CN102671703A - Metal complex catalyzer and application thereof for synthesizing cyclic carbonate - Google Patents
Metal complex catalyzer and application thereof for synthesizing cyclic carbonate Download PDFInfo
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 37
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 93
- -1 halide salt Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910000595 mu-metal Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002671 adjuvant Substances 0.000 abstract 2
- 230000002195 synergetic effect Effects 0.000 abstract 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000002924 oxiranes Chemical class 0.000 description 23
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the field of chemicals and discloses a metal complex catalyzer and application thereof for synthesizing cyclic carbonate. The catalyzer is one of metal complexes of zinc element, copper element, cadmium element, aluminum element, tin element, iron element, cobalt element or nickel element and can also be composited with metal salt synergistic adjuvant to prepare a composite catalyzer, and CO2 (carbon dioxide) and epoxy compound are utilized to prepare the cyclic carbonate by cycloaddition. The metal complex catalyzer for synthesizing the cyclic carbonate is simple to prepare, high in catalytic activity, low in cost, easy to separate, good in stability and reusability, can form a homogeneous catalyzer system, and has a good industrial application prospect. Besides, the metal salt synergistic adjuvant is easy to obtain.
Description
Technical field
The invention belongs to chemical field, relate to a kind of metal complex catalysts and application thereof that is used for synthesizing annular carbonate.Specifically relate to a kind of CO
2Zinc (copper, cadmium, aluminium, tin, iron, cobalt or nickel) metal complex catalysts and complex major catalyst and potassium (lithium or the sodium) slaine for preparing ethylene carbonate, propene carbonate and butylene with the epoxyalkane addition reaction coordinated composite catalyst that auxiliary agent forms and their application.
Background technology
Along with the aggravation of the whole world " greenhouse effects " and energy crisis, use CO
2, cheapness not only abundant but also can reduce CO as the C1 initiation material of some chemicals
2Discharge, reduce harm to environment.Because CO
2Character utmost point torpescence, at fixation of C O
2Reaction in the middle of the most successful, most typical one be to utilize CO
2With the reaction of epoxide through the cycloaddition synthesizing annular carbonate.The general formula of cyclic carbonate can be expressed as:
is because of its unique oxygen heterocycle five rings structure and physicochemical property; Being widely used in fields such as agricultural chemicals, medicine, resin, dyestuff, coating, electronic chemical product, food additives and solvent, is a kind of important fine chemicals intermediate and the organic solvent of function admirable.
CO
2The composition principle for preparing cyclic carbonate with the epoxide cycloaddition reaction is expressed with following reaction equation (1).
This technology is as far back as the sixties in 20th century; At first realized industrial applications by U.S. Jefferson company and German Huls company; At present; U.S. Union Carbide company, Huntsman company, DOW company etc., German Baye company, Basf company, Texaco company etc., Japanese Mitubishi company, Nippon Shokubai company, Asahi company etc.; China Hebei Chaoyang group, Tongling, Anhui Jin Tai company, Shandong stone are won all construction scale chemical industry process units such as magnificent company etc. and Romania, Korea, Korea S completely, year a total productive capacity reach more than 500,000 tons; And, along with CO
2The needs that reduce discharging and the continuous expansion of cyclic carbonate application, its production can significantly be increased.
