CN115819392A - Isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate - Google Patents
Isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate Download PDFInfo
- Publication number
- CN115819392A CN115819392A CN202211020725.8A CN202211020725A CN115819392A CN 115819392 A CN115819392 A CN 115819392A CN 202211020725 A CN202211020725 A CN 202211020725A CN 115819392 A CN115819392 A CN 115819392A
- Authority
- CN
- China
- Prior art keywords
- isothermal
- carbon dioxide
- catalyst
- reactor
- synthesis method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 120
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 60
- 239000001569 carbon dioxide Substances 0.000 claims description 60
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 23
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 230000003068 static effect Effects 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- 239000002815 homogeneous catalyst Substances 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000003507 refrigerant Substances 0.000 claims description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- -1 202 Chemical compound 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an isothermal synthesis method for preparing ethylene carbonate or propylene carbonate, belonging to the technical field of organic synthesis. By adopting the isothermal synthesis method of ethylene carbonate or propylene carbonate, the maximum temperature difference of all parts in the isothermal reactor is less than 5 ℃, the reaction temperature range is narrow, the temperature is easy to control and keep constant, the overtemperature and overpressure of the reactor can be effectively avoided, side reaction products are few, a crude product is easy to refine, the service life of the catalyst is long, the loss of the catalyst is small, and the isothermal synthesis method has a wide application prospect.
Description
Technical Field
The invention relates to an isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate, belonging to the technical field of organic synthesis.
Background
Ethylene carbonate and propylene carbonate are important organic chemicals, are important raw materials for producing electrolyte solvents of lithium ion batteries, and are also important raw materials for preparing dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate by a transesterification method.
The direct catalytic addition reaction of carbon dioxide and ethylene oxide or propylene oxide is a main method for preparing ethylene carbonate or propylene carbonate, and the main reaction equation is as follows:
C 2 H 4 o (ethylene oxide) + CO 2 (carbon dioxide) → C 3 H 4 O 3 (ethylene carbonate)
C 3 H 6 O (propylene oxide) + CO 2 (carbon dioxide) → C 4 H 6 O 3 (propylene carbonate)
In the industry, the addition reaction of carbon dioxide and ethylene oxide or propylene oxide generally adopts a homogeneous catalyst, the reaction is carried out under the conditions of 2.0-5.5 MPa and 100-200 ℃, and the reaction temperature ranges required to be controlled by different catalysts are different. However, the requirements of such catalysts on the reaction conditions are very severe, mainly because they require rapid removal of the heat of reaction and control of the reaction temperature within a very narrow window, which is mainly considered from the following aspects:
(1) On the one hand, the reaction is strongly exothermic with reduced volume, but the residence time required for the reaction to proceed sufficiently is relatively long. Along with the reaction, the temperature of the reaction liquid in which the catalyst is dissolved is increased sharply, the catalyst is easy to deactivate, and the loss amount of the catalyst is large;
(2) On the other hand, because the raw materials inevitably contain a small amount of impurities such as water content and the like, if the reaction heat cannot be removed in time, when the temperature deviates from an optimal reaction temperature window, a large amount of byproducts are generated due to the catalytic side reaction, so that the yield and selectivity of a main product are reduced, and the difficulty in separating and refining the product is increased. Taking ethylene oxide and carbon dioxide as raw materials to prepare ethylene carbonate as an example, the side reaction equation is as follows:
C 2 H 4 o (ethylene oxide) + H 2 O (water) → C 2 H 6 O 2 (ethylene glycol)
C 2 H 4 O (ethylene oxide) + C 2 H 6 O 2 (ethylene glycol) → C 4 H 10 O 3 (diethylene glycol)
C 2 H 4 O (ethylene oxide) + C 4 H 10 O 3 (diethylene glycol) → C 6 H 14 O 4 (triethylene glycol)
C 3 H 4 O 3 (ethylene carbonate) + H 2 O (water) → C 2 H 6 O 2 (ethylene glycol) + CO 2 (carbon dioxide)
Wherein, the boiling points of the by-product diethylene glycol and the ethylene carbonate are quite close to each other, and the difference is only 3 ℃, which easily causes that the indexes of the high-purity ethylene carbonate product do not reach the standard;
(3) Moreover, the steam pressure of ethylene oxide, propylene oxide and carbon dioxide is extremely sensitive to temperature fluctuation, and the local temperature rise in the reactor can cause the ethylene oxide or propylene oxide and carbon dioxide dissolved in the reaction liquid in the region to be rapidly gasified, so that the orderly progress of the reaction is damaged, the back mixing of the reaction liquid, the out-of-control reaction, the over-temperature and over-pressure of the reactor are caused, and even safety accidents are caused.
