CN113651691A - Method for preparing asymmetric oxalate through catalytic rectification - Google Patents
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- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The invention relates to a method for preparing asymmetric oxalate by catalytic rectification. The method adopts a catalytic rectifying tower to synthesize the asymmetric oxalate under the catalysis of a solid catalyst, removes light components of a product in time in the reaction process, and returns the unreacted symmetric oxalate and alcohol after separation to the reactive rectifying tower, thereby inhibiting the generation of byproducts, improving the selectivity, greatly reducing the separation difficulty, reducing the energy consumption and reducing the equipment investment.
Description
Technical Field
The invention relates to a method for preparing asymmetric oxalate by catalytic distillation, in particular to a method for synthesizing asymmetric oxalate by rectifying heterogeneous catalytic reaction.
Background
Asymmetric oxalic ester is commonly used for preparing various organic solvents, extractants, adhesives, plasticizers, and intermediates of various medicines and dyes, and can react with a plurality of heterocyclic compounds such as fatty acid ester. In the aspect of organic synthesis, the method is used for synthesizing thymine, and the thymine can be further prepared into medicaments such as Carbamine, phenobarbital, penicillin and the like and is an intermediate of medicaments such as azathioprine, sulfadoxine and the like; the asymmetric oxalate can be used for manufacturing organic substances such as plastic accelerators, dyes, cellulose esters and the like; in addition, the asymmetric oxalate can be used as a battery additive, and can be used as an auxiliary agent in textile industry, a lubricant resistant to low temperature and high pressure, and the like.
In 1978, the company of the Ministry of Japan built 1 set of 6000t/a dibutyl oxalate industrial scale production device, and the production line of dibutyl oxalate was completely mature. So far, a great deal of research has been carried out on the synthesis method of the symmetrical oxalate, but the preparation of the asymmetrical oxalate is very few, and only the following patents describe the synthesis of one of the asymmetrical oxalate.
CN 109053439 is a method for synthesizing ethyl methyl oxalate by taking symmetric dimethyl oxalate and ethanol as reaction raw materials and taking a catalyst as a mesoporous-microporous composite multifunctional alkaline catalyst in a fixed bed reactor under the conditions of normal pressure and 85 ℃, the conversion rate of dimethyl oxalate is 75 percent, and the selectivity of ethyl methyl oxalate is stabilized at about 85 percent. The conversion of this process is not high and the selectivity of ethyl methyl oxalate is low, limited by the reaction equilibrium.
CN 112279763 discloses a process for synthesizing ethyl methyl oxalate by homogeneous catalysis ester exchange, which comprises using dimethyl oxalate and ethanol as raw materials, using sodium ethoxide or zinc oxalate as a catalyst, obtaining ethyl methyl oxalate by reaction rectification and product separation, and distilling off the generated byproduct methanol from the top of the tower, wherein the total conversion rate of dimethyl oxalate is 99.12%, but the catalyst and the product are difficult to separate, the catalyst is easy to form salt, which causes blockage of a reboiler of the rectification tower, the catalyst cannot be reused, the inactivated catalyst is hazardous waste, and the treatment cost is high.
CN 110283071 proposes a system and a method for synthesizing ethyl methyl oxalate based on a microchannel reactor. According to the method, methanol and diethyl oxalate are continuously pumped into a microreactor by a high-pressure infusion pump, and a homogeneous phase sodium bicarbonate catalyst of 0.5mg/mL is adopted to carry out reaction at the temperature of 20 ℃. Although the method has low energy consumption, the diethyl oxalate is limited by thermodynamic equilibrium, the conversion rate is low (85 percent), the equipment investment cost is high, and the large-scale production is not easy to realize.
CN 112279762 provides a process for synthesizing ethyl methyl oxalate by heterogeneous catalysis ester exchange, which takes dimethyl oxalate and ethanol as raw materials, magnesium oxide precipitated by an excess sodium carbonate method as a catalyst, and carries out heterogeneous catalysis reaction in a pre-reactor. The product of the ethyl methyl oxalate and the byproduct of the methanol are obtained through the processes of reaction rectification, product separation, byproduct re-reaction circulation and the like. However, the preparation conditions of the magnesium oxide catalyst precipitated by the sodium carbonate method are harsh, and in addition, reaction raw materials and products are adsorbed on the surface of the catalyst, so that the performance of the catalyst after repeated use is reduced.