CO
2It is the highest oxidation state of carbon; The molecule quite stable; Be difficult to be activated; Even also need under uniform temperature, certain pressure and catalyst condition, just can carry out with the epoxide addition reaction that reactivity is higher, the cycloaddition reaction catalyst mainly contains [Darensbourg D J, et al.Coordination Chemistry Reviews such as quaternary ammonium salt, quaternary alkylphosphonium salt, alkali metal salt, alkali salt, transient metal complex, ionic liquid, metal oxide and functional resin; 1996, (153): 155-174; Shaikh A A G, et al.Chemical Review, 1996,96 (3): 951-976; Gao Zhiwen etc., catalysis journal, 1008,29 (9): 831-838).It is the quaternary ammonium salt catalyst of representative that early stage suitability for industrialized production adopts tetraethylammonium bromide; In temperature is that 150～200 ℃, pressure are under 5.0～8.0MPa condition about cycloaddition reaction 60min; The yield of epoxide is 98% [Austin M L, et al.US2773070,1956; Taylor G A, et al.GB2011401,1985; Wagner P, et al.US5350862,1994. Wang Zhanpings, synthetic fiber industry, 1996,19 (6), 52-53], unit mole transformation frequency (TOF) is about 1000h
-1, but such catalyst high temperature decomposes long-term other poly material of meeting generation [Yin Fangxi, Anhui chemical industry, 2003, (4): 25-26 of using easily; Liu Qingli, Henan chemical industry, 2005,22:26-27].In view of this, suitability for industrialized production cyclic carbonate ester catalyst replaces (Inaba M, et al.JP9067365,1997), wherein Liaoyang petro-chemical fiber research institute [Tang Zhanzhong, Liaoning chemical industry, 1995, (2): 6-7 by the KI system gradually; Industrial Catalysis, 1996, (3): 23-26; Chemical research and application; 1997,9 (4): 366-369] the KI/PEG400 composite catalyst of exploitation has obtained applying in the cyclic carbonate production at home, is that 120～140 ℃, pressure are under 2.5～3.0MPa condition about cycloaddition reaction 60min in temperature; The yield of epoxide is 99% [Tang Zhanzhong; Liaoning chemical industry, 1995, (5): 46-48; Petrochemical industry, 1996,25 (6): 409-413], TOF is about 700h
-1Actual industrial production temperature is that 150～190 ℃, pressure are under 4.0～5.0MPa condition about cycloaddition reaction 30min; The KI/PEG400 System Catalyst is because the participation of PEG400; Make metal ion separate increase with the positive negative electricity of halogen ion and cause I-ion necleophilic reaction ability to strengthen, under lower pressure, just can direct esterification react, improve the purpose product selectivity and obtained satisfactory result [Rokichi A with the aspect that reduces cost; Et al.Monatsch.Chem.1984,115:205-211; Cheng Ling etc., Speciality Petrochemicals progress, 9 (12): 44-52], but the PEG400 that exists just is easy and epoxide generation side reaction causes high polymer to produce, and must regularly replace [Zhou Xi etc., chemical journal, 2010,68 (9): 870-874 after long-time the use; Huang Huansheng etc., chemical industry technology and exploitation, 2007,36 (11): 15-19].Therefore, Chinese scholars is carrying out making great efforts untiringly for the research of this type of cycloaddition reaction catalyst always.
In recent years, Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences [Deng You congruence, CN1343668A (2002), CN1789258A (2006); Xia Chungu etc.; CN1566110A (2005); CN1566111A (2005), CN1631886A (2005), CN101037431A (2007)] and [Zhang Suojiang etc. of Chinese Academy Of Sciences Process Engineering Research Institute; CN1817877A (2006), CN102010397A (2010)] etc. research work have certain representativeness.
Wherein, Chinese patent CN1343668A discloses a kind of use nitrogen heterocyclic ring ionic liquid and halide or TBAB catalyst system, is that 100～140 ℃, pressure are that 1.5～4.5MPa, time are under the temperate condition of 4～8h in temperature, realizes CO
2Prepare cyclic carbonate with the epoxide cycloaddition reaction.
Chinese patent CN1631886A discloses a kind of use zinc salt and imidazoles (pyridine) halogeno salt ionic liquid and quaternary ammonium salt catalyst system, is that 50～200 ℃, pressure are under 0.5～5.0MPa condition in temperature, realizes CO
2Prepare cyclic carbonate with the epoxide cycloaddition reaction, reach 5000h in the TOF of zinc ion
-1
Chinese patent CN101037451A discloses a kind of use slaine and ionic liquid and quaternary ammonium salt catalyst system, is that 30～200 ℃, pressure are that 0.5～10.0MPa, time are under 0.5～6h condition in temperature, realizes CO
2Prepare cyclic carbonate with the epoxide cycloaddition reaction, reach 5727h in the TOF of zinc ion
-1
Chinese patent CN101474576A discloses a kind of use band phenyl ring Zn complex and quaternary ammonium salt catalyst system, is that 30～80 ℃, pressure are that 2～12MPa, time are under 1～24h condition in temperature, realizes CO
2Prepare cyclic carbonate with the epoxide cycloaddition reaction.