CN108484565B discloses a system for producing carbonate and a method for producing carbonate using the same. The invention is provided with a first bubble column, a second bubble column and a heat exchanger, reaction heat is removed by cooling reaction circulating materials through the heat exchanger, and the reaction temperature in the bubble column is controlled. However, the invention has the following disadvantages: in order to control the reaction material temperature at the outlet end of the bubble tower not to exceed the temperature, the circulating material can only be cooled by the heat exchanger, the circulating material temperature at the outlet of the heat exchanger is low, the reaction temperature at the inlet of the bubble tower is low, a large temperature difference exists between the inlet end and the outlet end in the first bubble tower and the second bubble tower, the reaction temperature interval is wide, the temperature of the whole reaction process cannot be controlled in the optimal reaction temperature interval, and then the yield of ethylene carbonate or propylene carbonate is reduced, a large number of reaction byproducts are generated, the catalyst is quickly inactivated, and the catalyst loss is large.
CN209456353U discloses a reaction device for synthesizing ethylene carbonate. The utility model discloses a set up reaction circulating pump, circulation liquid cooler, circulation liquid heater, first reactor bottom is connected to second reactor bottom through circulation liquid cooler, and circulation liquid heater's lower extreme is connected to circulation liquid cooler through the reaction circulating pump. The utility model has the following disadvantages: the circulating liquid of the first reactor is forcibly circulated by the reaction circulating pump, once the reaction circulating pump fails, reaction heat cannot be timely removed from the reaction system, the first reactor and the second reactor are over-temperature and over-pressure, and the device is stopped; under the conditions of large device scale and high reactor size, the temperature difference between the top of the first reactor and the bottom of the first reactor is large, which is not beneficial to controlling the reaction temperature in a narrow optimal reaction temperature window of the catalyst, reducing reaction byproducts, improving the yield of ethylene carbonate and prolonging the service life of the catalyst.
Therefore, the isothermal synthesis method of ethylene carbonate and propylene carbonate, which has the advantages of narrow reaction temperature range, easy control and constancy of temperature, effective avoidance of over-temperature and over-pressure of a reactor, few side reaction products, easy refining of crude products and long service life of catalysts, is provided, and has wide application prospect.
Disclosure of Invention
The invention aims to solve the problems of wide reaction temperature range, easy over-temperature and over-pressure of a reactor, more reaction byproducts, difficult refining and qualification of a crude product, short service life of a catalyst and high consumption of the catalyst in the prior art.
In order to achieve the above object, the present invention provides an isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate, comprising the steps of:
(1) Uniformly mixing ethylene oxide and/or propylene oxide and a catalyst by a static mixer, and introducing into the upper part of the isothermal reactor;
(2) After being distributed by a carbon dioxide feeding distribution control system, carbon dioxide is introduced into the isothermal reactor from the lower part of each layer of carbon dioxide distributor arranged in the isothermal reactor;
(3) Respectively adjusting the refrigerant consumption of each heat-transfer isothermal controller arranged in the isothermal reactor, and accurately controlling the reaction temperature of each region in the isothermal reactor to be in the optimal reaction temperature window of the catalyst;
(4) Discharging the reaction product from the bottom of the isothermal reactor, introducing the reaction product into a light component flash tank for flash evaporation, and removing light components dissolved in the reaction product;
(5) Discharging the reaction product after flash evaporation from the bottom of the light component flash evaporation tank, and introducing the reaction product into a catalyst separation and recovery tank to separate the product from the catalyst;
(6) The separated circulating catalyst is sent back to the static mixer, and the separated crude product gas is introduced into a crude product condenser;
(7) And introducing the condensed crude product into a crude product receiving tank, and finally refining to produce high-purity ethylene carbonate or propylene carbonate.
