，制备了高活性和高稳定性的甲醇制醋酸甲酯铑催化剂，利用该催化剂可以采用均相反应一步法完成醋酸甲酯的生产，工艺过程简单，技术先进可靠，生产成本低，经济效益好。
Description
技术领域
本发明属于化工技术领域，特别涉及一种甲醇制醋酸甲酯的催化剂体系及应用。
背景技术
醋酸甲酯在工业上有广泛的用途，是羰基化生产乙酸酐和加氢制备乙醇的原料，乙醇是大宗的化工品，广泛用于燃料、溶剂等领域，社会需求旺盛。用乙酸甲酯加氢法代替发酵法生产乙醇可以节约大量的粮食。醋酸甲酯同时也是一种良好的溶剂，用于代替丙酮、丁酮、醋酸乙酯、环戊烷等。美国的伊士曼公司在2005年时，就用醋酸甲酯代替丙酮溶剂，因为醋酸甲酯无毒，不属于限制使用的有机污染物排放，可以达到涂料、油墨、树脂、胶粘剂厂新的环保标准，日益受到人们的追捧。
醋酸甲酯的现有工业生产方法是通过两步法得到：甲醇先羰基合成制得醋酸，醋酸再与甲醇在强酸催化剂的作用下发生酯化反应得到该产品。该方法技术成熟，但工艺流程繁琐、能耗高、投资大，不经济；通常采用硫酸作催化剂，对材质要求高，污染大。
发明内容
本发明的目的在于针对以上问题，提供一种高稳定性、高活性的甲醇一步法制醋酸甲酯催化剂体系，以克服现有醋酸甲酯催化剂污染大、生产技术落后的缺点。
本发明目的通过下述技术方案来实现：
一种甲醇制醋酸甲酯催化剂体系，以羰基铑-有机配体-金属三者共同组成的络合物为催化剂，吗啉类化合物为有机配体，优选乙酰吗啉；钌、锇、镍、钴、铂、钯、锌、镉、汞、锰、钒、钛、镓、铟、铊、钨、铜、铝、锡、锑中的任意一种或多种金属盐为稳定剂；碘甲烷、氢碘酸、碘化锂、碘化钠、碘化钾、碘化铯和碘化镍中的至少一种碘化物为助催化剂。该催化剂体系应用于均相工艺一步法生产醋酸甲酯，反应的方程式为：
2CH3OH+CO→CH3COOCH3+H2O
所述的羰基铑为四氯二羰基铑、四溴二羰基铑或四碘二羰基铑。
所述的铑与有机配体的摩尔比优选为1︰(5-100)。
作为优选，所述铑与乙酰吗啉的摩尔比为1︰(20-60)。
所述稳定剂与铑的摩尔比为0.3:1-30:1。
本发明所述甲醇制醋酸甲酯催化剂采用包括下述主要步骤的方法制得：
先按比例称取各物质，然后用溶剂分别溶解羰基铑、乙酰吗啉和金属盐，再将溶解后的乙酰吗啉溶液和金属盐溶液在10-60℃条件下混和，然后在搅拌条件下将溶解后的羰基铑滴加到混和液中，滴加完毕后于15-50℃搅拌1-2小时即可。
为提高催化剂的使用效率，在上述生产醋酸甲酯的方法中，当反应完成后铑催化剂与反应产物通过闪蒸及蒸发等方式进行分离，铑催化剂返回反应釜循环使用，由于催化剂稳定性良好，蒸发过程几乎不会因沉淀而造成铑的损失。
与现有技术相比，本发明的有益效果是：
(一)、本发明通过在铑催化剂体系中加入乙酰吗啉类有机配体和金属稳定剂，制备了高活性和高稳定性的甲醇制醋酸甲酯铑催化剂，利用该催化剂可以采用均相反应一步法完成醋酸甲酯的生产。
(二)、工艺过程简单，技术先进可靠，生产成本低，代表了醋酸甲酯产业未来的发展方向。
具体实施方式
本说明书中公开的所有特征，或公开的所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，均可以任何方式组合。
实施例1：
本实施例甲醇制醋酸甲酯的铑催化剂是由铑、乙酰吗啉和锡共同组成，制备方法如下：
称取46.8克乙酰吗啉，溶于400ml乙酸中，于40℃和溶解有6.8克二水合氯化亚锡的200ml水溶液混和，然后在搅拌条件下将溶解8.2克四氯二羰基二铑的1000ml乙酸溶液滴加到混和液中，滴加完毕后再40℃搅拌1小时，即得所需铑催化剂。
将所得的铑催化剂用于甲醇制醋酸甲酯催化反应，使用方法如下：
在锆反应釜中，加入制得的铑催化剂，催化剂的加入量按铑计为520ppm，然后加入甲醇、碘化物、水和醋酸，用CO置换三次，关上釜盖，压入CO，在搅拌转速为400rpm，压力为3MPa、温度为180℃条件下反应8分钟，得到产品液。原料液和产品液各组分质量百分比见表1。产品醋酸甲酯STY为1340g/l.h。铑催化剂与产品液经蒸发分离后循环使用，铑损失率<0.03％。
| 组成 | 甲醇 | 醋酸 | 水 | 碘化氢+碘化锂 | 醋酸甲酯 |
| 原料液wt％ | 15.00 | 54.07 | 10.90 | 20.03 | 0 |
| 产品液wt％ | 0.96 | 41.12 | 18.81 | 18.15 | 20.96 |
实施例2：
本实施例甲醇制醋酸甲酯的铑催化剂是由铑、乙酰吗啉和钌共同组成，制备方法如下：
称取31.2克乙酰吗啉，溶于360ml乙酸中，于30℃和溶解有6.3克水合三氯化钌的250ml水溶液混和，然后在搅拌条件下将溶解13.4克四碘二羰基二铑的1000ml乙酸溶液滴加到混和液中，滴加完毕后再30℃搅拌2小时，即得所需铑催化剂。
将所得的铑催化剂用于甲醇制醋酸甲酯催化反应，使用方法如下：
在锆釜中，加入所制得的铑催化剂，催化剂的加入量按铑计为600ppm，，然后加甲醇、碘化物、水和醋酸，用CO置换三次，关上釜盖，压入CO，在搅拌转速为450rpm，压力为2.8MPa、温度为175℃条件下反应12分钟，得到产品液。原料液和产品液各组分质量百分比见表2。产品醋酸甲酯STY为1250g/l.h。铑催化剂与产品液经蒸发分离后循环使用，铑损失率<0.04％。
