CN114957010A - Application of catalyst in synthesis of dimethyl carbonate and dihydric alcohol by alcohol exchange method - Google Patents
Application of catalyst in synthesis of dimethyl carbonate and dihydric alcohol by alcohol exchange method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B01D3/14—Fractional distillation or use of a fractionation or rectification column
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
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Abstract
The invention discloses an application of a catalyst in synthesizing dimethyl carbonate and dihydric alcohol through alcohol exchange. The invention solves the problems of low solubility of the homogeneous catalyst in a reaction system, easy decomposition to generate precipitate and pipeline blockage in the prior art, and has the advantages of low catalyst price, repeated and cyclic use, high degree of continuity of the synthesis process and convenient operation.
Description
Technical Field
The invention relates to the technical field of dimethyl carbonate preparation, in particular to application of a catalyst in alcohol exchange synthesis of dimethyl carbonate and dihydric alcohol.
Background
Dimethyl carbonate (or called dimethyl carbonate, DMC) has the characteristics of no toxicity and easy biodegradation, has good reaction activity, is an environment-friendly green basic chemical raw material, is used as a solvent with excellent performance and an organic synthesis intermediate, and has wide application in the industrial fields of electrolyte solvents, polycarbonate, coatings, detergents, surfactants and the like.
At present, the main synthetic methods of the dimethyl carbonate are a methanol oxidation carbonylation method, a urea alcoholysis method and an alcohol exchange method (or called an ester exchange method). The methanol oxidation carbonylation method is divided into a liquid phase method and a gas phase method, the liquid phase method and the gas phase method both have wastewater discharge, the former adopts a copper compound, a catalyst is unstable and has strong corrosion to equipment, and the latter introduces toxic nitrogen oxide and has potential safety hazard of easy explosion. The direct alcoholysis of urea has poor reaction selectivity, low single-pass conversion rate, easy decomposition of urea and intermediate products to block pipeline and high cost. The alcohol exchange method has the advantages of mild reaction conditions, high yield, low equipment investment, high production safety, less waste residues and the like, and the co-produced dihydric alcohol is an important chemical raw material, so the alcohol exchange method is the main process applied in industry at present.
The industrial synthesis of dimethyl carbonate and diol by alcohol exchange process includes homogeneous phase process and heterogeneous phase process. The heterogeneous catalysts reported at present mainly comprise ion exchange resins, zeolite molecular sieves and metal oxide type solid base catalysts. CN101829554A discloses a silica-coated magnesium oxide catalyst with a flower-like structure, which is used for the exchange reaction of cyclic carbonate and methanol, the selectivity of dimethyl carbonate is 95%, the yield of dimethyl carbonate is obviously reduced after the catalyst is circulated for ten times, and the catalyst is easy to deactivate. Patent CN105344341A discloses a preparation method of a graphene oxide supported magnesium oxide catalyst, which is not favorable for industrial production. At present, heterogeneous catalysts are complex to prepare, have the problems of poor activity and stability, and are difficult to meet the large-scale requirement of alcohol exchange reaction. Compared with a heterogeneous catalyst, the homogeneous catalysis has the greatest advantages of high reaction efficiency, mild reaction conditions, high safety and easiness in large-scale production.
Homogeneous catalysts include alkali metal methoxides and acetates, and the like. The most reactive homogeneous catalyst reported to date is sodium methoxide. Patents CN101774888A and CN1569807A disclose a sodium methoxide homogeneous catalyst, which uses cyclopropane carbonate and methanol as raw materials to obtain higher DMC yield. However, the sodium methoxide catalyst has low solubility in the reaction system, and forms emulsion or paste when the concentration is too high, and meets water and CO 2 Is easy to decompose, not only blocks pipelines, but also generates a large amount of waste residues in industrial production, and reduces the yield of propylene glycol (1, 2-propylene glycol, PG) or Ethylene Glycol (EG). Therefore, in order to improve the utilization efficiency of the homogeneous catalyst, reduce energy consumption and reduce emission, it is urgently required to develop a catalyst capable of resisting water and CO 2 And the catalyst has higher activity, can be recycled, and a regeneration process, so that the catalyst cost is reduced, the raw material consumption is reduced, and the yield is improved.
Disclosure of Invention
The invention aims to solve the problems and provide an application of a catalyst in alcohol exchange synthesis of dimethyl carbonate and dihydric alcohol. The catalyst related by the method is cheap and easy to obtain, the stability is good, the process flow for separating the catalyst from the product is simple, the catalyst can be recycled, and the equipment cost is saved.
