CN114941144A - Method for electrochemically synthesizing dimethyl sebacate - Google Patents
Method for electrochemically synthesizing dimethyl sebacate Download PDFInfo
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Abstract
The invention discloses a method for electrochemically synthesizing dimethyl sebacate. The method comprises the steps of placing monomethyl adipate, an organic solvent, an electrolyte and a catalyst into an electrolytic cell for electrolytic reaction to generate a reaction solution containing dimethyl sebacate, and rectifying the reaction solution to obtain a dimethyl sebacate product, wherein the catalyst is a supported nickel-cerium catalyst. The invention can obviously reduce the generation of the electrolysis by-product 6-hydroxy methyl caproate and improve the current efficiency and the selectivity of dimethyl sebacate.
Description
Technical Field
The invention belongs to the field of organic electrochemical synthesis, and particularly relates to a method for electrochemically synthesizing dimethyl sebacate.
Technical Field
The dimethyl sebacate is an organic chemical raw material and an intermediate which are widely applied, is mainly applied to the fields of cold-resistant plasticizers, lubricating grease, adhesives and the like, and is also a main raw material of long-chain nylon, light stabilizers UV-770, UV-750 and the like. At present, dimethyl sebacate is mainly obtained by a castor oil cracking process, ricinoleic acid is firstly cracked under the conditions of high temperature and high pressure to generate sebacic acid, and then the sebacic acid and methanol are subjected to ester exchange reaction under the catalysis of acid to obtain the sebacic acid dimethyl sebacate, and the sebacic acid dimethyl ester is complex in steps, high in energy consumption and serious in pollution.
The dimethyl sebacate can be obtained by one step of Kolbe decarboxylation coupling by taking monomethyl adipate as a raw material through an electrochemical method, and the process is green and environment-friendly, but the selectivity of a target product in the prior art is low.
Disclosure of Invention
The inventor finds in research that the generation of the by-product methyl 6-hydroxycaproate is an important factor influencing the current efficiency in the electrochemical method, under the existing electrochemical conditions, the selectivity of the methyl 6-hydroxycaproate is about 5%, and in addition, the methyl 6-hydroxycaproate can be continuously polymerized with raw materials to generate heavy components, so that the selectivity and the current efficiency of the product dimethyl sebacate are reduced, and no effective means for solving the problem exists at present.
Aiming at the problems in the prior art, the invention provides a method for electrochemically synthesizing dimethyl sebacate, which can obviously reduce the generation of an electrolysis byproduct methyl 6-hydroxycaproate and improve the current efficiency and the selectivity of dimethyl sebacate.
In order to realize the purpose, the invention adopts the following technical scheme:
a method for electrochemically synthesizing dimethyl sebacate comprises the steps of placing monomethyl adipate, an organic solvent, an electrolyte and a catalyst into an electrolytic cell for electrolytic reaction to generate a reaction solution containing dimethyl sebacate, and rectifying the reaction solution to obtain a dimethyl sebacate product; wherein the catalyst is a supported nickel-cerium catalyst.
The novel supported nickel-cerium catalyst adopted by the invention can selectively adsorb the electrolysis byproduct methyl 6-hydroxycaproate, and catalyze the electrolysis byproduct methyl 6-hydroxycaproate to perform oxidation reaction under the action of an electric field to obtain the reaction raw material monomethyl adipate, so that the generation of the methyl 6-hydroxycaproate and the subsequent polymerization reaction are inhibited, and the current efficiency and the selectivity of the product dimethyl sebacate are effectively improved; the introduction of the organic ligand and the carrier can improve the dispersion degree of active center metal atoms of the main catalyst and the cocatalyst, effectively avoid the aggregation problem of the catalyst in use, and the active center metal forms a complex with the organic, so that the structure is more stable, coordination bonds formed by lone-pair electrons on N, P in a catalyst framework, Ni and Ce are easy to form interaction with hydroxyl, and the occurrence of oxidation reaction is promoted; meanwhile, the catalyst is environment-friendly, the post-treatment is simple, and the problem of environmental pollution can be avoided.
