CN114959748B - Electrochemical preparation method of erythritol - Google Patents

Electrochemical preparation method of erythritol Download PDF

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CN114959748B
CN114959748B CN202210460419.XA CN202210460419A CN114959748B CN 114959748 B CN114959748 B CN 114959748B CN 202210460419 A CN202210460419 A CN 202210460419A CN 114959748 B CN114959748 B CN 114959748B
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erythritol
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dialdehyde starch
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CN114959748A (en
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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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    • C25B3/00—Electrolytic production of organic compounds
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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
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Abstract

The invention provides an electrochemical preparation method of erythritol, which is carried out in a zero-pole-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 anode solution, and injecting the anode solution into an anode chamber; 2) Preparing an alkaline electrolyte aqueous solution, adding dialdehyde starch, polysorbate 80 and bis (2- (2-hydroxyphenyl) pyridine) beryllium into the alkaline electrolyte aqueous solution, uniformly stirring the mixture, taking the mixture as a cathode solution, and injecting the cathode solution into a cathode chamber; 3) And (3) introducing current into the electrolytic tank, heating to react, and preparing the p-aminophenol in the catholyte. The method has the advantages of wide raw material sources, 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 extremely widely distributed in nature, such as fruits, mushrooms, lichens, and the like. In addition, it is a natural sugar which has a sweet taste, and has a sweetness of 70% -80% of sucrose, and a caloric value of only 0.2kcal/g, and also exists in fermented foods and mammals.
Erythritol has unique nutritional characteristics, has relatively high digestibility and is easy to be rapidly absorbed by the small intestine; erythritol does not affect blood glucose and insulin levels, and is therefore suitable for diabetics; since bacteria in the oral cavity cannot utilize erythritol, dental caries is not generated.
Since erythritol has the above-mentioned excellent properties, it is widely used in industries such as candy, beverage, baked goods, health foods and medicines, and the like, and there is an increasing demand.
In the traditional process, erythritol is prepared by adopting a fermentation method, namely candida lipolytica (Candida Lipolytical) strain is adopted as a fermentation strain, and after slant preparation and shake flask seed culture, primary seed culture, secondary seed culture and fermentation in a fermentation tank are carried out to produce erythritol, so that the fermentation period is long, the equipment utilization rate is low, the energy consumption is high, the production condition is harsh, the bacteria are easy to dye, and the indexes are not easy to control.
Although the process for producing erythritol by means of glucose fermentation is mature, from the viewpoint of the whole industrial chain of erythritol production, the process for producing erythritol by means of glucose fermentation has certain defects in the aspects of economy, resource efficiency utilization, environmental protection, wastewater treatment and the like.
CN101336313a provides a method for producing erythrose or erythritol by electrolysis, which uses arabinonic acid or ribonucleotide to implement electrolytic decarboxylation to synthesize erythrose, and further uses hydrogenation to synthesize erythritol. The method is a two-step reaction, and has the defects of high raw material unit consumption, poor atom economy, low yield and the like.
Therefore, there is a need to develop a new method for preparing erythritol to solve various drawbacks existing 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 hydroxide. The method has the advantages of high conversion rate and selectivity, wide raw material sources, simple steps, high atom economy, less three wastes, low energy consumption and low cost.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides an electrochemical preparation method of erythritol, which is carried out in a zero-pole-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 anode solution, and injecting the anode solution into an anode chamber;
2) Preparing an alkaline electrolyte aqueous solution, adding dialdehyde starch, polysorbate 80 and bis (2- (2-hydroxyphenyl) pyridine) beryllium into the alkaline electrolyte aqueous solution, uniformly stirring the mixture, taking the mixture as a cathode solution, and injecting the cathode solution into a cathode chamber;
3) And (3) introducing current into the electrolytic tank, heating to react, and preparing the p-aminophenol in the catholyte.
In the method of the present invention, in step 1) and step 2), the alkaline electrolyte 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, respectively, preferably potassium hydroxide;
Preferably, the concentration of the aqueous alkaline electrolyte solution is 1-8wt%, for example 3wt%, 5wt%, 7wt%, preferably 4-6wt%.
In the process of the invention, in step 2), the mass ratio of dialdehyde starch to alkaline electrolyte aqueous solution is 1:1-6, for example 1:1, 1:3, 1:5, preferably 1:2-4.
In the process according to the invention, in step 2), the mass ratio of polysorbate 80 to dialdehyde starch is from 1:10 to 20, for example from 1:11, 1:14, 1:17, 1:19, preferably from 1:12 to 16.
