CN114959748A - Electrochemical preparation method of erythritol - Google Patents

Electrochemical preparation method of erythritol Download PDF

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Publication number
CN114959748A
CN114959748A CN202210460419.XA CN202210460419A CN114959748A CN 114959748 A CN114959748 A CN 114959748A CN 202210460419 A CN202210460419 A CN 202210460419A CN 114959748 A CN114959748 A CN 114959748A
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electrode
erythritol
hydroxide
alkaline electrolyte
catholyte
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栾谨鑫
杜旺明
钱向阳
张永振
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes

Abstract

The invention provides an electrochemical preparation method of erythritol, which is carried out in a zero-polar distance electrolytic cell, wherein the electrolytic cell comprises an anode chamber and a cathode chamber, the anode chamber and the cathode chamber are separated by a diaphragm, and the method comprises the following steps: 1) preparing an alkaline electrolyte aqueous solution as an anolyte, and injecting the anolyte into the anode chamber; 2) preparing an alkaline electrolyte aqueous solution, adding dialdehyde starch, polysorbate 80, bis (2- (2-hydroxyphenyl) pyridine) beryllium and long-chain alkyl quaternary ammonium base into the alkaline electrolyte aqueous solution, uniformly stirring the mixture to be used as catholyte, and injecting the catholyte into a cathode chamber; 3) and (3) introducing current into the electrolytic bath, heating to react, and preparing the p-aminophenol in the catholyte. The method has the advantages of wide raw material source, simple steps, high atom economy, less three wastes, low energy consumption and low cost.

Description

Electrochemical preparation method of erythritol
Technical Field
The invention belongs to the technical field of erythritol preparation, and relates to an electrochemical preparation method of erythritol.
Background
Erythritol is widely distributed in nature, such as fruits, mushrooms, lichens, etc. In addition, the sugar is also present in fermented foods and mammals, is a natural sugar, has sweet taste, has 70% -80% of sweetness of sucrose, and has only 0.2kcal/g of calorie.
Erythritol has unique nutritional characteristics, has relatively high digestibility, and is easily and rapidly absorbed by small intestine; erythritol does not affect the blood sugar level and the insulin level, so that the erythritol is suitable for diabetics to eat; because the bacteria in the oral cavity cannot utilize erythritol, tooth decay does not occur.
Due to the good characteristics of erythritol, erythritol is widely used in the industries of candies, beverages, baked goods, health foods, pharmaceuticals and the like, and the demand is increasing at present.
In the traditional process, erythritol is prepared by adopting a fermentation method, namely, a Candida lipolytica (Candida lipolytica) strain is adopted as a fermentation strain, and after slant preparation and shake flask seed culture, primary seed culture, secondary seed culture and fermentation tank fermentation are carried out to generate erythritol.
Although the process for producing erythritol by glucose fermentation is mature, the entire industrial chain of erythritol production has certain disadvantages in terms of economy, effective utilization of resources, environmental protection, wastewater treatment, and the like.
CN101336313A provides a method for continuously producing erythrose or erythritol by electrolysis, wherein erythrose is synthesized by electrolytic decarboxylation of arabinonic acid or ribonic acid, and erythritol is further synthesized by hydrogenation. The method is a two-step reaction and has the defects of high raw material consumption, poor atom economy, low yield and the like.
