CN110003163A - A kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate - Google Patents
A kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate Download PDFInfo
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- CN110003163A CN110003163A CN201910361616.4A CN201910361616A CN110003163A CN 110003163 A CN110003163 A CN 110003163A CN 201910361616 A CN201910361616 A CN 201910361616A CN 110003163 A CN110003163 A CN 110003163A
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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
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Abstract
The invention belongs to cyclic carbonate preparation technical fields, are related to a kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate.The present invention passes through cyclic spray gas-liquid contact technique, using " electrophilic-nucleophilic " difunctional system as catalyst, under the reaction pressure of 0.2~5.0MPa and 25~180 DEG C of reaction temperature, carbon dioxide and epoxyalkane are that raw material progress coupling reaction efficiently prepares cyclic carbonate.The present invention solves after olefin oxide rate reaches a certain level in the prior art, and the defect sharply declined is presented in reaction rate.Benefit of the invention is the efficiency for improving carbon dioxide and preparing cyclic carbonate with epoxyalkane coupling, has industrial application value.
Description
Technical field
The invention belongs to cyclic carbonate preparation technical field, it is related to a kind of cyclic spray formula gas-liquid contact technique and prepares ring
The method of shape carbonic ester is a kind of method for preparing cyclic carbonate by epoxyalkane and carbon dioxide coupling reaction.
Background technique
Carbon dioxide (CO2) it is used as tellurian important carbon source, carbohydrate can be converted by photosynthesis,
Oxygen is released simultaneously, this is to maintain one of most important reaction of ecological circulation.And now mankind's daily life and industrial production
Middle CO2Excessive emissions destroy " balance between revenue and expenditure " of nature so that CO2As the predominant gas for leading to greenhouse effects.Cause
This, CO2Emission reduction and chemically or physically fixation have become one of strategic research project of greatest concern in world wide.?
Under catalyst action, carbon dioxide can occur coupling reaction with epoxyalkane and prepare cyclic carbonate.These cyclic carbonates
Higher boiling, highly polar organic solvent as function admirable, in organic synthesis, cosmetics industry, gas separation, battery electrolyte
And the fields such as metal extraction extensive application.
Have both at home and abroad much about the patent report for preparing cyclic carbonate by carbon dioxide and epoxyalkane coupling at present
Road.Such as in US 4314945, McMullen synthesizes ring with carbon dioxide reaction using tetraalkyl quaternary ammonium salt catalysis epoxyalkane
Shape carbonic ester；In US 4786741 and US 4841072, Sachs and Harvey use respectively quaternary phosphine salt catalyst 2.5~
Under the pressure of 20MPa, the cycloaddition reaction of carbon dioxide and ethylene oxide is realized, is prepared for corresponding cyclic carbonate；?
In US 4931571, Weinstein, as catalyst, is catalyzed carbon dioxide and ring using season arsine halide salt at 90~200 DEG C
Oxidative ethane reacts synthesizing ethylene carbonate.And domestic some experts also achieve certain breakthrough in the field, such as in CN
In 1343668, Deng Youquan forms binary catalyst system using ionic liquid and alkali halide or tetrabutylammonium bromide,
100~140 DEG C are that epoxide is successfully changed into corresponding ring under 1.5~4.5MPa with carbon dioxide initial pressure
Shape carbonic ester；In CN 101003531, He Liangnian using the polyethylene glycol of quaternary ammonium salt or quaternary alkylphosphonium salt functionalization as catalyst,
The coupling reaction for realizing carbon dioxide and epoxyalkane has synthesized corresponding cyclic carbonate.The advantage of the catalyst is to hold
It easily recycles and recycles, be suitable for continuous production；In CN 101972674, Liu Binyuan has synthesized a kind of simple molecule
The interior tetradentate schiff base aluminum complex containing quaternary ammonium salt, the catalyst is for being catalyzed carbon dioxide and epoxyalkane coupling reaction
When, catalytic efficiency reaches as high as 3750mol cyclic carbonate/mol catalyst.In recent years, we also use tetradentate schiff base aluminium
Complex is as catalyst, under the synergistic effect of quaternary ammonium salt Huo quaternary alkylphosphonium salt, realizes the coupling of carbon dioxide and epoxyalkane
Reaction, has synthesized corresponding cyclic carbonate (CN 1416953, CN 1415416 and CN 1544431).
