CN110105169B - 环氧乙烷耦合合成气制备1,3-丙二醇的方法 - Google Patents
环氧乙烷耦合合成气制备1,3-丙二醇的方法 Download PDFInfo
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- CN110105169B CN110105169B CN201910509398.4A CN201910509398A CN110105169B CN 110105169 B CN110105169 B CN 110105169B CN 201910509398 A CN201910509398 A CN 201910509398A CN 110105169 B CN110105169 B CN 110105169B
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- ethylene oxide
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NVVMIVJVAAXSCG-UHFFFAOYSA-N [Na].C(C)N Chemical compound [Na].C(C)N NVVMIVJVAAXSCG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- MENWVOUYOZQBDM-UHFFFAOYSA-N butyl 3-hydroxypropanoate Chemical compound CCCCOC(=O)CCO MENWVOUYOZQBDM-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- XWDKRVSSHIJNJP-UHFFFAOYSA-N carbon monoxide;iridium Chemical group [Ir].[Ir].[Ir].[Ir].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] XWDKRVSSHIJNJP-UHFFFAOYSA-N 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- UKDLORMZNPQILV-UHFFFAOYSA-N ethyl 3-hydroxypropanoate Chemical compound CCOC(=O)CCO UKDLORMZNPQILV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
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- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
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- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- OVRRUKBOLSAMBL-UHFFFAOYSA-N lithium ethylazanide Chemical compound [Li+].CC[NH-] OVRRUKBOLSAMBL-UHFFFAOYSA-N 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical group [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- JMNBVZIBJMAJJU-UHFFFAOYSA-N lithium;methylazanide Chemical compound [Li+].[NH-]C JMNBVZIBJMAJJU-UHFFFAOYSA-N 0.000 description 1
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- ORPJQHHQRCLVIC-UHFFFAOYSA-N magnesium;propan-2-olate Chemical compound CC(C)O[Mg]OC(C)C ORPJQHHQRCLVIC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- CYQYCASVINMDFD-UHFFFAOYSA-N n,n-ditert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)N(C(C)(C)C)C(C)(C)C