Therefore, it is required to develop a new method for preparing erythritol so as to solve various disadvantages in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an electrochemical preparation method of erythritol, which takes dialdehyde starch as a raw material and improves the product yield by adding polysorbate 80, bis (2- (2-hydroxyphenyl) pyridine) beryllium and long-chain alkyl quaternary ammonium base. The method has the advantages of high conversion rate and selectivity, wide raw material source, simple steps, high atom economy, less three wastes, low energy consumption and low cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an electrochemical preparation method of erythritol, which is carried out in a zero-polar distance electrolytic cell, wherein the electrolytic cell comprises an anode chamber and a cathode chamber, the anode chamber and the cathode chamber are separated by a diaphragm, and the method comprises the following steps:
1) preparing an alkaline electrolyte aqueous solution as an anolyte, and injecting the anolyte into the anode chamber;
2) preparing an alkaline electrolyte aqueous solution, adding dialdehyde starch, polysorbate 80, bis (2- (2-hydroxyphenyl) pyridine) beryllium and long-chain alkyl quaternary ammonium base into the alkaline electrolyte aqueous solution, uniformly stirring the mixture to be used as catholyte, and injecting the catholyte into a cathode chamber;
3) and (3) introducing current into the electrolytic bath, heating to react, and preparing the p-aminophenol in the catholyte.
In the method, step 1) and step 2), the alkaline electrolyte is an aqueous solution, wherein the alkaline electrolyte is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide and triethylamine, preferably potassium hydroxide;
preferably, the concentration of the aqueous alkaline electrolyte solution is 1 to 8 wt%, such as 3 wt%, 5 wt%, 7 wt%, preferably 4 to 6 wt%.
In the method of the invention, step 2), the mass ratio of the dialdehyde starch to the alkaline electrolyte aqueous solution is 1:1-6, such as 1:1, 1:3, 1:5, preferably 1: 2-4.
In the method, step 2), the mass ratio of polysorbate 80 to dialdehyde starch is 1:10-20, such as 1:11, 1:14, 1:17 and 1:19, preferably 1: 12-16.
In the method, in the step 2), the mass ratio of the bis (2- (2-hydroxyphenyl) pyridine) beryllium to the dialdehyde starch is 1:100-200, such as 1:110, 1:140, 1:170, 1:190, preferably 1: 120-160.
In the method of the invention, step 2), the long-chain alkyl quaternary ammonium hydroxide is a quaternary ammonium hydroxide with an alkyl chain of C12-C18, preferably any one or a combination of at least two of dodecyl trimethyl ammonium hydroxide, tetradecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide and octadecyl trimethyl ammonium hydroxide, and more preferably dodecyl trimethyl ammonium hydroxide and/or tetradecyl trimethyl ammonium hydroxide;
preferably, the mass ratio of the long-chain alkyl quaternary ammonium hydroxide to the dialdehyde starch is 1:20-40, such as 1:22, 1:26, 1:28, 1:30, 1:36, 1:38, preferably 1: 24-32.
In the method of the invention, in the step 3), the voltage of the electrolytic bath is 2-3V, such as 2.0V, 2.2V, 2.4V, 2.5V, 2.7V, 2.9V and 3V, preferably 2.5-2.8V; the current density is 1200-2000A/m 2 E.g. 1200A/m 2 、1300A/m 2 、1400A/m 2 、1500A/m 2 、1600A/m 2 、1700A/m 2 、1800A/m 2 、1900A/m 2 、2000A/m 2 Preferably 1600-1800A/m 2 。
In the method of the present invention, step 3), the reaction is carried out at a temperature of 30 to 60 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 55 ℃, 60 ℃, preferably 40 to 50 ℃; the time is 5-20h, for example 5h, 10h, 15h, 20h, preferably 10-15 h.
In the method, in the step 3), the reaction comprises a reaction of directly generating erythritol by hydrolyzing the dialdehyde starch through a cathode, and a reaction of generating erythrose by hydrolyzing the dialdehyde starch and generating erythritol by reducing the erythrose through the cathode, wherein the reactions are synchronously performed in a cathode solution, and the reaction conditions are the same. After current is introduced into the catholyte and the temperature is raised, the dialdehyde starch is directly hydrolyzed by a cathode to generate erythritol, or the dialdehyde starch is hydrolyzed to generate erythrose, and the erythritol is reduced by the cathode to generate erythritol and a small amount of glycol;
after the reaction is finished, the catholyte obtained by the method can be subjected to post-treatment processes such as filtration, freezing crystallization and the like to obtain purified erythritol, and the operations involved in the post-treatment process are conventional methods in the field, and do not make specific requirements, and all realizable modes are available. For example, the catholyte can be filtered, concentrated to remove excess water, and the concentrate can be subjected to freeze crystallization to isolate erythritol.