In the invention, the organic solvent is one or more of alcohol, ether, nitrile and benzene, preferably one or more of methanol, ethanol, methyl tert-butyl ether and toluene; preferably, the mass ratio of the monomethyl adipate to the organic solvent is (0.1-2):1, preferably (0.3-1.5): 1.
In the invention, the electrolyte is an alkali metal-containing electrolyte, preferably one or more of sodium methoxide, potassium methoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and more preferably potassium methoxide and/or potassium hydroxide; preferably, the molar ratio of the electrolyte to monomethyl adipate is (0.1-0.45):1, preferably (0.15-0.4): 1.
In the invention, the catalyst is a molecular sieve supported nickel-cerium catalyst containing a phosphine ligand, preferably a Ni-Ce-X/ZSM-5 catalyst, wherein Ni is a main catalyst, Ce is an auxiliary catalyst, X is ligand bis (diisopropylamino) chlorophosphine, and a ZSM-5 molecular sieve is a carrier; preferably, the catalyst is used in an amount of 0.1 to 3 wt.%, preferably 0.5 to 2 wt.%, relative to the weight of monomethyl adipate.
In the present invention, the electrolytic cell comprises an anode and a cathode; preferably, the anode is a platinum electrode, a titanium-platinized electrode, a titanium-based PbO 2 Electrode, titanium-based IrO 2 One of the electrodes; preferably, the cathode is one of a gold electrode, a silver electrode and a titanium silver-plated electrode.
In the invention, the electrolysis temperature of the electrolysis reaction is 50-80 ℃, preferably 60-75 ℃; the electrolysis time is 5-18h, preferably 10-15 h.
In the invention, the electrolytic potential interval of the electrolytic reaction electrolytic cell is 2-4V, preferably 2.5-3.7V; the electrolytic current density interval is 1200-2000A/m 2 Preferably 1500-1800A/m 2 。
Rectification of the reaction solution is a routine operation in the art, and in some embodiments, the number of plates of the reaction solution subjected to rectification is 25-40, the reflux ratio is 0.5-4, the pressure is 2-5hPa, and the temperature of the column bottom is 180-200 ℃ for the target product dimethyl sebacate of the present invention.
Another object of the present invention is to provide a method for preparing a catalyst.
A preparation method of a supported nickel-cerium catalyst is disclosed, wherein the catalyst is adopted by the method for electrochemically synthesizing dimethyl sebacate, and the preparation method of the catalyst comprises the following steps:
s1: washing the molecular sieve with water, draining, soaking with dilute acid, washing with water, and drying to obtain an activated molecular sieve carrier;
s2: mixing a Ni-containing compound and a Ce-containing compound in water, adding a dilute acid to adjust the pH value of the solution, adding a phosphine ligand and a molecular sieve, stirring, filtering, and then placing a filter cake in an alkali solution for soaking to obtain a catalyst precursor;
s3: and filtering, washing and drying the catalyst precursor, and roasting, crushing and tabletting to obtain the supported nickel-cerium catalyst.
In the present invention, the activation temperature of S1 is 20 to 30 ℃.
In the invention, the Ni-containing compound of S2 is selected from one or more of nickel chloride, nickel acetate, nickel sulfate, and nickel nitrate, preferably nickel chloride; the Ce-containing compound is selected from one or more of cerium chloride, cerium nitrate, cerium oxalate and cerium acetate, and is preferably cerium chloride; preferably, the molar ratio of the Ni element to the Ce element is 1 (0.1-0.3), preferably 1 (0.1-0.2); preferably, the mass ratio of Ni to phosphine ligand is 1 (1-3), preferably 1 (1.5-2.5).
In the invention, the mass ratio of Ni to the carrier in S2 is 1 (10-20), preferably 1 (12-18).
In the invention, the pH value of S2 is 1-2.
In the present invention, the temperature of the stirring step S2 is 70 to 85 ℃.
In the invention, the drying temperature of S3 is 90-100 ℃, and the drying time is 8-12 h; the roasting temperature is 430-530 ℃, and the roasting time is 3-5 h.
Compared with the prior art, the invention has the beneficial effects that:
the method can obviously reduce the generation of an electrolysis by-product of 6-methyl hydroxycaproate, improve the current efficiency and the selectivity of dimethyl sebacate, and the selectivity can reach 86.5 percent.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to these examples.
