CN114409628A - Method and system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition - Google Patents
Method and system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition Download PDFInfo
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- CN114409628A CN114409628A CN202210059631.5A CN202210059631A CN114409628A CN 114409628 A CN114409628 A CN 114409628A CN 202210059631 A CN202210059631 A CN 202210059631A CN 114409628 A CN114409628 A CN 114409628A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 52
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 36
- 238000006352 cycloaddition reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002262 Schiff base Substances 0.000 claims abstract description 15
- JCSHYFOSLVIDGY-UHFFFAOYSA-N imidazol-1-yl hydrogen carbonate Chemical compound OC(=O)ON1C=CN=C1 JCSHYFOSLVIDGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims abstract description 4
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 claims description 2
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-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
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 description 10
- -1 halogen anions Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- GYTMUNSNMBRSEW-UHFFFAOYSA-N hydrogen carbonate;1h-imidazol-1-ium Chemical compound OC(O)=O.C1=CNC=N1 GYTMUNSNMBRSEW-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/19—
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- 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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
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- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
Abstract
The invention provides a method and a system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition, which comprises the following steps: taking Schiff base metal and imidazole bicarbonate as catalysts, and carbon dioxide and an epoxy compound as raw materials, and carrying out cycloaddition reaction to generate cyclic carbonate, wherein the structural formula of the Schiff base metal catalyst is as follows:
wherein R is ethyl, phenyl, cyclohexyl or naphthyl, M is copper, manganese, zinc or aluminum, and X is Cl, Br, CH3、CH3CO2、BF4Or PF6(ii) a The structural formula of the imidazole bicarbonate is as follows:
wherein R is1Is methyl, ethyl, propyl, n-butyl, n-pentyl or n-hexyl. The method can reduce the temperature and pressure required by the reaction, reduce the energy consumption of the reaction and simultaneously improve the reaction efficiency.
Description
Technical Field
The invention relates to the technical field of preparation of cyclic carbonate, in particular to a method and a system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition.
Background
The cyclic carbonate is an important chemical product and has wide application and prospect in the fields of lithium ion battery electrolytes, degradable polymer monomers, organic synthetic intermediates and the like. The cyclic carbonate is industrially synthesized by a cycloaddition reaction of carbon dioxide and an epoxy compound. The prior art adopts metal halide and ammonium salt as catalysts, and the preparation is carried out under the conditions of the reaction temperature of 100 ℃ and 150 ℃ and the reaction operating pressure of 2.0-5.0 MPa. However, both the metal halide and the ammonium salt contain halogen anions, which cause severe corrosion to metal equipment under high-temperature and high-pressure reaction conditions, and put high demands on the material of the reactor. Meanwhile, most reactors used in the prior art are kettle reactors, carbon dioxide and epoxy compounds cannot be sufficiently mixed, and the gas/liquid phase interfacial area is small, so that the reaction needs to be carried out under higher operating pressure, and the reaction rate is lower.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition, which adopts Schiff base metal and imidazole bicarbonate as catalysts, has good catalytic activity, fully reduces reaction temperature, improves the selectivity of the cyclic carbonate, and simultaneously does not contain halogen anions, reduces the corrosion to metal equipment, and effectively prolongs the service life of the equipment.
The second purpose of the invention is to provide a system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition, which is characterized in that a micro interface unit is arranged in a reactor to disperse and crush carbon dioxide into micro bubbles at a micron level, so that the gas-liquid mass transfer area of the carbon dioxide and an epoxy compound is increased, the operation temperature and pressure can be reduced, and the raw material conversion rate and the product yield are increased.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a method for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition, which comprises the following steps: taking Schiff base metal and imidazole bicarbonate as catalysts, and carbon dioxide and an epoxy compound as raw materials, and carrying out cycloaddition reaction to generate cyclic carbonate, wherein the structural formula of the Schiff base metal catalyst is as follows:
wherein R is ethyl, phenyl, cyclohexyl or naphthyl, M is copper, manganese, zinc or aluminum, and X is Cl, Br, CH3、CH3CO2、BF4Or PF6；
The structural formula of the imidazole bicarbonate is as follows:
wherein R is1Is methyl, ethyl, propyl, n-butyl, n-pentyl or n-hexyl.