According to the method, the prepared erythritol comprises any one or combination of at least two of D- (-) -meso-erythritol, (D) -erythritol and (L) -erythritol, wherein the proportion of the D- (-) -meso-erythritol is 50-70%, the proportion of the (D) -erythritol is 20-30%, and the proportion of the (L) -erythritol is 10-20%, and the total content of the erythritol is 100%.
In the invention, the zero-polar distance electrolytic cell comprises an anode electrode, a diaphragm and a cathode electrode;
preferably, the electrolytic cell has a zero-polar distance sandwich structure consisting of an anode electrode, a diaphragm and a cathode electrode.
Preferably, the membrane is a cation exchange membrane, preferably any one or a combination of at least two of Nafion 117, Nafion 115, Nafion212, Nafion427, and Nafion 551, and more preferably Nafion 427. The selected cation exchange membrane has selective permeability, allows only cations to pass through, reduces voltage, and has high conductivity, high mechanical strength, strong acid and strong base resistance.
Preferably, the anode electrode is selected from a titanium-platinum (Pt/Ti) electrode, a titanium-based noble metal oxide coating (e.g., RuO) 2 a/Ti) electrode, a pure platinum electrode, or a combination of at least two, more preferably a titanium-platinized electrode or a titanium-based noble metal oxide-coated electrode, said noble metal being selected from Ir, Pb or Ru, more preferably a titanium-based noble metal oxide-coated electrode.
Preferably, the cathode electrode is selected from a nickel electrode, more preferably any one of a nickel mesh electrode, a nickel plate electrode, a graphite electrode with a raney nickel plating layer, or a combination of at least two thereof, and more preferably a graphite electrode with a raney nickel plating layer.
In the method of the present invention, the material of the electrolytic cell is PP, PTFE and titanium, preferably titanium.
In an experiment for preparing erythritol, the invention discovers that the solubility of dialdehyde starch in an alkaline electrolyte water system can be remarkably increased by taking the dialdehyde starch as an electrochemical reaction raw material and adding polysorbate 80. And meanwhile, bis (2- (2-hydroxyphenyl) pyridine) beryllium is added as an auxiliary agent, wherein the existence of pyridyl can reduce the reduction electromotive force of the surface of a cathode Ni electrode, the reduction electromotive force has catalytic activity on the electric reduction of water and dialdehyde starch, and the existence of hydroxyphenyl enables the bis (2- (2-hydroxyphenyl) pyridine) beryllium to have hydrophobicity in an electrolytic system and be easily attached to the surface of the electrode to form a hydrophobic region, and the stability and the conductivity of the hydrophobic region of the electrode are improved through beryllium ions. In the catholyte, bis (2- (2-hydroxyphenyl) pyridine) beryllium simultaneously reduces water and aldehyde group reduction electromotive force on the surface of a Ni electrode and promotes the reduction of dialdehyde starch, and absorbs the dialdehyde starch on the surface of the electrode to form a conductive and hydrophobic surface, so that the dialdehyde starch and erythrose can be easily subjected to electron reduction on the surface of the electrode to form erythritol, the hydrogen evolution reaction is inhibited, and the current efficiency is improved. In addition, the diffusion coefficient of erythrose to the surface of the electrode is increased by adding the long-chain alkyl quaternary ammonium base, so that the erythrose is promoted to diffuse to the surface of the electrode to carry out reduction reaction, and the erythritol is obtained.
Compared with the prior art, the method has the advantages of wide raw material source, high conversion rate, high product selectivity, simple steps, mild reaction conditions, low operation risk, less three wastes and low energy consumption, and is suitable for wide industrial application.