The purpose of the invention is realized by the following technical scheme:
the application of a catalyst in synthesizing dimethyl carbonate and dihydric alcohol through alcohol exchange is characterized in that cyclohexane carbonate or cyclopropane carbonate and methanol are used as raw materials, alkali metal carbonate is used as a catalyst, alcohol exchange reaction is carried out, and the dimethyl carbonate and the dihydric alcohol are simultaneously generated, wherein the alkali metal carbonate is one or a mixture of potassium carbonate, rubidium carbonate and cesium carbonate. The catalyst consists of carbonates of alkali metals, so that CO can be avoided 2 And water, reducing catalyst deactivation.
Further, the alkali metal carbonate is one or two of potassium carbonate, rubidium carbonate or cesium carbonate, and potassium carbonate is preferred because the solubility of potassium carbonate is moderate and the cost is low;
further, the molar ratio of the alkali metal carbonate to the ethylene carbonate (or ethylene carbonate, EC) or the propylene carbonate (or propylene carbonate, PC) in the catalyst is between 0.1 and 10.0%, preferably between 0.5 and 2.0%, which not only ensures better reaction speed, but also reduces the cost of the catalyst.
The alcohol exchange reaction is carried out in a reaction system, the reaction system comprises an alcohol exchange reaction unit, a methanol (Me), dihydric alcohol and catalyst separation unit, a methanol and dihydric alcohol separation unit and a catalyst recovery unit, the alcohol exchange reaction unit is used for the alcohol exchange reaction and consists of a rectification reactor, the methanol, the dihydric alcohol and catalyst separation unit is used for separating a catalyst and consists of a falling film evaporator, a separation circulating tank and a separation circulating pump, the methanol and dihydric alcohol separation unit is used for refining the recovered methanol and the recovered dihydric alcohol, and the catalyst recovery unit is used for the circulation of the catalyst and consists of a catalyst circulating pump.
Further, the alcohol exchange synthesis of dimethyl carbonate and diol specifically comprises the following steps:
(1) alcohol exchange reaction: respectively feeding ethylene carbonate or cyclopropane carbonate, methanol and catalyst materials into a rectification reactor of the reaction unit through respective feeding pumps, carrying out alcohol exchange reaction under the action of a catalyst, simultaneously generating dimethyl carbonate and dihydric alcohol, extracting an azeotrope of the methanol and the dimethyl carbonate from the top of the rectification reactor, and extracting a mixed material comprising the methanol, the dihydric alcohol and the catalyst from the bottom of the rectification reactor;
(2) catalyst separation: the mixed material extracted from the bottom of the rectification reactor enters the methanol, dihydric alcohol and catalyst separation unit, is evaporated by the falling film evaporator, steam enters the separation circulating tank, the steam of the mixture of the methanol and the dihydric alcohol is obtained from the top of the separation circulating tank, the mixture of the dihydric alcohol and the catalyst flows out from the bottom, and is conveyed to the falling film evaporator by the separation circulating pump for circular evaporation;
(3) and (3) separating the dihydric alcohol: obtaining steam of a mixture of methanol and dihydric alcohol from the top of the separation circulating tank, feeding the steam into a methanol and dihydric alcohol separation unit, and separating and recovering a methanol material and a dihydric alcohol material, wherein the dihydric alcohol is ethylene glycol or 1, 2-propylene glycol;
(4) and (3) catalyst circulation: and partial material at the bottom of the falling-film evaporator enters the rectification reactor through the catalyst circulating pump for cyclic utilization.
Further, the falling-film evaporator is operated under reduced pressure, and the pressure is between 5 and 15 kPa;
further, the rectification reactor is a plate tower, and the operating pressure is between 50 and 120 kPa;
further, the rectification reactor is divided into three sections, the uppermost section is a rectification section, the lower two sections are reaction sections, the raw material of the ethylene carbonate or the propylene carbonate and the catalyst are fed between the first section and the second section, and the raw material of the methanol is fed between the second section and the third section;
further, the tower bottom operation temperature of the rectification reactor is between 70 and 100 ℃.
Compared with the prior art, the invention has the following technical effects:
(1) the invention takes alkali carbonate as catalyst, the alkali carbonate is potassium carbonate, rubidium carbonate or cesium carbonate, the catalyst is composed of carbonate of alkali metal, CO is avoided 2 And water, the catalyst being affected by CO in the system 2 The catalyst has the advantages of small influence on water, high activity and good stability, overcomes the problem of decomposition and inactivation of the catalyst, can greatly reduce the using amount of the catalyst and the discharge amount of waste residues by recycling, reduces the production cost, and simultaneously improves the yield of the ethylene glycol and the 1, 2-propylene glycol.