In the prior art, epoxy carbonate generally reacts with carbon dioxide and epoxy compound under the catalysis of metal halide and ammonium salt, but the reaction has the following problems: the adopted catalyst metal halide and ammonium salt both contain halogen anions, and the halogen anions can corrode metal equipment under the conditions of high temperature and high pressure, so that the service life of the equipment is seriously influenced.
In order to solve the technical problems, the invention provides a method for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition, which adopts Schiff base metal and imidazole bicarbonate as catalysts, has good catalytic activity, fully reduces the reaction temperature, improves the selectivity of the cyclic carbonate, does not contain halogen anions, reduces the corrosion to metal equipment, and effectively prolongs the service life of the equipment.
Preferably, the cycloaddition reaction comprises: the carbon dioxide is crushed into micro-bubbles with micron grade through a micro interface, and then is mixed with an epoxy compound to carry out cycloaddition reaction under the catalysis of a catalyst. By combining the micro-interface crushing and the carbon dioxide cycloaddition reaction, the gas-liquid mass transfer area between the carbon dioxide and the epoxy compound is increased, the reaction rate is increased, and the energy consumption is reduced.
Preferably, the epoxy compound is ethylene oxide, propylene oxide, epichlorohydrin, butyloxirane, styrene oxide, isopropyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, or cyclohexene oxide.
Preferably, the temperature of the cycloaddition reaction is from 25 ℃ to 80 ℃, preferably 40 ℃. The reaction temperature may be 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or the like.
Preferably, the pressure of the cycloaddition reaction is 0.1 to 0.3MPa, preferably 0.2 MPa. The reaction pressure may be 0.1MPa, 0.2MPa, 0.3MPa, or the like.
The invention also provides a system for preparing the cyclic carbonate by catalyzing the cycloaddition of the carbon dioxide, and the system applies the method to prepare the cyclic carbonate.
Preferably, the system comprises: a reactor and a micro-interface unit; the micro interface unit is arranged inside the reactor; the side wall of the reactor is sequentially connected with a first feeding pipeline for introducing an epoxy compound and a second feeding pipeline for introducing carbon dioxide from top to bottom; the second feeding pipeline is connected with the micro interface unit to disperse and break the carbon dioxide into micro bubbles at a micron level.
Preferably, the micro-interface unit comprises a first micro-interface generator and a second micro-interface generator, the first micro-interface generator is arranged above the second micro-interface generator, and the outlet of the first micro-interface generator is opposite to the outlet of the second micro-interface generator.
Preferably, the outlets of the first micro-interface generator and the second micro-interface generator are both provided with a bubble distributor, the bubble distributor is conical, and the bubble distributor is provided with a plurality of distribution holes.
Preferably, the first micro-interface generator and the second micro-interface generator are one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
Preferably, the micro-bubbles of the micron level are micro-bubbles with the diameter of more than or equal to 1 μm and less than 1 mm.
In the prior art, most reactors used in the cycloaddition reaction are tank reactors, carbon dioxide and an epoxy compound cannot be sufficiently mixed in the reactors, the gas/liquid phase interfacial area is small, the reaction needs to be carried out under higher operating pressure, and the reaction rate is lower. According to the invention, the micro-interface unit is arranged in the reactor, so that carbon dioxide is dispersed and crushed into micro-bubbles at the micron level, and the micro-bubbles are mixed with the epoxy compound to form a gas-liquid emulsion, so that the gas-liquid mass transfer area between the carbon dioxide and the epoxy compound is increased, the operation temperature and pressure can be reduced, the energy consumption required by the reaction is reduced, and the reaction rate can be effectively increased; in addition, the micro-interface unit is arranged in the reactor, so that the occupied area is small, and the intrinsic safety is high.
The micro-interface unit comprises a first micro-interface generator and a second micro-interface generator, and the two micro-interface generators are adopted for simultaneously dispersing and crushing carbon dioxide and improving the dispersing and crushing efficiency; when the two micro-interface generators are arranged, the first micro-interface generator is positioned above, the second micro-interface generator is positioned below, and the outlets of the first micro-interface generator and the second micro-interface generator are opposite, so that two micro-bubble flows are oppositely flushed, the uniform distribution of micro-bubbles is promoted, and the gas-liquid mass transfer area is further increased; the bubble distributor is also arranged to promote the uniform distribution of the micro-bubbles, improve the dispersion effect and prevent coalescence among the micro-bubbles.
