CN107827862A - A kind of method that nickel-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate - Google Patents
A kind of method that nickel-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate Download PDFInfo
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- CN107827862A CN107827862A CN201711275386.7A CN201711275386A CN107827862A CN 107827862 A CN107827862 A CN 107827862A CN 201711275386 A CN201711275386 A CN 201711275386A CN 107827862 A CN107827862 A CN 107827862A
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- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 54
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 52
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 239000000126 substance Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 30
- RNGSTWPRDROEIW-UHFFFAOYSA-N [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RNGSTWPRDROEIW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 239000003426 co-catalyst Substances 0.000 claims abstract description 18
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 4
- 230000021615 conjugation Effects 0.000 claims description 23
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- HDVPIMZXLWNIIP-UHFFFAOYSA-N nickel 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Ni].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 HDVPIMZXLWNIIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002924 oxiranes Chemical class 0.000 claims 4
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims 1
- YNZSKFFENDBGOV-UHFFFAOYSA-N [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [V].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YNZSKFFENDBGOV-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 150000002118 epoxides Chemical class 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- -1 cyclic carbonate ester Chemical class 0.000 abstract 1
- 229960004424 carbon dioxide Drugs 0.000 description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 238000000926 separation method Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- 238000000746 purification Methods 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 241000790917 Dioxys <bee> Species 0.000 description 5
- 229910002090 carbon oxide Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000005677 organic carbonates Chemical class 0.000 description 3
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical class CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical class C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- 235000013844 butane Nutrition 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical class C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/18—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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- 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
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- 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
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Abstract
The invention discloses a kind of method that nickel-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate, raw material is used as by the use of carbon dioxide and epoxides, to be conjugated nickel-porphyrin capillary copolymer material as heterogeneous catalyst, tetra-n-butyl ammonium bromide is co-catalyst, in the case where normal temperature and pressure is solvent-free, efficient green catalytically synthesizing cyclic carbonate ester is realized.The major advantage of this method is that method for preparing catalyst is simple, and cost is low, and catalytic activity is high, and structural behaviour is stable, easily recovery, repeats and utilizes；Reaction condition is gentle, speed is fast and safe operation, suitable for large-scale industrial production.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of nickel-base catalyst chemical recycling of carbon dioxide prepares ring-type
The method of carbonic ester.
Background technology
With the progress of the development human civilization of society, especially industrial great development with rapid changepl. never-ending changes and improvements, for fossil energy
The consumption requirements in source increasingly increase.With a large amount of uses of fossil fuel, the concentration of carbon dioxide quickly raises, and turns into a kind of master
Greenhouse gases are wanted, cause a series of environment and ecological problem.Meanwhile carbon dioxide is used as a kind of widely distributed, rich reserves, honest and clean
Valency is easy to get, is renewable, be nontoxic, the non-flammable preferable resource of carbon one.No matter from the angle that environmental protection or renewable resource utilize
Degree considers that the research in terms of the capture and chemical conversion of carbon dioxide is all significant.Using carbon dioxide as Material synthesis
Organic carbonate is exactly an exemplary of its recycling, has been realized in industrialized production at present.
Organic carbonate is a kind of green chemical with characteristics such as higher boiling, low-steam pressure, low toxicities, has been widely used in
The multiple fields such as solvent, detergent, lithium battery electrolytes, fuel additive.Organic carbonate can be divided into linear carbonate
And cyclic carbonate.Wherein cyclic carbonate is widely used as the electrolyte of lithium battery, with the fast development of new energy, market pair
It is increasing in the demand of high-quality cyclic carbonate.
From the perspective of Green Chemistry and sustainable development, using carbon dioxide and epoxides as Material synthesis carbonic ester
Provide a kind of safe and clean, sustainable, high atom economy new way.Current industrialized carbon dioxide and ring
The process that oxygen prepares cyclic carbonate mainly has two kinds of catalyst system and catalyzings：Polyethylene glycol/KI system and quaternary ammonium salt system.The former
Iodine can be generated during the course of the reaction, causes finished product to turn to be yellow, and product quality declines；And the pressure that the latter needs during the course of the reaction
Power is higher, and to the security of production operation, the requirement for performance that equipment is pressure-resistant is higher, and equipment cost is high.
At present, with CO2It is raw material with cyclic carbonate, in the reaction system of synthesizing annular carbonate, has developed
A series of catalyst, as quaternary ammonium salt, quaternary alkylphosphonium salts, organic base, ionic liquid, metal oxide, metal complex, feature are organic
Polymeric material and metalloporphyrin etc..2013, Deng et al. research group was using salen Al/Co and three ethynylbenzenes to be single
Body, by Sonogashira coupling reactions, microporous polymer catalyst Al-CMP and Co-CMP are prepared for, in the reaction system
In achieve preferable catalytic effect, and the just desirable good yield under normal temperature and pressure conditionses, while catalyst may be used also
Recycling [Nat.Commun., 2013,4,1-7].2016, Xiao Fengshou taught seminar with tetravinyl Cob altporphyrin
For monomer, by the method for radical polymerization, catalyst Co/POP-TPP is made, at 29 DEG C, when pressure is 0.1MPa, reaction
24h, achieves satisfied result, catalyst can circulation and stress use, and by low concentration CO2As research object, have
Certain industrial application value [J.Catal., 2016,338,202].
