CN114941144B - 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. According to the method, monomethyl adipate, an organic solvent, electrolyte and a catalyst are placed in an electrolytic cell for electrolytic reaction to generate a reaction solution containing dimethyl sebacate, and the reaction solution is rectified to obtain a dimethyl sebacate product, wherein the catalyst is a supported nickel-cerium catalyst. The invention can obviously reduce the generation of the electrolytic byproduct methyl 6-hydroxycaproate and improve the current efficiency and the selectivity of dimethyl sebacate.
Description
Technical Field
The invention belongs to the field of electrochemical synthesis, and particularly relates to a method for electrochemically synthesizing dimethyl sebacate.
Technical Field
Dimethyl sebacate is an organic chemical raw material and an intermediate with wide application, 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 stabilizer UV-770, UV-750 and the like. At present, dimethyl sebacate mainly comes from a castor oil cracking process, ricinoleic acid is cracked under high temperature and high pressure to generate sebacic acid, and then the sebacic acid and methanol undergo transesterification under the acid catalysis to obtain the dimethyl sebacate, which has the advantages of complex steps, higher energy consumption and serious pollution.
By taking adipic acid monomethyl ester as a raw material, the dimethyl sebacate can be obtained through one step of Kolbe decarboxylation coupling by an electrochemical method, and the process is environment-friendly, but the selectivity of a target product in the prior art is very low.
Disclosure of Invention
The inventors found in the study that the formation of by-product methyl 6-hydroxycaproate is an important factor affecting the current efficiency in the electrochemical method, and under the existing electrochemical conditions, the selectivity of methyl 6-hydroxycaproate is about 5%, and in addition, the methyl 6-hydroxycaproate can continue to polymerize with the raw materials to form 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 existing in the prior art, the invention provides a method for electrochemically synthesizing dimethyl sebacate, which can obviously reduce the generation of electrolytic byproducts, namely 6-hydroxycaproic acid methyl ester, and improve the current efficiency and the selectivity of the dimethyl sebacate.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the method comprises the steps of placing monomethyl adipate, an organic solvent, an electrolyte and a catalyst in 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 electrolytic byproduct methyl 6-hydroxycaproate, and catalyze the electrolytic byproduct methyl 6-hydroxycaproate to perform oxidation reaction under the action of an electric field to obtain the reaction raw material monomethyl adipate, inhibit the generation of the methyl 6-hydroxycaproate and the subsequent polymerization reaction, and effectively improve the current efficiency and the selectivity of the product dimethyl sebacate; the introduction of the organic ligand and the carrier can improve the dispersity of metal atoms of active centers of the main catalyst and the cocatalyst, effectively avoid the aggregation problem of the catalyst in use, lead the active center metal to form a complex with the organic compound, lead the structure to be more stable, lead the lone pair electrons on N, P in the catalyst framework to easily form interaction with hydroxyl groups with coordination bonds formed by Ni and Ce, and promote the occurrence of oxidation reaction; 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 tertiary butyl ether and toluene; preferably, the weight ratio of monomethyl adipate to organic solvent is (0.1-2): 1, preferably (0.3-1.5): 1.
In the present 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, 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 phosphine ligand, preferably a Ni-Ce-X/ZSM-5 catalyst, wherein Ni is a main catalyst, ce is a cocatalyst, X is ligand bis (diisopropylamino) chlorophosphine, and 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 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 5-18 hours, preferably 10-15 hours.
In the invention, the electrolysis potential interval of the electrolysis reaction electrolytic cell is 2-4V, preferably 2.5-3.7V; the electrolysis current density interval is 1200-2000A/m 2 Preferably 1500-1800A/m 2 。
The rectification of the reaction solution is conventional in the art, and in some embodiments, for the target product dimethyl sebacate of the present invention, the reaction solution is rectified at a tray number of 25-40, a reflux ratio of 0.5-4, a pressure of 2-5hPa, and a column bottom temperature of 180-200 ℃.
Another object of the present invention is to provide a method for preparing the catalyst.
The preparation method of the supported nickel-cerium catalyst is characterized in that the catalyst is adopted in the method for electrochemically synthesizing dimethyl sebacate, and 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 dilute acid to adjust the pH value of the solution, adding phosphine ligand and molecular sieve, stirring, filtering, and then placing the 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 the catalyst precursor to obtain the supported nickel-cerium catalyst.