In the process of the invention, in step 2), the mass ratio of the bis (2- (2-hydroxyphenyl) pyridine) beryllium to the dialdehyde starch is from 1:100 to 200, for example from 1:110, 1:140, 1:170, 1:190, preferably from 1:120 to 160.
In the method of the present invention, in the step 2), the long-chain alkyl quaternary ammonium base is a quaternary ammonium base with a C12-C18 alkyl chain, 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, more preferably dodecyl trimethyl ammonium hydroxide and/or tetradecyl trimethyl ammonium hydroxide;
Preferably, the mass ratio of long chain alkyl quaternary ammonium base to dialdehyde starch is 1:20-40, e.g., 1:22, 1:26, 1:28, 1:30, 1:36, 1:38, preferably 1:24-32.
In the process according to the invention, in step 3), the cell voltage is 2-3V, for example 2.0V, 2.2V, 2.4V, 2.5V, 2.7V, 2.9V, 3V, preferably 2.5-2.8V; the current density is 1200-2000A/m 2, for example 1200A/m2、1300A/m2、1400A/m2、1500A/m2、1600A/m2、1700A/m2、1800A/m2、1900A/m2、2000A/m2, preferably 1600-1800A/m 2.
In the process of the invention, in step 3), the reaction is carried out at a temperature of 30-60 ℃, for example 30 ℃,40 ℃,50 ℃, 55 ℃, 60 ℃, preferably 40-50 ℃; the time is 5-20h, for example 5h, 10h, 15h, 20h, preferably 10-15h.
In the method, in the step 3), the reaction comprises a reaction of directly generating erythritol by cathode hydrolysis of the dialcohol starch, and also comprises a reaction of generating erythrose by cathode hydrolysis of dialdehyde starch and generating erythritol by cathode reduction of erythrose, wherein the reactions are synchronously carried out in catholyte, and the reaction conditions are the same. After current is introduced into the catholyte and the temperature is raised, the dialcohol starch is directly hydrolyzed by a cathode to generate erythritol, or dialdehyde starch is hydrolyzed to generate erythrose, and simultaneously the erythrose is reduced by the cathode to produce erythritol and a small amount of ethylene glycol;
after the reaction is finished, the obtained catholyte can be subjected to post-treatment processes such as filtration, freezing crystallization and the like to obtain purified erythritol, and the post-treatment processes comprise the operation of the conventional method in the field, do not have specific requirements, and can be realized in all modes. For example, the catholyte may be filtered and then concentrated to remove excess water, and the concentrate may be subjected to freeze crystallization and separation to yield the product erythritol.
According to the method, the prepared erythritol comprises any one or at least two of D- (-) -meso-erythritol, (D) -erythritol and (L) -erythritol, wherein the D- (-) -meso-erythritol accounts for 50-70%, the (D) -erythritol accounts for 20-30%, and the (L) -erythritol accounts for 10-20% based on 100% of the total erythritol.
In the invention, the zero-pole-distance electrolytic tank comprises an anode electrode, a diaphragm and a cathode electrode;
Preferably, the electrolytic cell has a zero-pole-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, nafion 551, more preferably Nafion427. The selected cation exchange membrane has selective permeability, only allows cations to pass through, and has the advantages of reduced voltage, high conductivity, high mechanical strength and strong acid and alkali resistance.
Preferably, the anode electrode is selected from any one or a combination of at least two of a titanium platinized (Pt/Ti) electrode, a titanium-based noble metal plated (e.g. RuO 2/Ti) electrode, a pure platinum electrode, further preferably a titanium platinized electrode or a titanium-based noble metal plated oxide coated electrode, the noble metal being selected from Ir, pb or Ru, more preferably a titanium-based noble metal plated oxide coated electrode.
Preferably, the cathode electrode is selected from nickel electrodes, more preferably any one or a combination of at least two of nickel mesh electrodes, nickel plate electrodes and graphite electrodes with Raney nickel plating layers, and even more preferably graphite electrodes with Raney nickel plating layers.
In the method of the invention, the electrolytic tank is made of PP, PTFE and titanium, preferably titanium.