CYQYCASVINMDFD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- XQBKHDFIPARBOX-UHFFFAOYSA-N osmium(3+) Chemical compound [Os+3] XQBKHDFIPARBOX-UHFFFAOYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DATIMHCCPUZBTD-UHFFFAOYSA-N pentane Chemical compound CCCCC.CCCCC DATIMHCCPUZBTD-UHFFFAOYSA-N 0.000 description 1
- LTIXUBRRKREIPS-UHFFFAOYSA-N pentyl 3-hydroxypropanoate Chemical compound CCCCCOC(=O)CCO LTIXUBRRKREIPS-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052573 porcelain Chemical group 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- NBRBEIWJQOMRHD-UHFFFAOYSA-N potassium ethylazanide Chemical compound [K+].CC[NH-] NBRBEIWJQOMRHD-UHFFFAOYSA-N 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- BRUZZEMTHTULBO-UHFFFAOYSA-N potassium;methylazanide Chemical compound [K+].[NH-]C BRUZZEMTHTULBO-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- MIDAHAFCJFVHFD-UHFFFAOYSA-N propan-2-yl 3-hydroxypropanoate Chemical compound CC(C)OC(=O)CCO MIDAHAFCJFVHFD-UHFFFAOYSA-N 0.000 description 1
- KNCDNPMGXGIVOM-UHFFFAOYSA-N propyl 3-hydroxypropanoate Chemical compound CCCOC(=O)CCO KNCDNPMGXGIVOM-UHFFFAOYSA-N 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- KXDHHKIAGHRLRO-UHFFFAOYSA-N sodium methylazanide Chemical compound [Na+].[NH-]C KXDHHKIAGHRLRO-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- NSXCURRVJMPAPA-UHFFFAOYSA-N tert-butyl 3-hydroxypropanoate Chemical compound CC(C)(C)OC(=O)CCO NSXCURRVJMPAPA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
环氧乙烷耦合合成气制备1,3‑丙二醇的方法,涉及制备1,3‑丙二醇的领域,环氧乙烷、一氧化碳和醇类分子通过开环‑羰化‑酯化的催化反应制备3‑羟基丙酸酯,以及3‑羟基丙酸酯通过加氢的催化反应制备1,3‑丙二醇。环氧乙烷、一氧化碳和醇的催化反应是使用N,O‑配体配位的金属络合物催化剂,在有机溶剂和助剂作用下实现3‑羟基丙酸酯的制备,3‑羟基丙酸酯的产率可以达到97%。3‑羟基丙酸酯和氢气的催化反应是使用含铜混金属硅氧催化剂,1,3‑丙二醇的产率可以达到73%。第二步加氢催化反应中生成的醇可以循环用于第一步开环‑羰化‑酯化催化反应。
Description
技术领域
本发明涉及制备1,3-丙二醇的领域,尤其涉及环氧乙烷耦合合成气制备1,3-丙二醇的方法。
背景技术
1,3-丙二醇是一种防冻剂,也是多种增塑剂、洗涤剂、防腐剂和乳化剂的合成原料。1,3-丙二醇更重要的应用是聚合用单体。1,3-丙二醇与对苯二甲酸发生聚合反应生成聚对苯二甲酸丙二醇酯(PTT),PTT是一种新型聚酯材料,可制作纤维丝,生产高质量的地毯以及其它面料,也可用于塑料制品。在本领域中,更引人关注的研究是发明一种既经济有效又有工艺优势的1,3-丙二醇的制备路线。