In the invention, the activation temperature of S1 is 20-30 ℃.
In the invention, the Ni-containing compound described in 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 Ni element to 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 the Ni to the carrier of S2 is 1 (10-20), preferably 1 (12-18).
In the invention, the pH value of S2 is 1-2.
In the invention, the temperature of the stirring of the S2 is 70-85 ℃.
In the invention, the drying temperature of S3 is 90-100 ℃, and the drying time is 8-12h; the roasting temperature is 430-530 ℃, and the roasting time is 3-5h.
Compared with the prior art, the invention has the beneficial effects that:
the method can obviously reduce the generation of the electrolytic byproduct methyl 6-hydroxycaproate, improve the current efficiency and the selectivity of the dimethyl sebacate, and the selectivity can reach 86.5 percent.
Detailed Description
The present invention will be described in further detail with reference to 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 tertiary butyl ether, toluene, a ridge reagent, AR, purity >99%;
potassium methoxide, micin, purity >95%;
potassium hydroxide, carbofuran, purity >85%;
potassium carbonate, sodium hydroxide, alar Ding Shiji, purity >99%;
platinum electrode, gold electrode, silver electrode, tim new materials technologies limited;
titanium platinized electrode, siantan gold Co., ltd, plated 1 μm;
titanium-based PbO 2 Electrode, titanium-based IrO 2 Electrodes, jiangsu Yi Itanium electrode Co., ltd;
nickel chloride, nickel acetate, nickel sulfate, cerium chloride, cerium nitrate, cerium acetate, and carbofuran reagent with purity >98%.
Bis (diisopropylamino) chlorophosphine, alar Ding Shiji, purity >97%.
1, 2-bis-diphenylphosphinoethane, alar Ding Shiji, purity >98%.
ZSM-5 molecular sieve, ji Cang nano material science and technology Co., ltd., silicon-aluminum ratio of 30-40.
Neutral alumina, ala Ding Shiji, 60-100 mesh, purity >75%.
Other materials or reagents are commercially available, unless otherwise specified.
Gas chromatographic analysis conditions of the product: island body gas chromatograph GC2010, DB-5 column, sample inlet temperature: 200 ℃; detector temperature: 350 ℃; heating program: keeping at 50 ℃ for 4min, and raising the temperature to 100 ℃ at 5 ℃/min; raising the temperature to 300 ℃ at 25 ℃ per minute and keeping the temperature for 5 minutes.
The content of metal ions in the catalyst is detected by inductively coupled plasma emission spectroscopy (ICP), and the specific analysis conditions are as follows: agilent-720 type inductively coupled plasma emitter with power of 1.25KW, plasma air flow of 16mL/min, auxiliary air flow of 1.6mL/min, atomizer flow of 0.9mL/min, one reading time of 4s, instrument stabilization time of 16s, sample introduction delay of 45s, pump speed of 17rpm, cleaning time of 50s and reading times of 3 times.
The electrolytic cell is a diaphragm-free plate-frame type electrolytic cell, and is available from Hangzhou Siao electrochemical instruments.
The product rectification adopts a rectifying tower, triangular spiral packing with the diameter of 2.5mm, the tower plate number 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 by 300mL of 0.3mol/L dilute nitric acid for 2 hours, washed and dried at 80 ℃ to obtain the activated ZSM-5 molecular sieve carrier.
10.11g of nickel chloride (0.0780 mol) and 2.48g of cerium acetate (0.0078 mol) are mixed into 500g of distilled water, the pH is regulated to 1.2 by 0.5mol/L of dilute hydrochloric acid, 4.6g of bis (diisopropylamino) chlorophosphine and an activated ZSM-5 molecular sieve carrier are added under stirring, and the temperature is raised to 75 ℃ and the mixture is stirred for 12 hours; cooling to room temperature, filtering, and placing the solid in 0.15mol/L KOH solution for soaking for 2 hours to obtain catalyst precursor slurry.
Filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 90 ℃ for 12 hours, roasting at 530 ℃ for 3 hours, crushing, tabletting and forming to obtain the catalyst 1. The ICP analysis shows that the Ni content in the catalyst 1 is 4.70wt% and the Ce content in the catalyst 1 is 1.12wt%.