In the experiment for preparing erythritol, the invention discovers that the solubility of the dialdehyde starch in an alkaline electrolyte water system can be obviously increased by taking the dialdehyde starch as an electrochemical reaction raw material and adding the polysorbate 80. Meanwhile, bis (2- (2-hydroxyphenyl) pyridine) beryllium is added as an auxiliary agent, wherein the existence of pyridyl can reduce the reduction electromotive force on the surface of a cathode Ni electrode, the catalytic activity is realized on the electric reduction of water and dialdehyde starch, meanwhile, the existence of hydroxyphenyl can ensure that the bis (2- (2-hydroxyphenyl) pyridine) beryllium has hydrophobicity in an electrolytic system, is easy to adhere to the surface of the electrode, forms a hydrophobic region, and improves the stability and the conductivity of the electrode hydrophobic region through beryllium ions. In the cathode liquid, the bis (2- (2-hydroxyphenyl) pyridine) beryllium reduces the reduction electromotive force of water and aldehyde groups on the surface of the Ni electrode simultaneously, promotes the reduction of dialdehyde starch, and is adsorbed on the surface of the electrode to form a conductive and hydrophobic surface, so that electrons on the surface of the electrode are more easily reduced into erythritol by dialdehyde starch and erythrose, hydrogen evolution reaction is inhibited, and current efficiency is improved. In addition, the invention also increases the diffusion coefficient of the erythrose to the electrode surface by adding the long-chain alkyl quaternary ammonium base, thereby promoting the erythrose to diffuse to the electrode surface for reduction reaction to obtain the erythritol.
Compared with the prior art, the method has the advantages of wide raw material sources, 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 method provided by the present invention is further described in detail by the following examples, but the present invention is not limited thereto.
The sources of the reagent raw materials used in the examples and comparative examples of the present invention are as follows, and the other reagent raw materials are common commercial products unless otherwise specified:
polysorbate 80: acla Ding Shiji, pharmaceutical grade;
dodecyl trimethyl ammonium hydroxide: the western chemical technologies company, inc, purity 40wt.% in water;
Tetradecyltrimethylammonium hydroxide: the western chemical technologies company, inc, purity 40wt.% in water;
Cetyl trimethylammonium hydroxide: the western chemical technologies company, inc, purity 40wt.% in water;
Octadecyl trimethyl ammonium hydroxide: the western chemical technologies company, inc, purity 40wt.% in water;
Dialdehyde starch: the purity of Shandong Mole chemical industry Co., ltd is more than 80%;
sodium hydroxide: the purity of the chemical reagent for ridge is AR,98%;
potassium hydroxide: the purity of the chemical reagent for ridge is AR,98%;
Bis (2- (2-hydroxyphenyl) pyridine) beryllium: ara Ding Shiji, purity AR,99%.
Zero pole pitch electrolyzer: jiangsu AnKate technologies Co., ltd.
The test methods used in the examples and comparative examples of the present invention are as follows:
Erythritol analysis method:
Chromatograph: waters; chromatographic column: ALLTECH PREVAIL Carbohydrate ES (4.6 mm. Times.250 mm,5 μm); mobile phase: acetonitrile/water (3/1); flow rate: 1.0mL/min; a detector: RI 2000 differential refractive detector; column temperature: 30 ℃; sample injection volume: 10. Mu.L; the quantitative method comprises the following steps: external standard curve method.
In the following examples erythritol was characterized by hydrogen spectroscopy using a nuclear magnetic resonance apparatus (Brucker ARX-400).
Example 1
The method for electrochemically preparing erythritol comprises the following steps:
The zero-pole-distance electrolytic cell is adopted, the electrolytic cell is made of PP, a nickel screen electrode is adopted as a cathode electrode, a titanium platinized electrode is adopted as an anode electrode, and a Nafion 117 cation exchange membrane is adopted as a diaphragm.
1) 216G of 7.4wt% potassium methoxide aqueous solution was prepared as an anolyte and injected into the anode chamber of the electrolyzer.
2) 216G of 7.4wt% 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 prepare a catholyte, which was injected into the cathode chamber.
3) And (3) introducing current into the electrolytic tank, wherein the voltage of the electrolytic tank is 2.0V, the current density of the electrolytic tank is 1200A/m 2, heating to 30 ℃, then carrying out reaction, stopping the reaction after 20 hours of reaction, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5 hours, and filtering to obtain the erythritol product.
The erythritol nuclear magnetic resonance spectroscopy data are as follows:
1H NMR(600MHz,CDCl3)：δ3.65(2H)，3.81(2H)，3.56(2H)，3.58(2H)，3.38(2H)。
In the embodiment, the conversion rate of the raw material dialdehyde starch is 91.2%, the selectivity of the synthesized erythritol is 89.3%, and the current efficiency is 92.3%; the erythritol product had a D- (-) -meso-erythritol content of 50wt%, a (D) -erythritol content of 30wt% and a (L) -erythritol content of 20wt%.