早在1960年,英国Eisenmann、Yamartino、Howard和Jr.研究了环氧丙烷、CO和甲醇在Co2(CO)8催化作用下生成3-羟基丁酸甲酯主产物,产率20.8%~40.3%,同时会产生其它副产物(J.Org.Chem.1961,26,2102-2104)。该反应条件比较苛刻,CO压力需要53~400bar,温度需要110~190℃。1963年供职于美国Hercules Powder公司研究中心的Heck报道使用NaCo(CO)4催化环氧乙烷、CO和甲醇的反应,在133atm压力和65℃下得到55%产率的3-羟基丙酸甲酯,但是副产物偏多且组分复杂(J.Am.Chem.Soc.1963,85,1460-1463)。1996年美国Shell公司宣称实现了1,3-丙二醇的工业化生产,公司专利描述该法以环氧乙烷、CO、H2为原料,通过氢甲酰化一步法制备1,3-丙二醇(US3463819)。随后Shell公司专利报道两步法,即环氧乙烷与CO、H2通过氢甲酰化反应制得3-羟基丙醛,然后加氢得到1,3-丙二醇(US5545766)。
尽管Shell公司已经宣称通过氢甲酰化法实现了1,3-丙二醇的工业化生产,但是其它方法也被研究报道,其中突出的方法是以Heck在1963年报道的反应为基础,再进一步进行加氢反应制备1,3-丙二醇,为与Shell公司的氢甲酰化法区别,该法被称为氢甲酯化法。
在氢甲酯化法的实验研究中,1990年(US4973741)和1992年(US5135901)EastmanKodak公司专利述及金属铑、钌、膦配体、第五主族元素化合物促进剂组成的催化剂体系,催化环氧乙烷、CO、H2以及C1-6直链醇或苄醇反应制备3-羟基丙酸酯;实施例中指出在反应温度70℃和初始压力137.9bar下,环氧乙烷的转化率为26.3%~90.3%,3-羟基丙酸甲酯的选择性为12.3%~43.5%。2002年(US6348632B1)和2003年(US6521801B1)SamsungElectronics公司教导使用金属钴和氮配体组成的催化剂体系,催化环氧乙烷、CO和醇反应制备3-羟基丙酸酯。实施例中指出在反应温度60~80℃和初始压力34~80bar下,环氧乙烷的转化率为45.19%~95.27%,3-羟基丙酸甲酯的选择性为78.45%~93.31%。SamsungElectronics公司也在2002年(CN1355160A)专利请求3-羟基丙酸酯的加氢反应制备1,3-丙二醇,使用Cu-Si-O主催化剂,并加入少量Re、Pd、Ru、Pt、Rh、Ag、Se、Te、Mo、Mn(以铜计量为0.001~10mol%)助剂。实施例中显示在反应温度145~150℃和初始压力62~69bar下,3-羟基丙酸甲酯的转化率为82.90%~97.92%,1,3-丙二醇的选择性为84.28%~89.63%。
目前该领域的研究显示,氢甲酯化法没有实现工业化生产,因此合理的催化剂体系的发明以及经济有效又有工艺优势的1,3-丙二醇的制备路线的设计是关键点。
发明内容
本发明的目的在于解决现有技术中的上述问题,提供环氧乙烷耦合合成气制备1,3-丙二醇的方法。
为达到上述目的,本发明采用如下技术方案:
环氧乙烷耦合合成气制备1,3-丙二醇的方法,合成路线如下:
催化剂1为金属配体络合物,催化剂2为含铜的混金属硅氧化物。
所述金属配体络合物为N,O-配体配位的金属络合物,N,O-配体配位的金属络合物的结构如下:
金属M选自镍、钴、钌、铑、钯、铂、锇、铱、铁、铜、铬中的一种,优选自钴、钌、铑、铱中的一种;N,O配体是以N和O为配位原子的有机基团,N和O分别与中心金属M有σ-键作用;B是连接两个N,O配体的桥联有机基团,并与氮原子键联;X是指阴离子型的基团或原子或中性的基团,n是指X的数目,X和n的选择满足N,O配体和M配位后保持M中心合理的氧化态和配位数,X选自H、CO、卤素、拟卤素、烷基、烷氧基、烷巯基、芳基、苄基、胺基、氢氧基、羧酸基中的一种,X优选自H、CO、Cl、SCN、甲基、乙基、甲氧基、乙氧基、异丙醇氧基、苯基、苄基、甲胺基、乙胺基、OH、甲酸基、醋酸基中的一种。
所述含铜的混金属硅氧化物的结构式为M'uCuvSiyOz,u、v、y、z值的选择以保持整个通式分子的总的零氧化态值为准则,其中M'选自锌、锰、钡、镧系金属、钴、银、金、镍、钾中的一种或两种或三种优选地,含铜的混金属硅氧化物中,优选地,铜的含量为20%~70%,硅的含量为10%~30%,氧的含量为10%~40%,M'的含量为0.5%~10%。
本发明中,环氧乙烷耦合合成气制备1,3-丙二醇的方法包含两步催化反应,第一步是环氧乙烷、一氧化碳和醇类分子通过开环-羰化-酯化的催化反应制备3-羟基丙酸酯,第二步是生成的3-羟基丙酸酯通过加氢的催化反应制备1,3-丙二醇,第二步反应中生成的醇类分子副产物可以循环用于第一步的反应。