Example 2
78.0g of ZSM-5 molecular sieve is taken, washed by deionized water at 25 ℃, soaked by 300mL of 0.3mol/L dilute nitric acid for 2 hours, washed and dried at 80 ℃ to obtain the activated ZSM-5 molecular sieve carrier.
10.47g of nickel acetate (0.0882 mol) and 4.31g of cerium nitrate (0.0123 mol) are mixed into 500g of distilled water, the pH is regulated to 2 by 0.5mol/L of dilute hydrochloric acid, 7.8g of bis (diisopropylamino) chlorophosphine and an activated ZSM-5 molecular sieve carrier are added under stirring, and the temperature is raised to 70 ℃ and the mixture is stirred for 12 hours; cooling to room temperature, filtering, and placing the solid in 0.15mol/L KOH solution for soaking for 2 hours to obtain catalyst precursor slurry.
Filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 95 ℃ for 10 hours, roasting at 500 ℃ for 3.5 hours, crushing, tabletting and forming to obtain the catalyst 2. The ICP analysis shows that the Ni content in catalyst 2 is 5.60wt% and the Ce content is 2.00wt%.
Example 3
59.95g of ZSM-5 molecular sieve is taken, washed by deionized water at 25 ℃ and soaked for 2 hours by 250mL of 0.3mol/L dilute nitric acid, and dried at 80 ℃ after washing, thus obtaining the activated ZSM-5 molecular sieve carrier.
8.13g of nickel chloride (0.0628 mol) and 2.63g of cerium chloride (0.0107 mol) are mixed in 500g of distilled water, the pH is regulated to 1.5 by 0.5mol/L of dilute hydrochloric acid, 7.4g of bis (diisopropylamino) chlorophosphine and an activated ZSM-5 molecular sieve carrier are added under stirring, and the temperature is raised to 80 ℃ and the mixture is stirred for 12 hours; cooling to room temperature, filtering, and placing the solid in 0.15mol/L KOH solution for soaking for 2 hours to obtain catalyst precursor slurry.
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. The ICP analysis shows that the Ni content in the catalyst 3 is 5.10wt% and the Ce content is 2.06wt%.
Example 4
64.25g of ZSM-5 molecular sieve is taken, washed by deionized water at 25 ℃, soaked by 250mL of 0.3mol/L dilute nitric acid for 2 hours, washed and dried at 80 ℃ to obtain the activated ZSM-5 molecular sieve carrier.
14.17g of nickel sulfate (0.0916 mol) and 5.81g of cerium acetate (0.0183 mol) are mixed in 500g of distilled water, the pH is regulated to 1 by 0.5mol/L of dilute hydrochloric acid, 13.5g of ZSM-5 molecular sieve carrier activated by bis (diisopropylamino) chlorophosphine is added under stirring, and the temperature is raised to 85 ℃ and the mixture is stirred for 12 hours; cooling to room temperature, filtering, and placing the solid in 0.15mol/L KOH solution for soaking for 2 hours to obtain catalyst precursor slurry.
Filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 100 ℃ for 8 hours, roasting at 430 ℃ for 5 hours, crushing, tabletting and forming to obtain the catalyst 4. The ICP analysis shows that the Ni content in the catalyst 4 is 6.30wt% and the Ce content is 2.99wt%.
Example 5
51.39g of ZSM-5 molecular sieve is taken, washed by deionized water at 25 ℃ and soaked for 2 hours by 250mL of 0.3mol/L dilute nitric acid, and dried at 80 ℃ after washing, thus obtaining the activated ZSM-5 molecular sieve carrier.
9.23g of nickel chloride (0.0712 mol) and 5.27g of cerium chloride (0.0214 mol) were mixed in 500g of distilled water, the pH was adjusted to 1.7 with 0.5mol/L of dilute hydrochloric acid, 12.6g of bis (diisopropylamino) chlorophosphine and the activated ZSM-5 molecular sieve carrier were added in a stirred state, and the mixture was stirred at 82℃for 12 hours; cooling to room temperature, filtering, and placing the solid in 0.15mol/L KOH solution for soaking for 2 hours to obtain catalyst precursor slurry.
Filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 90 ℃ for 10 hours, roasting at 450 ℃ for 4.5 hours, crushing, tabletting and forming to obtain the catalyst 5. The ICP analysis shows that the Ni content in the catalyst 5 is 5.90wt% and the Ce content in the catalyst 5 is 4.21wt%.
Example 6
47.20g of neutral alumina is taken, washed by deionized water at 25 ℃ and then soaked in 300mL of 0.3mol/L dilute nitric acid for 2 hours, and dried at 80 ℃ after washing, thus obtaining the activated alumina carrier.
9.89g of nickel chloride (0.0763 mol) and 4.84g of cerium acetate (0.0153 mol) are mixed into 500g of distilled water, the pH is regulated to 1.4 by 0.5mol/L of dilute hydrochloric acid, 6.8g of 1, 2-bis (diphenylphosphine) ethane and an activated alumina carrier are added under stirring, and the temperature is raised to 80 ℃ and the mixture is stirred for 12 hours; cooling to room temperature, filtering, and placing the solid in 0.15mol/L KOH solution for soaking for 2 hours to obtain catalyst precursor slurry.
Filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 100 ℃ for 8 hours, roasting at 500 ℃ for 3 hours, crushing, tabletting and forming to obtain the catalyst 6. The ICP analysis revealed that the catalyst 6 had a Ni content of 7.40wt% and a Ce content of 3.53wt%.
Example 7
Monomethyl adipate (80 g,0.5057 mol), toluene (270 g) and potassium methoxide (14.19 g,0.2023 mol) were stirred and mixed uniformly before transferring to an electrolyzer, and catalyst 1 (1.62 g,2.0 wt%) was added. The anode of the electrolytic tank adopts a titanium platinized electrode, the cathode adopts a gold electrode, the temperature of the electrolytic tank is raised to 60 ℃, the electrolytic tank is electrified to start electrolytic reaction, the electrode potential of the electrolytic tank is 2.5V, and the current density is 1500A/m 2 Electrolysis time is 15h. After the reaction, filtering to remove the solid catalyst, separating out the reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of raw material monomethyl adipate was 88.9%, the selectivity of product dimethyl sebacate was 84.9%, the selectivity of by-product methyl 6-hydroxycaproate was 0.07%, and the reaction current efficiency was 75.6%.
Example 8
Monomethyl adipate (80 g,0.5057 mol), methyl tertiary butyl ether (101.25 g) and potassium hydroxide (8.51 g,0.1517 mol) were stirred and mixed uniformly before transferring to an electrolyzer, and catalyst 2 (0.405 g,0.5 wt%) was added. The anode of the electrolytic tank adopts titanium-based PbO 2 The electrode, the cathode adopts silver electrode, the temperature of the electrolytic tank is raised to 65 ℃, the electrolytic reaction is started by electrifying, the electrode potential of the electrolytic tank is 3.0V, and the current density is 1600A/m 2 Electrolysis time 13h. After the reaction, filtering to remove the solid catalyst, separating out the reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of raw material adipic acid monomethyl ester was 89.7%, the selectivity of product dimethyl sebacate was 84.2%, the selectivity of by-product methyl 6-hydroxycaproate was 0.15%, and the reaction current efficiency was 76.2%.
Example 9
Monomethyl adipate (80 g,0.5057 mol), methanol (81 g) and potassium hydroxide (5.68 g,0.1011 mol) were stirred and mixed uniformly before transferring to an electrolyzer, and catalyst 3 (1.053 g,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 cell is electrified to start electrolytic reaction, the electrode potential of the electrolytic cell is 3.2V, and the current density is 1700A/m 2 The electrolysis time is 12h. After the reaction, filtering to remove the solid catalyst, separating out the reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of raw material adipic acid monomethyl ester was 91.3%, the selectivity of product dimethyl sebacate was 86.5%, the selectivity of by-product methyl 6-hydroxycaproate was 0.04%, and the reaction current efficiency was 76.7%.