Detailed Description
The preparation process provided by the present invention is further illustrated in detail by the following examples, but the present invention is not limited thereto.
The sources of the raw materials of the reagents used in the examples and comparative examples of the present invention are as follows, and the other raw materials of the reagents are all common commercial products unless otherwise specified:
polysorbate 80: an alatin reagent, pharmaceutical grade;
dodecyl trimethyl ammonium hydroxide: west asia chemical science and technology limited, purity 40 wt.% in water;
tetradecyltrimethylammonium hydroxide: west asia chemical science and technology limited, purity 40 wt.% in water;
hexadecyl trimethyl ammonium hydroxide: west asia chemical science and technology limited, purity 40 wt.% in water;
octadecyl trimethyl ammonium hydroxide: west asia chemical science and technology limited, purity 40 wt.% in water;
dialdehyde starch: shandong Moore chemical Co., Ltd., purity > 80%;
sodium hydroxide: chemical reagent of Xilongu, purity AR, 98%;
potassium hydroxide: chemical reagent of Xilongu, purity AR, 98%;
bis (2- (2-hydroxyphenyl) pyridine) beryllium: aladdin reagent, purity AR, 99%.
Zero polar distance electrolytic cell: jiangsu Ankat science and technology Co.
The test methods used in the examples of the invention and the comparative examples are as follows:
erythritol analysis method:
chromatograph: waters; a chromatographic column: alltech Prevail Carbohydrate ES (4.6 mm. times.250 mm,5 μm); mobile phase: acetonitrile/water (3/1); flow rate: 1.0 mL/min; a detector: an RI 2000 type differential refraction detector; column temperature: 30 ℃; sample injection volume: 10 mu L of the solution; the quantitative method comprises the following steps: external standard curve method.
Erythritol used in the following examples was subjected to hydrogen spectrum structural characterization using a nuclear magnetic resonance spectrometer (Brucker ARX-400).
Example 1
Electrochemically preparing erythritol by the steps of:
a zero-polar-distance electrolytic tank is adopted, the material of the electrolytic tank is PP, a nickel mesh electrode is adopted as a cathode electrode, a titanium platinum electrode is adopted as an anode electrode, and a Nafion 117 cation exchange membrane is adopted as a diaphragm.
1) 216g of 7.4 wt% aqueous solution of potassium methoxide as an anolyte was injected into the anode chamber of the electrolytic cell.
2) 216g of a 7.4 wt% potassium methoxide aqueous solution was prepared, and then 200g of dialdehyde starch, 20g of polysorbate 80, 2g of bis (2- (2-hydroxyphenyl) pyridine) beryllium and 10g of dodecyltrimethylammonium hydroxide were added and stirred uniformly to serve as a catholyte, which was injected into the cathode chamber.
3) The current is introduced into the electrolytic cell, the voltage of the electrolytic cell is 2.0V, and the current density of the electrolytic cell is 1200A/m 2 Heating to 30 ℃ for reaction, stopping the reaction after 20h of reaction, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5h, and filtering to obtain the erythritol product.
Erythritol nuclear magnetic hydrogen spectroscopy data were as follows:
1H NMR(600MHz,CDCl 3 )：δ3.65(2H)，3.81(2H)，3.56(2H)，3.58(2H)，3.38(2H)。
in the embodiment, the conversion rate of the dialdehyde starch serving as the raw material is 91.2%, the selectivity of the synthesized erythritol is 89.3%, and the current efficiency is 92.3%; the erythritol product contains 50 wt% of D- (-) -meso-erythritol, 30 wt% of (D) -erythritol and 20 wt% of (L) -erythritol.
Example 2
Electrochemically preparing erythritol by the steps of:
adopting a zero polar distance electrolytic tank made of PTFE, adopting a nickel plate electrode as a cathode electrode and adopting Ti-based RuO as an anode electrode 2 The anode and the diaphragm adopt Nafion 115 cation exchange membranes.