The content of the invention
The technical problems to be solved by the invention are deposited inefficient in a mild condition for the current reaction system
Problem, there is provided a kind of synthesis step is simple, raw material is cheap and easy to get, high catalytic efficiency, the stable heterogeneous catalyst easily reclaimed, normal
Under normal temperature and pressure, condition of no solvent, efficient catalytic is converted into cyclic carbonate, can be widely applied to field of industrial production.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of method that nickel-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate, original is used as using carbon dioxide and epoxides
Material, to be conjugated nickel-porphyrin capillary copolymer material as heterogeneous catalyst, tetra-n-butyl ammonium bromide is co-catalyst, in normal temperature and pressure
Under solvent-free, 12-48h to be reacted, has synthesized cyclic carbonate in high yield, heterogeneous catalyst separation is simple, washable recovery, and
It can realize and repeatedly use.
The conjugation nickel-porphyrin capillary copolymer material uses Scholl coupling reactions, using nickel tetraphenylporphyrin to be single
Body, use the anhydrous AlCl of low cost3Catalyst preparation obtains, and its eliminant is as follows：
。
The epoxide is expoxy propane, epoxy butane, epoxychloropropane, epoxy bromopropane, styrene oxide, benzene
Base glycidol ether or cyclohexene oxide.
The dosage of the active component of the heterogeneous catalyst is 0.2~0.5mol% of epoxide dosage.
The dosage of the co-catalyst is 3.6~7.2mol% of epoxide.
The conjugation nickel-porphyrin capillary copolymer material can be replaced with conjugation nickel-porphyrin bibenzyl amine capillary copolymer material,
The conjugation nickel-porphyrin bibenzyl amine capillary copolymer material uses Scholl coupling reactions, using nickel tetraphenylporphyrin and benzylamine as
Monomer, use anhydrous AlCl3Catalyst preparation obtains, and its structural formula is as follows：
。
Beneficial effects of the present invention：1) present invention utilizes and is conjugated nickel-porphyrin/conjugation nickel-porphyrin bibenzyl amine microporous polymer material
Material and tetra-n-butyl ammonium bromide are realized under normal temperature and pressure conditionses, efficient catalytic CO as bicomponent catalyst2And epoxides
Synthesizing annular carbonate, mass energy is saved, reduce the requirement to press device in production, substantially increase the peace of operation
Quan Xing；2) catalyst amount is low, high catalytic efficiency, reaction time are short, product is easily isolated purifying, is easy to actual industrial to operate；
3) any organic solvent need not be added, it is green；4) catalyst raw material used in is easy to get, cost is low, the quick letter of synthesis
It is single.Heterogeneous catalyst separation is simple, washable recovery, and can realize and repeatedly use（More than 20 times）.
Specific implementation method
The present invention is further described in the examples below, but the merely illustrative purposes of discussion of these embodiments, should not be solved
It is interpreted as the implementation limitation of the present invention.
Embodiment 1
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.5mol%）Catalyst conjugation nickel
Porphyrin capillary copolymer material, 12.5mmol expoxy propane and 0.675mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through dioxy
It is 0.1MPa to change carbon and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 36h, room temperature cooling, slowly discharges remaining two
After carbonoxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 89%.
Embodiment 2
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.3mol%）Catalyst conjugation nickel
Porphyrin capillary copolymer material, 12.5mmol epoxy butanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through titanium dioxide
Carbon and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly discharges remaining dioxy
After changing carbon, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 87%.
Embodiment 3
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.45mol%）Catalyst conjugation nickel
Porphyrin capillary copolymer material, 12.5mmol epoxychloropropane and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through dioxy
It is 0.1MPa to change carbon and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly discharges remaining two
After carbonoxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 89%.
Embodiment 4
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.4mol%）Catalyst conjugation nickel
Porphyrin capillary copolymer material, 12.5mmol epoxy bromopropanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through dioxy
It is 0.1MPa to change carbon and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly discharges remaining two
After carbonoxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 88%.
Embodiment 5
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.2mol%）Catalyst conjugation nickel
Porphyrin capillary copolymer material, 12.5mmol styrene oxides and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through dioxy
It is 0.1MPa to change carbon and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly discharges remaining two
After carbonoxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 85%.
Embodiment 6
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.2mol%）Catalyst conjugation nickel
Porphyrin capillary copolymer material, 12.5mmol phenyl glycidyl ethers and 0.45mmol co-catalyst tetra-n-butyl ammonium bromides, lead to
It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 24h, room temperature cooling, slowly release is surplus
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 83%.