Through the technical scheme, the invention has the following beneficial effects:
(1) Regulating the amount of carbon dioxide introduced into each area of the isothermal reactor through a carbon dioxide feeding distribution control system to roughly control the reaction temperature of each area in the isothermal reactor; the method comprises the following steps of accurately controlling the reaction temperature of each area in the isothermal reactor to be within the optimal reaction temperature window of a catalyst by adjusting the refrigerant consumption of each heat-transfer isothermal controller arranged in the isothermal reactor; the maximum temperature difference of each area in the reactor is less than 5 ℃, and isothermal reaction is realized;
(2) The byproducts generated by the reaction are few, and the ethylene carbonate or propylene carbonate has high selectivity and high yield, so the raw material consumption is low, and the method is favorable for further refining a crude product to produce high-purity ethylene carbonate or propylene carbonate;
(3) The temperature of the reactor is easy to control and constant, and the over-temperature and over-pressure of the reactor and even the safety accidents caused by the untimely heat transfer of the reactor are greatly reduced.
Drawings
Fig. 1 is a schematic diagram of an embodiment of an isothermal synthesis system for preparing ethylene carbonate or propylene carbonate according to the present invention.
FIG. 2 is a schematic view of the arrangement of the radial thermometers and the axial thermometers in a certain zone of the isothermal reactor of the present invention.
Description of the reference numerals
101. A carbon dioxide pressure stabilizing tank, 102, a static mixer, 103, an isothermal reactor, 104, a light component flash tank, 105, a catalyst separation and recovery tank, 106, a crude product condenser, 107, a crude product receiving tank, 108, a heat transfer isothermal controller, 109, a carbon dioxide distributor, 110, a carbon dioxide feed distribution control system, 201, carbon dioxide, 202, ethylene oxide or propylene oxide, 203, a catalyst, 204, a reaction product, 205, a reaction product after flash evaporation, 206, a circulating catalyst, 207, a crude product gas, 208, a condensed crude product
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate, which comprises the following steps:
(1) Uniformly mixing ethylene oxide and/or propylene oxide and a catalyst by a static mixer, and introducing into the upper part of the isothermal reactor;
(2) After being distributed by a carbon dioxide feeding distribution control system, carbon dioxide is introduced into the isothermal reactor from the lower part of each layer of carbon dioxide distributor arranged in the isothermal reactor;
(3) Respectively adjusting the refrigerant consumption of each heat-transfer isothermal controller arranged in the isothermal reactor, and accurately controlling the reaction temperature of each region in the isothermal reactor to be in the optimal reaction temperature window of the catalyst;
(4) Discharging the reaction product from the bottom of the isothermal reactor, introducing the reaction product into a light component flash tank for flash evaporation, and removing light components dissolved in the reaction product;
(5) Discharging the reaction product after flash evaporation from the bottom of the light component flash tank, and introducing the reaction product into a catalyst separation and recovery tank to separate the product from the catalyst;
(6) The separated circulating catalyst is sent back to the static mixer, and the separated crude product gas is introduced into a crude product condenser;
(7) And introducing the condensed crude product into a crude product receiving tank, and finally refining to produce high-purity ethylene carbonate or propylene carbonate.
According to the invention, preferably, the carbon dioxide feed distribution control system is associated with the reaction temperature of each zone in the isothermal reactor, and the reaction temperature of each zone in the isothermal reactor is roughly controlled within the optimal reaction temperature window of the catalyst by adjusting the amount of carbon dioxide entering each reaction zone.
According to the invention, it is preferred that each zone of the isothermal reactor is provided with at least 2 sets of radial thermometers and 2 sets of axial thermometers.
According to the invention, it is preferred that the maximum temperature difference everywhere inside the isothermal reactor is less than 5 ℃.
According to the invention, it is preferred that the maximum temperature difference everywhere inside the isothermal reactor is less than 3 ℃.
According to the present invention, preferably, the catalyst is a homogeneous catalyst, more preferably tetraethylammonium bromide. The homogeneous catalyst (e.g., tetraethylammonium bromide) can be used by dissolving it in an organic solvent (e.g., ethylene carbonate and/or propylene carbonate) and then mixing it with ethylene oxide and/or propylene oxide in a static mixer.