1) 212g of a 5.7 wt% aqueous sodium methoxide solution was prepared as an anolyte, which was then injected into the anode compartment of the electrolytic cell.
2) 212g of a 5.7 wt% sodium methoxide aqueous solution was prepared, and then 100g of dialdehyde starch, 5g of polysorbate 80, 0.5g of bis (2- (2-hydroxyphenyl) pyridine) beryllium and 2.5g of tetradecyltrimethylammonium hydroxide were added thereto and stirred uniformly to prepare a catholyte, which was then poured into the cathode chamber.
3) The current is introduced into the electrolytic cell, the voltage of the electrolytic cell is 2.2V, and the current density of the electrolytic cell is 1400A/m 2 Heating to 40 ℃ for reaction, stopping the reaction after the reaction lasts for 15h, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5h, and filtering to obtain the erythritol product.
In the embodiment, the conversion rate of the dialdehyde starch serving as the raw material is 92%, the selectivity of the synthesized erythritol is 87.3%, and the current efficiency is 90.6%; the D- (-) -meso-erythritol content in the erythritol product is 60 wt%, (D) -erythritol content is 25 wt%, and (L) -erythritol content is 15 wt%.
Example 3
Electrochemically preparing erythritol by the steps of:
adopting a zero polar distance electrolytic bath which is made of titanium, adopting a nickel plate electrode as a cathode electrode and adopting Ti-based IrO as an anode electrode 2 The anode and the diaphragm adopt a Nafion212 cation exchange membrane.
1) 208g of 3.9 wt% potassium hydroxide aqueous solution is prepared as an anolyte and injected into the anode chamber of the electrolytic cell.
2) 208g of a 3.9 wt% potassium hydroxide aqueous solution was prepared, and then 50g of dialdehyde starch, 4.2g of polysorbate 80, 0.3g of bis (2- (2-hydroxyphenyl) pyridine) beryllium and 1.6g of cetyltrimethylammonium hydroxide were added thereto and stirred uniformly to serve as a catholyte, which was injected into the cathode chamber.
3) The current is introduced into the electrolytic cell, the voltage of the electrolytic cell is 2.4V, and the current density of the electrolytic cell is 1600A/m 2 Heating to 50 ℃ for reaction, stopping the reaction after 10h of reaction, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5h, and filtering to obtain the erythritol product.
In the example, the conversion rate of the dialdehyde starch as the raw material is 90.5%, the selectivity of the synthesized erythritol is 89.3%, and the current efficiency is 89.3%; the erythritol product contains 70 wt% of D- (-) -meso-erythritol, 20 wt% of (D) -erythritol and 10 wt% of (L) -erythritol.
Example 4
Electrochemically preparing erythritol by the steps of:
adopts a zero polar distance electrolytic bath which is made of titanium, a cathode electrode adopts a graphite electrode with a Raney nickel coating, and an anode electrode adopts Ti-based PbO 2 The anode and the diaphragm adopt a Nafion427 cation exchange membrane.
1) 208g of 3.9 wt% sodium hydroxide aqueous solution is prepared as an anolyte and injected into the anode chamber of the electrolytic cell.
2) 208g of a 3.9 wt% aqueous sodium hydroxide solution was prepared, and then 33.3g of dialdehyde starch, 2.1g of polysorbate 80, 0.28g of bis (2- (2-hydroxyphenyl) pyridine) beryllium and 1.38g of tetradecyltrimethylammonium hydroxide were added thereto and stirred uniformly to prepare a catholyte, which was then poured into the cathode chamber.
3) The current is introduced into the electrolytic cell, the voltage of the electrolytic cell is 2.5V, and the current density of the electrolytic cell is 1800A/m 2 Heating to 60 ℃, reacting, stopping the reaction after 5h, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5h, and filtering to obtain the erythritol product.