| 组成 | 甲醇 | 醋酸 | 水 | 碘甲烷+碘化钠 | 醋酸甲酯 |
| 原料液wt％ | 20.00 | 51.45 | 9.03 | 19.52 | 0 |
| 产品液wt％ | 1.31 | 38.78 | 19.73 | 17.50 | 22.68 |
实施例3：
本实施例为对比实施例。
为了便于对比，除催化剂采用无有机配体和金属盐稳定剂添加的四氯二羰基二铑外，其余条件均与实施例1相同。
产品醋酸甲酯STY为1380g/l.h。铑催化剂与产品液经蒸发分离后，铑损失率>87％。
实施例4：本实施例为对比实施例。
为了便于对比，催化剂四氯二羰基二铑中添加了与实施例相同量的乙酰吗啉，但未添加金属盐稳定剂，其余条件均与实施例1相同。
产品醋酸甲酯STY为1310g/l.h。铑催化剂与产品液经蒸发分离后，铑损失率>3％。
实施例5：
本实施例为对比实施例。
为了便于对比，催化剂四氯二羰基二铑中添加了与实施例相同量的锡，但未添加乙酰吗啉，其余条件均与实施例1相同。
产品醋酸甲酯STY为1260g/l.h。铑催化剂与产品液经蒸发分离后，铑损失率>5％。
由以上实施例可知，同时加入了乙酰吗啉和金属稳定剂的铑催化剂络合物在甲醇制醋酸甲酯的反应中，既表现出良好的催化活性，又具有良好的稳定性，具有很好的市场推广前景。
本发明并不局限于上述实施例中记载，也可扩展到任何在本说明书中披露的新特征或任何新的组合，以及披露的任一新的方法或过程的步骤或任何新的组合。
Claims (2)
1.一种甲醇制醋酸甲酯催化剂体系，其特征在于：该催化剂体系以羰基铑-有机配体-金属三者共同组成的络合物为催化剂，其中，吗啉类化合物为有机配体；钌、锇、镍、钴、铂、钯、锌、镉、汞、锰、钒、钛、镓、铟、铊、钨、铜、铝、锡、锑中的任意一种或多种金属盐为稳定剂；碘甲烷、氢碘酸、碘化锂、碘化钠、碘化钾、碘化铯和碘化镍中的至少一种碘化物为助催化剂；所述的羰基铑为四氯二羰基铑、四溴二羰基铑或四碘二羰基铑；所述稳定剂与铑的摩尔比为0.3:1-30:1；所述的有机配体为乙酰吗啉；所述铑与乙酰吗啉的摩尔比为1︰20-60。
2.根据权利要求1所述的甲醇制醋酸甲酯催化剂体系，其特征在于：该催化剂应用于均相工艺一步法生产醋酸甲酯，反应的方程式为：
2CH3OH+CO→CH3COOCH3+H2O。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611070791.0A CN106694049B (zh) | 2016-11-29 | 2016-11-29 | 一种醋酸甲酯催化剂体系及应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611070791.0A CN106694049B (zh) | 2016-11-29 | 2016-11-29 | 一种醋酸甲酯催化剂体系及应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106694049A CN106694049A (zh) | 2017-05-24 |
| CN106694049B true CN106694049B (zh) | 2019-07-30 |
Family
ID=58935025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611070791.0A Expired - Fee Related CN106694049B (zh) | 2016-11-29 | 2016-11-29 | 一种醋酸甲酯催化剂体系及应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106694049B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999127B (zh) * | 2017-11-28 | 2020-03-31 | 西南化工研究设计院有限公司 | 一种甲醇一步法制醋酸甲酯催化剂及应用 |
| CN107892648B (zh) * | 2017-11-28 | 2019-06-04 | 西南化工研究设计院有限公司 | 一种甲醇一步法制醋酸甲酯的方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978055A (zh) * | 2005-12-08 | 2007-06-13 | 中国科学院化学研究所 | 一种羰基合成催化体系及应用 |
| CN101279294A (zh) * | 2008-05-22 | 2008-10-08 | 西南化工研究设计院 | 乙酸甲酯羰基合成乙酸酐的铑催化剂及其制备方法 |
| CN106140156A (zh) * | 2015-04-20 | 2016-11-23 | 中国科学院大连化学物理研究所 | 一种活性炭负载的铑基催化剂及其制备方法和应用 |
-
2016