In view of the above, the problems of low conversion rate and selectivity of the reaction, difficult recycling of the liquid catalyst, high energy consumption of the reaction process, high equipment investment and the like still exist in the asymmetric oxalate synthesis process.
Disclosure of Invention
The invention aims to provide a method for preparing asymmetric oxalate through catalytic reaction rectification so as to improve the reaction efficiency in the preparation process of the asymmetric oxalate, aiming at solving the problems that the existing batch reaction has low yield and is difficult to industrialize. The method adopts a catalytic rectifying tower to synthesize asymmetric oxalate under the catalysis of a solid catalyst; and in the reaction process, the light components of the product are removed in time, and the unreacted symmetrical oxalate and the unreacted alcohol after separation are returned to the reaction rectifying tower, so that the generation of byproducts is inhibited, the selectivity is improved, the separation difficulty is greatly reduced, the energy consumption is reduced, and the equipment investment is reduced.
The technical scheme of the invention is as follows:
a method for preparing asymmetric oxalate by catalytic distillation comprises the following process steps:
(1) the symmetrical oxalate is fed from the upper part of the catalytic rectifying tower filler, and the alcohol enters the reaction section from the lower part of the catalytic rectifying tower filler to carry out heterogeneous catalytic reaction.
(2) The product enters a rectifying section of a catalytic rectifying tower, a light component product is extracted from the top of the tower after separation, and the unreacted symmetrical oxalate, alcohol and the asymmetric oxalate generated by the reaction are extracted from the bottom of the tower.
(3) After separation, the unreacted symmetrical oxalate and alcohol are returned to the feeding position of the reactive distillation column for recycling.
The feed molar ratio of the symmetrical oxalate to the alcohol is as follows: 1:1 to 1: 20.
The catalytic distillation tower is a packed tower, the number of theoretical plates is 22-28, and the structural form can be divided into: a rectifying section, a reaction section and a stripping section; the theoretical plate number of the rectifying section is 2-6, the theoretical plate number of the reaction section is 8-10, and the theoretical plate number of the stripping section is 8-10; the feeding position of the alcohol is 3-10 th plates, and the feeding position of the symmetrical oxalate is 10-16 th plates.
The operating pressure of the catalytic rectifying tower is 0.1-8.0 MPa, and the reflux ratio of the catalytic rectifying tower is 1-10: 1.
The operation temperature of the catalytic distillation tower is as follows: 60-200 ℃, and the temperature of a tower kettle is as follows: 60-220 ℃, and the tower top temperature is as follows: 60 to 110 ℃.
The solid catalyst is filled in the middle of a filler interlayer of the reaction section, and the catalyst: 0.1-0.6% of filler: 1 (volume ratio).
The packing is corrugated plate, and the corrugated plate packing can be independently selected from at least one of 350Y orifice plate corrugated packing, BX500 wire mesh corrugated packing and CY700 wire mesh corrugated packing.
The solid catalyst comprises a solid base catalyst or a solid acid catalyst.
The solid base catalyst comprises one or more of alkali metal loaded by taking alumina as a carrier, a sodium Y-type basic molecular sieve and quaternary ammonium ion exchange resin.
The solid acid catalyst comprises one or more of a molecular sieve, a zirconia-based mixed oxide and an acidic ion exchange resin.
In the alkali metal catalyst loaded with the alumina as the carrier, the carrier is the alumina, the active component is the halogenated metal, and the loading amount is 1-60%; the halogenated metal is potassium fluoride, sodium fluoride, potassium chloride or sodium chloride.
The zirconia-based mixed oxide is composed of 50-90 wt% of zirconia, 5-40 wt% of cerium dioxide and 1-30 wt% of lanthanum oxide.
The molecular sieve comprises one of SAPO molecular sieve, H-ZSM-5 molecular sieve, HM molecular sieve, SBA molecular sieve, beta zeolite molecular sieve and mordenite molecular sieve.
The alcohol is one or more of methanol, ethanol, propanol and butanol.