具体地,第一步反应即合成路线中环氧乙烷、一氧化碳和醇类分子的开环-羰化-酯化的催化反应制备3-羟基丙酸酯,包括如下步骤:
1)将环氧乙烷、一氧化碳和醇类分子在有机溶剂、催化剂1和助剂下进行反应,反应温度为30~190℃,反应压力为1~150atm,反应时间为0.1~200h;其中,反应温度优选30~150℃,反应压力优选1~120atm,反应时间优选1~180h。
所述有机溶剂选自醇、醚、饱和烷烃、饱和芳烃的至少一种,优选自甲醇、乙醇、丙醇、丁醇、戊醇、二甲醚、乙醚、甲基叔丁基醚、四氢呋喃、2,6-氧环、戊烷、己烷、庚烷、辛烷、苯、甲苯、二甲苯、三甲苯;所述醇类分子为C1~C20碳数的醇,醇类分子优选自甲醇、乙醇、丙醇、丁醇、戊醇的至少一种,;
2)将步骤1)反应后的产物体系进行相分离,形成水相、有机相和沉淀物相,并使产物3-羟基丙酸酯最大限度地留在有机相中;
3)收集步骤2)中有机相,分离出产物3-羟基丙酸酯和有机溶剂,产物3-羟基丙酸酯用于下一步反应;或无需分离3-羟基丙酸酯和有机溶剂,直接用于下一步反应。
具体地,第二步反应即合成路线中3-羟基丙酸酯的加氢催化反应制备1,3-丙二醇,包括如下步骤:
4)将步骤3)中分离出来的3-羟基丙酸酯或含3-羟基丙酸酯的有机相在氢气、有机溶剂和催化剂2下反应,反应温度为80~400℃,反应压力为20~150atm,反应时间为0.1~200h,反应温度优选90~270℃,氢气压力优选30~120atm,反应时间优选0.5~150h,有机溶剂选自醚、饱和烷烃、饱和芳烃,优选自甲醇、戊烷、己烷、庚烷、苯、甲苯;
5)将反应后的产物体系进行分离,收集1,3-丙二醇、醇类副产物和有机溶剂;醇类副产物投入到1)中循环使用。
本发明中,所述助剂选自碱性金属氧化物、主族金属烷氧基化合物、主族金属胺基化合物、主族金属羧基化合物、金属羰基化合物、路易斯碱性的含氮化合物中的至少一种;特别地,碱性金属氧化物选自氧化锂、氧化钠、氧化钾、氧化镁;主族金属烷氧基化合物选自醇锂、醇钠、醇钾、醇镁、醇钙、醇锶、醇钡、醇铝、醇镓,优选自甲醇锂、甲醇钠、甲醇钾、乙醇锂、乙醇钠、乙醇钾、异丙醇锂、异丙醇钠、异丙醇钾、甲醇镁、乙醇镁、异丙醇镁;主族金属胺基化合物选自烷胺基锂、烷胺基钠、烷胺基钾、烷胺基镁、烷胺基钙,优选自甲胺基锂、甲胺基钠、甲胺基钾、甲胺基镁、甲胺基钙、乙胺基锂、乙胺基钠、乙胺基钾、乙胺基镁、乙胺基钙、三甲硅基胺基锂、三甲硅基胺基钠、三甲硅基胺基钾;主族金属羧基化合物选自甲酸锂、甲酸钠、甲酸钾、乙酸锂、乙酸钠、乙酸钾、甲酸镁、乙酸镁、甲酸钙、乙酸钙;金属羰基化合物选自羰基钴、羰基铁、羰基鉬、羰基钨、羰基铬、羰基钌、羰基铱、羰基铑;路易斯碱性的含氮化合物选自烷基胺、含氮杂环化合物,优选自三甲胺、三乙胺、三异丙基胺、三叔丁基胺、二甲基苯基胺、吡咯、吡唑、三氮唑、咪唑、吲哚、吡啶、2-羟基吡啶、3-羟基吡啶、4-羟基吡啶。
本发明中,步骤2)中将反应后的产物体系进行相分离的方法如下:加入蒸馏水产生水相,加入有机溶剂形成有机相,加入沉淀剂形成沉淀相;其中,有机溶剂选自醇、醚、饱和烷烃、饱和芳烃、酯、C5以上的长链烯烃、C4以上的长链炔烃中的至少一种,优选自乙醚、甲基叔丁基醚、戊烷、己烷、庚烷、苯、甲苯、己烯、辛烯中的至少一种,沉淀剂选自布朗斯特酸、布朗斯特碱、路易斯酸、路易斯碱、硅胶、分子筛、氧化铝、高岭土、水滑石、离子交换树脂中的至少一种,优选自NaOH、KOH、Na2CO3、NaHCO3、K2CO3、KHCO3、硅胶、分子筛、氧化铝、高岭土、水滑石、离子交换树脂中的至少一种,相分离的方法选自萃取、静置、离心机分离、过滤、蒸馏、过柱或减压抽提。
步骤3)有机相中3-羟基丙酸酯产物与有机溶剂的分离和步骤5)中加氢反应后产物体系的分离,分离方法选自蒸馏、精馏、柱色谱、柱分离或减压抽提。
本发明的环氧乙烷、一氧化碳和醇在有机溶剂中的催化反应可以为间歇过程、连续过程或其组合实施。本发明的3-羟基丙酸酯与氢气的催化反应也可以间歇过程、连续过程或其组合实施。本发明的方法是将这两方面的催化反应结合在一起实施时,由此,3-羟基丙酸酯与氢气反应生成的醇经分离后可以联结到环氧乙烷、一氧化碳和醇在有机溶剂中的反应中,循环使用。
相对于现有技术,本发明技术方案取得的有益效果是:
1、本发明将环氧乙烷、一氧化碳和醇生成3-羟基丙酸酯的反应与3-羟基丙酸酯与氢气生成1,3-丙二醇和醇的反应结合到一起,其中,醇类分子被引入第一步反应生成3-羟基丙酸酯中间产物,3-羟基丙酸酯中间产物再通过第二步加氢反应将醇类分子还原出来,因此,该法借助醇类分子,满足环氧乙烷和合成气制备1,3-丙二醇的原子经济性反应,因而第二步中的副产物醇可以循环用于第一步反应。该方法不同于Shell公司的氢甲酰化两步法,因为在主原料环氧乙烷和合成气中引入醇参与形成中间产物3-羟基丙酸酯。