(2) The catalyst has high solubility in a reaction system, effectively avoids the problem of blockage of a reactor and a pipeline, can effectively improve the stable reliability of continuous operation in industrial production, and reduces energy consumption and safety risk.
(3) The catalyst is simple to recover, the equipment investment is low, the degree of continuity is high, and the large-scale production is facilitated.
Drawings
FIG. 1 is a schematic diagram of the process of the present invention for alcohol exchange synthesis of dimethyl carbonate and diol.
Detailed Description
The spirit of the present invention will be further described with reference to the accompanying drawings and specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
The reaction system for synthesizing dimethyl carbonate and dihydric alcohol by alcohol exchange comprises an alcohol exchange reaction unit 100, a methanol, dihydric alcohol and catalyst separation unit 200, a methanol and dihydric alcohol separation unit 300 and a catalyst recovery unit 400, wherein the alcohol exchange reaction unit is used for alcohol exchange reaction and consists of a rectification reactor, the methanol, dihydric alcohol and catalyst separation unit is used for separating a catalyst and consists of a falling film evaporator, a separation circulation tank and a separation circulation pump, the methanol and dihydric alcohol separation unit is used for refining recovered methanol and dihydric alcohol, and the catalyst recovery unit is used for catalyst circulation and consists of a catalyst circulation pump.
The alcohol exchange synthesis of dimethyl carbonate and dihydric alcohol specifically comprises the following steps:
(1) alcohol exchange reaction: feeding the materials of the cyclic ethane carbonate or the cyclic propane carbonate, the methanol and the catalyst into a rectification reactor of the reaction unit 100 through a feed pump respectively, carrying out alcohol exchange reaction under the action of the catalyst, simultaneously generating the dimethyl carbonate and the dihydric alcohol, extracting an azeotrope of the methanol and the dimethyl carbonate from the top of the rectification reactor, and extracting a mixed material comprising the methanol, the dihydric alcohol and the catalyst from the bottom of the rectification reactor;
(2) catalyst separation: the mixed material extracted from the bottom of the rectification reactor enters the methanol, dihydric alcohol and catalyst separation unit 200, is evaporated by the falling-film evaporator, steam enters the separation circulating tank, the steam of the mixture of the methanol and the dihydric alcohol is obtained from the top of the separation circulating tank, the mixture of the dihydric alcohol and the catalyst flows out from the bottom of the separation circulating tank, and is conveyed to the falling-film evaporator by the separation circulating pump for cyclic evaporation;
(3) and (3) separating dihydric alcohol: obtaining steam of a mixture of methanol and dihydric alcohol from the top of the separation circulation tank, feeding the steam into a methanol and dihydric alcohol separation unit 300, and separating and recovering a methanol material and a dihydric alcohol material, wherein the dihydric alcohol is ethylene glycol or propylene glycol;
(4) and (3) catalyst circulation: and partial materials at the bottom of the falling-film evaporator enter the rectification reactor for recycling through the catalyst circulating pump of the catalyst recovery unit 400.
The cyclic Ethane Carbonate (EC) was fed at 70kmol/hr, corresponding to 5 million tons of dimethyl carbonate produced annually, the methanol/cyclic ethane carbonate molar ratio was 9, and the catalyst feed amount was 0.6% molar ratio of EC. The temperature of the bottom of the column was set at 70 ℃ and the pressure at the top of the column was set at 80 kPa. After the operation is stable, after methanol and DMC are extracted from the tower top, the product at the tower bottom is taken out for gas chromatography analysis after the reaction.
Conveying the tower bottom product to reduced pressure falling film evaporation treatment, adding the prepared raw material liquid into the tower bottom product subjected to reduced pressure falling film evaporation again to carry out the reaction, repeating the reaction for 10 times, wherein the experimental result is as follows:
TABLE 1EC and methanol reaction rectification cycle experiment
| Number of repeated use | EC conversion (%) | Catalyst content after concentration (%) |
| 1 | 97.6 | 13.9 |
| 2 | 96.9 | 12.5 |
| 3 | 97.2 | 10.4 |
| 4 | 96.6 | 14.3 |
| 5 | 97.0 | 17.2 |
| 6 | 96.1 | 9.8 |
| 7 | 97.7 | 12.5 |
| 8 | 97.9 | 20.8 |
| 9 | 98.6 | 20.0 |
| 10 | 98.2 | - |
As can be seen from table 1, the use of the alkali metal carbonate catalyst has good reactivity and mild reaction conditions, and the catalyst can be stably circulated 10 times.