This shows that slaine and ionic liquid and quaternary ammonium salt catalyst are combined to integrally formed composite catalyst to CO
2Have tangible high activity with the epoxide cycloaddition reaction, but these catalyst systems in various degree theory of Application of ion liquid all, and ion liquid preparation complicated, cost an arm and a leg and problem such as corrosivity needs further demonstration and inquires into.
The obvious advantage amount of being to use of homogeneous catalyst is few and catalytic activity is high, and shortcoming is later separation and reuses difficulty.Chinese patent CN1789258A discloses a kind of use NaOH, NaCO
3Strong basic ion exchange resin Deng modifying supports gold, and the Chinese patent CN1568851A disclosed chitosan loaded zinc bromide of disclosed activated carbon supported tetraethylammonium bromide, CN1796384A and the disclosed resin-carried solid catalysts such as ionic liquid of CN101239965A are being realized CO
2All obtained certain effect with the epoxide cycloaddition reaction is active with the catalyst separation aspect of performance, but the life-span of heterogeneous catalysis remain further research, leaving industrial applications still has a segment distance.
In sum, with regard to CO
2Prepare the cyclic carbonate reaction with the epoxide cycloaddition reaction, to the quaternary salt of present industrial applications and the problem of KI system existence, select a suitable homogeneous catalyst extremely important, such catalyst need satisfy following condition.
(1) in lower temperature and pressure, short time, obtains comparatively ideal yield and selectivity.
(2) catalyst has the long life-span, and the side reaction high polymer generates few.
(3) impurity abilities such as catalyst adaptation water, alcohol are strong.
(4) be easy to separate, be convenient to reclaim.
(5) preparation is easy, moderate cost.
But, also do not meet the catalyst of these conditions in the market.
Summary of the invention
The objective of the invention is above-mentioned technical problem, a kind of composition catalyst for preparing simple, efficient, low-cost, easily separated and good stability is provided to the existence of existing industrializeding catalyst technology.
Another object of the present invention provides this catalyst at CO
2Cycloaddition prepares the application in the cyclic carbonate with epoxide.
The present invention is studying zinc (copper) salt and quaternary ammonium salt quaternary alkylphosphonium salt in great detail in early stage) [Liu Xiaoqin etc., CN100388978C (2008) on the composition catalyst basis for preparing of part complex reaction; CN101856625A (2010)], deeply inquire into CO
2Cycloaddition prepares the reaction mechanism of cyclic carbonate with epoxide, with zinc (copper, cadmium, aluminium, tin, iron, cobalt or nickel etc.) quaternary ammonium salt! quaternary alkylphosphonium salt) and catalyst applications such as metal ligand thing is in CO
2With the epoxide cycloaddition reaction, simultaneously to CO
2, impurity effect such as the water unavoidably brought into of epoxide and recycling catalyst raw material and alcohol; Introducing has the theories such as slaine auxiliary agent of functions such as coordination and conditioned reaction acid-base value concurrently; Propose a kind of composition catalyst for preparing simple, efficient, low-cost, easily separated and good stability, thereby accomplish the invention that is used for cycloaddition reaction synthesizing annular carbonate technology.
The objective of the invention is to realize through following technical proposal:
A kind of metal complex catalysts of synthesizing annular carbonate, this catalyst is made up of a kind of of metal complex of following column element: zinc, copper, cadmium, aluminium, tin, iron, cobalt or nickel.