2、第一步和第二步使用不同的催化剂体系,相应的催化反应原理也是不相同的,第一步的反应为开环-羰化-酯化反应,即环氧乙烷开环,进而发生一氧化碳插入,最后与醇发生酯化反应;第二步的反应为双重氢化反应,即3-羟基丙酸酯与一分子H2反应生成3-羟基丙醛和醇、3-羟基丙醛再进一步与一分子H2反应生成1,3-丙二醇。
3、采用不同的催化剂具有高效的目的:在第一步反应中N,O-配体配位的金属络合物,该氮、氧配体稳定的金属催化剂能高效催化环氧乙烷、CO和醇反应生成3-羟基丙酸酯,这类配体属于非膦配体,但不同于以往报道的含氮配体(US6348632B1、US6521801B1、CN106431921A、CN107349962A、CN107459451A),使用这种氮、氧配体稳定的金属催化剂,在助剂和有机溶剂中,可在温和条件下催化环氧乙烷、CO和醇反应生成3-羟基丙酸酯,其中环氧乙烷的转化率可达到99%,3-羟基丙酸酯的生成选择性最高达到98%。在第二步反应中,含铜的混金属硅氧化物催化剂可以有效催化3-羟基丙酸酯加氢反应制备1,3-丙二醇,并产生醇副产物,其中1,3-丙二醇的产率可以达到73%,副产物醇经分离后用于第一步的反应。
4、本发明所述的环氧乙烷、一氧化碳和醇在有机溶剂中的催化反应,其中有机溶剂包含醇,由此,当选择有机溶剂醇时,选择的醇需要与反应物中的醇相同,一是提高反应物中一种分子的浓度有助于反应向产物的动力学转化,二是保持单一的3-羟基丙酸酯产物的生成。
附图说明
图1为实施例9产物的气相色谱图。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白,以下结合附图和实施例,对本发明做进一步详细说明。
环氧乙烷、一氧化碳和醇在有机溶剂中的催化反应步骤如下:
选取2000mL反应器,进行N2冲洗至少三次后,依次加入N,O-配体金属络合物、助剂、环氧乙烷、醇、有机溶剂,其中催化剂的金属浓度为1mmol/L、助剂的浓度为2mmol/L、环氧乙烷的浓度为400mmol/L、醇的浓度为400mmol/L。关闭进样阀,调节反应器温度至预定值,调节搅拌速率至预定值,调节反应时间至预定值,接通一氧化碳钢瓶,调节反应器压力至预定值,开启反应。反应结束后,将反应器冷却至0℃,缓慢泄压至常压,抽取反应液处理后进行气相色谱分析,数据结果进行记录。
实施例1~18
选取结构式I的催化剂1进行探索,实施例以甲醇为溶剂、甲醇钠为助剂。在以甲醇为溶剂时,甲醇也是其中的反应物之一,因此甲醇的浓度大大过量,可不予浓度计量。在保持压力50atm和时间4h下,进行温度变化分别为40、60、80、100、120、140℃的反应,结果记录于表1的实施例1~6;保持温度80℃和时间4h下进行压力变化分别为5、10、30、50、70、90、100、120atm的反应,结果记录于表1实施例7~13;保持温度80℃和压力30atm下进行时间变化分别为1、2、3、5、6h的反应,结果记录于表1实施例14~18,如图1所示为实施例9产物的气相色谱图。
表1
实施例 | 温度/℃ | 压力/atm | 反应时间/h | EO转化/% | 3-HMP选择性/% |
1 | 40 | 50 | 4 | 22.3 | 84.3 |
2 | 60 | 50 | 4 | 59.0 | 86.2 |
3 | 80 | 50 | 4 | 96.9 | 96.5 |
4 | 100 | 50 | 4 | 95.4 | 69.5 |
5 | 120 | 50 | 4 | 96.4 | 56.7 |
6 | 140 | 50 | 4 | 98.3 | 26.8 |
7 | 80 | 5 | 4 | 23.4 | 76.8 |
8 | 80 | 10 | 4 | 66.7 | 80.1 |
9 | 80 | 30 | 4 | 96.3 | 95.5 |
10 | 80 | 70 | 4 | 94.5 | 78.2 |
11 | 80 | 90 | 4 | 96.2 | 96.1 |
12 | 80 | 100 | 4 | 97.8 | 97.3 |
13 | 80 | 120 | 4 | 98.9 | 98.8 |
14 | 80 | 30 | 1 | 26.3 | 86.5 |
15 | 80 | 30 | 2 | 43.8 | 89.9 |
16 | 80 | 30 | 3 | 56.2 | 87.1 |
17 | 80 | 30 | 5 | 98.8 | 95.2 |
18 | 80 | 30 | 6 | 99.6 | 98.6 |
实施例19~48
使用上述结构式I的催化剂1,以甲醇为溶剂,在温度80℃、压力30atm和时间4h下进行助剂变化的反应,结果记录于表2实施例19~32。