Example 2
The method for electrochemically preparing erythritol comprises the following steps:
The zero-pole-distance electrolytic cell is adopted, the electrolytic cell is made of PTFE, a cathode electrode is a nickel plate electrode, an anode electrode is a Ti-based RuO 2 anode, and a diaphragm is a Nafion 115 cation exchange membrane.
1) 212G of 5.7wt% sodium methoxide aqueous solution was prepared as an anolyte and injected into the anode chamber of the electrolyzer.
2) 212G of a 5.7wt% aqueous sodium methoxide solution was prepared, followed by adding 100g of dialdehyde starch, 5g of polysorbate 80, 0.5g of bis (2- (2-hydroxyphenyl) pyridine) beryllium and 2.5g of tetradecyl trimethyl ammonium hydroxide, stirring well, and injecting into a cathode chamber as a catholyte.
3) And (3) introducing current into the electrolytic tank, wherein the voltage of the electrolytic tank is 2.2V, the current density of the electrolytic tank is 1400A/m 2, heating to 40 ℃, performing reaction, stopping the reaction after 15 hours of reaction, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5 hours, and filtering to obtain the erythritol product.
In the embodiment, the conversion rate of the raw material dialdehyde starch is 92%, the selectivity of the synthesized erythritol is 87.3%, and the current efficiency is 90.6%; d- (-) -meso-erythritol content of 60wt%, (D) -erythritol content of 25wt%, and (L) -erythritol content of 15wt% in the erythritol product.
Example 3
The method for electrochemically preparing erythritol comprises the following steps:
The zero-pole-distance electrolytic cell is made of titanium, a cathode electrode is a nickel plate electrode, an anode electrode is a Ti-based IrO 2 anode, and a diaphragm is a Nafion 212 cation exchange membrane.
1) 208G of potassium hydroxide aqueous solution with the concentration of 3.9wt% is prepared as anolyte and is injected into the anode chamber of the electrolytic cell.
2) 208G of a 3.9wt% strength aqueous potassium hydroxide solution was prepared, followed by addition of 50g of dialdehyde starch, 4.2g of polysorbate 80, 0.3g of bis (2- (2-hydroxyphenyl) pyridine) beryllium and 1.6g of cetyltrimethylammonium hydroxide, stirring well, and pouring into a cathode chamber as a catholyte.
3) And (3) introducing current into the electrolytic tank, wherein the voltage of the electrolytic tank is 2.4V, the current density of the electrolytic tank is 1600A/m 2, heating to 50 ℃, then carrying out reaction, stopping the reaction after reacting for 10 hours, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5 hours, and filtering to obtain the erythritol product.
In the embodiment, the conversion rate of the raw material dialdehyde starch is 90.5%, the selectivity of the synthesized erythritol is 89.3%, and the current efficiency is 89.3%; d- (-) -meso-erythritol content of 70wt%, (D) -erythritol content of 20wt%, and (L) -erythritol content of 10wt% in the erythritol product.
Example 4
The method for electrochemically preparing erythritol comprises the following steps:
the zero-pole-distance electrolytic tank is made of titanium, the cathode electrode is a graphite electrode with a Raney nickel coating, the anode electrode is a Ti-based PbO 2 anode, and the diaphragm is a Nafion 427 cation exchange membrane.
1) 208G of aqueous sodium hydroxide solution with the concentration of 3.9wt percent is prepared as anolyte and is injected into the anode chamber of the electrolytic cell.
2) 208G of aqueous sodium hydroxide solution with a concentration of 3.9wt% 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 and stirred uniformly to prepare a catholyte, which was injected into the cathode chamber.
3) And (3) introducing current into the electrolytic tank, wherein the voltage of the electrolytic tank is 2.5V, the current density of the electrolytic tank is 1800A/m 2, heating to 60 ℃, performing reaction, stopping the reaction after 5 hours of reaction, filtering catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5 hours, and filtering to obtain an erythritol product.
In the embodiment, the conversion rate of the raw material dialdehyde starch is 89.1%, the selectivity of the synthesized erythritol is 91%, and the current efficiency is 90.2%; the erythritol product had a D- (-) -meso-erythritol content of 55wt%, a (D) -erythritol content of 30wt% and a (L) -erythritol content of 15wt%.