The main raw material information is as follows:
monomethyl adipate, Syngnathus chemical Co., Ltd., purity > 98%;
methanol, ethanol, methyl tert-butyl ether, toluene, julonga reagent, AR, purity > 99%;
potassium methoxide, mcoline, purity > 95%;
potassium hydroxide, carbofuran, purity > 85%;
potassium carbonate, sodium hydroxide, an alatin reagent, purity > 99%;
platinum electrodes, gold electrodes, silver electrodes, tim new materials science and technology ltd;
a titanium platinum plating electrode, Siam Tai gold, Inc., plating layer 1 μm;
titanium-based PbO 2 Electrode, titanium-based IrO 2 Electrodes, Jiangsu Yintum electrodes, Inc.;
nickel chloride, nickel acetate, nickel sulfate, cerium chloride, cerium nitrate, cerium acetate and a carbofuran reagent, wherein the purity is more than 98 percent.
Bis (diisopropylamino) chlorophosphine, avadin reagent, purity > 97%.
1, 2-bis-diphenylphosphinoethane, an avadin reagent, with a purity of > 98%.
ZSM-5 molecular sieve, Jicang nanometer material science and technology limited, and the silica-alumina ratio is 30-40.
Neutral alumina, an Aladdin reagent, 60-100 meshes and the purity is more than 75 percent.
Other raw materials or reagents are commercially available unless otherwise specified.
Gas chromatography analysis conditions of the product: shimadzu gas chromatograph GC2010, DB-5 column, injection port temperature: 200 ℃; detector temperature: 350 ℃; temperature rising procedure: keeping at 50 deg.C for 4min, and increasing to 100 deg.C at 5 deg.C/min; raising the temperature to 300 ℃ at a speed of 25 ℃/min, and keeping the temperature for 5 min.
The content of metal ions in the catalyst is detected by adopting inductively coupled plasma emission spectroscopy (ICP), and the specific analysis conditions are as follows: the Agilent-720 type inductively coupled plasma emission instrument has the power of 1.25KW, the plasma gas flow rate of 16mL/min, the auxiliary gas flow rate of 1.6mL/min, the atomizer flow rate of 0.9mL/min, one-time reading of 4s, the instrument stabilization time of 16s, the sample introduction delay of 45s, the pump speed of 17rpm, the cleaning time of 50s and the reading times of 3 times.
The electrolytic cell is a diaphragm-free plate-and-frame type electrolytic cell, and is available from Hangzhou Sao electrochemical instruments Co.
The product rectification adopts a rectifying tower, 2.5mm triangular spiral packing, the number of tower plates is 40, the reflux ratio is 0.5, the pressure is 2hPa, the temperature of a tower bottom is 200 ℃, and the product dimethyl sebacate with the temperature of 124-128 ℃ is obtained at the tower top.
Example 1
87.58g of ZSM-5 molecular sieve is taken, washed by deionized water at 25 ℃, soaked for 2 hours by 300mL of 0.3mol/L dilute nitric acid, washed and dried at 80 ℃ to obtain the activated ZSM-5 molecular sieve carrier.
Mixing 10.11g of nickel chloride (0.0780mol) and 2.48g of cerium acetate (0.0078mol) in 500g of distilled water, adjusting the pH to 1.2 by using 0.5mol/L dilute hydrochloric acid, adding 4.6g of bis (diisopropylamino) chlorophosphine and an activated ZSM-5 molecular sieve carrier under the stirring state, heating to 75 ℃, and stirring for 12 hours; cooling to room temperature, filtering, and soaking the solid in 0.15mol/L KOH solution for 2h to obtain catalyst precursor slurry.
And filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 90 ℃ for 12h, roasting at 530 ℃ for 3h, crushing, tabletting and forming to obtain the catalyst 1. The ICP analysis confirmed that the Ni content was 4.70 wt% and the Ce content was 1.12 wt% in the catalyst 1.
Example 2
And (2) taking 78.0g of ZSM-5 molecular sieve, washing with deionized water at 25 ℃, then soaking in 300mL of 0.3mol/L dilute nitric acid for 2h, washing, and drying at 80 ℃ to obtain the activated ZSM-5 molecular sieve carrier.