The symmetrical oxalate is one or more of dimethyl oxalate, diethyl oxalate, dibutyl oxalate and diamyl oxalate.
The invention has the beneficial effects that:
(1) the reaction process and the rectification process can be simultaneously realized in one device, thereby simplifying the process flow, saving the equipment investment and reducing the operation cost.
(2) Compared with the prior art using a homogeneous catalyst, the catalyst is a heterogeneous catalyst and is filled in a rectifying tower, the heterogeneous catalyst does not need to be separated from reaction products, the separation cost is greatly reduced in the using process, and the environmental protection problem that carbonized waste liquid and solid wastes are generated in the using process of the homogeneous catalytic reaction rectifying catalyst is avoided.
(3) The traditional intermittent process is limited by reaction balance, the conversion rate of the symmetrical oxalate is lower, and the application of the reactive distillation in the invention breaks the limitation of the reaction balance, so that the reaction is carried out towards the direction of generating the asymmetrical oxalate, and the conversion rate of reactants is improved to a greater extent (more than 99%).
(4) The light components can be removed quickly, the reaction speed is accelerated, and the yield of the asymmetric oxalate is improved.
Drawings
FIG. 1 is a schematic diagram of a catalytic distillation reaction apparatus.
1-symmetrical oxalate feeding port 2-alcohol feeding port 3-light component discharging port 4-heavy component discharging port 5-rectifying section 6-catalytic filler reaction section 7-stripping section
On the reaction device, the invention does not need a pre-reaction device, and the raw materials can directly enter the tower for reaction, thereby saving the equipment investment.
Detailed Description
The following examples will further illustrate the process provided by the present invention but the invention is not limited to the examples listed but also includes any other known variations within the scope of the claims claimed herein.
The reactor is a catalytic reaction rectifying tower and comprises a rectifying section, a catalytic packing reaction section and a stripping section, the material is 304, the inner diameter is 300mm, the structural packing height of the reaction section is 6m, the rectifying section height is 1m, and the stripping section height is 5 m. The structural form can be divided into: a rectification section: 2 theoretical plates; a reaction section: 12 theoretical plates; a stripping section: 10 theoretical plates; a total of 24 theoretical plates.
The packing of the reaction section is loaded with a catalyst, the packing is BX500 wire mesh corrugated packing, and the catalyst takes alumina as a carrier to load alkali metal. In the following examples, the catalysts are specifically: the carrier is alumina, the active component is potassium fluoride, and the loading capacity is 10%.
The catalyst filling mode is as follows: the catalyst and the corrugated plate filler are mixed and stirred according to the volume ratio of 0.6:1, so that the catalyst is uniformly distributed in the pore diameter of the corrugated plate filler, and then the catalyst is loaded into a reaction section (from top to bottom, 3-12 theoretical plates) of a rectifying tower.
The gas chromatographic analysis of the product was as follows: KB-1701(30 m.times.0.32 mm.times.0.50 μm) capillary chromatography column, FID hydrogen flame detector; the initial temperature is 50 ℃, the temperature is kept for 3min, the final temperature is 250 ℃, the temperature is kept for 8min, and the heating rate is 8 ℃ min-1(ii) a The temperature of the detector is 250 ℃, the temperature of the vaporization chamber is 250 ℃, and the flow rate of the carrier gas is 40 mL/min-1The sample size was 0.2. mu.L, and the split ratio was 1/30.
Example 1
Dimethyl oxalate is preheated and then fed from the upper part of the filler of the catalytic distillation tower structure, ethanol enters from the lower part of the filler of the catalytic distillation tower structure, and the dimethyl oxalate and the ethanol react in the catalytic reaction section. And (3) feeding the tower bottom material of the reactive distillation tower to an ethanol distillation tower, returning the unreacted ethanol after separation to the feeding position of the ethanol, feeding the tower bottom liquid of the ethanol distillation tower to a product separation tower, obtaining high-purity ethyl methyl oxalate at the tower bottom, and returning the unreacted dimethyl oxalate and the diethyl oxalate generated by the reaction in the tower top liquid to the feeding position of the dimethyl oxalate.