Examples 1 to 5
Preparing a raw material liquid with the molar ratio of methanol to cyclic ethane carbonic ester of 10, uniformly mixing, adding the raw material liquid into a rectifying reactor kettle, and respectively adding 0.1, 0.3, 0.5, 1.0 and 2.0mol percent of K into the rectifying reactor kettle 2 CO 3 The conversion rate of the cyclic ethane carbonate is improved from 81.9 percent to 99.9 percent (relative to the cyclic ethane carbonate), the DMC selectivity is 100.0 percent, and the EG selectivity is more than 99.3 percent.
Examples 6 to 7
Preparing a raw material liquid with the molar ratio of methanol to cyclic ethane carbonic ester of 10, uniformly mixing, adding the raw material liquid into a rectifying reactor kettle, and respectively adding 0.1 mol% and 0.3 mol% of Na into the rectifying reactor kettle 2 CO 3 (relative to the cyclic ethane carbonate), the cyclic ethane carbonate conversion increased from 71.6% to 82.9%, the DMC selectivity was also 100.0%, and the EG selectivity was 99.8% and 99.4%, respectively.
Example 8
Preparing a raw material liquid with the molar ratio of methanol to cyclic ethane carbonic ester of 10, uniformly mixing, adding the raw material liquid into a rectifying reactor kettle, and respectively adding 0.3 mol% of Rb into the rectifying reactor kettle 2 CO 3 (relative to the cyclic ethane carbonate), the cyclic ethane carbonate conversion was 92.6%, the DMC selectivity was 100.0%, and the EG selectivity was 99.8%.
Example 9
Preparing a raw material liquid with the molar ratio of methanol to cyclic ethane carbonic ester of 10, uniformly mixing, adding the raw material liquid into a rectifying reactor kettle, and respectively adding 0.3 mol% of Cs into the rectifying reactor kettle 2 CO 3 (relative to the cyclic ethane carbonate), the cyclic ethane carbonate conversion was 93.2%, the DMC selectivity was 100.0%, and the EG selectivity was 99.6%.
TABLE 2 product composition of the EC and methanol alcohol exchange reaction under different conditions
As can be seen from Table 2, examples 1 to 9 were carried out in a rectification reactor, alcohol exchange reaction was carried out using EC and methanol, methanol as a raw material was refluxed to the top of the reaction column, and the components in the column bottom were analyzed by gas chromatography, and the products included dimethyl carbonate (DMC) and Ethylene Glycol (EG) as main products, and Ethylene Glycol Monomethyl Ether (EGME) and diethylene glycol (DEG) as by-products. EC conversion and EG selectivity were thus calculated, with DMC selectivity of 100% due to the absence of other carbonate based compounds in the product.
Examples 10 to 14
Preparing a raw material liquid with the molar ratio of methanol to cyclopropane carbonate of 10, uniformly mixing, adding the raw material liquid into a rectification reactor kettle, and respectively adding 0.1, 0.3, 0.5, 1.0 and 2.0mol percent of K into the reaction rectification kettle 2 CO 3 (relative to cyclopropane carbonate), the cyclopropane carbonate conversion increased from 76.4% to 99.3%, the DMC selectivity was 100.0%, and the EG selectivity was above 99.3%, as detailed in Table 3.
Performing activity evaluation in a rectification reactor, performing alcohol exchange reaction by using PC and methanol, fully refluxing raw material methanol and the top of the reaction process, and analyzing components in a tower kettle by using gas chromatography, wherein the product comprises main products of dimethyl carbonate (DMC) and Propylene Glycol (PG), and byproducts of Propylene Glycol Monomethyl Ether (PGME) and dipropylene glycol (DPG). From this, PC conversion and PG selectivity were calculated, and DMC selectivity was 100% due to the absence of other carbonate-based compounds in the product.
TABLE 3 product composition of the alcohol exchange reaction of PC with MeOH under various conditions
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The application of the catalyst in synthesizing dimethyl carbonate and dihydric alcohol through alcohol exchange is characterized in that cyclohexane carbonate or cyclopropane carbonate and methanol are used as raw materials, alkali metal carbonate is used as the catalyst, alcohol exchange reaction is carried out, and the dimethyl carbonate and the dihydric alcohol are generated simultaneously.
2. The use of a catalyst in the alcohol exchange synthesis of dimethyl carbonate and diol according to claim 1, wherein said alkali metal carbonate is selected from one or more of potassium carbonate, rubidium carbonate and cesium carbonate.