In the embodiment, the conversion rate of the dialdehyde starch serving as the raw material is 89.1%, the selectivity of the synthesized erythritol is 91%, and the current efficiency is 90.2%; the erythritol product contains 55 wt% of D- (-) -meso-erythritol, 30 wt% of (D) -erythritol and 15 wt% of (L) -erythritol.
Example 5
Electrochemically preparing erythritol by the steps of:
adopts a zero polar distance electrolytic bath which is made of titanium, a cathode electrode adopts a graphite electrode with a Raney nickel coating, and an anode electrode adopts Ti-based PbO 2 The anode and the diaphragm adopt Nafion 551 cation exchange membranes.
1) 202g of 1 wt% aqueous solution of triethylamine as an anolyte was injected into the anode compartment of the electrolytic cell.
2) 202g of a 1 wt% aqueous triethylamine solution was prepared, and then 100g of dialdehyde starch, 8.3g of polysorbate 80, 0.63g of bis (2- (2-hydroxyphenyl) pyridine) beryllium and 2.5g of octadecyl trimethyl ammonium hydroxide were added thereto, stirred uniformly, and injected into the cathode chamber as a catholyte.
3) The current is introduced into the electrolytic cell, the voltage of the electrolytic cell is 2.8V, and the current density of the electrolytic cell is 2000A/m 2 And heating to 55 ℃ for reaction, stopping the reaction after the reaction is carried out for 5h, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5h, and filtering to obtain the erythritol product.
In the embodiment, the conversion rate of the dialdehyde starch serving as the raw material is 90.8%, the selectivity of the synthesized erythritol is 87.6%, and the current efficiency is 89.1%; the D- (-) -meso-erythritol content in the erythritol product is 60 wt%, (D) -erythritol content is 20 wt%, and (L) -erythritol content is 20 wt%.
Comparative example 1
An erythritol product was prepared according to the procedure of example 1, except that polysorbate 80 was not added to the catholyte, and the other operations and parameters were the same as in example 1.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 52%, the selectivity of the synthesized erythritol is 61.5%, and the current efficiency is 63.9%; the D- (-) -meso-erythritol content in the erythritol product is 65 wt%, (D) -erythritol content is 25 wt%, (L) -erythritol content is 10 wt%.
Comparative example 2
Referring to the method of example 1, except for replacing polysorbate 80 with polysorbate 20 in the catholyte, the other operations and parameters were the same as in example 1, an erythritol product was prepared.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 66%, the selectivity of the synthesized erythritol is 78.1%, and the current efficiency is 75.2%; the D- (-) -meso-erythritol content in the erythritol product is 66 wt%, (D) -erythritol content is 22 wt%, (L) -erythritol) content is 12 wt%.
Comparative example 3
An erythritol product was prepared by following the procedure of example 1, except that bis (2- (2-hydroxyphenyl) pyridine) beryllium was not added to the catholyte, and the other operations and parameters were the same as in example 1.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 36%, the selectivity of the synthesized erythritol is 52%, and the current efficiency is 48.7%; the erythritol product contains 54 wt% of D- (-) -meso-erythritol, 28 wt% of (D) -erythritol and 18 wt% of (L) -erythritol.
Comparative example 4
With reference to the procedure of example 1, an erythritol product was prepared except that bis (2- (2-hydroxyphenyl) pyridine) beryllium was replaced with 2- (4-hydroxyphenyl) pyridine in the catholyte and the other operations and parameters were the same as in example 1.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 39%, the selectivity of the synthesized erythritol is 54%, and the current efficiency is 49.3%; the D- (-) -meso-erythritol content in the erythritol product is 52 wt%, (D) -erythritol content is 30 wt%, (L) -erythritol) content is 18 wt%.
Comparative example 5
With reference to the procedure of example 1, except that bis (2- (2-hydroxyphenyl) pyridine) beryllium was replaced with 2- (2-hydroxyphenyl) benzothiazole beryllium in the catholyte, the other operations and parameters were the same as in example 1, to obtain erythritol.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 41%, the selectivity of the synthesized erythritol is 56%, and the current efficiency is 51.5%; the D- (-) -meso-erythritol content in the erythritol product is 55 wt%, (D) -erythritol content is 30 wt%, (L) -erythritol content is 15 wt%.