When the feeding pipelines are arranged, the first feeding pipeline is positioned above the second feeding pipeline, the epoxy compound is conveyed by the first feeding pipeline, the carbon dioxide is conveyed by the second feeding pipeline, the carbon dioxide is a gas, part of the carbon dioxide is not dissolved in the epoxy compound and directly flows upwards, and the epoxy compound conveyed by the first feeding pipeline flows downwards from the upper part and is combined with the unreacted carbon dioxide for continuous reaction, so that the improvement of the conversion rate of raw materials is facilitated.
Preferably, the reactor is connected with a flash tank, the flash tank is connected with a distillation column, and after the reaction product in the reactor is subjected to flash evaporation treatment by the flash tank, one part of the reaction product flows into the distillation column, and the other part of the reaction product flows back to the reactor.
Preferably, the system further comprises an epoxy compound storage tank and a carbon dioxide storage tank, wherein the epoxy compound storage tank is connected with the first feeding pipeline, and the carbon dioxide storage tank is connected with the second feeding pipeline.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for preparing the cyclic carbonate by catalyzing the cycloaddition of the carbon dioxide, the Schiff base metal and the imidazole bicarbonate are used as the catalysts, and the good catalytic activity of the catalysts is utilized, so that the reaction temperature is fully reduced, the selectivity of the cyclic carbonate is improved, and the catalysts do not contain halogen anions, so that the corrosion to metal equipment is reduced; by adopting the micro-interface enhanced reaction system, the gas/liquid phase interfacial area of the carbon dioxide and the epoxy compound can be increased, the reaction operation pressure is reduced, the reaction rate is increased, the occupied area of the reaction system is small, and the intrinsic safety is high.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic structural diagram of a system for preparing cyclic carbonate by catalytic carbon dioxide cycloaddition provided in example 1 of the present invention;
FIG. 2 shows a catalyst SH provided in example 1 of the present invention4Nuclear magnetic hydrogen spectrum of al (cl);
FIG. 3 shows a catalyst SH provided in example 1 of the present invention4Nuclear magnetic carbon spectrum of Al (Cl);
FIG. 4 shows a catalyst [ C ] provided in example 1 of the present invention1C6Im[HCO3]Nuclear magnetic hydrogen spectrum of (4);
FIG. 5 shows catalyst [ C ] provided in example 1 of the present invention1C6Im[HCO3]Nuclear magnetic carbon spectrum of (1).
Wherein:
10-a carbon dioxide storage tank; a 20-epoxy compound storage tank;
30-a second feed line; 40-a first feed line;
50-a reactor; 60-a second micro-interface generator;
70-a bubble distributor; 80-a first micro-interface generator;
90-a flash tank; 100-distillation column.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Referring to fig. 1, this embodiment provides a system for preparing cyclic carbonate through catalytic carbon dioxide cycloaddition, including: a reactor 50 and a micro interface unit; the micro interface unit is arranged inside the reactor 50; the side wall of the reactor 50 is sequentially connected with a first feeding pipeline 40 for introducing epoxy compounds and a second feeding pipeline 30 for introducing carbon dioxide from top to bottom; the second feed line 30 is connected to a micro interface unit to disperse and break the carbon dioxide into micro bubbles of micron order. The micro-bubbles in micron level are micro-bubbles with the diameter of more than or equal to 1 μm and less than 1 mm.
The micro-interface unit comprises a first micro-interface generator 80 and a second micro-interface generator 60, wherein the first micro-interface generator 80 is arranged above the second micro-interface generator 60, and the outlet of the first micro-interface generator 80 is opposite to the outlet of the second micro-interface generator 60.
Specifically, the outlets of the first micro-interface generator 80 and the second micro-interface generator 60 are both provided with a bubble distributor 70, the bubble distributor 70 is conical, and the bubble distributor 70 is provided with a plurality of distribution holes.