According to the invention, the weight ratio of catalyst to ethylene oxide or propylene oxide is preferably 1:500-1000 (e.g., 1:650-800.
According to the invention, the ratio of the weight of ethylene oxide or propylene oxide to the total weight of carbon dioxide is preferably 1:0.7-1.2 (e.g., 1:0.8-1.05.
According to the present invention, it is preferable that the plurality of heat-transferring isothermal controllers are provided, an axial distance between two adjacent heat-transferring isothermal controllers is 1 to 3 times (e.g., 1 time, 1.5 times, 2 times, 2.5 times, 3 times, and a range of any two points) the diameter of the isothermal reactor, and an axial height of a single heat-transferring isothermal controller is 1 to 5 times (e.g., 1 time, 1.5 times, 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times, and a range of any two points) the diameter of the isothermal reactor.
According to the invention, preferably, the isothermal reactor diameter is between 0.1 and 10m (for example, 0.2m, 0.5m, 0.8m, 1m, 1.5m, 2m, 2.5m, 3m, 3.5m, 4m, 4.5m, 5m, 5.5m, 6m, 7m, 8m, 9m, 10m, and the ranges consisting of any two of the above), preferably between 0.5 and 1.5m.
According to the invention, the axial distance of the lowermost carbon dioxide distributor in the isothermal reactor from the reaction product outlet of the isothermal reactor preferably represents a ratio of 1 to 20%, preferably 10 to 15%, of the total height of the isothermal reactor.
According to the invention, preferably, the number of the heat transfer isothermal controllers is 3-10.
According to the present invention, preferably, the carbon dioxide feed distribution control system divides the carbon dioxide into 3-10 strands (e.g., 3 strands, 4 strands, 5 strands, 6 strands, 7 strands, 8 strands, 9 strands, 10 strands).
According to the present invention, preferably, the carbon dioxide feed distribution control system divides the carbon dioxide into 4 strands; more preferably, the weight ratio of 4 strands of carbon dioxide in the flow direction of ethylene oxide or propylene oxide and catalyst is, in order, 1:1.5-2.5:2.5-3.5:3.5-4.5, preferably 1:1.8-2.1:2.8-3.2:3.8-4.
According to the present invention, preferably, the carbon dioxide feed distribution control system divides the carbon dioxide into 6 strands; more preferably, the weight ratio of 6 strands of carbon dioxide in the flow direction of ethylene oxide or propylene oxide and catalyst is 1:1.5-2.5:2.5-3.5:3.5-4.5:4.5-5.5:5.5-6.5, preferably 1:1.8-2.3:2.9-3.4:3.7-4.2:4.6-5.3:5.7-6.4.
According to the present invention, preferably, the conditions of the flash evaporation include: the temperature is 135-150 deg.C and the pressure is-0.1-0.2 MPaG.
According to the present invention, preferably, the conditions of the separation include: the temperature is 135-150 deg.C, and the pressure is-0.1-0.05 MPaG. More preferably, in order to maintain the continuous and stable reaction process, the catalyst obtained from the bottom of the catalyst recovery tank is divided into two parts, one part is used as the circulating catalyst and returned to the static mixer, and the rest is discharged; at the same time, the corresponding fresh catalyst needs to be continuously replenished to keep the concentration of the catalyst in the isothermal reactor stable. The amount of catalyst discharged is recorded as the loss of catalyst, and in general, the loss of catalyst can be expressed in terms of the amount of catalyst discharged (kg) per 1 ton of EC or PC product produced.
According to the present invention, preferably, the operating conditions of the raw product condenser comprise: the temperature is 80-90 ℃ and the pressure is-0.1 to 0.1MPaG.
According to the invention, the pressure inside the isothermal reactor 103 is preferably comprised between 3.5 and 4.5MPaG.
The present invention will be described in detail below by way of examples. In the following examples of the present invention, the following examples,
ethylene carbonate (or propylene carbonate) selectivity = amount of ethylene oxide or propylene oxide species consumed to ethylene carbonate or propylene carbonate/(amount of ethylene oxide or propylene oxide species at the isothermal reactor inlet-amount of ethylene oxide or propylene oxide species at the isothermal reactor outlet) × 100%.