Comparative example 6
With reference to the procedure of example 1, an erythritol product was prepared except that bis (2- (2-hydroxyphenyl) pyridine) beryllium was replaced with bis (2- (2-pyridyl) phenol) beryllium in the catholyte and the other operations and parameters were the same as in example 1.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 37%, the selectivity of the synthesized erythritol is 51%, and the current efficiency is 45.3%; the D- (-) -meso-erythritol content in the erythritol product is 50 wt%, (D) -erythritol content is 27 wt%, (L) -erythritol) content is 23 wt%.
Comparative example 7
An erythritol product was prepared according to the procedure of example 1, except that the catholyte was not supplemented with a long chain alkyl quaternary ammonium hydroxide, and the other operations and parameters were the same as in example 1.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 74%, the selectivity of the synthesized erythritol is 71%, and the current efficiency is 75.9%; the D- (-) -meso-erythritol content in the erythritol product is 60 wt%, (D) -erythritol content is 25 wt%, (L) -erythritol) content is 15 wt%.
Comparative example 8
With reference to the procedure of example 1, except that dodecyltrimethylammonium hydroxide was replaced with tetramethylammonium hydroxide in the catholyte, the other operations and parameters were the same as in example 1, to produce an erythritol product.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 71%, the selectivity of the synthesized erythritol is 73%, and the current efficiency is 76.1%; the D- (-) -meso-erythritol content in the erythritol product is 59 wt%, (D) -erythritol content is 24 wt%, (L) -erythritol content is 17 wt%.
Comparative example 9
With reference to the procedure of example 1, except that the zero-pitch cell was substituted for the non-diaphragm plate-and-frame cell, the catholyte used in example 1 was used as the electrolyte, and the other operations and parameters were the same as in example 1, to produce an erythritol product.
In the comparative example, the conversion rate of the raw material dialdehyde starch is 45%, the selectivity of the synthesized erythritol is 21%, and the current efficiency is 23.5%; the D- (-) -meso-erythritol content in the erythritol product is 62 wt%, (D) -erythritol content is 25 wt%, (L) -erythritol content is 13 wt%.

Claims (10)

1. A process for the electrochemical production of erythritol characterized by being carried out in a zero-pitch cell comprising an anode compartment and a cathode compartment, wherein the anode compartment and the cathode compartment are separated by a membrane, the process steps comprising:
1) preparing an alkaline electrolyte aqueous solution as an anolyte, and injecting the anolyte into the anode chamber;
2) preparing an alkaline electrolyte aqueous solution, adding dialdehyde starch, polysorbate 80, bis (2- (2-hydroxyphenyl) pyridine) beryllium and long-chain alkyl quaternary ammonium base into the alkaline electrolyte aqueous solution, uniformly stirring the mixture to be used as catholyte, and injecting the catholyte into a cathode chamber;
3) and (3) introducing current into the electrolytic bath, heating to react, and preparing the p-aminophenol in the catholyte.
2. The preparation method according to claim 1, characterized in that in step 1) and step 2), the alkaline electrolyte is aqueous solution, wherein the alkaline electrolyte is selected from any one or combination of at least two of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide and triethylamine, preferably potassium hydroxide;
preferably, the concentration of the aqueous alkaline electrolyte solution is 1 to 8 wt%, preferably 4 to 6 wt%.
3. The method according to claim 1 or 2, wherein the mass ratio of the dialdehyde starch to the aqueous solution of alkaline electrolyte in the step 2) is 1:1-6, preferably 1: 2-4.
4. The method according to any one of claims 1 to 3, wherein the mass ratio of polysorbate 80 to dialdehyde starch in step 2) is 1:10-20, preferably 1: 12-16.