The flow rate of dimethyl oxalate in a catalytic rectifying tower is 200kg/h, the flow rate of ethanol is 100kg/h (namely the molar ratio of dimethyl oxalate to ethanol is 17: 22), the pressure of the catalytic rectifying tower is 0.6MPa, the feeding position of dimethyl oxalate is a 3 rd theoretical plate, the feeding position of ethanol is a 12 th theoretical plate, the reaction temperature is 90 ℃, the temperature of a tower bottom is 120 ℃, the temperature of a tower top is 70 ℃, and the reflux ratio is 10:1, the product at the tower bottom of the reactive rectifying tower is subjected to gas phase analysis, the content of dimethyl oxalate is shown in table 1, the conversion rate of dimethyl oxalate is 99.2%, and the purity of the subsequently separated ethyl methyl oxalate product is 99.7%.
TABLE 1
| Oxalic acid dimethyl ester | Ethanol | Oxalic acid methyl ethyl ester | Oxalic acid diethyl ester | |
| Tower kettle (mass%) | 0.82 | 8.48 | 88.25 | 2.45 |
Example 2
The flow rate of dimethyl oxalate in a catalytic rectifying tower is 200kg/h, the flow rate of ethanol is 100kg/h, the pressure of the catalytic rectifying tower is 0.6MPa, the feeding position of dimethyl oxalate is 11 th theoretical plates, the feeding position of ethanol is 2 nd theoretical plates, the reaction temperature is 90 ℃, the temperature of a tower bottom is 115 ℃, the temperature of a tower top is 65 ℃, and the reflux ratio is 8:1, the product in the tower bottom of the reactive rectifying tower is analyzed by gas phase, the content is shown in Table 2, the conversion rate of dimethyl oxalate is 99.1%, and the purity of the methyl ethyl oxalate product after subsequent separation is 99.3%.
TABLE 2
| Oxalic acid dimethyl ester | Ethanol | Oxalic acid methyl ethyl ester | Oxalic acid diethyl ester | |
| Tower kettle (mass%) | 0.83 | 6.22 | 82.82 | 10.13 |
Example 3
The flow rate of dimethyl oxalate in the catalytic rectifying tower is 200kg/h, the flow rate of ethanol is 100kg/h, the pressure of the catalytic rectifying tower is 0.8MPa, the feeding position of dimethyl oxalate is 12 th theoretical plates, the feeding position of ethanol is 3 rd theoretical plates, the reaction temperature is 90 ℃, the temperature of a tower bottom is 120 ℃, the temperature of a tower top is 70 ℃, and the reflux ratio is 10:1, the product in the tower bottom of the reactive rectifying tower is analyzed by gas phase, the content is shown in Table 3, the conversion rate of dimethyl oxalate is 99.2%, and the purity of the methyl ethyl oxalate product after subsequent separation is 99.5%.
TABLE 3
| Oxalic acid dimethyl ester | Ethanol | Oxalic acid methyl ethyl ester | Oxalic acid diethyl ester | |
| Tower kettle (mass%) | 0.83 | 6.78 | 84.29 | 8.10 |
Example 4
The flow rate of dimethyl oxalate in the catalytic rectifying tower is 200kg/h, the flow rate of ethanol is 100kg/h, the pressure of the catalytic rectifying tower is 0.8MPa, the feeding position of dimethyl oxalate is a 12 th theoretical plate, the feeding position of ethanol is a 2 nd theoretical plate, the reaction temperature is 90 ℃, the temperature of a tower bottom is 125 ℃, the temperature of a tower top is 68 ℃, and under the condition of a reflux ratio of 8:1, the product in the tower bottom of the reactive rectifying tower is analyzed in a gas phase, the content is shown in Table 4, the conversion rate of dimethyl oxalate is 99.0%, and the purity of the methyl ethyl oxalate product after subsequent separation is 99.5%.
TABLE 4
| Oxalic acid dimethyl ester | Ethanol | Oxalic acid methyl ethyl ester | Oxalic acid diethyl ester | |
| Tower kettle (mass%) | 0.82 | 8.03 | 87.14 | 4.01 |
The invention is not the best known technology.