Example 5
The method for electrochemically preparing erythritol comprises the following steps:
The zero-pole-distance electrolytic tank is made of titanium, the cathode electrode is a graphite electrode with a Raney nickel coating, the anode electrode is a Ti-based PbO 2 anode, and the diaphragm is a Nafion 551 cation exchange membrane.
1) 202G of 1wt% triethylamine aqueous solution is prepared as anolyte and injected into the anode chamber of the electrolytic cell.
2) 202G of a 1wt% strength 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 trimethylammonium hydroxide were added and stirred uniformly to prepare a catholyte, which was injected into the cathode chamber.
3) And (3) introducing current into the electrolytic tank, wherein the voltage of the electrolytic tank is 2.8V, the current density of the electrolytic tank is 2000A/m 2, heating to 55 ℃, then carrying out reaction, stopping the reaction after 5 hours of reaction, filtering the catholyte, concentrating to remove 60% of water, freezing and crystallizing the concentrated solution at 0 ℃ for 5 hours, and filtering to obtain the erythritol product.
In the embodiment, the conversion rate of the raw material dialdehyde starch is 90.8%, the selectivity of the synthesized erythritol is 87.6%, and the current efficiency is 89.1%; d- (-) -meso-erythritol content of 60wt%, (D) -erythritol content of 20wt%, and (L) -erythritol content of 20wt% in the erythritol product.
Comparative example 1
With reference to the method of example 1, except that polysorbate 80 was not added to the catholyte, the other operations and parameters were the same as in example 1, to produce erythritol product.
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 erythritol product had a D- (-) -meso-erythritol content of 65wt%, a (D) -erythritol content of 25wt% and a (L) -erythritol content of 10wt%.
Comparative example 2
With reference to the process of example 1, except that polysorbate 80 was replaced with polysorbate 20 in the catholyte, the other operations and parameters were the same as in example 1, resulting in an erythritol product.
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 erythritol product had a D- (-) -meso-erythritol content of 66wt%, a (D) -erythritol content of 22wt% and a (L) -erythritol content of 12wt%.
Comparative example 3
With reference to the method of example 1, except that no bis (2- (2-hydroxyphenyl) pyridine) beryllium was added to the catholyte, the other operations and parameters were the same as in example 1, to prepare erythritol product.
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 had a D- (-) -meso-erythritol content of 54wt%, a (D) -erythritol content of 28wt% and a (L) -erythritol content of 18wt%.
Comparative example 4
With reference to the method of example 1, erythritol product was produced by the same procedure and parameters as in example 1 except that bis (2- (2-hydroxyphenyl) pyridine) beryllium was replaced with 2- (4-hydroxyphenyl) pyridine in catholyte.
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 erythritol product had a D- (-) -meso-erythritol content of 52wt%, a (D) -erythritol content of 30wt% and a (L) -erythritol content of 18wt%.
Comparative example 5
With reference to the method of example 1, erythritol products were produced with the exception that bis (2- (2-hydroxyphenyl) pyridine) beryllium was replaced with 2- (2-hydroxyphenyl) benzothiazole beryllium in catholyte, and the other operations and parameters were the same as those of example 1.
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 erythritol product had a D- (-) -meso-erythritol content of 55wt%, a (D) -erythritol content of 30wt% and a (L) -erythritol content of 15wt%.
Comparative example 6
With reference to the method of example 1, erythritol products were produced with the exception 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 erythritol product had a D- (-) -meso-erythritol content of 50wt%, a (D) -erythritol content of 27wt% and a (L) -erythritol content of 23wt%.
Comparative example 7
With reference to the method of example 1, except that long-chain alkyl quaternary ammonium base was not added to the catholyte, the other operations and parameters were the same as in example 1, and erythritol product was produced.
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 erythritol product had a D- (-) -meso-erythritol content of 60wt%, a (D) -erythritol content of 25wt% and a (L) -erythritol content of 15wt%.
Comparative example 8
With reference to the process of example 1, the erythritol product was prepared by the same procedure and parameters as in example 1 except that dodecyltrimethylammonium hydroxide was replaced with tetramethylammonium hydroxide in the catholyte.
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 erythritol product had a D- (-) -meso-erythritol content of 59wt%, a (D) -erythritol content of 24wt% and a (L) -erythritol content of 17wt%.
Comparative example 9
With reference to the method of example 1, only the zero-pole-distance electrolytic cell was replaced with a diaphragm-free plate-and-frame electrolytic cell, the catholyte of example 1 was used as the electrolyte, and the erythritol product was produced by the same operations and parameters as those of example 1.