Mixing 10.47g of nickel acetate (0.0882mol) and 4.31g of cerium nitrate (0.0123mol) in 500g of distilled water, adjusting the pH to 2 by using 0.5mol/L of dilute hydrochloric acid, adding 7.8g of bis (diisopropylamino) chlorophosphine and an activated ZSM-5 molecular sieve carrier under the stirring state, heating to 70 ℃, and stirring for 12 hours; cooling to room temperature, filtering, and soaking the solid in 0.15mol/L KOH solution for 2h to obtain catalyst precursor slurry.
And filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 95 ℃ for 10h, roasting at 500 ℃ for 3.5h, crushing, tabletting and forming to obtain the catalyst 2. The ICP analysis confirmed that the Ni content was 5.60 wt% and the Ce content was 2.00 wt% in catalyst 2.
Example 3
And (2) taking 59.95g of ZSM-5 molecular sieve, washing with deionized water at 25 ℃, then soaking in 250mL of 0.3mol/L dilute nitric acid for 2h, washing, and drying at 80 ℃ to obtain the activated ZSM-5 molecular sieve carrier.
Mixing 8.13g of nickel chloride (0.0628mol) and 2.63g of cerium chloride (0.0107mol) in 500g of distilled water, adjusting the pH to 1.5 by using 0.5mol/L dilute hydrochloric acid, adding 7.4g of bis (diisopropylamino) chlorophosphine and an activated ZSM-5 molecular sieve carrier under the stirring state, heating to 80 ℃, and stirring for 12 hours; cooling to room temperature, filtering, and soaking the solid in 0.15mol/L KOH solution for 2h to obtain catalyst precursor slurry.
And filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 95 ℃ for 9 hours, roasting at 450 ℃ for 4 hours, crushing, tabletting and forming to obtain the catalyst 3. ICP analysis confirmed that Ni contained 5.10 wt% and Ce contained 2.06 wt% in catalyst 3.
Example 4
And (2) taking 64.25g of ZSM-5 molecular sieve, washing with deionized water at 25 ℃, then soaking in 250mL of 0.3mol/L dilute nitric acid for 2h, washing, and drying at 80 ℃ to obtain the activated ZSM-5 molecular sieve carrier.
Mixing 14.17g of nickel sulfate (0.0916mol) and 5.81g of cerium acetate (0.0183mol) in 500g of distilled water, adjusting the pH to 1 by using 0.5mol/L diluted hydrochloric acid, adding 13.5g of ZSM-5 molecular sieve carrier activated by bis (diisopropylamino) chlorophosphine under the stirring state, heating to 85 ℃, and stirring for 12 hours; cooling to room temperature, filtering, and soaking the solid in 0.15mol/L KOH solution for 2h to obtain catalyst precursor slurry.
And filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 100 ℃ for 8h, roasting at 430 ℃ for 5h, crushing, tabletting and forming to obtain the catalyst 4. ICP analysis confirmed that the Ni content was 6.30 wt% and the Ce content was 2.99 wt% in catalyst 4.
Example 5
And (2) taking 51.39g of ZSM-5 molecular sieve, washing the ZSM-5 molecular sieve with deionized water at 25 ℃, then soaking the ZSM-5 molecular sieve in 250mL of 0.3mol/L dilute nitric acid for 2h, washing the ZSM-5 molecular sieve, and drying the ZSM-5 molecular sieve at 80 ℃ to obtain the activated ZSM-5 molecular sieve carrier.
Mixing 9.23g of nickel chloride (0.0712mol) and 5.27g of cerium chloride (0.0214mol) in 500g of distilled water, adjusting the pH to 1.7 by using 0.5mol/L dilute hydrochloric acid, adding 12.6g of bis (diisopropylamino) chlorophosphine and an activated ZSM-5 molecular sieve carrier under the stirring state, heating to 82 ℃, and stirring for 12 hours; cooling to room temperature, filtering, and soaking the solid in 0.15mol/L KOH solution for 2h to obtain catalyst precursor slurry.
And filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 90 ℃ for 10h, roasting at 450 ℃ for 4.5h, crushing, tabletting and forming to obtain the catalyst 5. ICP analysis confirmed that in catalyst 5, Ni content was 5.90 wt% and Ce content was 4.21 wt%.