In the method for preparing cyclic carbonate of above-mentioned report, it is all made of the reaction work of traditional autoclave or shell and tube
Skill.In these processes, after the conversion ratio of epoxyalkane reaches a certain level, decline sharply is presented in reaction rate, is caused
Take a long time the conversion almost for realizing epoxyalkane.The thus reaction process low efficiency of autoclave or tubular type, energy
Consumption is high.
Summary of the invention
The object of the present invention is to provide a kind of reaction process by cyclic spray formula to reinforce gas-liquid mass transfer, efficiently realizes two
The method of carbonoxide and epoxyalkane coupling reaction synthesizing annular carbonate.
Technical solution of the present invention:
A kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate, using cyclic spray reactor, with
" electrophilic-nucleophilic " bifunctional catalyst is catalyst, in the reaction pressure of 0.2~5.0MPa and 25~180 DEG C of reaction temperature
Under, carbon dioxide and epoxyalkane are that raw material progress coupling reaction prepares cyclic carbonate.
Reaction process are as follows: the cyclic carbonate containing catalyst is added in cyclic spray reactor, it will by heat exchanger
Starting material is heated to reaction temperature, and being passed through carbon dioxide to reaction system pressure is reaction pressure；It is reacted again to cyclic spray
It is passed through epoxyalkane and carbon dioxide in device, and keeps reaction pressure；After charging, the reaction was continued all disappears to epoxyalkane
Reaction mass in cyclic spray reactor, is then transferred in flash tank by consumption, and after carbon dioxide is discharged, vacuum distillation is obtained
To cyclic carbonate, the residual solution containing catalyst is recycled as lower batch reaction starting material.
Mass ratio 50:1~50000:1 of the epoxyalkane and catalyst.
The molar ratio of the epoxyalkane and carbon dioxide is 1:1.
In described " electrophilic-nucleophilic " bifunctional catalyst, the general formula of " electrophilic " part is M1 a[M2(CN)b L1 c]d·x
[M3 mXn]·y L2·z H2O；In formula, M1And M3Selected from Zn2+、Co2+、Ni2+、Fe2+、Fe3+、Ca2+、Mg2+、Cu2+、Cr3+、Al3+、
Sn2+、Cd2+Or Pb2+, preferably Zn2+、Co2+、Ni2+、Fe2+Or Fe3+；M2Selected from Co3+、Ni2+、Fe2+、Fe3+、Cr3+、Mn3+Or Cu2 +；L1For with M2Interior boundary's ligand of coordination, selected from the monodentate or multidentate ligand formed with C, H, N, O, P and S；X is F-、Cl-、Br-、
I-、NO3 -、CH3COO-、SO4 2-, methyl benzoate, p-methyl benzenesulfonic acid root, o-nitrophenol oxygen, p- nitrophenol oxygen,
The aryloxy group anions such as m- nitrophenol oxygen or organic carboxyl acid root anion；L2Selected from water-soluble hetero atom organic complexing agent,
Such as: one or more of alcohol, aldehyde, ketone, ether, ester, amide, urea, nitrile, sulfide mixing, preferably the tert-butyl alcohol, isopropanol,
Ethylene glycol, propylene glycol, glycol monoethyl ether, dimethoxy-ethane and tert-pentyl alcohol；A, b, d, m and n be zero or value meet it is positive and negative
Charge number balance, wherein b is positive integer；X is positive number, and c, y and z are zero or positive number.The general formula of " nucleophilic " part is R1R2 3YX1's
Salt, in formula: R1For C1~C16Alkyl, R2For C1~C6Alkyl or phenyl；Y is nitrogen, phosphorus or arsenic element；X1For Cl-1、Br-1、I-1、
NO3 -1、CH3COO-1、ClO4 -1、BF4 -1、OH-1、BPh4 -1Or N3 -1Monovalence anion." electrophilic " partially quality with " nucleophilic " part
Than for 1:1~1:50.