Described catalyst, wherein metal complex is formed through complex reaction by a kind of and a kind of halogen-containing quaternary ammonium salt of the halide salt of zinc, copper, cadmium, aluminium, tin, iron, cobalt or nickel or halogen-containing quaternary alkylphosphonium salt, and its reaction equation is as shown in the formula shown in (2).
MX
n+R
4LX→[R
4L]
m[M
aX
b] (2)
In the formula, the M-metal; The X-halogen; The R-alkyl or phenyl; L-N, P, n, m, a, b-chemical valence balance numeral, n=1～3, m=1～3, a=1～2, b=1～6.With halide salt and quaternary ammonium halides salt is example, metal complex general structure [Duhlev R, et al..Acta.Cryst.1988,44:1696-1698; Scott B, et al.J.Am.Chem.Soc.1991,113 (14): 5253-5258; Wu B, et al.Z.Anorg.Allg.Chem.2006,632:684-688] can be described as respectively: [R
4N]
2MX
4[R
4N]
2M
2X
6
The preparation method of metal complex catalysts proposed by the invention adopts the solvent heating means of common direct addition reaction, and concrete preparation method can be with reference to Chinese patent CN100388978C and CN101856625A.
Described catalyst, wherein halogen-containing quaternary ammonium salt are tetramethyl ammonium halide, tetraethyl ammonium halide, tetrapropyl ammonium halide, tetrabutyl ammonium halide or cetyl trimethyl ammonium halide; Halogen-containing quaternary alkylphosphonium salt is the tetraethyl phosphonium halide, methyl tripropyl phosphonium halide, methyl tributyl phosphonium halide, methyl triphenyl phosphonium halide, ethyl triphenyl phosphonium halide, tetraphenyl ammonium halide or tetraphenyl phosphonium halide.
A kind of composite catalyst of metal-containing complex of synthesizing annular carbonate; This composite catalyst is made up of the collaborative auxiliary agent of above-mentioned metal complex catalysts (being a kind of complex of above-mentioned zinc, copper, cadmium, aluminium, tin, iron, cobalt or nickel) and slaine; Wherein, The mass fraction of metal complex catalysts is 90%～99.9%, and the mass fraction of the collaborative auxiliary agent of slaine is 0.1～10%; The mass fraction of preferable alloy composition catalyst is 95%～99.8%, and the mass fraction of the collaborative auxiliary agent of slaine is 0.2%～5%.
Described composite catalyst, wherein the collaborative auxiliary agent of slaine is one or more in the halide, carbonate, phosphate, silicate, sulfate, nitrate, acetate of lithium, potassium or sodium element.
Above-mentioned catalyst (being a kind of complex of above-mentioned zinc, copper, cadmium, aluminium, tin, iron, cobalt or nickel) is at CO
2Cycloaddition prepares the application in the cyclic carbonate with epoxide.
Described application, its detailed directions is:
Ratio in epoxide 20～55mL adding metal complex catalysts 0.01～0.2g is dissolved in metal complex catalysts in the raw material epoxide, adds agitated reactor sealing back and stirs, and it is fully mixed, and feeds CO then
2It is 0.5～5.0MPa that gas is kept reaction pressure, is preferably 2.5～3.5MPa, when being heated to 40～160 ℃, is preferably 80～140 ℃, under agitation reacts 0.2～1.5h, is preferably 0.5～1h, the CO of continuous supplement consumed in the course of reaction
2The agitated reactor product adopts rectification under vacuum to obtain the cyclic carbonate product.Agitated reactor product and rectifying product adopt gas chromatographic analysis, and rectification under vacuum still bottom product contains the recovery catalyst, directly is used for catalytic reaction next time.
Said composite catalyst (a kind of complex and the collaborative auxiliary agent of slaine that are above-mentioned zinc, copper, cadmium, aluminium, tin, iron, cobalt or nickel are formed) is at CO
2Cycloaddition prepares the application in the cyclic carbonate with epoxide.