Example 6
47.20g of neutral alumina is taken, washed by deionized water at 25 ℃, soaked for 2 hours by 300mL of 0.3mol/L dilute nitric acid, washed and dried at 80 ℃ to obtain the activated alumina carrier.
Mixing 9.89g of nickel chloride (0.0763mol) and 4.84g of cerium acetate (0.0153mol) in 500g of distilled water, adjusting the pH to 1.4 by using 0.5mol/L diluted hydrochloric acid, adding 6.8g of 1, 2-bis (diphenylphosphinoethane) and an activated alumina carrier under the stirring state, heating to 80 ℃, and stirring for 12 hours; cooling to room temperature, filtering, and soaking the solid in 0.15mol/L KOH solution for 2h to obtain catalyst precursor slurry.
And filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 100 ℃ for 8h, roasting at 500 ℃ for 3h, crushing, tabletting and forming to obtain the catalyst 6. The ICP analysis confirmed that the Ni content was 7.40 wt% and the Ce content was 3.53 wt% in the catalyst 6.
Example 7
Monomethyl adipate (80g, 0.5057mol), toluene (270g) and potassium methoxide (14.19g, 0.2023mol) were mixed well with stirring and transferred to an electrolytic cell, and catalyst 1(1.62g, 2.0 wt%) was added. The anode of the electrolytic cell adopts a titanium platinized electrode, the cathode adopts a gold electrode, the electrolytic cell is heated to 60 ℃, the electrolytic reaction is started by electrifying, the electrode potential of the electrolytic cell is 2.5V, and the current density is 1500A/m 2 And the electrolysis time is 15 h. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of the monomethyladipate as a raw material was 88.9%, the selectivity of the product dimethyl sebacate was 84.9%, the selectivity of the by-product methyl 6-hydroxycaproate was 0.07%, and the reaction current efficiency was 75.6%.
Example 8
Monomethyl adipate (80g, 0.5057mol), methyl tert-butyl ether (101.25g) and potassium hydroxide (8.51g, 0.1517mol) were stirred, mixed well and transferred to an electrolytic cell, and catalyst 2(0.405g, 0.5 wt%) was added. The anode of the electrolytic bath adopts titanium-based PbO 2 The cathode of the electrode adopts a silver electrode, the temperature of the electrolytic cell is raised to 65 ℃, the electrolytic reaction is started by electrifying, the potential of the electrode of the electrolytic cell is 3.0V, and the current density is 1600A/m 2 And the electrolysis time is 13 h. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of the monomethyladipate, a raw material, was 89.7%, the selectivity of the product, dimethyl sebacate, was 84.2%, the selectivity of the by-product, methyl 6-hydroxycaproate, was 0.15%, and the reaction current efficiency was 76.2%.
Example 9
Uniformly stirring and mixing monomethyl adipate (80g, 0.5057mol), methanol (81g) and potassium hydroxide (5.68g, 0.1011mol), and transferring to an electric furnaceTo the decomposer, catalyst 3(1.053g, 1.3 wt%) was added. The anode of the electrolytic cell adopts a platinum electrode, the cathode adopts a silver electrode, the electrolytic cell is heated to 70 ℃, the electrolytic reaction is started by electrifying, the electrode potential of the electrolytic cell is 3.2V, and the current density is 1700A/m 2 And the electrolysis time is 12 h. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion rate of the monomethyladipate as a raw material was 91.3%, the selectivity of the product dimethyl sebacate was 86.5%, the selectivity of the by-product methyl 6-hydroxycaproate was 0.04%, and the reaction current efficiency was 76.7%.
Example 10
Monomethyl adipate (80g, 0.5057mol), ethanol (54g) and potassium methoxide (5.32g, 0.0759mol) were mixed well with stirring and transferred to an electrolytic cell, and catalyst 4(1.377g, 1.7 wt%) was added. The anode of the electrolytic cell adopts titanium-based IrO 2 The cathode of the electrode is a titanium silver-plated electrode, the temperature of the electrolytic cell is raised to 75 ℃, the electrolytic reaction is started by electrifying, the potential of the electrode of the electrolytic cell is 3.7V, and the current density is 1800A/m 2 And the electrolysis time is 10 h. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion rate of the monomethyladipate as a raw material was 91.2%, the selectivity of the product dimethyl sebacate was 85.4%, the selectivity of the by-product methyl 6-hydroxycaproate was 0.09%, and the reaction current efficiency was 74.9%.