The epoxyalkane is ethylene oxide or propylene oxide.
Beneficial effects of the present invention:
(1) cyclic spray formula reaction process can effectively strengthen gas-liquid, promote reaction efficiency；
(2) reaction can carry out under lower pressure carbon dioxide.
(3) it solves the problems, such as that the extent of reaction is low in the prior art, there is good industrial application value.
Detailed description of the invention
Fig. 1 is the process flow chart of cyclic spray formula gas-liquid contact catalytic preparation of cyclic carbonic ester.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
The process flow of cyclic spray formula gas-liquid contact catalytic preparation of cyclic carbonic ester of the invention is as shown in Figure 1, main
Reactor be cyclic spray reactor.
Embodiment 1:
It is added in the cyclic spray reactor that effective volume is 20L and contains 182g " electrophilic-nucleophilic " bifunctional catalyst
4.0Kg propene carbonate, wherein " electrophilic " partially be Zn3[Fe(CN)5PPh3]2·2.8[ZnCl2]·2tBuOH0.9H2O,
" nucleophilic " is partially tetrabutylammonium bromide, and the two mass ratio is 1:1.Reaction unit is started, and passes through heat exchanger for starting material
25 DEG C are heated to, being passed through carbon dioxide to reaction system pressure is 0.2MPa.Be continuously added in 3 hours 9.1Kg propylene oxide and
6.9Kg carbon dioxide (equimolar amounts) needs to keep epoxyalkane consistent with the inlet amount of carbon dioxide during charging, and system
Pressure maintains 0.2MPa.After to be fed, the reaction was continued 60 minutes.Reaction mass is transferred in flash tank, discharge two
After carbonoxide, vacuum distillation obtains about 16Kg propene carbonate (selectivity > 99.5%), and the residual solution containing catalyst is as starting
Material is recycled.
Embodiment 2:
It is added in the cyclic spray reactor that effective volume is 20L containing 9g " electrophilic-nucleophilic " bifunctional catalyst
4.0Kg propene carbonate, wherein " electrophilic " is partially Zn3[Fe(CN)5PPh3]2·2.8[ZnCl2]·2tBuOH0.9H2O, " parent
Core " is partially tetrabutylammonium bromide, and the two mass ratio is 1:5.Reaction unit is started, and is heated starting material by heat exchanger
To 110 DEG C, being passed through carbon dioxide to reaction system pressure is 2.0MPa.Be continuously added in 1 hour 9.1Kg propylene oxide and
6.9Kg carbon dioxide (equimolar amounts) needs to keep epoxyalkane consistent with the inlet amount of carbon dioxide during charging, and system
Pressure maintains 2.0MPa.After to be fed, the reaction was continued 10 minutes.Reaction mass is transferred in flash tank, discharge two
After carbonoxide, vacuum distillation obtains about 16Kg propene carbonate (selectivity > 99.5%), and the residual solution containing catalyst is as starting
Material is recycled.
Embodiment 3:
It is added in the cyclic spray reactor that effective volume is 20L containing 9g " electrophilic-nucleophilic " bifunctional catalyst
4.0Kg propene carbonate, wherein " electrophilic " is partially Zn3[Co(CN)3(PPh3)3]2·1.8[ZnCl2]·2CH3OH0.9H2O,
" nucleophilic " is partially tetrabutylammonium bromide, and the two mass ratio is 1:50.Reaction unit is started, and passes through heat exchanger for starting material
180 DEG C are heated to, being passed through carbon dioxide to reaction system pressure is 5.0MPa.Be continuously added in 1 hour 9.1Kg propylene oxide and
6.9Kg carbon dioxide (equimolar amounts) needs to keep epoxyalkane consistent with the inlet amount of carbon dioxide during charging, and system
Pressure maintains 5.0MPa.After to be fed, the reaction was continued 5 minutes.Reaction mass is transferred in flash tank, dioxy is discharged
After changing carbon, vacuum distillation obtains about 16Kg propene carbonate (selectivity > 99.5%), and the residual solution containing catalyst is as starting material
Material is recycled.