使用上述结构式I的催化剂1,以吡啶为助剂,在温度80℃、压力30atm和时间4h下进行溶剂变化的反应,此时以甲醇为反应物,醇的浓度计量为400mmol/L。结果记录于表2实施例33~41。
使用上述结构式I的催化剂1,以吡啶为助剂,甲基叔丁基醚为溶剂,在温度80℃、压力30atm和时间4h下进行醇变化的反应。结果记录于表2实施例42~48。
表2
实施例 | 醇 | 助剂 | 溶剂 | EO转化率/% | 3-羟基丙酸酯选择性/% |
19 | - | 乙醇钠 | 甲醇 | 56.8 | 78.9 |
20 | - | 乙醇镁 | 甲醇 | 46.5 | 86.4 |
21 | - | 二异丙基胺基锂 | 甲醇 | 52.3 | 88.6 |
22 | - | 乙酸钠 | 甲醇 | 31.1 | 91.2 |
23 | - | 碳酸钠 | 甲醇 | 48.5 | 52.6 |
24 | - | 三乙胺 | 甲醇 | 47.9 | 90.1 |
25 | - | 二甲基苯基胺基锂 | 甲醇 | 56.2 | 76.2 |
26 | - | 吡啶 | 甲醇 | 68.9 | 93.5 |
27 | - | 吡咯 | 甲醇 | 70.2 | 91.6 |
28 | - | 2-羟基吡啶 | 甲醇 | 68.5 | 90.1 |
29 | - | 3-羟基吡啶 | 甲醇 | 96.2 | 98.6 |
30 | - | 4-羟基吡啶 | 甲醇 | 86.8 | 96.8 |
31 | - | 咪唑 | 甲醇 | 78.5 | 90.2 |
32 | - | 吲哚 | 甲醇 | 50.6 | 80.1 |
33 | 甲醇 | 吡啶 | 乙醚 | 86.5 | 90.2 |
34 | 甲醇 | 吡啶 | 四氢呋喃 | 90.1 | 88.2 |
35 | 甲醇 | 吡啶 | 甲基叔丁基醚 | 80.6 | 84.9 |
36 | 甲醇 | 吡啶 | 戊烷 | 85.3 | 90.2 |
37 | 甲醇 | 吡啶 | 己烷 | 86.2 | 87.6 |
38 | 甲醇 | 吡啶 | 苯 | 86.9 | 67.5 |
39 | 甲醇 | 吡啶 | 甲苯 | 90.6 | 56.8 |
40 | 甲醇 | 吡啶 | 1-己烯 | 78.9 | 60.8 |
41 | 甲醇 | 吡啶 | 1-辛烯 | 70.6 | 68.1 |
42 | 乙醇 | 吡啶 | 甲基叔丁基醚 | 74.6 | 80.5 |
43 | 正丙醇 | 吡啶 | 甲基叔丁基醚 | 86.2 | 86.9 |
44 | 异丙醇 | 吡啶 | 甲基叔丁基醚 | 47.5 | 43.6 |
45 | 正丁醇 | 吡啶 | 甲基叔丁基醚 | 72.3 | 79.8 |
46 | 异丁醇 | 吡啶 | 甲基叔丁基醚 | 45.8 | 32.9 |
47 | 叔丁醇 | 吡啶 | 甲基叔丁基醚 | 42.1 | 43.0 |
48 | 正戊醇 | 吡啶 | 甲基叔丁基醚 | 86.7 | 90.7 |
实施例49~55
本部分实施例是考察上述N,O-配体下不同金属络合物催化剂的反应性能。在此情况下,选择甲醇为醇反应物,吡啶为助剂,甲基叔丁基醚为溶剂,在温度80℃、压力30atm和时间4h下进行金属变化的N,O配体金属络合物催化剂作用下的反应,结果记录于表3实施例49~32。
表3
实施例 | 金属 | EO转化率/% | 3-HMP选择性/% |
49 | 钌 | 76.9 | 50.8 |
50 | 铑 | 60.6 | 61.3 |
51 | 钯 | 33.5 | 43.4 |
52 | 铂 | 45.3 | 56.1 |
53 | 锇 | 30.6 | 39.7 |
54 | 铱 | 20.9 | 16.9 |
55 | 铁 | 13.8 | 7.9 |
实施例56~74
本部分实施例为考察不同N,O-配体金属钴络合物催化剂的反应性能,分别选取结构式II~XX的催化剂1进行反应。在此情况下,选择甲醇为醇反应物,吡啶为助剂,甲基叔丁基醚为溶剂,在温度80℃、压力30atm和时间4h下进行N,O配体变化的钴络合物催化剂作用下的反应,结果记录于表4实施例56~74。
表4
实施例 | 催化剂 | EO转化率/% | 3-HMP选择性/% |
56 | II | 80.3 | 94.7 |
57 | III | 71.1 | 87.1 |
58 | IV | 83.9 | 75.4 |
59 | V | 91.1 | 79.5 |
60 | VI | 66.4 | 80.9 |
61 | VII | 43.6 | 72.8 |
62 | VIII | 79.4 | 86.1 |
63 | VIV | 56.1 | 91.6 |
64 | X | 60.3 | 87.6 |
65 | XI | 86.9 | 73.9 |
66 | XII | 93.5 | 47.2 |