5. The method according to any one of claims 1 to 4, wherein the mass ratio of bis (2- (2-hydroxyphenyl) pyridine) beryllium to dialdehyde starch in step 2) is 1:100-200, preferably 1: 120-160.
6. The method according to any one of claims 1 to 5, wherein in step 2), the long-chain alkyl quaternary ammonium hydroxide is a quaternary ammonium hydroxide having an alkyl chain of C12 to C18, preferably any one or a combination of at least two of dodecyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octadecyltrimethylammonium hydroxide, more preferably dodecyltrimethylammonium hydroxide and/or tetradecyltrimethylammonium hydroxide;
preferably, the mass ratio of the long-chain alkyl quaternary ammonium base to the dialdehyde starch is 1:20-40, preferably 1: 24-32.
7. The production method according to any one of claims 1 to 6, wherein in step 3), the cell voltage is 2 to 3V, preferably 2.5 to 2.8V; the current density is 1200-2000A/m 2 Preferably 1600-1800A/m 2 。
8. The method according to any one of claims 1 to 7, wherein in step 3), the reaction is carried out at a temperature of 30 to 60 ℃, preferably 40 to 50 ℃; the time is 5-20h, preferably 10-15 h.
9. The production method according to any one of claims 1 to 8, wherein the zero-pole-distance electrolytic cell comprises an anode electrode, a separator, a cathode electrode;
preferably, the electrolytic cell has a zero-polar distance sandwich structure consisting of an anode electrode, a diaphragm and a cathode electrode.
10. The method according to any one of claims 1 to 9, wherein the membrane is a cation exchange membrane, preferably any one or a combination of at least two of Nafion 117, Nafion 115, Nafion212, Nafion427, and Nafion 551, more preferably Nafion 427; and/or
The anode electrode is selected from any one of or the combination of at least two of a titanium-plated platinum electrode, a titanium-based noble metal oxide-coated electrode and a pure platinum electrode, preferably the titanium-plated platinum electrode or the titanium-based noble metal oxide-coated electrode, and the noble metal is selected from Ir, Pb or Ru, and more preferably the titanium-based noble metal oxide-coated electrode; and/or
The cathode electrode is selected from a nickel electrode, preferably any one of a nickel mesh electrode, a nickel plate electrode and a graphite electrode with a Raney nickel coating or a combination of at least two of the nickel mesh electrode, the nickel plate electrode and the graphite electrode, and more preferably the graphite electrode with the Raney nickel coating.
CN202210460419.XA 2022-04-28 2022-04-28 Electrochemical preparation method of erythritol Pending CN114959748A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2783283A (en) * 1955-11-25 1957-02-26 John W Sloan Hydrogenolysis of dialdehyde starch to erythritol and ethylene glycol
US5756865A (en) * 1995-10-04 1998-05-26 Cerestar Holding B.V. Method for production of tetritols, specifically meso-erythritol
US20110272291A1 (en) * 2006-02-08 2011-11-10 Stapley Jonathan A Methods for the electrolytic production of erythritol
CN105473765A (en) * 2013-08-16 2016-04-06 活力食品添加剂公司 Methods for simultaneous electrolytic decarboxylation and reduction of sugars

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2783283A (en) * 1955-11-25 1957-02-26 John W Sloan Hydrogenolysis of dialdehyde starch to erythritol and ethylene glycol
US5756865A (en) * 1995-10-04 1998-05-26 Cerestar Holding B.V. Method for production of tetritols, specifically meso-erythritol
US20110272291A1 (en) * 2006-02-08 2011-11-10 Stapley Jonathan A Methods for the electrolytic production of erythritol
CN105473765A (en) * 2013-08-16 2016-04-06 活力食品添加剂公司 Methods for simultaneous electrolytic decarboxylation and reduction of sugars

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王良东;陈建文;吴嘉麟;: "淀粉糖醇的研究与开发", 食品工业科技, no. 12, 25 December 2008 (2008-12-25), pages 281 - 284 *

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