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 erythritol product had a D- (-) -meso-erythritol content of 62% by weight, a (D) -erythritol content of 25% by weight, and a (L) -erythritol content of 13% by weight.

Claims (22)

1. A method of electrochemically producing erythritol in a zero-pole-pitch electrolyzer comprising an anode compartment and a cathode compartment, wherein the anode compartment and the cathode compartment are separated by a membrane, the method comprising:
1) Preparing an alkaline electrolyte aqueous solution as an anode solution, and injecting the anode solution into an anode chamber;
2) Preparing an alkaline electrolyte aqueous solution, and then 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, and injecting the mixture into a cathode chamber as a cathode solution, wherein the long-chain alkyl quaternary ammonium base is quaternary ammonium base with a C12-C18 alkyl chain;
3) And (3) introducing current into the electrolytic tank, heating to react, and preparing erythritol in the catholyte.
2. The method according to claim 1, wherein in step 1) and step 2), the aqueous 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, respectively.
3. The method according to claim 1, wherein the concentration of the aqueous alkaline electrolyte solution in step 1) and step 2) is 1 to 8wt%.
4. The method according to claim 3, wherein the concentration of the aqueous alkaline electrolyte solution is 4 to 6wt%.
5. The method according to claim 1, wherein in the step 2), the mass ratio of the dialdehyde starch to the alkaline electrolyte aqueous solution is 1:1-6.
6. The method according to claim 5, wherein the mass ratio of the dialdehyde starch to the alkaline electrolyte aqueous solution is 1:2-4.
7. The method according to claim 1, wherein in step 2), the mass ratio of polysorbate 80 to dialdehyde starch is 1:10-20.
8. The method according to claim 7, wherein in the step 2), the mass ratio of polysorbate 80 to dialdehyde starch is 1:12-16.
9. The method according to claim 1, wherein in step 2), the mass ratio of the bis (2- (2-hydroxyphenyl) pyridine) beryllium to the dialdehyde starch is 1:100-200.
10. The method of claim 9, wherein the mass ratio of bis (2- (2-hydroxyphenyl) pyridine) beryllium to dialdehyde starch is 1:120-160.
11. The method according to claim 1, wherein in the step 2), the long-chain alkyl quaternary ammonium base is 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.
12. The method according to claim 1, wherein in the step 2), the mass ratio of the long-chain alkyl quaternary ammonium base to the dialdehyde starch is 1:20-40.
13. The method of claim 12, wherein the mass ratio of long-chain alkyl quaternary ammonium base to dialdehyde starch is 1:24-32.
14. The method according to claim 1, wherein in step 3), the cell voltage is 2 to 3V and the current density is 1200 to 2000A/m 2.
15. The method of claim 14, wherein the cell voltage is 2.5-2.8V and the current density is 1600-1800A/m 2.
16. The method according to claim 1, wherein in step 3), the reaction is carried out at a temperature of 30 to 60 ℃ for a time of 5 to 20 hours.
17. The method of claim 16, wherein the reaction is carried out at a temperature of 40-50 ℃ for a time of 10-15 hours.
18. The method of claim 1, wherein the zero-pole-pitch electrolyzer comprises an anode electrode, a diaphragm, and a cathode electrode.
19. The method of claim 18, wherein the membrane is a cation exchange membrane; and/or
The anode electrode is selected from any one or a combination of at least two of a titanium platinized electrode, a titanium-based noble metal oxide coated electrode and a pure platinum electrode; and/or
The cathode electrode is selected from nickel electrodes.
20. The method of claim 19, wherein the membrane is any one or a combination of at least two of Nafion 117, nafion 115, nafion 212, nafion 427, nafion 551.
21. The method of claim 19, wherein the noble metal is selected from Ir, pb, or Ru.
22. The method of claim 19, wherein the cathode electrode is selected from any one or a combination of at least two of a nickel mesh electrode, a nickel plate electrode, and a graphite electrode with a raney nickel plating.
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Citations (1)

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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

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US2783283A (en) * 1955-11-25 1957-02-26 John W Sloan Hydrogenolysis of dialdehyde starch to erythritol and ethylene glycol
GB9520231D0 (en) * 1995-10-04 1995-12-06 Cerestar Holding Bv Method for the production of tetritols,specifically meso-erythritol
US9133554B2 (en) * 2006-02-08 2015-09-15 Dynamic Food Ingredients Corporation Methods for the electrolytic production of erythritol

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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

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Title
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