Embodiment 4:
It is added in the cyclic spray reactor that effective volume is 20L containing 9g " electrophilic-nucleophilic " bifunctional catalyst
4.0Kg ethylene carbonate, wherein " electrophilic " is partially Zn3[Fe(CN)6]2·2.1[ZnCl2]·1.8tBuOH1.2H2O, " parent
Core " is partially tetrabutylammonium iodide, and the two mass ratio is 1:2.Reaction unit is started, and is heated starting material by heat exchanger
To 110 DEG C, being passed through carbon dioxide to reaction system pressure is 2.0MPa.Be continuously added in 1 hour 8.0Kg ethylene oxide and
8.0Kg carbon dioxide (equimolar amounts) needs to keep epoxyalkane consistent with the inlet amount of carbon dioxide during charging, and system
Pressure maintains 2.0MPa.After to be fed, the reaction was continued 10 minutes.Reaction mass is transferred in flash tank, discharge two
After carbonoxide, vacuum distillation obtains about 16Kg ethylene carbonate (selectivity > 99.5%), and the residual solution containing catalyst is as starting
Material is recycled.
Embodiment 5:
It is added in the cyclic spray reactor that effective volume is 20L and contains 0.16g " electrophilic-nucleophilic " bifunctional catalyst
4.0Kg ethylene carbonate, wherein " electrophilic " partially be Zn3[Fe(CN)6]2·2.1[ZnCl2]·1.8tBuOH1.2H2O, " parent
Core " is partially tetrabutylammonium iodide, and the two mass ratio is 1:5.Reaction unit is started, and is heated starting material by heat exchanger
To 180 DEG C, being passed through carbon dioxide to reaction system pressure is 5.0MPa.Be continuously added in 2 hours 8.0Kg ethylene oxide and
8.0Kg carbon dioxide (equimolar amounts) needs to keep epoxyalkane consistent with the inlet amount of carbon dioxide during charging, and system
Pressure maintains 5.0MPa.After to be fed, the reaction was continued 10 minutes.Reaction mass is transferred in flash tank, discharge two
After carbonoxide, vacuum distillation obtains about 16Kg ethylene carbonate (selectivity > 99.5%), and the residual solution containing catalyst is as starting
Material is recycled.
Claims (3)
1. a kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate, which is characterized in that use cyclic spray
Reactor, using electrophilic-nucleophilic bifunctional catalyst as catalyst, in the anti-of the reaction pressure of 0.2~5.0MPa and 25~180 DEG C
At a temperature of answering, carbon dioxide and epoxyalkane are that raw material progress coupling reaction prepares cyclic carbonate；Specific reaction process is as follows:
The cyclic carbonate containing catalyst is added in cyclic spray reactor, is heated to starting material instead by heat exchanger
Temperature is answered, being passed through carbon dioxide to reaction system pressure is reaction pressure；Epoxyalkane is passed through into cyclic spray reactor again
And carbon dioxide, and keep reaction pressure；After charging, the reaction was continued all consumes to epoxyalkane, then sprays circulation
The reaction mass penetrated in reactor is transferred in flash tank, and after carbon dioxide is discharged, vacuum distillation obtains cyclic carbonate, contains
The residual solution of catalyst is recycled as lower batch reaction starting material；
Mass ratio 50:1~50000:1 of the epoxyalkane and catalyst；
The molar ratio of the epoxyalkane and carbon dioxide is 1:1.