Described application, its detailed directions is:
Ratio in epoxide 20～55mL adding composite catalyst 0.01～0.2g is dissolved in composite catalyst in the raw material epoxide, adds agitated reactor sealing back and stirs, and it is fully mixed, and feeds CO then
2It is 0.5～5.0MPa that gas is kept reaction pressure, is preferably 2.5～3.5MPa, when being heated to 40～160 ℃, is preferably 80～140 ℃, under agitation reacts 0.2～1.5h, is preferably 0.5～1h, the CO of continuous supplement consumed in the course of reaction
2The agitated reactor product adopts rectification under vacuum to obtain the cyclic carbonate product.Agitated reactor product and rectifying product adopt gas chromatographic analysis, and rectification under vacuum still bottom product contains the recovery catalyst, directly is used for catalytic reaction next time.
Beneficial effect of the present invention:
Metal complex catalysts preparation technology provided by the invention is simple, and the collaborative auxiliary agent of slaine is cheap and easy to get, the active height of catalyst and composite catalyst, and catalyst structure is formed stable.With oxirane is example, and the conversion ratio of oxirane is 90%～99.9%, and the selectivity of ethylene carbonate is 85%～99.9%; TOF in metal complex is the highest near 15000h
-1Simultaneously, this catalyst and composite catalyst can be dissolved in the product solvent and form homogeneous catalyst system, can liquid phase circulate, and this catalyst and composite catalyst are carried convenient, and simple to operate, serviceability is good repeatedly, has prospects for commercial application.
The specific embodiment
By the following examples the present invention is further elaborated, but the present invention is not limited to following examples.
Embodiment 1
Take by weighing 22.52gZnBr
2Be dissolved in respectively in the absolute ethyl alcohol of 100ml and 50ml with the 42.03g tetraethylammonium bromide, then both Hybrid Heating boiled to 50 ℃, and keep about 30min, be cooled to room temperature, filter, 60 ℃ of dryings under vacuum state promptly get 59.56g white powder [(C
2H
5)
4N]
2ZnBr
4Catalyst.
Embodiment 2
In autoclave, add Zn complex [(C
2H
5)
4N]
2ZnBr
4Catalyst 0.17mmol; The sealing back feeds CO
2Displaced air 2-3 time, metering is pressed into oxirane 0.5mol, adds CO
2Boost to 2.5MPa; Be warming up to 90 ℃ of reaction 40min, when pressure is lower than 3MPa, replenish CO
2To 3MPa, remain unchanged until the still pressure; Cooling, take out still liquid and adopt rectification under vacuum to obtain the ethylene carbonate product, weighing is also used gas chromatographic analysis, and the yield 99.5% of ethylene carbonate is 4390h in the TOF of metal complex
-1
Embodiment 3
In autoclave, be metered into Zn complex [(C
2H
5)
4N]
2ZnBr
4Catalyst 0.22mmol and expoxy propane 0.5mol; The sealing back feeds CO
2Displaced air 2-3 time boosts to 2.5MPa; Be warming up to 90 ℃ of reaction 40min, when pressure is lower than 3MPa, replenish CO
2To 3MPa, remain unchanged until the still pressure; Cooling, taking-up still liquid adopt rectification under vacuum to obtain the propene carbonate product, and weighing is also used gas chromatographic analysis.The yield 99.2% of propene carbonate is 3382h in the TOF of metal complex
-1
Embodiment 4
Be metered into Zn complex [(C
2H
5)
4N]
2ZnBr
4Catalyst 0.28mmol and 1,2-epoxy butane 0.5mol; Other is with embodiment 3, and the yield 99.0% of butylene is 2652h in the TOF of metal complex
-1
Embodiment 5
Under embodiment 2 conditions, catalyst changes complex [(C into
2H
5)
4N]
2ZnI
4Catalyst 0.08mmol, the yield 99.2% of ethylene carbonate is 9300h in the TOF of metal complex
-1
Embodiment 6
Under embodiment 2 conditions, catalyst changes complex [(C into
6H
5)
4P]
2ZnI
4Catalyst 0.05mmol, the yield 99.5% of ethylene carbonate is 14925h in the TOF of metal complex
-1
Embodiment 7
Under embodiment 2 conditions, add entry 0.25mol in the autoclave, catalyst changes Zn complex [(C into
6H
5)
4P]
2ZnI
40.05mmol and 0.003mmolK
3PO
4, the yield 19.4% of ethylene glycol, the yield 80.6% of ethylene carbonate is 12090h in the TOF of metal complex
-1
Embodiment 8
Under embodiment 2 associative operation conditions, catalyst changes copper complex [(C into
3H
7)
4N]
2Cu
2Br
60.06mmol reaction temperature is 120 ℃, the reaction time is 30min, and the yield 88.6% of ethylene carbonate is 14766h in the TOF of metal complex
-1
Embodiment 9
Under embodiment 2 associative operation conditions, catalyst changes aluminum complex [(C into
3H
7)
4N]
2Al
2Cl
60.1mmol reaction temperature is 120 ℃, the reaction time is 30min, and the yield 76.5% of ethylene carbonate is 7650h in the TOF of metal complex
-1
Embodiment 10
Under embodiment 2 associative operation conditions, catalyst changes nickel complex [(C into
2H
5)
4N]
2NiCl
40.2mmol reaction temperature is 120 ℃, the reaction time is 30min, and the yield 80.2% of ethylene carbonate is 4010h in the TOF of metal complex
-1
Embodiment 11
Under embodiment 3 associative operation conditions, catalyst changes complex [(C into
6H
5)
4P]
2ZnBr
40.08mmol and 0.006mmolK
2CO
3, reaction temperature is 120 ℃, the reaction time is 30min, uses the yield 99.1% of propene carbonate first, is 12388h in the TOF of metal complex
-1On this basis, the propene carbonate product is isolated in decompression distillation, reclaim catalyst circulation and use 10 times, in the TOF of metal complex all greater than 12000h
-1More than; And, do not find that accessory substances such as multiethylene-glycol and Merlon generate through chromatography.
Comparing embodiment 12
Under embodiment 3 conditions, catalyst is (C
2H
5)
4NBr 0.7mmol does not find the generation of propene carbonate, is 0h in the TOF of catalyst
-1
Comparing embodiment 13
Under embodiment 3 associative operation conditions, catalyst is (C
2H
5)
4NBr 0.4mmol, answering temperature is 120 ℃, and the reaction time is 30min, and the yield 13.8% of propene carbonate is 345h in the TOF of metal complex
-1
Comparing embodiment 14
Under embodiment 3 associative operation conditions, catalyst is 0.8mmol KI, 2.9mmol PEG400, and 0.003mmol K
2CO
3, answering temperature is 120 ℃, and the reaction time is 30min, and the yield 60.6% of propene carbonate is 758h in the TOF of KI
-1, the TOF that adds up to KI/PEG is 164h
-1
Claims (11)
1. the metal complex catalysts of a synthesizing annular carbonate is characterized in that this catalyst is made up of a kind of of metal complex of column element down: zinc, copper, cadmium, aluminium, tin, iron, cobalt or nickel.
2. catalyst according to claim 1; It is characterized in that metal complex is formed through complex reaction by a kind of and a kind of halogen-containing quaternary ammonium salt of the halide salt of zinc, copper, cadmium, aluminium, tin, iron, cobalt or nickel or halogen-containing quaternary alkylphosphonium salt, its reaction equation is as shown in the formula shown in (2):
MX
n+R
4LX→[R
4L]
m[M
aX
b] (2)
In the formula, the M-metal; The X-halogen; The R-alkyl or phenyl; L-N, P, n, m, a, b-chemical valence balance numeral, n=1～3, m=1～3, a=1～2, b=1～6.
3. catalyst according to claim 2 is characterized in that halogen-containing quaternary ammonium salt is tetramethyl ammonium halide, tetraethyl ammonium halide, tetrapropyl ammonium halide, tetrabutyl ammonium halide or cetyl trimethyl ammonium halide; Halogen-containing quaternary alkylphosphonium salt is tetraethyl phosphonium halide, methyl tripropyl phosphonium halide, methyl tributyl phosphonium halide, methyl triphenyl phosphonium halide, ethyl triphenyl phosphonium halide, tetraphenyl ammonium halide or tetraphenyl phosphonium halide.