67 | XIII | 69.5 | 86.4 |
68 | XIV | 81.3 | 68.1 |
69 | XV | 92.4 | 81.5 |
70 | XVI | 40.5 | 76.4 |
71 | XVII | 76.9 | 73.8 |
72 | XVIII | 63.1 | 91.8 |
73 | XVIV | 40.3 | 56.4 |
74 | XX | 83.6 | 49.8 |
3-羟基丙酸酯和氢气的催化反应步骤如下:
含铜的混金属硅氧化合物催化剂的制备:称取一定量的Cu(NO3)2·3H2O和M'(NO3)m·nH2O,溶解于一定量的蒸馏水中,在搅拌下加入一定量的硅溶胶溶液,搅拌使之均一,然后加热至60~95℃,加入一定量的Na2CO3溶液,使得金属离子与硅溶胶最大限度地形成沉淀物,并老化4~8h;过滤收集沉淀物,用去离子水充分洗涤,确保洗涤液中不再含有Na+以及其它金属离子,将沉淀物置于120℃下烘干24h,然后在350~600℃下焙烧4~10h,得到含铜的混金属硅氧化合物催化剂。依据投入的金属离子量以及洗涤掉的金属离子量进行测算,得到结构式分别为Zn0.1Cu2.1SiO3.3、Mn0.15Cu1.8SiO3.5、La0.3Cu2.2SiO3.6、Zn0.1Mn0.1Cu1.7SiO3.4、Zn0.1La0.2Cu2.4SiO3.5、Mn0.15La0.2Cu2.2SiO3.6的催化剂。
含铜的混金属硅氧化合物催化剂的还原活化:将催化剂造粒成40~70目大小。称取一定量的催化剂,装填于反应管中间,反应管前后两端空间装填惰性石英砂或瓷圈,装填的密度以保证气路以及液相路在反应过程中设定压力下通顺,且气密性良好,气相路以及液相路流速相对均衡。通入H2(5%vol)/N2混合还原气,将温度从室温在设定时间30min内升到50℃;然后在400min内升到300℃,在此温度下通还原气550min;继续通还原气,在60min内降至设定温度。
3-羟基丙酸酯和氢气的催化反应:在上述设定温度下,将H2(5%vol)/N2混合还原气切换为H2气,气体流量设定为30~48mL/min,反应管压力设定为40~68atm,用计量泵压入含3-羟基丙酸酯和有机溶剂组成的溶液,3-羟基丙酸酯和有机溶剂的体积比设定为1:10,溶液流量设定为0.02~0.10mL/min。每隔一段时间取样分析,待催化剂的活性稳定后,按固定的时间取样分析,结果记录于表中。
实施例75~111
取用催化剂Mn0.15Cu1.8SiO3.5作为催化剂2。为对该催化剂2的反应性能有充分的理解,在实施例中,选择3-羟基丙酸甲酯(3-HMP)为反应物,在保持溶剂己烷、压力60atm、H2流速34mL/min、3-HMP流速0.06mL/min下,进行温度变化分别为140、145、150、155、160、165、170、180、190、200℃的反应,结果记录于表5实施例75~84;在保持溶剂己烷、温度160℃、H2流速34mL/min、3-HMP流速0.06mL/min下,进行压力变化分别为40、45、50、55、58、62、64、66、68atm的反应,结果记录于表5实施例85~93;在保持溶剂己烷、温度160℃、压力60atm、3-HMP流速0.06mL/min下,进行H2流速变化分别为30、32、36、38、42、45、48mL/min的反应,结果记录于表5实施例94~100;在保持溶剂己烷、温度160℃、压力60atm、H2流速34mL/min下,进行3-HMP流速变化分别为0.02、0.03、0.04、0.05、0.08、0.10mL/min的反应,结果记录于表5实施例101~106;在保持压力60atm、温度160℃、H2流速34mL/min、3-HMP流速0.06mL/min下,进行溶剂变化分别为戊烷、苯、甲苯、甲醇、四氢呋喃的反应,结果记录于表5实施例107~111。
表5
实施例112~118
本部分实施例考察催化剂Mn0.15Cu1.8SiO3.5对不同3-羟基丙酸酯的加氢催化反应性能。在此情况下,使用溶剂己烷,保持温度160℃、压力60atm、H2流速34mL/min和3-羟基丙酸酯流速0.06mL/min下进行反应,结果记录于表6实施例112~118。
表6
实施例 | 3-羟基丙酸酯 | 3-羟基丙酸酯转化率/% | 1,3-PDO选择性/% |
112 | 3-羟基丙酸乙酯 | 80.6 | 76.9 |
113 | 3-羟基丙酸正丙酯 | 75.9 | 83.1 |
114 | 3-羟基丙酸异丙酯 | 62.9 | 66.8 |
115 | 3-羟基丙酸正丁酯 | 76.4 | 70.1 |
116 | 3-羟基丙酸异丁酯 | 43.2 | 58.2 |
117 | 3-羟基丙酸叔丁酯 | 30.1 | 46.2 |