Example 10
Monomethyl adipate (80 g,0.5057 mol), ethanol (54 g) and potassium methoxide (5.32 g,0.0759 mol) were stirred and mixed uniformly before transferring to an electrolyzer, and catalyst 4 (1.377 g,1.7 wt%) was added. Titanium-based IrO is adopted as an anode of the electrolytic cell 2 The electrode, the cathode adopts titanium silver plating electrode, the temperature of the electrolytic tank is raised to 75 ℃, the electrolytic reaction is started by electrifying, and the electrode of the electrolytic tank is electrifiedBit 3.7V, current density 1800A/m 2 The electrolysis time is 10h. After the reaction, filtering to remove the solid catalyst, separating out the reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of raw material adipic acid monomethyl ester was 91.2%, the selectivity of product dimethyl sebacate was 85.4%, the selectivity of by-product methyl 6-hydroxycaproate was 0.09%, and the reaction current efficiency was 74.9%.
Example 11
Monomethyl adipate (80 g,0.5057 mol), methanol (40.5 g) and potassium carbonate (6.99 g,0.0506 mol) were stirred and mixed uniformly before transferring to an electrolyzer, and catalyst 5 (2.43 g,3.0 wt%) was added. The anode of the electrolytic tank adopts a titanium platinized electrode, the cathode adopts a silver electrode, the electrolytic tank is heated to 65 ℃, the electrolytic tank is electrified to start electrolytic reaction, the electrode potential of the electrolytic tank is 3.5V, and the current density is 1700A/m 2 Electrolysis time is 15h. After the reaction, filtering to remove the solid catalyst, separating out the reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of raw material adipic acid monomethyl ester was 88.3%, the selectivity of product dimethyl sebacate was 83.7%, and the selectivity of by-product methyl 6-hydroxycaproate was 0.42%, and the reaction current efficiency was 74.2%.
Example 12
Monomethyl adipate (80 g,0.5057 mol), toluene (405 g) and sodium hydroxide (9.10 g,0.2276 mol) were stirred and mixed uniformly before transferring to an electrolyzer, and catalyst 6 (0.203 g,0.25 wt%) was added. The anode of the electrolytic cell adopts a platinum electrode, the cathode adopts a titanium silver plating electrode, the electrolytic cell is heated to 65 ℃, the electrolytic cell is electrified to start electrolytic reaction, the electrode potential of the electrolytic cell is 3.0V, and the current density is 1600A/m 2 The electrolysis time is 12h. After the reaction, filtering to remove the solid catalyst, separating out the reaction liquid, and rectifying the obtained crude mixture to obtain the product dimethyl sebacate.
In this example, the conversion of raw material adipic acid monomethyl ester was 87.5%, the selectivity of product dimethyl sebacate was 83.4%, the selectivity of 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 procedure and process conditions described in example 3, except that: in the step S2, only nickel chloride, bis (diisopropylamino) chlorophosphine and molecular sieve are added, and cerium chloride as a cocatalyst is not added, and other operation conditions are the same as in the example 3.
Dimethyl sebacate was prepared according to the procedure and process conditions in example 9, except that: the reaction was conducted using catalyst A instead of catalyst 3, and the other operations were conducted in the same manner as in example 9.
In this comparative example, the conversion of raw material adipic acid monomethyl ester was 76.2%, the selectivity of product dimethyl sebacate was 81.2%, the selectivity of 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 procedure and process conditions of example 3, except that: in the step S2, only nickel chloride, cerium chloride and molecular sieve are added, and ligand bis (diisopropylamino) chlorophosphine is not added, and other operating conditions are the same as in example 3.
Dimethyl sebacate was prepared according to the procedure and process conditions in example 9, except that: the reaction was conducted using catalyst B instead of catalyst 3, and the other operations were conducted in the same manner as in example 9.
In this comparative example, the conversion of raw material adipic acid monomethyl ester was 75.3%, the selectivity of product dimethyl sebacate was 80.8%, the selectivity of 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 procedure and process conditions in example 9, except that: the reaction was conducted in the same manner as in example 9 except that the catalyst was not used.
In this comparative example, the conversion of raw material adipic acid monomethyl ester was 72.8%, the selectivity of product dimethyl sebacate was 75.6%, the selectivity of by-product methyl 6-hydroxycaproate was 4.98%, and the reaction current efficiency was 60.2%.