Example 11
Monomethyl adipate (80g, 0.5057mol), methanol (40.5g) and potassium carbonate (6.99g, 0.0506mol) were stirred and mixed well before transferring to the cell and catalyst 5(2.43g, 3.0 wt%) was added. The anode of the electrolytic cell adopts a titanium platinized electrode, the cathode adopts a silver electrode, the electrolytic cell is heated to 65 ℃, the electrolytic reaction is started by electrifying, the electrode potential of the electrolytic cell is 3.5V, and the current density is 1700A/m 2 And the electrolysis time is 15 h. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of the monomethyladipate as a raw material was 88.3%, the selectivity of the product, dimethyl sebacate, was 83.7%, the selectivity of the by-product, methyl 6-hydroxycaproate, was 0.42%, and the reaction current efficiency was 74.2%.
Example 12
Monomethyl adipate (80g, 0.5057mol), toluene (405g) and sodium hydroxide (9.10g, 0.2276mol) were mixed well with stirring and transferred to an electrolytic cell, and catalyst 6(0.203g, 0.25 wt%) was added. The anode of the electrolytic cell adopts a platinum electrode, the cathode adopts a titanium silver-plated electrode, the temperature of the electrolytic cell is raised to 65 ℃, the electrolytic reaction is started by electrifying, the electrode potential of the electrolytic cell is 3.0V, and the current density is 1600A/m 2 And the electrolysis time is 12 h. After the reaction is finished, filtering to remove the solid catalyst, separating out reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion rate of the monomethyladipate as a raw material was 87.5%, the selectivity of the product dimethylsebacate was 83.4%, the selectivity of the by-product methyl 6-hydroxycaproate was 0.65%, and the reaction current efficiency was 74.3%.
Comparative example 1
Catalyst a was prepared according to the method and process conditions in example 3, with the difference that: in the step S2, only nickel chloride, bis (diisopropylamino) chlorophosphine, and molecular sieve were added, and the operation conditions were the same as in example 3 except that cerium chloride was not added as a co-catalyst.
Dimethyl sebacate was prepared according to the method and process conditions in example 9, with the difference that: the reaction was carried out using catalyst A instead of catalyst 3, and the procedure was the same as in example 9.
In the comparative example, the conversion of the starting material monomethyl adipate was 76.2%, the selectivity of the product dimethyl sebacate was 81.2%, the selectivity of the by-product methyl 6-hydroxycaproate was 2.68%, and the reaction current efficiency was 67.5%.
Comparative example 2
Catalyst B was prepared according to the method and process conditions in example 3, with the difference that: in the step S2, only nickel chloride, cerium chloride and molecular sieve were added, and the ligand bis (diisopropylamino) chlorophosphine was not added, and the other operating conditions were the same as in example 3.
Dimethyl sebacate was prepared according to the method and process conditions in example 9, with the difference that: the reaction was carried out using catalyst B instead of catalyst 3, in the same manner as in example 9.
In the comparative example, the conversion rate of the monomethyladipate as a raw material was 75.3%, the selectivity of the product dimethyl sebacate was 80.8%, the selectivity of the by-product methyl 6-hydroxycaproate was 3.12%, and the reaction current efficiency was 65.9%.
Comparative example 3
Dimethyl sebacate was prepared according to the method and process conditions of example 9, with the difference that: the reaction was carried out in the same manner as in example 9 except that no catalyst was used.
In the comparative example, the conversion rate of the raw material monomethyl adipate was 72.8%, the selectivity of the product dimethyl sebacate was 75.6%, the selectivity of the by-product methyl 6-hydroxycaproate was 4.98%, and the reaction current efficiency was 60.2%.