118 | 3-羟基丙酸正戊酯 | 56.2 | 43.1 |
实施例119~123
本部分实施例考察不同催化剂Zn0.1Cu2.1SiO3.3、La0.3Cu2.2SiO3.6、Zn0.1Mn0.1Cu1.7SiO3.4、Zn0.1La0.2Cu2.4SiO3.5、Mn0.15La0.2Cu2.2SiO3.6对3-羟基丙酸甲酯的催化反应性能。在此情况下,使用溶剂己烷,保持温度160℃、压力60atm、H2流速34mL/min和3-羟基丙酸甲酯流速0.06mL/min下进行反应,结果记录于表7实施例119~123。
表7
实施例1~74表明环氧乙烷、一氧化碳和醇催化反应可以制备3-羟基丙酸酯,实施例75~123表明3-羟基丙酸酯和氢气催化反应可以制备1,3-丙二醇。进一步地,在第一步催化反应中,3-羟基丙酸酯产物需要从体系中分离出来,再进行加氢催化反应时可以有效地制备1,3-丙二醇,没有分离的产物体系在进行催化加氢反应时,生成1,3-丙二醇产物的效果很低或几乎没有效果。特别地,本发明的环氧乙烷、一氧化碳和醇的催化反应不能一步生成1,3-丙二醇,上述结果说明,上述的两步反应需要使用不同的催化剂体系。
表6中实施例的结果说明系列3-羟基丙酸酯加氢反应生成产物1,3-丙二醇和副产物醇,表2中的实施例结果说明这些副产物醇可以用于与环氧乙烷和一氧化碳的反应生成相应的3-羟基丙酸酯。
Claims (7)
1.环氧乙烷耦合合成气制备1,3-丙二醇的方法,其特征在于合成路线如下:
催化剂1为金属配体络合物,催化剂2为含铜的混金属硅氧化物;所述金属配体络合物为N,O-配体配位的金属络合物,N,O-配体配位的金属络合物的结构如下:
金属M选自镍、钴、钌、铑、钯、铂、锇、铱、铁、铜、铬中的一种;N,O配体是以N和O为配位原子的有机基团,N和O分别与中心金属M有σ-键作用;B是连接两个N,O配体的桥联有机基团,并与氮原子键联;X是指羰基基团,n是指X的数目,n的选择满足N,O配体和M配位后保持M中心合理的氧化态和配位数;
所述含铜的混金属硅氧化物的结构式为M'uCuvSiyOz,u、v、y、z值的选择以保持整个通式分子的总的零氧化态值为准则,其中M'选自锌、锰、钡、镧系金属、钴、银、金、镍、钾中的至少一种;
所述助剂选自主族金属烷氧基化合物、主族金属羧基化合物、主族金属胺基化合物、路易斯碱性的含氮化合物的至少一种。
2.如权利要求1所述的环氧乙烷耦合合成气制备1,3-丙二醇的方法,其特征在于:合成路线中环氧乙烷、一氧化碳和醇类分子的开环-羰化-酯化的催化反应制备3-羟基丙酸酯包括如下步骤:
1)将环氧乙烷、一氧化碳和醇类分子在有机溶剂、催化剂1和助剂下进行反应,所述有机溶剂选自醇、醚、饱和烷烃、饱和芳烃的至少一种;
2)将步骤1)反应后的产物体系进行相分离,形成水相、有机相和沉淀物相,并使产物3-羟基丙酸酯留在有机相中;
3)收集步骤2)中有机相,分离出产物3-羟基丙酸酯和有机溶剂,产物3-羟基丙酸酯用于下一步反应;或无需分离3-羟基丙酸酯和有机溶剂,直接用于下一步反应。
3.如权利要求2所述的环氧乙烷耦合合成气制备1,3-丙二醇的方法,其特征在于步骤1)中,反应温度为30~190 ℃,反应压力为1~150 atm,反应时间为0.1~200 h。
4.如权利要求2所述的环氧乙烷耦合合成气制备1,3-丙二醇的方法,其特征在于:所述醇类分子选自甲醇、乙醇、丙醇、丁醇、戊醇的至少一种。
5.如权利要求2所述的环氧乙烷耦合合成气制备1,3-丙二醇的方法,其特征在于:合成路线中3-羟基丙酸酯的加氢催化反应制备1,3-丙二醇包括如下步骤:
4) 将步骤3)中分离出来的3-羟基丙酸酯或含3-羟基丙酸酯的有机相在氢气、有机溶剂和催化剂2下反应,有机溶剂选自醇、醚、饱和烷烃、饱和芳烃;
5) 将反应后的产物体系进行分离,收集1,3-丙二醇、醇类副产物和有机溶剂;醇类副产物投入到1)中循环使用。
6.如权利要求5所述的环氧乙烷耦合合成气制备1,3-丙二醇的方法,其特征在于步骤4)中,反应温度为80~400 ℃,反应压力为20~150 atm,反应时间为0.1~200 h。
7.如权利要求2所述的环氧乙烷耦合合成气制备1,3-丙二醇的方法,其特征在于:步骤2)中将反应后的产物体系进行相分离的方法如下:加入蒸馏水产生水相,加入有机溶剂形成有机相,加入沉淀剂形成沉淀相;其中,有机溶剂选自醇、醚、饱和烷烃、饱和芳烃、酯、C5以上的长链烯烃、C4以上的长链炔烃中的至少一种,沉淀剂选自布朗斯特酸、布朗斯特碱、路易斯酸、路易斯碱、硅胶、分子筛、氧化铝、高岭土、水滑石、离子交换树脂中的至少一种,相分离的方法选自萃取、静置、离心机分离、过滤、蒸馏、过柱或减压抽提。
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