Example 1
The embodiment provides an isothermal synthesis system method for preparing ethylene carbonate, which comprises the following steps:
(1) After uniformly mixing ethylene oxide 202 and a catalyst 203 by a static mixer 102, introducing the mixture into the upper part of an isothermal reactor 103;
(2) Carbon dioxide 201 enters a carbon dioxide pressure stabilizing tank 101, is distributed by a carbon dioxide feeding distribution control system 110, and then is introduced into the isothermal reactor 103 from the lower part of each layer of carbon dioxide distributor 109 arranged in the isothermal reactor 103; the pressure inside the isothermal reactor 103 was 4MPaG;
(3) Respectively adjusting the refrigerant consumption of each heat-transfer isothermal controller 108 arranged in the isothermal reactor 103, and accurately controlling the reaction temperature of each region in the isothermal reactor 103 to be within the optimal reaction temperature window of the catalyst;
(4) Discharging the reaction product 204 from the bottom of the isothermal reactor 103, introducing into a light component flash tank 104 for flash evaporation, and removing light components dissolved in the reaction product 204; wherein the flash conditions include: the temperature was 140 ℃ and the pressure was 0.1MPaG.
(5) Discharging the reaction product 205 after the flash evaporation from the bottom of the light component flash tank 104, and introducing the reaction product into the catalyst separation and recovery tank 105 to separate the product from the catalyst; wherein the separation conditions include: the temperature was 145 ℃ and the pressure was-0.09 MPaG.
(6) The separated circulating catalyst 206 is sent back to the static mixer 102, and the separated crude product gas 207 is introduced into the crude product condenser 106; the operating conditions of the raw product condenser 106 include, among others: the temperature was 85 ℃ and the pressure was-0.09 MPaG.
(7) The condensed crude product 208 is introduced into the crude product receiving tank 107, and finally sent to be refined to produce high-purity ethylene carbonate.
Wherein the carbon dioxide feed distribution control system 110 is associated with the reaction temperature of each zone in the isothermal reactor 103, and the reaction temperature of each zone in the isothermal reactor 103 is roughly controlled within the optimal reaction temperature window of the catalyst by adjusting the amount of carbon dioxide entering each reaction zone. The carbon dioxide feeding distribution control system divides the carbon dioxide into 4 strands, and along the flow direction of ethylene oxide and catalyst, the weight ratio of 4 strands of carbon dioxide is 1:2:3:4.
wherein, 3 groups of radial thermometers and 3 groups of axial thermometers are arranged in each area of the isothermal reactor 103.
Wherein the catalyst is a homogeneous catalyst tetraethylammonium bromide organic solution.
The number of the heat transfer isothermal controllers 108 is 4 (from top to bottom, 1#, 2#, 3#, and 4# heat transfer isothermal controllers respectively), the axial distance between two adjacent heat transfer isothermal controllers is 2 meters, and the axial height of a single heat transfer isothermal controller 108 is 3 meters. Wherein the isothermal reactor 103 has a diameter of 0.8 meter and a height of 20 meters.
The process data of the isothermal synthesis method of ethylene carbonate are shown in table 1.
Example 2
The isothermal synthesis method of ethylene carbonate used is the same as in example 1, with the following differences: 6 heat-transferring temperature controllers 108 (1 #, 2#, 3#, 4#, 5#, and 6# heat-transferring isothermal controllers from top to bottom) are arranged in the isothermal reactor 103, the axial distance between two adjacent heat-transferring isothermal controllers is 1 meter, and the axial height of a single heat-transferring isothermal controller 108 is 2 meters. The carbon dioxide feed distribution control system divides the carbon dioxide into 6 streams, and the weight ratio of the 6 streams of carbon dioxide is 1:2:3:4:5:6.
the process data of the isothermal synthesis method of ethylene carbonate are shown in table 1.
TABLE 1
Example 3
The isothermal synthesis method used was the same as in example 1, with the difference that: propylene carbonate is prepared by adopting propylene oxide and carbon dioxide as raw materials, and the adopted homogeneous catalyst is composite modified ionic liquid.