4. the composite catalyst of the metal-containing complex of a synthesizing annular carbonate; It is characterized in that this composite catalyst is made up of the collaborative auxiliary agent of the described metal complex catalysts of claim 1 and slaine; Wherein, The mass fraction of metal complex catalysts is 90%～99.9%, and the mass fraction of the collaborative auxiliary agent of slaine is 0.1～10%; The mass fraction of preferable alloy composition catalyst is 95%～99.8%, and the mass fraction of the collaborative auxiliary agent of slaine is 0.2%～5%.
5. composite catalyst according to claim 4 is characterized in that the collaborative auxiliary agent of slaine is one or more in the halide, carbonate, phosphate, silicate, sulfate, nitrate, acetate of lithium, potassium or sodium element.
6. the described catalyst of claim 1 is at CO
2Cycloaddition prepares the application in the cyclic carbonate with epoxide.
7. application according to claim 6 is characterized in that detailed directions is:
Ratio in epoxide 20～55mL adding metal complex catalysts 0.01～02g is dissolved in metal complex catalysts in the raw material epoxide, adds agitated reactor sealing back and stirs, and it is fully mixed, and feeds CO then
2It is 0.5～5.0MPa that gas is kept reaction pressure, is preferably 2.5～3.5MPa, when being heated to 40～160 ℃, is preferably 80～140 ℃, under agitation reacts 0.2～1.5h, is preferably 0.5～1h, the CO of continuous supplement consumed in the course of reaction
2The agitated reactor product adopts rectification under vacuum to obtain the cyclic carbonate product.
8. application according to claim 7 is characterized in that rectification under vacuum still bottom product contains the recovery catalyst, directly is used for catalytic reaction next time.
9. the described composite catalyst of claim 4 is at CO
2Cycloaddition prepares the application in the cyclic carbonate with epoxide.
10. application according to claim 9 is characterized in that detailed directions is:
Ratio in epoxide 20～55mL adding composite catalyst 0.01～0.2g is dissolved in composite catalyst in the raw material epoxide, adds agitated reactor sealing back and stirs, and it is fully mixed, and feeds CO then
2It is 0.5～5.0MPa that gas is kept reaction pressure, is preferably 2.5～3.5MPa, when being heated to 40～160 ℃, is preferably 80～140 ℃, under agitation reacts 0.2～1.5h, is preferably 0.5～1h, the CO of continuous supplement consumed in the course of reaction
2The agitated reactor product adopts rectification under vacuum to obtain the cyclic carbonate product.
11. application according to claim 10 is characterized in that rectification under vacuum still bottom product contains the recovery catalyst, directly is used for catalytic reaction next time.
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| TWI601571B (en) * | 2016-12-07 | 2017-10-11 | 財團法人工業技術研究院 | Catalyst and method for synthesizing cyclic carbonate by the same |
| CN107626308A (en) * | 2017-08-30 | 2018-01-26 | 江南大学 | One kind is used for CO2The hydrotalcite carried with doped Au catalyst and preparation method of cycloaddition reaction and bisphenol synthesis F |
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| CN107715912A (en) * | 2016-08-10 | 2018-02-23 | 江苏苏博特新材料股份有限公司 | The method and reaction unit of its synthesizing cyclic carbonate ester of a kind of heterogeneous catalysis and application |
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| CN107626308B (en) * | 2017-08-30 | 2020-08-04 | 江南大学 | For CO2Hydrotalcite loaded gold-doped catalyst for cycloaddition reaction and bisphenol F synthesis and preparation method thereof |
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| CN109382128B (en) * | 2018-10-29 | 2022-04-01 | 兰州大学 | Method and catalyst for catalytic synthesis of cyclic carbonate |
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