2. a kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate according to claim 1, special
Sign is, in the electrophilic-nucleophilic bifunctional catalyst, the mass ratio of electrophilic moiety and nucleophilic moiety is 1:1~1:50；
The general formula of electrophilic moiety is M1 a[M2(CN)bL1 c]d·x[M3 mXn]·y L2·z H2O；In formula, M1And M3Selected from Zn2+、Co2 +、Ni2+、Fe2+、Fe3+、Ca2+、Mg2+、Cu2+、Cr3+、Al3+、Sn2+、Cd2+Or Pb2+；M2Selected from Co3+、Ni2+、Fe2+、Fe3+、Cr3 +、Mn3+Or Cu2+；L1For with M2Interior boundary's ligand of coordination, selected from the monodentate or multidentate ligand formed with C, H, N, O, P and S；X is
Aryloxy group anion or organic carboxyl acid root anion；L2Selected from water-soluble hetero atom organic complexing agent, including alcohol, aldehyde, ketone, ether,
The mixing of one or more of ester, amide, urea, nitrile, sulfide；A, b, d, m and n are zero or value meets positive and negative charge number
Balance, wherein b is positive integer；X is positive number, and c, y and z are zero or positive number；
The general formula of nucleophilic moiety is R1R2 3YX1Salt, in formula: R1For C1~C16Alkyl, R2For C1~C6Alkyl or phenyl；Y be nitrogen,
Phosphorus or arsenic element；X1For Cl-1、Br-1、I-1、NO3 -1、CH3COO-1、ClO4 -1、BF4 -1、OH-1、BPh4 -1Or N3 -1Monovalence anion.
3. a kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate according to claim 2, special
Sign is that the X is F-、Cl-、Br-、I-、NO3 -、CH3COO-、SO4 2-, it is methyl benzoate, p-methyl benzenesulfonic acid root, o-
Nitrophenol oxygen, p- nitrophenol oxygen or m- nitrophenol oxygen；The L2For the tert-butyl alcohol, isopropanol, ethylene glycol, the third two
Alcohol, glycol monoethyl ether, dimethoxy-ethane or tert-pentyl alcohol.
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| CN201910361616.4A CN110003163A (en) | 2019-04-30 | 2019-04-30 | A kind of method that cyclic spray formula gas-liquid contact technique prepares cyclic carbonate |
| PCT/CN2020/077112 WO2020220813A1 (en) | 2019-04-30 | 2020-02-28 | Method for preparing cyclic carbonate ester using circulation loop gas-liquid contact process |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684005A (en) * | 2019-10-31 | 2020-01-14 | 大连理工大学 | Cyclic injection type continuous reaction process for preparing cyclic carbonate |
| CN111072623A (en) * | 2019-12-30 | 2020-04-28 | 江苏奥克化学有限公司 | Method for preparing ethylene carbonate by cyclic injection mixing method |
| CN111072452A (en) * | 2019-12-30 | 2020-04-28 | 江苏奥克化学有限公司 | Method for preparing ethylene glycol |
| WO2020220813A1 (en) * | 2019-04-30 | 2020-11-05 | 大连理工大学 | Method for preparing cyclic carbonate ester using circulation loop gas-liquid contact process |
| CN113321688A (en) * | 2021-06-10 | 2021-08-31 | 大连理工大学 | Bifunctional catalyst and method for preparing cyclic carbonate and polycarbonate by using same in external loop reaction process |
| CN113501803A (en) * | 2021-07-14 | 2021-10-15 | 张文进 | Preparation method of high-purity ethylene carbonate and propylene carbonate |
| CN114700114A (en) * | 2022-03-17 | 2022-07-05 | 大连理工大学 | Water-phase bifunctional catalyst and method for preparing dihydric alcohol by using same in external loop reaction process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020220813A1 (en) * | 2019-04-30 | 2020-11-05 | 大连理工大学 | Method for preparing cyclic carbonate ester using circulation loop gas-liquid contact process |
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| CN113321688A (en) * | 2021-06-10 | 2021-08-31 | 大连理工大学 | Bifunctional catalyst and method for preparing cyclic carbonate and polycarbonate by using same in external loop reaction process |
| CN113321688B (en) * | 2021-06-10 | 2022-03-29 | 大连理工大学 | Bifunctional catalyst and method for preparing cyclic carbonate and polycarbonate by using same in external loop reaction process |
| CN113501803A (en) * | 2021-07-14 | 2021-10-15 | 张文进 | Preparation method of high-purity ethylene carbonate and propylene carbonate |
| CN114700114A (en) * | 2022-03-17 | 2022-07-05 | 大连理工大学 | Water-phase bifunctional catalyst and method for preparing dihydric alcohol by using same in external loop reaction process |
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