The process data of the isothermal synthesis method of propylene carbonate are shown in table 2.
Example 4
The isothermal synthesis system used was the same as in example 2, except that: propylene carbonate is prepared by adopting propylene oxide and carbon dioxide as raw materials, and the adopted homogeneous catalyst is composite modified ionic liquid.
The process data of the isothermal synthesis method of propylene carbonate are shown in table 2.
TABLE 2
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate is characterized by comprising the following steps:
(1) Uniformly mixing ethylene oxide and/or propylene oxide and a catalyst by a static mixer, and introducing into the upper part of the isothermal reactor;
(2) After being distributed by a carbon dioxide feeding distribution control system, carbon dioxide is introduced into the isothermal reactor from the lower part of each layer of carbon dioxide distributor arranged in the isothermal reactor;
(3) Respectively adjusting the refrigerant consumption of each heat-transfer isothermal controller arranged in the isothermal reactor, and accurately controlling the reaction temperature of each area in the isothermal reactor to be in the optimal reaction temperature window of the catalyst;
(4) Discharging the reaction product from the bottom of the isothermal reactor, introducing the reaction product into a light component flash tank for flash evaporation, and removing light components dissolved in the reaction product;
(5) Discharging the reaction product after flash evaporation from the bottom of the light component flash evaporation tank, and introducing the reaction product into a catalyst separation and recovery tank to separate the product from the catalyst;
(6) The separated circulating catalyst is sent back to the static mixer, and the separated crude product gas is introduced into a crude product condenser;
(7) And introducing the condensed crude product into a crude product receiving tank, and finally refining to produce high-purity ethylene carbonate or propylene carbonate.
2. The isothermal synthesis method according to claim 1, wherein the carbon dioxide feed distribution control system is associated with the reaction temperature of each zone in the isothermal reactor, and the reaction temperature of each zone in the isothermal reactor is roughly controlled within the optimal reaction temperature window of the catalyst by adjusting the amount of carbon dioxide entering each reaction zone.
3. The isothermal synthesis process according to claim 1 or 2, characterized in that the maximum temperature difference everywhere inside the isothermal reactor is less than 5 ℃.
4. The isothermal synthesis process according to claim 1 or 2, characterized in that the maximum temperature difference everywhere inside the isothermal reactor is less than 3 ℃.
5. The isothermal synthesis method according to claim 1, characterized in that said catalyst is a homogeneous catalyst.
6. The isothermal synthesis method according to claim 1, characterized in that the weight ratio of catalyst to ethylene oxide or propylene oxide is 1:500-1000, preferably 1:650-800.
7. The isothermal synthesis method according to claim 1, characterized in that the ratio of the weight of ethylene oxide or propylene oxide to the total weight of carbon dioxide is 1:0.7-1.2, preferably 1:0.8-1.05.
8. The isothermal synthesis method according to claim 1, wherein the number of the heat-transfer isothermal controllers is multiple, the axial distance between two adjacent heat-transfer isothermal controllers is 1-3 times of the diameter of the isothermal reactor, and the axial height of a single heat-transfer isothermal controller is 1-5 times of the diameter of the isothermal reactor;
preferably, the number of the heat transfer isothermal controllers is 3-10;
more preferably, the carbon dioxide feed distribution control system divides the carbon dioxide into 3 to 10 streams.
9. The isothermal synthesis method according to claim 8, wherein the carbon dioxide feed distribution control system divides carbon dioxide into 4 streams;
preferably, the weight ratio of 4 strands of carbon dioxide in the flow direction of ethylene oxide or propylene oxide and catalyst is 1:1.5-2.5:2.5-3.5:3.5-4.5, preferably 1:1.8-2.1:2.8-3.2:3.8-4.