Claims (9)
1. The method for electrochemically synthesizing the dimethyl sebacate is characterized in that monomethyl adipate, an organic solvent, an electrolyte and a catalyst are placed in an electrolytic cell for electrolytic reaction to generate a reaction solution containing the dimethyl sebacate, and the reaction solution is rectified to obtain a dimethyl sebacate product; wherein the catalyst is a supported nickel-cerium catalyst.
2. The process according to claim 1, wherein the organic solvent is one or more of an alcohol, an ether, a nitrile, benzene, preferably one or more of methanol, ethanol, methyl tert-butyl ether, toluene;
preferably, the mass ratio of the monomethyl adipate to the organic solvent is (0.1-2):1, preferably (0.3-1.5): 1.
3. The method according to claim 1 or 2, characterized in that the electrolyte is an alkali metal-containing electrolyte, preferably one or more of sodium methoxide, potassium methoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, more preferably potassium methoxide and/or potassium hydroxide;
preferably, the molar ratio of the electrolyte to monomethyl adipate is (0.1-0.45):1, preferably (0.15-0.4): 1.
4. The process according to any one of claims 1 to 3, wherein the catalyst is a molecular sieve supported nickel-cerium catalyst comprising a phosphine ligand, preferably a Ni-Ce-X/ZSM-5 catalyst, wherein Ni is the main catalyst, Ce is the co-catalyst, X is the ligand bis (diisopropylamino) chlorophosphine, and ZSM-5 molecular sieve is the support;
preferably, the catalyst is used in an amount of 0.1 to 3% by weight, preferably 0.5 to 2% by weight, relative to the weight of monomethyl adipate.
5. The method of any one of claims 1-4, wherein the electrolytic cell comprises an anode and a cathode;
preferably, the anode is a platinum electrode, a titanium-platinum-plated electrode, a titanium-based PbO 2 Electrode, titanium-based IrO 2 One of the electrodes;
preferably, the cathode is one of a gold electrode, a silver electrode and a titanium silver-plated electrode;
and/or the electrolysis temperature of the electrolysis reaction is 50-80 ℃, preferably 60-75 ℃; the electrolysis time is 5-18h, preferably 10-15 h;
and/or the electrolytic potential interval of the electrolytic reaction electrolytic cell is 2-4V, preferably 2.5-3.7V; the electrolytic current density interval is 1200-2000A/m 2 Preferably 1500- 2 。
6. A method for preparing a supported nickel-cerium catalyst, wherein the catalyst is used in the method for electrochemically synthesizing dimethyl sebacate according to any one of claims 1 to 5, and the method for preparing the catalyst comprises the following steps:
s1: washing the molecular sieve with water, draining, soaking with dilute acid, washing with water, and drying to obtain an activated molecular sieve carrier;
s2: mixing a Ni-containing compound and a Ce-containing compound in water, adding a dilute acid to adjust the pH value of the solution, adding a phosphine ligand and a molecular sieve, stirring, filtering, and then placing a filter cake in an alkali solution for soaking to obtain a catalyst precursor;
s3: and filtering, washing and drying the catalyst precursor, and roasting, crushing and tabletting to obtain the supported nickel-cerium catalyst.
7. The method for preparing a catalyst according to claim 6, wherein the temperature of the activation of S1 is 20-30 ℃.
8. The method for preparing the catalyst according to claim 6, wherein the Ni-containing compound of S2 is selected from one or more of nickel chloride, nickel acetate, nickel sulfate and nickel nitrate, preferably nickel chloride; the Ce-containing compound is selected from one or more of cerium chloride, cerium nitrate, cerium oxalate and cerium acetate, preferably cerium chloride;
preferably, the molar ratio of the Ni element to the Ce element is 1 (0.1-0.3), preferably 1 (0.1-0.2);
preferably, the mass ratio of Ni to phosphine ligand is 1 (1-3), preferably 1 (1.5-2.5);
and/or the mass ratio of the Ni to the carrier is 1 (10-20), preferably 1 (12-18) in S2;
and/or, the pH value of S2 is 1-2;
and/or the temperature of the S2 during stirring is 70-85 ℃.
9. The method for preparing the catalyst according to claim 6, wherein the drying temperature of S3 is 90-100 ℃, and the drying time is 8-12 h; the roasting temperature is 430-530 ℃, and the roasting time is 3-5 h.
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