Embodiment 7
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.4mol%）Catalyst conjugation nickel
Porphyrin capillary copolymer material, 12.5mmol cyclohexene oxides and 0.45mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through two
Carbonoxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 12h, room temperature cooling, slowly discharges remaining
After carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 84%.
Embodiment 8
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.2mol%）Catalyst conjugation nickel
Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol expoxy propane and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through
Carbon dioxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is remaining
Carbon dioxide after, filter to isolate catalyst, after purification cyclic carbonate separation yield be 88%.
Embodiment 9
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.5mol%）Catalyst conjugation nickel
Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol epoxy butanes and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, are passed through
Carbon dioxide and to keep pressure be 0.1MPa, under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is remaining
Carbon dioxide after, filter to isolate catalyst, after purification cyclic carbonate separation yield be 84%.
Embodiment 10
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.3mol%）Catalyst conjugation nickel
Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol epoxychloropropane and 0.9mmol co-catalyst tetra-n-butyl ammonium bromides, lead to
It is 0.1MPa to enter carbon dioxide and keep pressure, and under the conditions of temperature is 25 DEG C, after stirring 48h, room temperature cooling, slowly release is surplus
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 89%.
Embodiment 11
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.3mol%）Catalyst conjugation nickel
Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol epoxy bromopropanes and 0.45mmol co-catalyst tetra-n-butyl ammonium bromides,
It is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 12h, and room temperature cooling, slowly release
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 86%.
Embodiment 12
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.3mol%）Catalyst conjugation nickel
Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol styrene oxides and 0.45mmol co-catalyst tetra-n-butyl ammonium bromides,
It is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 36h, and room temperature cooling, slowly release
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 80%.
Embodiment 13
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.2mol%）Catalyst conjugation nickel
Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol phenyl glycidyl ethers and 0.45mmol co-catalyst tetran-butylphosphonium bromides
Ammonium, it is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 24h, and room temperature cooling, slowly
After discharging remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 78%.
Embodiment 14
The method that the nickel-base catalyst chemical recycling of carbon dioxide of the present embodiment prepares cyclic carbonate, step are as follows：
Into 10mL stainless steel autoclave, 50mg is sequentially added（Active component nickel 0.4mol%）Catalyst conjugation nickel
Porphyrin bibenzyl amine capillary copolymer material, 12.5mmol cyclohexene oxides and 0.675mmol co-catalyst tetra-n-butyl ammonium bromides,
It is 0.1MPa to be passed through carbon dioxide and keep pressure, under the conditions of temperature is 25 DEG C, after stirring 12h, and room temperature cooling, slowly release
After remaining carbon dioxide, catalyst is filtered to isolate, the separation yield for obtaining cyclic carbonate after purification is 82%.
The content of active component is on the basis of the dosage of epoxide in above-described embodiment.
Claims (6)
1. a kind of method that nickel-base catalyst chemical recycling of carbon dioxide prepares cyclic carbonate, it is characterised in that using carbon dioxide and
Epoxides is as raw material, and to be conjugated vanadium porphyrin capillary copolymer material as heterogeneous catalyst, tetra-n-butyl ammonium bromide is urged to help
Agent, in the case where normal temperature and pressure is solvent-free, 12-48h is reacted, realize efficient green catalysis carbon dioxide synthesizing annular carbonate.
2. the method that nickel-base catalyst chemical recycling of carbon dioxide according to claim 1 prepares cyclic carbonate, its feature exist
In：The conjugation nickel-porphyrin capillary copolymer material uses Scholl coupling reactions, using nickel tetraphenylporphyrin as monomer, uses
Anhydrous AlCl3Catalyst preparation obtains, and its structural formula is as follows：
。
3. the method that nickel-base catalyst chemical recycling of carbon dioxide according to claim 1 prepares cyclic carbonate, its feature exist
In：The epoxide is expoxy propane, epoxy butane, epoxychloropropane, epoxy bromopropane, styrene oxide, phenyl contracting
Water glycerin ether or cyclohexene oxide.
4. the method that nickel-base catalyst chemical recycling of carbon dioxide according to claim 1 prepares cyclic carbonate, its feature exist
In：The dosage of the active component of the heterogeneous catalyst is 0.2~0.5mol% of epoxide dosage.
5. the method that nickel-base catalyst chemical recycling of carbon dioxide according to claim 1 prepares cyclic carbonate, its feature exist
In：The dosage of the co-catalyst is 3.6~7.2mol% of epoxide.
6. the method that cyclic carbonate is prepared according to any described nickel-base catalyst chemical recycling of carbon dioxide of claim 1 ~ 5, its
It is characterised by：The conjugation nickel-porphyrin capillary copolymer material can use conjugation nickel-porphyrin bibenzyl amine capillary copolymer material generation
Replace, the conjugation nickel-porphyrin bibenzyl amine capillary copolymer material uses Scholl coupling reactions, with nickel tetraphenylporphyrin and benzyl
Amine is monomer, uses anhydrous AlCl3Catalyst preparation obtains, and its structural formula is as follows：
。
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