Claims (18)
1. The method for electrochemically synthesizing dimethyl sebacate is characterized in that monomethyl adipate, an organic solvent, electrolyte and a catalyst are placed in an electrolytic cell for electrolytic reaction to generate a reaction solution containing dimethyl sebacate, and the reaction solution is rectified to obtain a dimethyl sebacate product; wherein the catalyst is a supported nickel-cerium catalyst containing phosphine ligands.
2. The method of claim 1, wherein the organic solvent is one or more of an alcohol, an ether, a nitrile, and benzene.
3. The method according to claim 2, wherein the organic solvent is one or more of methanol, ethanol, methyl tert-butyl ether, toluene;
the mass ratio of the monomethyl adipate to the organic solvent is (0.1-2) 1.
4. A process according to claim 3, characterized in that the ratio by mass of monomethyl adipate to organic solvent is (0.3-1.5): 1.
5. The method according to claim 1 or 2, wherein the electrolyte is an alkali metal-containing electrolyte.
6. The method of claim 5, wherein the electrolyte is one or more of sodium methoxide, potassium methoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate;
the molar ratio of the electrolyte to the monomethyl adipate is (0.1-0.45): 1.
7. The method of claim 6, wherein the electrolyte is potassium methoxide and/or potassium hydroxide;
the molar ratio of the electrolyte to the monomethyl adipate is (0.15-0.4): 1.
8. The method of claim 1, wherein the catalyst is a phosphine ligand-containing molecular sieve supported nickel-cerium catalyst.
9. The method of claim 8, wherein the catalyst is a Ni-Ce-X/ZSM-5 catalyst, wherein Ni is a main catalyst, ce is a co-catalyst, X is a ligand bis (diisopropylamino) chlorophosphine, and ZSM-5 molecular sieve is a carrier;
the catalyst is used in an amount of 0.1 to 3% by weight relative to the monomethyl adipate.
10. The process according to claim 9, wherein the catalyst is used in an amount of 0.5 to 2% by weight relative to the monomethyl adipate.
11. The method of claim 1, wherein the electrolytic cell comprises an anode and a cathode;
and/or the electrolysis temperature of the electrolysis reaction is 50-80 ℃; the electrolysis time is 5-18h;
and/or the electrolysis potential interval of the electrolysis reaction electrolytic cell is 2-4V; the electrolysis current density interval is 1200-2000A/m 2 。
12. The method of claim 11, wherein the anode is a platinum electrode, a titanium platinized electrode, a titanium-based PbO 2 Electrode, titanium-based IrO 2 One of the electrodes;
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 60-75 ℃; the electrolysis time is 10-15h;
and/or the electrolysis potential interval of the electrolysis reaction electrolytic cell is 2.5-3.7V; the electrolysis current density interval is 1500-1800A/m 2 。
13. The method according to claim 1, wherein the method for preparing the catalyst comprises the steps of:
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 dilute acid to adjust the pH value of the solution, adding phosphine ligand and molecular sieve, stirring, filtering, and then placing the 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 the catalyst precursor to obtain the supported nickel-cerium catalyst.
14. The method of claim 13, wherein the temperature of S1 activation is 20-30 ℃.
15. The method of claim 14, wherein the Ni-containing compound of S2 is selected from one or more of nickel chloride, nickel acetate, nickel sulfate, nickel nitrate; the Ce-containing compound is selected from one or more of cerium chloride, cerium nitrate, cerium oxalate and cerium acetate;
and/or the mass ratio of the Ni to the carrier in S2 is 1 (10-20);
and/or S2, wherein the pH value is 1-2;
and/or the temperature during stirring in the step S2 is 70-85 ℃.
16. The method of claim 15, wherein the Ni-containing compound of S2 is nickel chloride; the Ce-containing compound is cerium chloride;
the mole ratio of Ni element to Ce element is 1 (0.1-0.3);
the mass ratio of Ni to phosphine ligand is 1 (1-3);
and/or the mass ratio of the Ni to the carrier in the S2 is 1 (12-18).
17. The method according to claim 16, wherein the molar ratio of the Ni element to the Ce element of S2 is 1 (0.1-0.2);
the mass ratio of Ni to phosphine ligand is 1 (1.5-2.5).
18. The method of claim 13, wherein S3 is at a temperature of 90-100 ℃ for a time of 8-12 hours; the roasting temperature is 430-530 ℃, and the roasting time is 3-5h.
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