3. Use of a catalyst in the alcohol-exchange synthesis of dimethyl carbonate and glycols according to claim 1, wherein the molar ratio of alkali metal carbonate to said ethylene carbonate or propylene carbonate is between 0.1 and 10%.
4. The use of a catalyst in the alcohol exchange synthesis of dimethyl carbonate and diol according to claim 1, wherein the alkali metal carbonate is potassium carbonate and the molar ratio of the alkali metal carbonate to the ethylene carbonate or the propylene carbonate is between 0.5 and 2.0%.
5. The use of a catalyst in the alcohol-exchange synthesis of dimethyl carbonate and diol according to claim 1, wherein the alcohol-exchange reaction is carried out in a reaction system comprising: an alcohol exchange reaction unit (100), a methanol, glycol and catalyst separation unit (200), a methanol and glycol separation unit (300), and a catalyst recovery unit (400), wherein,
the alcohol exchange reaction unit (100) is used for alcohol exchange reaction and consists of a rectification reactor,
the methanol, dihydric alcohol and catalyst separation unit (200) is used for separating catalyst and consists of a falling film evaporator, a separation circulating tank and a separation circulating pump,
the methanol and glycol separation unit (300) is used to achieve refining of recovered methanol and glycol,
the catalyst recovery unit (400) is used for the circulation of the catalyst and consists of a catalyst circulation pump.
6. The use of the catalyst according to claim 5 in the alcohol-exchange synthesis of dimethyl carbonate and diol, wherein the alcohol-exchange synthesis of dimethyl carbonate and diol comprises the following steps:
(1) alcohol exchange reaction: feeding the materials of the cyclohexane carbonate or the cyclopropane carbonate, the methanol and the catalyst into a rectification reactor of the alcohol exchange reaction unit (100) through respective feeding pumps respectively, carrying out alcohol exchange reaction under the action of the catalyst, simultaneously generating the dimethyl carbonate and the dihydric alcohol, extracting an azeotrope of the methanol and the dimethyl carbonate from the top of the rectification reactor, and extracting a mixed material comprising the methanol, the dihydric alcohol and the catalyst from the bottom of the rectification reactor;
(2) catalyst separation: the mixed material extracted from the bottom of the rectification reactor enters the methanol, dihydric alcohol and catalyst separation unit (200), is evaporated by the falling-film evaporator, steam enters the separation circulating tank, the steam of the mixture of the methanol and the dihydric alcohol is obtained from the top of the separation circulating tank, the mixture of the dihydric alcohol and the catalyst flows out from the bottom of the separation circulating tank, and is conveyed to the falling-film evaporator by the separation circulating pump for circular evaporation;
(3) and (3) separating the dihydric alcohol: obtaining steam of a mixture of methanol and dihydric alcohol from the top of the separation circulation tank, feeding the steam into a methanol and dihydric alcohol separation unit (300), and separating and recovering a methanol material and a dihydric alcohol material, wherein the dihydric alcohol is ethylene glycol or 1, 2-propylene glycol;
(4) and (3) catalyst circulation: and partial material at the bottom of the falling-film evaporator enters the rectification reactor through the catalyst circulating pump for cyclic utilization.
7. Use of a catalyst in the alcohol exchange synthesis of dimethyl carbonate and glycols according to claim 6 wherein the falling film evaporator is operated at reduced pressure, between 5 and 15 kPa.
8. Use of a catalyst in the alcohol exchange synthesis of dimethyl carbonate and glycols according to claim 6, wherein the rectification reactor is a tray column operating at a pressure between 50-120 kPa.
9. The use of a catalyst in the alcohol exchange synthesis of dimethyl carbonate and diol according to claim 6, wherein the rectification reactor is divided into three sections, the uppermost section is a rectification section, the lower two sections are reaction sections, the raw material ethylene carbonate or propylene carbonate and the catalyst are fed between the first and second sections, and the raw material methanol is fed between the second and third sections.
10. The use of a catalyst in the alcohol exchange synthesis of dimethyl carbonate and diol according to claim 6, wherein the operating temperature of the bottom of the rectification reactor is between 70 and 100 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115466181A (en) * | 2022-09-05 | 2022-12-13 | 天津凯美特化工科技有限公司 | Method for producing dimethyl carbonate by ester exchange using long-acting catalyst |
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| JP2003342237A (en) * | 2002-05-30 | 2003-12-03 | Mitsubishi Chemicals Corp | Method for producing dimethyl carbonate and ethylene glycol |
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