Claims (10)
1. A method for preparing asymmetric oxalate by catalytic distillation is characterized by comprising the following steps:
(1) symmetrical oxalate is fed from the upper part of the catalytic rectifying tower filler, and alcohol enters a reaction section from the lower part of the catalytic rectifying tower filler to carry out heterogeneous catalytic reaction;
(2) the product enters a rectifying section of a catalytic rectifying tower, a light component product is extracted from the top of the tower after separation, and the unreacted symmetrical oxalate, alcohol and the asymmetric oxalate generated by the reaction are extracted from the bottom of the tower;
(3) after separation, the unreacted symmetrical oxalate and alcohol are returned to the feeding position of the reactive distillation column for recycling.
2. The catalytic distillation process for preparing asymmetric oxalate according to claim 1, wherein the molar ratio of the symmetric oxalate to the alcohol is: 1: 1-1: 20;
the catalytic rectifying tower is a packed tower, the number of theoretical plates is 22-28, and the catalytic rectifying tower is divided into a rectifying section, a reaction section and a stripping section; the theoretical plate number of the rectifying section is 2-6, the plate number of the reaction section is 8-10, and the plate number of the stripping section is 8-10; the feeding position of the alcohol is 3-10 th plates, and the feeding position of the symmetrical oxalate is 10-16 th plates;
the operating pressure of the catalytic rectifying tower is 0.1-8.0 MPa, and the reflux ratio of the catalytic rectifying tower is 1-10: 1;
the operation temperature of the catalytic distillation tower is as follows: 60-200 ℃, and the temperature of a tower kettle is as follows: 60-220 ℃, and the tower top temperature is as follows: 60-110 ℃;
the solid catalyst is filled in the middle of a filler interlayer of the reaction section, and the catalyst: 0.1-0.6% of filler: 1 (volume ratio).
3. The catalytic distillation process for preparing asymmetric oxalate according to claim 1, wherein said solid catalyst comprises a solid base catalyst or a solid acid catalyst.
4. The method for preparing asymmetric oxalate by catalytic distillation as claimed in claim 1, wherein said solid base catalyst comprises one or more of alkali metal, sodium Y-type basic molecular sieve and quaternary ammonium ion exchange resin loaded on alumina.
5. The catalytic distillation process for preparing asymmetric oxalate ester according to claim 1, wherein said solid acid catalyst comprises one or more of molecular sieve, zirconia-based mixed oxide and acidic ion exchange resin.
6. The method for preparing asymmetric oxalate through catalytic rectification according to claim 4, wherein in the catalyst using alumina as a carrier and loading alkali metal, the carrier is alumina, the active component is halogenated metal, and the loading amount is 1-60%.
7. The method for preparing asymmetric oxalate through catalytic rectification according to claim 5, wherein the zirconia-based mixed oxide is composed of 50-90 wt% of zirconia, 5-40 wt% of ceria and 1-30 wt% of lanthanum oxide;
the molecular sieve comprises one of SAPO molecular sieve, H-ZSM-5 molecular sieve, HM molecular sieve, SBA molecular sieve, beta zeolite molecular sieve and mordenite molecular sieve.
8. The method for preparing asymmetric oxalate through catalytic distillation according to claim 1, wherein the alcohol is one or more of methanol, ethanol, propanol and butanol; the symmetrical oxalate is one or more of dimethyl oxalate, diethyl oxalate, dibutyl oxalate and diamyl oxalate.
9. The catalytic distillation process for preparing asymmetric oxalate according to claim 1, wherein said packing is corrugated plate, and the corrugated plate packing can be independently selected from at least one of 350Y pore plate corrugated packing, BX500 wire mesh corrugated packing and CY700 wire mesh corrugated packing.
10. The catalytic distillation process for preparing asymmetric oxalate according to claim 6, wherein said metal halide is potassium fluoride, sodium fluoride, potassium chloride or sodium chloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057579A (en) * | 2021-12-08 | 2022-02-18 | 河北工业大学 | Method for preparing asymmetric carbonate by rectifying catalytic reaction of symmetric carbonate |
| CN114292182A (en) * | 2021-12-14 | 2022-04-08 | 沈阳化工大学 | Method for synthesizing efficient catalyst from alkyl oxalate |
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