In this embodiment, the first micro-interface generator 80 and the second micro-interface generator 60 are one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator, and a gas-liquid linkage micro-interface generator.
With continued reference to fig. 1, the reactor 50 is connected to a flash tank 90, the flash tank 90 is connected to a distillation column 100, and after the reaction product in the reactor 50 is subjected to flash evaporation treatment by the flash tank 90, a part of the reaction product flows into the distillation column, and the other part of the reaction product flows back to the reactor 50.
The system of this embodiment further includes an epoxy compound storage tank 20 and a carbon dioxide storage tank 10, the epoxy compound storage tank 20 being connected to the first feed line 40 and the carbon dioxide storage tank 10 being connected to the second feed line 30.
The method for preparing cyclic carbonate of this example is as follows: the Schiff base metal and the imidazole bicarbonate catalyst are loaded into a reactor 50, propylene oxide and carbon dioxide are introduced into the reactor 50 to react under the conditions that the pressure is 0.2MPa and the reaction temperature is 40 ℃, the reaction product enters a flash tank 90, the carried propylene oxide and the carried cyclic carbonate are vaporized in the flash tank 90 and enter a rectifying tower, and the catalyst at the bottom is conveyed back to the reactor 50.
The epoxypropane and the cyclic carbonate are separated in the rectifying tower, the epoxypropane is distilled out from the top of the rectifying tower and recovered, and the product cyclic carbonate flows out from the bottom of the rectifying tower.
In this embodiment, the central metal element M of the Schiff base metal compound is aluminum, the bridging group R is naphthyl, and R of the imidazole bicarbonate1Is methyl, R2Is n-hexyl.
The production strength of the cyclic carbonate was found to be 580kg/m3H, the nuclear magnetic hydrogen spectrum is shown in FIG. 2.
Examples 2 to 4
The system and method for producing carbonate by reacting propylene oxide with carbon dioxide according to example 1 were employed to change the central metal element M of the schiff base metal compound, and the results are shown in table 1:
TABLE 1
Examples 5 to 7
The method for producing a cyclic carbonate by reacting propylene oxide with carbon dioxide in example 1 was adopted, and the bridging group R of the schiff base aluminum compound was changed, and the results are shown in table 2:
TABLE 2
| Examples | R | Cyclic carbonate production Strength (kg/m)3·h) |
| 5 | Ethyl SH1-Al(Cl) | 482 |
| 6 | Cyclohexyl SH2-Al(Cl) | 511 |
| 7 | Phenyl SH3-Al(Cl) | 542 |
Examples 8 to 12
Using the method for preparing cyclic carbonate by reacting propylene oxide with carbon dioxide in example 1, R of imidazole bicarbonate was changed1And R2The results are shown in table 3:
TABLE 3
Examples 13 to 16
The method for producing a cyclic carbonate by reacting propylene oxide with carbon dioxide in example 1 was employed, and the results are shown in table 4, with the reaction temperature being changed:
TABLE 4
Examples 17 to 18
The results of varying the reaction pressure in the method for producing a cyclic carbonate by reacting propylene oxide with carbon dioxide in example 1 are shown in table 5:
TABLE 5
It can be seen from the experimental data of examples 1 to 21 that the cyclic carbonate prepared by using schiff base metal and imidazole bicarbonate as catalysts to catalyze carbon dioxide ring synthesis still has good production strength even under low temperature and low pressure conditions, so that the invention realizes reaction under lower temperature and pressure conditions by using schiff base metal and imidazole bicarbonate as catalysts to catalyze carbon dioxide ring synthesis and limiting reaction temperature and reaction pressure, reduces reaction energy consumption, and has higher reaction efficiency.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A method for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition is characterized by comprising the following steps: taking Schiff base metal and imidazole bicarbonate as catalysts, and carbon dioxide and an epoxy compound as raw materials, and carrying out cycloaddition reaction to generate cyclic carbonate, wherein the structural formula of the Schiff base metal catalyst is as follows:
wherein R is ethyl, phenyl, cyclohexyl or naphthyl, M is copper, manganese, zinc or aluminum, and X is Cl, Br, CH3、CH3CO2、BF4Or PF6；
The structural formula of the imidazole bicarbonate is as follows:
wherein R is1Is methyl, ethyl, propyl, n-butyl, n-pentyl or n-hexyl.