10. The isothermal synthesis method according to claim 8, wherein the carbon dioxide feed distribution control system divides carbon dioxide into 6 strands;
preferably, the weight ratio of 6 strands of carbon dioxide in the flow direction of ethylene oxide or propylene oxide and catalyst is 1:1.5-2.5:2.5-3.5:3.5-4.5:4.5-5.5:5.5-6.5, preferably 1:1.8-2.3:2.9-3.4:3.7-4.2:4.6-5.3:5.7-6.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211020725.8A CN115819392B (en) | 2022-08-24 | 2022-08-24 | Isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211020725.8A CN115819392B (en) | 2022-08-24 | 2022-08-24 | Isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115819392A true CN115819392A (en) | 2023-03-21 |
| CN115819392B CN115819392B (en) | 2024-07-23 |
Family
ID=85523187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211020725.8A Active CN115819392B (en) | 2022-08-24 | 2022-08-24 | Isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115819392B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN205046024U (en) * | 2015-02-02 | 2016-02-24 | 中国石油天然气股份有限公司 | Reaction device for synthesizing ethylene carbonate from ethylene oxide and carbon dioxide |
| CN106478585A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The control method of ethylene carbonate building-up process |
| CN113072530A (en) * | 2021-03-19 | 2021-07-06 | 中建安装集团有限公司 | Device and method for producing electronic-grade ethylene carbonate |
| CN116020350A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Reactor for synthesizing carbonic ester, system and method for synthesizing carbonic ester |
-
2022
- 2022-08-24 CN CN202211020725.8A patent/CN115819392B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN205046024U (en) * | 2015-02-02 | 2016-02-24 | 中国石油天然气股份有限公司 | Reaction device for synthesizing ethylene carbonate from ethylene oxide and carbon dioxide |
| CN106478585A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | The control method of ethylene carbonate building-up process |
| CN113072530A (en) * | 2021-03-19 | 2021-07-06 | 中建安装集团有限公司 | Device and method for producing electronic-grade ethylene carbonate |
| CN116020350A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Reactor for synthesizing carbonic ester, system and method for synthesizing carbonic ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115819392B (en) | 2024-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP4049748A1 (en) | Gas-liquid bubbling bed reactor, reaction system and method for synthesizing carbonate | |
| CN104761429B (en) | A kind of method for producing dimethyl carbonate and ethylene glycol | |
| CN112961058B (en) | Process method for preparing glycol maleate | |
| CN102775274B (en) | System and method for preparing ethylene glycol through oxalate hydrogenation | |
| CN110003007A (en) | Coal-ethylene glycol carbonylation dimethyl oxalate rectifying and purifying system and method | |
| CN102548950B (en) | Process for preparing alkanediol and dialkyl carbonate | |
| CN101830807B (en) | Synthesizing device and process for alkyl nitrite | |
| CN113072530B (en) | Device and method for producing electronic-grade ethylene carbonate | |
| CN112876452A (en) | Preparation method and reaction device of lactide | |
| CN103804142A (en) | System and method used for preparing glycol via hydrogenation of oxalic ester | |
| CN105536654A (en) | Large-scale axial multistage-mixing heat exchange type oxydehydrogenation reactor for butylene | |
| CN101108790B (en) | Method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction | |
| CN1364152A (en) | Method for the continuous production of methyl formiate | |
| CN115819392B (en) | Isothermal synthesis method for preparing ethylene carbonate and/or propylene carbonate | |
| CN106588863A (en) | System and process for preparing cyclic carbonate by using composite ionic liquid catalyst | |
| WO2022155762A1 (en) | Preparation method for lactide and reaction device | |
| US20240174628A1 (en) | Method for continuously preparing crude ethylene sulfate | |
| CN218530864U (en) | Isothermal synthesis system for preparing ethylene carbonate and/or propylene carbonate and device suitable for exothermic reaction | |
| CN108658766A (en) | A kind of device and method of coproduction ethylene glycol and dimethyl carbonate | |
| CN101898930A (en) | Device for producing cyclohexane by adding hydrogen in benzene and synthesis process | |
| CN112441996A (en) | Process for preparing tetrahydrofuran | |
| CN103073452A (en) | Method for removing phosgene | |
| CN204939338U (en) | A kind of reactive system of coking crude benzene hydrogenation technique | |
| CN116020350A (en) | Reactor for synthesizing carbonic ester, system and method for synthesizing carbonic ester | |
| CN209338426U (en) | A kind of equipment of coproduction ethylene glycol and dimethyl carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |