CN117362175A - Method for synthesizing dimethyl fumarate and dimethyl maleate through acetylene dicarbonylation - Google Patents

Method for synthesizing dimethyl fumarate and dimethyl maleate through acetylene dicarbonylation Download PDF

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CN117362175A
CN117362175A CN202311331962.0A CN202311331962A CN117362175A CN 117362175 A CN117362175 A CN 117362175A CN 202311331962 A CN202311331962 A CN 202311331962A CN 117362175 A CN117362175 A CN 117362175A
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acetylene
reaction
dimethyl
dicarbonylation
catalyst
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何林
曹彦伟
谭雨诺
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides

Abstract

The invention provides a method for synthesizing dimethyl fumarate and dimethyl maleate by acetylene dicarbonylation, which takes acetylene, carbon monoxide and methyl nitrite as raw materials, and the temperature is 60-200 ℃ under the action of a supported palladium catalyst o C. And (3) under the pressure of 0.1-6 MPa, performing acetylene dicarbonylation reaction for 0.5-48 h to obtain dimethyl fumarate and dimethyl maleate compounds. The invention uses methyl nitrite to replace methanol, adopts a supported palladium catalyst, does not need any auxiliary agent, and does not directly use O 2 Avoiding the problems of explosion limit, corrosive auxiliary agent and catalyst separation and circulation in the prior acetylene dicarbonylation process, and overcoming the problems of the prior artThe method has the advantages of high utilization rate of the reaction atoms, mild reaction conditions, high product yield and the like, and the byproduct NO can be recycled, so that the method is suitable for industrial production and has wide application prospect.

Description

Method for synthesizing dimethyl fumarate and dimethyl maleate through acetylene dicarbonylation
Technical Field
The invention relates to a method for preparing dimethyl fumarate and dimethyl maleate by acetylene dicarbonylation, in particular to a method for preparing dimethyl fumarate and dimethyl maleate by acetylene dicarbonylation under the action of a supported catalyst by taking methyl nitrite as a raw material, belonging to the technical field of synthetic chemistry.
Background
C4 oxygenates such as 1, 4-butanedioic acid, dimethyl succinate, dimethyl fumarate and dimethyl maleate are used in a wide variety of fields such as medicine, fine chemicals, degradable polymers, etc. For example, dimethyl fumarate, enteric capsules for the treatment of relapsing Multiple Sclerosis (MS) alone; dimethyl succinate can be subjected to transesterification to obtain the product with molecular weight up to 5.95X10 5 Poly (butylene succinate) (PBS). At present, the C4 compounds are mainly obtained by adopting a butadiene method, a maleic anhydride method, a 1, 4-dichlorobutene method, an acetylene aldehyde method and an acetylene carbonylation method, and the compounds are mutually converted through hydrogenation, hydrolysis, esterification and other processes. The method for preparing dimethyl fumarate and dimethyl maleate by using the acetylene carbonylation method is characterized in that methanol, acetylene and CO are used as raw materials, and the dimethyl fumarate and the dimethyl maleate are generated through a catalytic conversion process in the presence of a catalyst, an auxiliary agent and an oxidant. This process has been found to date for more than 50 years, but as a useful reaction, no commercial report has been made at present (see: chemical progress, 2021, 33 (2): 243-253; angew. Chem. Int. Ed. 2023, 62, e202307570; ACS Catal. 2021, 11, 9242-9251; J. Catal. 2022,413, 762). Further analysis, the following key issues limit the industrial applicability of this process:
(1) Explosion limit: CO, acetylene and air explosion limit, and CO and air mixed explosion limit is 12.5% -80%; the explosion limit of acetylene in the air is 2.3-72.3%. In the method disclosed in Chinese patent CN202210143998 and CN202210086473, the mixture of air, CO and acetylene is introduced in the reaction conditions disclosed in the method, and the ratio of the mixture to the gas is as follows: 2.5 MPa:2.6 MPa:0.4 MPa or 3.0MPa:2.0 MPa:0.5 MPa; in a similar method disclosed in Chinese patent CN202210143998, the total pressure of the mixed gas of air, CO and acetylene is 4 MPa in the disclosed reaction conditions, wherein the total pressure of CO is 1.8 MPa and the total pressure of acetylene is 11 mmol. According to the explosion limit index of the acetylene and the CO in the air, the experimental conditions disclosed in the patent are all within the explosion limit of the CO and the acetylene/air. Thus, a slight mishandling causes explosion risks, which are detrimental to safe production and are the biggest obstacle in industrial application.
(2) Corrosive auxiliary agent: in the reports of Chinese patent CN202210143998, and Chinese patent CN202210143998, CN202210086473 and the latest documents (Angew. Chem. Int. Ed. 2023, 62, e202307570; ACS Catal. 2021, 11, 9242-9251; J. Catal. 2022,413, 762), the addition of corrosive iodized salt auxiliary agents is required. In the oxidative carbonylation reaction of most of the iodic salt at the root, the iodine auxiliary agent can produce corrosive hydroiodic acid in the reaction process, so that corrosion to equipment and loss of active metal are unavoidable. In the method disclosed in chinese patent CN201910860411, although an oxidizing agent is not used in the disclosed reaction conditions, a homogeneous catalyst and a corrosive halogen salt are used and a strong acid is required to be added additionally, which is not beneficial to the separation and circulation of a noble metal catalyst, and is easy to corrode reaction equipment, and is also not beneficial to industrial production. Therefore, from the prior technical means, the industrial application of the acetylene dicarbonylation has a certain technical difficulty. The new catalytic process of the double carbonylation of the acetylene is sought to bypass the problems of explosion limit, corrosive auxiliary agent, product separation and other pain points, and is a necessary way for realizing the application of the double carbonylation of the acetylene.
Disclosure of Invention
The invention mainly aims to provide a method for synthesizing dimethyl fumarate and dimethyl maleate by acetylene dicarbonylation by taking methyl nitrite as a raw material, so as to overcome the defects of the existing acetylene dicarbonylation technology.
The invention relates to a method for synthesizing dimethyl fumarate and dimethyl maleate by acetylene dicarbonylation, which takes acetylene, carbon monoxide and methyl nitrite as raw materials, and the temperature is 60-200 ℃ under the action of a supported palladium catalyst o C. And (3) under the pressure of 0.1-10 MPa, performing acetylene dicarbonylation reaction for 0.5-48 h to obtain dimethyl fumarate and dimethyl maleate compounds. The reaction formula is as follows:
the molar ratio of the raw materials of acetylene, carbon monoxide and methyl nitrite is 1:2:2-1:100:6.
In the supported palladium catalyst, the carrier is one or more of active carbon, porous polymer, alumina, titanium oxide, cerium oxide, magnesium oxide and molecular sieve, and the palladium loading amount is 0.05-10wt%. The supported gold catalyst is prepared by taking palladium nitrate, palladium chloride, palladium bromide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, sodium chloropalladate, potassium chloropalladate and the like as palladium precursors and adopting an impregnation method, a precipitation method, an atomic deposition method, a liquid phase reduction method or a gas phase reduction method. The molar ratio of the acetylene to the active metal in the supported catalyst is 100:1-10000:1.
The acetylene dicarbonylation reaction can be carried out under the condition of no solvent, and can also be carried out in a reaction solvent, wherein the reaction solvent comprises one or more of tetrahydrofuran, ethyl acetate, methanol, acetonitrile, dioxane, toluene and cyclohexane.
The reactions described in the present invention are carried out in batch tank reactors or in continuous tube reactors.
In summary, compared with the prior art, the invention has the following advantages:
1. the invention bypasses the difficulties of the traditional technology, replaces methanol with methyl nitrite, adopts a supported palladium catalyst, does not need any auxiliary agent and does not directly use O 2 The problems of explosion limit, corrosive auxiliary agent use, catalyst separation circulation and the like in the existing acetylene double-carbonylation process are avoided, and the technical pain points in the prior art are overcome;
2. the invention has high utilization rate of reaction atoms, and the byproduct is NO which can be recycled;
3. the method has the advantages of mild reaction conditions, high product yield and the like, is suitable for industrial production, has wide application prospect, and has good development prospect based on the current C4 oxygen-containing compounds such as 1, 4-succinic acid, 1, 4-butanediol, dimethyl succinate, dimethyl fumarate and dimethyl maleate.
Detailed Description
The process for the preparation of dimethyl fumarate and dimethyl maleate according to the invention by the double carbonylation of acetylene is described in further detail below with reference to the specific examples.
Example 1
Adding 2g of active carbon powder into 0.0001 mol/L palladium nitrate aqueous solution of 8 mL, fully soaking for 24 hours, drying, calcining for 3 hours at 500 ℃ in inert atmosphere, and reducing for 2 hours at 300 ℃ in hydrogen to obtain Pd/C catalyst, wherein the Pd/C catalyst is marked as catalyst 1;
adding catalyst 1 (10 mg), tetrahydrofuran 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into 50 mL reactor, heating to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 2
Pd/C catalyst preparation: adding 2g of activated carbon powder into an acetonitrile solution of 8 mL of 0.0001 mol/L palladium acetate, fully soaking for 24 hours, drying, calcining for 3 hours at 500 ℃ in an inert atmosphere, and then reducing for 2 hours at 300 ℃ in hydrogen to obtain a Pd/C catalyst, wherein the Pd/C catalyst is marked as a catalyst 2;
adding catalyst 2 (10 mg), tetrahydrofuran 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into 50 mL reactor, heating to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 3
Pd/C catalyst preparation: adding 2g of active carbon powder into 0.0001 mol/L acetone solution of 8 mL, fully soaking for 24 hours, drying, calcining for 3 hours at 500 ℃ in inert atmosphere, and then reducing for 2 hours at 300 ℃ in hydrogen to obtain Pd/C catalyst, and marking as catalyst 3;
catalyst 3 (10 mg), tetrahydrofuran 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite, 2 MPa CO are respectively added into a 50 mL reaction kettle,placing the reaction kettle into a heating kettle to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 4
Pd/C catalyst preparation: adding 2g of active carbon powder into 8 mL of 0.0001 mol/L potassium chloropalladate aqueous solution, fully soaking for 24 hours, drying, calcining for 3 hours at 500 ℃ in inert atmosphere, and then reducing for 2 hours at 300 ℃ in hydrogen to obtain Pd/C catalyst, and marking as catalyst 7;
adding catalyst 7 (10 mg), tetrahydrofuran 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into 50 mL reactor, heating to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 5
Pd/Al 2 O 3 And (3) preparing a catalyst: 2g of Al 2 O 3 Adding the powder into 8 mL of 0.0001 mol/L palladium nitrate aqueous solution, fully soaking for 24h, drying, calcining at 500 ℃ for 3h in a muffle furnace, and reducing at 300 ℃ for 2h in hydrogen to obtain Pd/Al 2 O 3 A catalyst, labeled catalyst 4;
adding catalyst 4 (10 mg), tetrahydrofuran 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into 50 mL reactor, heating to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 6
Pd/TiO 2 And (3) preparing a catalyst: 2g of TiO 2 Adding the powder into 8 mL of 0.0001 mol/L palladium nitrate aqueous solution, soaking for 24 hr, drying, and treating horseCalcining for 3h at 500 ℃ in a furs, and then reducing for 2h at 300 ℃ in hydrogen to obtain Pd/TiO 2 A catalyst, labeled catalyst 5;
adding catalyst 5 (10 mg), tetrahydrofuran 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into 50 mL reactor, heating to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 7
Pd/CeO 2 And (3) preparing a catalyst: 2g CeO 2 Adding the powder into 8 mL of 0.0001 mol/L acetonitrile solution of palladium acetate, fully soaking for 24h, drying, calcining at 500 ℃ for 3h in a muffle furnace, and reducing at 300 ℃ for 2h in hydrogen to obtain Pd/TiO 2 A catalyst, labeled catalyst 6;
adding catalyst 6 (10 mg), tetrahydrofuran 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into 50 mL reactor, heating to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 8
Adding catalyst 1 (10 mg), methanol 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into a 50 mL reactor, heating the reactor to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 9
Adding catalyst 1 (10 mg), ethyl acetate 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into a 50 mL reaction kettle, and heating the reaction kettle to 130 o C, reaction 12h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 10
Adding catalyst 1 (10 mg), dioxane 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into a 50 mL reaction kettle, and heating the reaction kettle to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 11
Adding catalyst 1 (10 mg), acetonitrile 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into a 50 mL reaction kettle, and heating the reaction kettle to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 12
Adding catalyst 1 (10 mg), cyclohexane 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into a 50 mL reaction kettle, and heating the reaction kettle to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 13
Adding catalyst 1 (10 mg), toluene 5 mL, 3 mmol acetylene, 8 mmol methyl nitrite and 2 MPa CO into a 50 mL reactor, heating the reactor to 130 o C, reaction 12 h. After the reaction is finished, dodecane is used as an internal standard, sampling and detection are carried out, the detection method is a GC method using dodecane-n-hexane as an internal standard, the yield and the selectivity of dimethyl fumarate and dimethyl maleate are calculated, and the result is shown in the specificationTable 1.
Example 14
Adding catalyst 1 (10 mg) into a 50 mL reaction kettle, charging 3 mmol of acetylene, 8 mmol of methyl nitrite, respectively, toluene 5 mL, charging 2 MPa of CO, heating the reaction kettle to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Example 15
Adding catalyst 1 (10 mg) into a 50 mL reaction kettle, charging 3 mmol of acetylene, 8 mmol of methyl nitrite and 2 MPa of CO, and heating the reaction kettle to 130 o C, reaction 12 h. After the reaction, 5 mL tetrahydrofuran dissolution product was added, dodecane was used as an internal standard, sampling and detection were performed by GC method using dodecane as an internal standard, and the yields and selectivity of dimethyl fumarate and dimethyl maleate were calculated, and the results are shown in table 1.
Example 16
Adding catalyst 1 (10 mg) into a 50 mL reaction kettle, charging 3 mmol of acetylene, 8 mmol of methyl nitrite, respectively, toluene 5 mL, charging 4 MPa of CO, heating the reaction kettle to 130 o C, reaction 12 h. After the reaction, the yield and selectivity of dimethyl fumarate and dimethyl maleate were calculated by using dodecane as an internal standard and a GC method using dodecane as an internal standard, and the results are shown in Table 1.
Examples 17 to 21
According to the reaction conditions in examples 1 to 7, the catalyst after the completion of the reaction was recovered, and stability was examined under the same reaction conditions, and after the completion of the reaction, dodecane was used as an internal standard, sampling and detecting, wherein the detecting method is a GC method using dodecan-hexane as an internal standard, and the yield and the selectivity of dimethyl fumarate and dimethyl maleate are calculated, and the results are shown in table 1.
As can be seen from the data in Table 1, the method for preparing dimethyl fumarate and dimethyl maleate by double carbonylation of acetylene and the catalyst thereof have the advantages of high reaction activity, good selectivity, good catalyst stability and wide application prospect.
The inventors have also conducted experiments with other materials, conditions, and the like listed in the present specification, with reference to examples 1 to 21, and have achieved the corresponding effects.

Claims (6)

1. A method for synthesizing dimethyl fumarate and dimethyl maleate by acetylene dicarbonylation is characterized in that acetylene, carbon monoxide and methyl nitrite are used as raw materials, and under the action of a supported palladium catalyst, the temperature is 60-200 DEG C o C. And (3) under the pressure of 0.1-6 MPa, performing acetylene dicarbonylation reaction for 0.5-48 h to obtain dimethyl fumarate and dimethyl maleate compounds.
2. The method for synthesizing dimethyl fumarate and dimethyl maleate by double carbonylation of acetylene according to claim 1, wherein the method comprises the following steps: the molar ratio of the raw materials of acetylene, carbon monoxide and methyl nitrite is 1:2:2-1:100:6.
3. The method for synthesizing dimethyl fumarate and dimethyl maleate by double carbonylation of acetylene according to claim 1, wherein the method comprises the following steps: in the supported palladium catalyst, the carrier is one or more of active carbon, porous polymer, alumina, titanium oxide, cerium oxide, magnesium oxide and molecular sieve, and the palladium loading amount is 0.05-10wt%.
4. The method for synthesizing dimethyl fumarate and dimethyl maleate by double carbonylation of acetylene according to claim 1, wherein the method comprises the following steps: the molar ratio of the acetylene to the active metal in the supported catalyst is 100:1-10000:1.
5. The method for synthesizing dimethyl fumarate and dimethyl maleate by double carbonylation of acetylene according to claim 1, wherein the method comprises the following steps: the acetylene dicarbonylation reaction is carried out under the condition of a solvent, and the reaction solvent is one or more of methanol, tetrahydrofuran, acetonitrile, dioxane, ethyl acetate, toluene, xylene and cyclohexane.
6. The method for synthesizing dimethyl fumarate and dimethyl maleate by double carbonylation of acetylene according to claim 1, wherein the method comprises the following steps: the acetylene dicarbonylation reaction is carried out in a batch kettle reactor or in a continuous tubular reactor.
CN202311331962.0A 2023-10-16 2023-10-16 Method for synthesizing dimethyl fumarate and dimethyl maleate through acetylene dicarbonylation Pending CN117362175A (en)

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