2. The method of claim 1, wherein the cycloaddition reaction comprises: the carbon dioxide is crushed into micro-bubbles with micron grade through a micro interface, and then is mixed with an epoxy compound to carry out cycloaddition reaction under the catalysis of a catalyst.
3. The method of claim 1, wherein the epoxy compound is ethylene oxide, propylene oxide, epichlorohydrin, butyl oxirane, styrene oxide, isopropyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, or cyclohexene oxide.
4. The process according to claim 1, wherein the temperature of the cycloaddition reaction is 25-80 ℃, preferably 40 ℃.
5. The process according to claim 1, characterized in that the pressure of the cycloaddition reaction is 0.1-0.3MPa, preferably 0.2 MPa.
6. A system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition, which is characterized in that the cyclic carbonate is prepared by the method of any one of claims 1 to 5.
7. The system of claim 6, wherein the system comprises: a reactor and a micro-interface unit; the micro interface unit is arranged inside the reactor; the side wall of the reactor is sequentially connected with a first feeding pipeline for introducing an epoxy compound and a second feeding pipeline for introducing carbon dioxide from top to bottom; the second feeding pipeline is connected with the micro interface unit to disperse and break the carbon dioxide into micro bubbles at a micron level.
8. The system of claim 7, wherein the micro-interface assembly comprises a first micro-interface generator and a second micro-interface generator, the first micro-interface generator being disposed above the second micro-interface generator, and the first micro-interface generator being opposite the outlet of the second micro-interface generator.
9. The system of claim 8, wherein the outlets of the first and second micro-interface generators are provided with bubble distributors, the bubble distributors are tapered, and the bubble distributors are provided with a plurality of distribution holes.
10. The system of claim 7, wherein the reactor is connected with a flash tank, the flash tank is connected with a distillation column, and after the reaction product in the reactor is subjected to flash evaporation treatment by the flash tank, one part of the reaction product flows into the rectification column, and the other part of the reaction product flows back to the reactor.
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| CN115739179A (en) * | 2022-11-01 | 2023-03-07 | 南京大学 | Composite polymer catalyst, and preparation method and application thereof |
| WO2023138074A1 (en) * | 2022-01-19 | 2023-07-27 | 南京延长反应技术研究院有限公司 | Method and system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition |
| CN116514741A (en) * | 2023-07-04 | 2023-08-01 | 山东民基新材料科技有限公司 | Process for producing epoxy chloropropane by utilizing micro-interface reaction |
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| CN111961026A (en) * | 2020-08-25 | 2020-11-20 | 南京延长反应技术研究院有限公司 | Reinforced micro-interface preparation system and method for cyclic carbonate |
| CN112058191A (en) * | 2020-08-25 | 2020-12-11 | 南京延长反应技术研究院有限公司 | Micro-interface preparation system and method for cyclic carbonate |
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| CN111961026A (en) * | 2020-08-25 | 2020-11-20 | 南京延长反应技术研究院有限公司 | Reinforced micro-interface preparation system and method for cyclic carbonate |
| CN112058191A (en) * | 2020-08-25 | 2020-12-11 | 南京延长反应技术研究院有限公司 | Micro-interface preparation system and method for cyclic carbonate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023138074A1 (en) * | 2022-01-19 | 2023-07-27 | 南京延长反应技术研究院有限公司 | Method and system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition |
| CN115739179A (en) * | 2022-11-01 | 2023-03-07 | 南京大学 | Composite polymer catalyst, and preparation method and application thereof |
| CN115739179B (en) * | 2022-11-01 | 2024-04-09 | 南京大学 | Composite high-molecular catalyst and preparation method and application thereof |
| CN116514741A (en) * | 2023-07-04 | 2023-08-01 | 山东民基新材料科技有限公司 | Process for producing epoxy chloropropane by utilizing micro-interface reaction |
| CN116514741B (en) * | 2023-07-04 | 2023-09-26 | 山东民基新材料科技有限公司 | Process for producing epoxy chloropropane by utilizing micro-interface reaction |
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