- 2016-11-29 CN CN201611070791.0A patent/CN106694049B/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978055A (zh) * | 2005-12-08 | 2007-06-13 | 中国科学院化学研究所 | 一种羰基合成催化体系及应用 |
| CN101279294A (zh) * | 2008-05-22 | 2008-10-08 | 西南化工研究设计院 | 乙酸甲酯羰基合成乙酸酐的铑催化剂及其制备方法 |
| CN106140156A (zh) * | 2015-04-20 | 2016-11-23 | 中国科学院大连化学物理研究所 | 一种活性炭负载的铑基催化剂及其制备方法和应用 |
Non-Patent Citations (1)
| Title |
|---|
| 新型含乙酰吗啉的乙酸酐铑催化剂的制备及应用;张华西 等;《天然气化工》;20111231;第36卷(第3期);第5-6页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106694049A (zh) | 2017-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101966457B (zh) | 一种高活性羰基加氢钌炭催化剂的制备方法 | |
| CN106946894A (zh) | 钯基双金属催化剂在hbiw催化氢解反应中的应用 | |
| CN103691451B (zh) | 一种气相甲醇羰基化合成甲酸甲酯的催化剂及其制备方法和应用 | |
| CN103785408B (zh) | 一种草酸二甲酯加氢制备乙醇酸甲酯的催化剂及合成方法 | |
| CN101549292A (zh) | 一种苯环加氢合成环己烯催化剂及其制备方法 | |
| CN106694049B (zh) | 一种醋酸甲酯催化剂体系及应用 | |
| CN102863335B (zh) | 一种丁二酸二酯的制备方法 | |
| CN113492021A (zh) | 铑催化剂的制备方法 | |
| CN102126960A (zh) | 一种对硝基苯甲醛的高选择性合成方法 | |
| CN102218344B (zh) | 羰基化合成醋酸的3,5-二羧基吡唑铱配合物催化剂及其制备方法和应用 | |
| CN106748772B (zh) | 一种醋酸甲酯的生产方法 | |
| CN102643237B (zh) | 1h-咪唑-4-甲酸的制备方法 | |
| CN101279294B (zh) | 乙酸甲酯羰基合成乙酸酐的铑催化剂及其制备方法 | |
| CN102319562A (zh) | 苯选择加氢制环己烯的催化剂的制备方法及通过该方法制备的催化剂 | |
| CN106694045B (zh) | 3:1型Mg/Li双金属催化剂及其制备方法和应用 | |
| CN107892648B (zh) | 一种甲醇一步法制醋酸甲酯的方法 | |
| CN104874423B (zh) | 一种含铑、钌双金属催化剂的制备方法 | |
| CN113548944A (zh) | 一种由苯甲醛催化加氢制备苯甲醇的方法 | |
| CN104646058A (zh) | 一种含铜配合物催化剂及其制备方法与应用 | |
| CN101745396B (zh) | 一种制备丁二酸二烷基酯的催化剂及其制备方法 | |
| CN101293213B (zh) | 羰基合成乙酸酐的铑催化剂及其制备方法 | |
| CN102259028A (zh) | 均相催化甲醇羰基化合成醋酸的铱催化剂及其制备方法和应用 | |
| CN102836711A (zh) | 一种用于苯选择加氢制环己烯的催化剂及其制备方法 | |
| CN108047276B (zh) | 一种合成乙酰丙酮钌(ⅲ)的方法 | |
| CN113582860B (zh) | 一种n-甲基一乙醇胺的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191213 Address after: 611436 No.777, Xinghua 10th Road, dengshuang Town, Xinjin County, Chengdu City, Sichuan Province (Industrial Park) Patentee after: HAO HUA (CHENGDU) TECHNOLOGY Co.,Ltd. Address before: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610225 Patentee before: SOUTHWEST RESEARCH & DESIGN INSTITUTE OF CHEMICAL INDUSTRY |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190730 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |