CN114807990A - Method for preparing erythritol by electrochemical method - Google Patents
Method for preparing erythritol by electrochemical method Download PDFInfo
- Publication number
- CN114807990A CN114807990A CN202110059961.XA CN202110059961A CN114807990A CN 114807990 A CN114807990 A CN 114807990A CN 202110059961 A CN202110059961 A CN 202110059961A CN 114807990 A CN114807990 A CN 114807990A
- Authority
- CN
- China
- Prior art keywords
- erythritol
- diepoxybutane
- nafion
- reaction
- anode
- Prior art date
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- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 title claims abstract description 74
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000004386 Erythritol Substances 0.000 title claims abstract description 70
- 229940009714 erythritol Drugs 0.000 title claims abstract description 70
- 235000019414 erythritol Nutrition 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002848 electrochemical method Methods 0.000 title abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 35
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 16
- 238000005580 one pot reaction Methods 0.000 claims abstract description 15
- 238000005341 cation exchange Methods 0.000 claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 78
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
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- 238000007142 ring opening reaction Methods 0.000 claims description 17
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 11
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- 238000002360 preparation method Methods 0.000 claims description 10
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 5
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- SAUBRJOIKMVSRU-UHFFFAOYSA-N 1,4-dichlorobutane-2,3-diol Chemical compound ClCC(O)C(O)CCl SAUBRJOIKMVSRU-UHFFFAOYSA-N 0.000 claims description 2
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides a method for preparing erythritol by an electrochemical method. The method takes 1, 3-butadiene as a raw material to prepare the erythritol by a paired electrolysis one-pot method. The method adopts a zero-polar-distance electrolytic tank with a cation exchange membrane, 1, 3-butadiene as a raw material is subjected to anodic oxidation to obtain 1, 4-dibromo-2, 3-dihydroxybutane, anolyte is subjected to cathodic reduction to obtain 1,2,3, 4-diepoxybutane, the obtained catholyte is directly acidified without treatment to obtain erythritol, and the erythritol is subjected to neutralization treatment to obtain pure erythritol. 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
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a method for preparing erythritol by an electrochemical method.
Background
Erythritol is widely distributed in nature, such as fruits, mushrooms, lichens, etc. In addition, the sugar exists in fermented foods and mammals, is a natural sugar with sweet taste, has sweetness of 70-80% of cane sugar, and has calorie of only 0.2 kcal/g. Erythritol is a four-carbon sugar alcohol with molecular formula of CH 4 O 4 H 10 The chemical structure is as follows:
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 erythritol is not available to the bacteria in the mouth, 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.
Although erythritol exists in natural plants, the content thereof is low, the extraction and separation costs are high, and it is not suitable for industrial production. At present, the erythritol is produced by three main methods, namely chemical synthesis, microbial fermentation and electrochemical synthesis. The chemical synthesis method mainly uses 2-butylene-1, 4-butanediol as a raw material to produce erythritol. The existing chemical synthesis method has the problems of low conversion rate, high cost, safety and the like, and the industrial production of erythritol mainly utilizes glucose for fermentation. The erythritol is produced in large scale at home and abroad by adopting a microbial fermentation method, and most of the used microorganisms are food-grade high-permeability yeast.
Although the process for producing erythritol by glucose fermentation is mature, the whole industrial chain of erythritol production has certain defects in the aspects of economy, effective resource utilization, environmental protection, wastewater treatment and the like.
Documents (J.H.Hartman et al./Toxicology 378 (2017)) 114. about.124 and TOXICOLOGICAL SCIENCES 115 (2)), (2010) 322. about.329) report that epoxybutene can reduce and activate molecular oxygen complex by cytochrome P450 monooxygenase, thereby carrying out monooxygenation reactions such as hydroxylation, epoxidation and the like on the substrate. This method does not allow control of the metabolic process and does not have specific selectivity for oxygenated products. Therefore, for a long time, the production cost is too high, and the market attention is not obtained.
Organic electrochemical synthesis reactions avoid the use of toxic or hazardous oxidizing and reducing agents, but instead utilize the cleanest reactant "electrons". Compared with other synthesis methods, the method has the following advantages:
1) different products can be synthesized by changing electrode potential
2) The reaction can be stopped by cutting off the current of the external circuit in the synthesis process
3) For spontaneous organic electrosynthesis reactions, products and electrical energy can also be obtained simultaneously.
Because the reaction condition of the electrosynthesis technology is mild, easy to control, less in three wastes and environment-friendly, the synthesis method is increasingly valued by people.
American DFI company (Dynamic Foods Ingredients) developed a two-step synthesis method of erythritol from hexose (patent US20110272291A 1). Firstly, oxidizing oxygen in an alkaline aqueous solution to obtain pentasaccharate, then performing electrochemical oxidation decarboxylation to obtain erythrose, and performing in-situ reduction on an anodic electrooxidation reaction solution in a cathode chamber to obtain erythritol. Compared with a fermentation method, the method for producing erythritol with the same quality has the advantages of shorter use time, less three wastes, continuous production and great cost advantage. However, the erythritol product obtained by the method needs to undergo two-step reaction, namely, chemical oxidative decarboxylation and then electrochemical oxidative decarboxylation-reduction, the atom economy of the reaction is low, and the reaction solution needs to be neutralized by acid and alkali through ion exchange resin for many times.
Disclosure of Invention
In the 60 s of the 20 th century, the technology for preparing ethylene by cracking by using naphtha and the like as raw materials is rapidly developed, and the by-product C4 fraction can be separated while ethylene and propylene are prepared by cracking, so that a large amount of cheap raw materials are provided for the production of butadiene, and the method becomes a main method for producing butadiene. At present, the butadiene as a byproduct of ethylene cracking accounts for more than 90% of the capacity of a butadiene production device, and a new opportunity is brought to the downstream deep processing of butadiene.
Epoxybutene (EPB), formula C 4 H 6 O, is a novel fine chemical intermediate, and can prepare hundreds of important subsequent products from epoxybutene. Relates to a plurality of fields of bulk chemicals, fine chemicals, special chemicals and the like, is the best synthetic raw material of various drug intermediates, chiral compounds, novel flame retardants and functional polymer materials, and is a fine chemical which is in short supply at home and abroad. The annual production capacity of butadiene in the world is relatively surplus, and the fine chemical raw materials in China are very short, so that the epoxybutene is prepared by oxidizing butadiene under the condition, the commercialization of the epoxybutene becomes possible, and the epoxybutene has wide application.
The epoxy compound has a three-membered oxygen ring structure in a molecule and active chemical property, and under the action of an alkaline or acidic catalyst, the three-membered ring is easy to open and generates an addition reaction with nucleophilic substances such as water, alcohol, phenol or carboxylic acid to generate an intermediate.
Under the background, aiming at the defects of the existing erythritol synthesis technology by an electrochemical method, the invention aims to provide a method for preparing erythritol by a paired electrolysis one-pot method by using 1, 3-butadiene as a raw material. The method for preparing erythritol by using 1, 3-butadiene as the raw material has the advantages of wide raw material source, concise steps, high atom economy, less three wastes, low energy consumption and low cost.
The specific technical scheme is as follows:
a method for preparing erythritol by a paired electrolysis one-pot process, comprising the steps of:
s1: introducing 1, 3-butadiene into a halide-containing solution in an anode chamber of an electrolytic cell to obtain a halohydrin compound;
s2: allowing the anolyte to pass through a cathode chamber of an electrolytic cell to carry out saponification reaction to obtain 1,2,3, 4-diepoxybutane;
s3: acidifying 1,2,3, 4-diepoxybutane, and carrying out epoxy hydrolysis ring-opening reaction to obtain erythritol;
wherein the electrolytic bath in S1 and S2 is a zero-polar-distance chamber electrolytic bath with a diaphragm.
According to the method, 1, 3-butadiene which is an industrially easily available raw material is subjected to anodic oxidation to obtain 1, 4-dibromo-2, 3-dihydroxybutane, anolyte is subjected to cathodic reduction to obtain 1,2,3, 4-diepoxybutane, the obtained catholyte is directly subjected to acidification and ring opening without treatment, and pure erythritol is obtained through freezing and crystallization after neutralization treatment.
In the invention, the electrolytic cells of S1 and S2 consist of an anode, a diaphragm and a cathode; preferably, the electrolytic cell forms a zero-polar-distance sandwich structure through a mesh anode, a diaphragm and a mesh cathode, the voltage of the electrolytic cell is 3.3V-4.2V, the current efficiency is 75% -90%, the current is 5-10A, and the current density is 667-1333A/m 2 . Preferably, the anode material is titanium-plated platinum (Pt/Ti) or titanium-based noble metal oxide coating (RuO) 2 /Ti) electrode, pure platinum, a coated electrode with a polymer material as a matrix and graphite, preferably a titanium-platinized and/or titanium-based noble metal oxide-plated coating, more preferably a titanium-based noble metal oxide-plated coating.
In one embodiment, the polymer resin containing the conductive coating comprises a coating polymer material containing lead dioxide, platinum, gold and the like on the surface, wherein the polymer material can be selected from resin materials such as polypropylene, polyformaldehyde, polyethylene, polyimide, nylon materials, polyether ether ketone, polylactic acid, polyphenylsulfone and the like, and the coating can be prepared by selective electrodeposition or selective evaporation deposition or magnetron sputtering deposition.
In one embodiment, the thickness of the anodic plating layer may preferably be 0.5 to 3 μm. Preferably, the membrane is a cation exchange membrane, preferably one or more of Nafion 117, Nafion 115, Nafion 212, Nafion 427 and Nafion 551, more preferably Nafion 427. The diaphragm is a cation exchange membrane, has selective permeability, allows cations to pass through, reduces voltage, has high conductivity and mechanical strength, and resists strong acid and strong base. Preferably, the cathode material is one or more of stainless steel, platinum and graphite, preferably 316L stainless steel mesh and/or porous graphite plate, more preferably 316L stainless steel mesh.
In one embodiment, the zero-polar-distance diaphragm electrolyzer shell is processed by non-conductive high polymer resin and is in the form of a plate frame, the plate frame and the electrodes are isolated by insulating gaskets, the aspect ratio is 1:1-1:10, the preferred aspect ratio is 1:2-1:4, and more preferably 1:3, the thickness of the electrodes depends on materials, and the metal or alloy material can be selected from 2-5mm, preferably 3-4mm, and more preferably 3 mm. The thickness of the high molecular resin plate frame is 10-30mm, preferably 10-20mm, more preferably 10mm, and the flow velocity on the surface of the electrode can be effectively improved.
In the present invention, the halide in S1 includes, but is not limited to, one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide and ammonium bromide, preferably sodium bromide and/or potassium bromide, more preferably sodium bromide; preferably, the halide is added in a catalytic amount, preferably in a halide to water ratio of 1:100 to 4:100, more preferably 2:100 to 3: 100.
In the present invention, the solution in S1 is an aqueous solution.
In the invention, a cosolvent acetonitrile is added into the solution of S1; preferably, the ratio of acetonitrile to water is from 1:1 to 1:6, preferably from 1:2 to 1: 4.
In the invention, the water in the S2 generates hydrogen evolution reaction at the cathode, and the free hydroxide ions participate in saponification cyclization reaction.
In the invention, the aqueous solution of the 1,2,3, 4-diepoxybutane in the S3 is alkaline, and the pH value is 10-14, preferably 11-12.
In the present invention, sulfuric acid and/or hydrobromic acid is used as a neutralizing agent in S3.
In the present invention, the ring-opening reaction is carried out in S3 under a strongly acidic condition, and the pH is 1 to 3, preferably 1 to 2.
Illustratively, the erythritol preparation method is as follows:
I. paired electrolysis for preparing 1,2,3, 4-diepoxybutane
The preparation of 1,2,3, 4-diepoxybutane and the like by using the assembled zero-polar distance electrolytic cell is carried out as follows:
placing the anolyte containing acetonitrile, water and sodium bromide in a 1000mL raw material storage tank, turning on a magnetic circulating pump, and turning on a constant temperature bath to stabilize the temperature of the anolyte at 25 ℃.
And (3) placing the catholyte containing acetonitrile, water and sodium bromide into a 1000mL storage tank, opening a magnetic circulating pump, and opening a constant-temperature bath to stabilize the temperature of the catholyte at 25 ℃.
And (3) turning on a direct-current power supply, electrolyzing by adopting constant current, introducing 1, 3-butadiene gas, and transferring the obtained bromohydrin anode reaction solution into a cathode chamber by a peristaltic pump for saponification and ring closure reaction.
The reactions that mainly occur during electrolysis are as follows:
anode chamber reaction:
and (3) cathode chamber reaction:
during electrolysis, sodium bromide is circulated in the electrolyte as a redox catalyst.
The preferable system of the anolyte is a mixed system of acetonitrile, water and sodium bromide, wherein the acetonitrile mainly plays a role in dissolving 1, 3-butadiene, and the water mainly dissolves sodium bromide and has an addition bromohydrin reaction with bromine generated by electrooxidation and an olefin double bond.
Wherein the proportion of acetonitrile and water has obvious influence on the conductivity, pH and reaction rate of the reaction system.
Sodium bromide acts as a redox catalyst and its content has a significant influence on the reaction efficiency and the selectivity of the electrolysis.
The catholyte is mainly a mixed solution of acetonitrile, water and sodium bromide, and the preferred volume of the catholyte is the same as that of the anolyte.
II, generating erythritol by acidic ring-opening reaction of electrolytic reaction liquid
And (3) the electrolytic reaction liquid after the cathode chamber reaction is alkaline, neutralizing and acidifying the cathode reaction liquid by adding acid, and finally carrying out an acidic ring-opening reaction on the 1,2,3, 4-diepoxybutane compound to generate the 1,2,3, 4-butanetetraol.
The acidic environment is critical to the reaction, and the ring-opening reaction is preferably strongly acidic. The selection of acid relates to the treatment of three wastes and the recovery and reuse of materials.
Working up the reaction mixture and continuously operating the process
The feed liquid after the ring opening reaction can be directly concentrated to remove excessive hydrobromic acid and water, and the concentrated solution is frozen and crystallized. The precipitated erythritol can be filtered to obtain a product.
Another object of the present invention is to provide an erythritol product.
An erythritol product is prepared by the erythritol preparation method.
In the present invention, the erythritol includes, but is not limited to, one or more of D- (-) -meso-erythritol, (D) -erythritol, and (L) -erythritol. Among them, D- (-) -meso-erythritol is erythritol.
Still another object of the present invention is to provide a use of the paired electrolysis one-pot method for producing alcohol.
Use of a pair-wise electrolytic one-pot process for the preparation of an alcohol as described above, which process can be used for the preparation of an epoxide of a diene or a dialcohol of a diene, preferably for the preparation of any of erythritol, 1, 4-dichloro-2, 3-dihydroxybutane, epoxybutene, 1,2,3, 4-diepoxybutane, 3-butene-1, 2-diol, 3, 4-diepoxy-1, 2-butanediol, when a conjugated olefin containing two or more double bonds, or an isolated olefin containing two or more double bonds is used as the starting material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method has the advantages of high atom utilization rate, good atom economy, green and environment-friendly electrolytic process and accordance with the concept and principle of green chemistry.
(2) By adjusting the electrolysis conditions, the method can produce various products such as 1, 4-dibromo-2, 3-dihydroxybutane, epoxybutene, 1,2,3, 4-diepoxybutane, 3-butene-1, 2-diol, 3, 4-diepoxy-1, 2-butanediol and the like, provides a new synthetic route for partial epoxidation, full epoxidation and the like of butadiene, and is also suitable for other conjugated or isolated olefins.
Drawings
FIG. 1 shows a zero-polar-distance chambered electrolytic cell with a diaphragm, wherein the proton exchange membrane, the liquid inlet, the electrode chamber, the liquid outlet, the porous electrode and the electric connection terminal are arranged in sequence.
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 main chemical reagents are as follows:
1, 3-butadiene: aladdin reagent, purity AR, > 99.0% (GC),
acetonitrile: chemical reagent for Xilongu, purity AR, 99%,
sodium bromide: chemical reagent for Xilongu, purity AR, 98%,
glucose: chemical reagent for Xilongu, purity AR, 98%,
potassium hydroxide: chemical reagent for Xilongu, purity AR, 98%,
deionized high purity water, and is prepared on site. Zero polar distance electrolytic cell:
the high polymer resin plate frame with the length of 150mm and the width of 50mm, the insulating gasket, the mesh anode, the cation exchange membrane, the mesh cathode, the insulating gasket and the high polymer resin plate frame are sequentially stacked and fixed and pressed by a stainless steel screw with an insulating sleeve. The cathode and the anode are connected with a direct current power supply through leads, the cathode chamber and the anode chamber of the electrolytic cell are respectively connected with a liquid storage tank, and the liquid storage tank is connected with a constant temperature bath. And connecting a1, 3-butadiene steel cylinder with a flowmeter with an anolyte storage tank.
Analytical test instruments and conditions:
the detection method of 1, 3-butadiene, epoxybutene and 1,2,3, 4-diepoxybutane comprises the following steps: GC external standard quantitation: gas chromatography instrument model: agilent DB-5; sample injector: an autosampler injector; a detector: a FID detector; the temperature of the detector is 300 ℃; a chromatographic column: capillary chromatography columns (30m × 0.25mm × 0.25 μm); carrier gas, namely 99.999 percent of high-purity nitrogen with the flow rate of 1 mL/min; the temperature of a sample inlet is 280 ℃; the sample injection volume is 1 mu L; heating procedure, wherein the initial temperature is 50 ℃, and keeping for 2 min; heating to 80 ℃ at the speed of 5 ℃/min; then the temperature is raised to 280 ℃ at the speed of 15 ℃/min and kept for 15 min. The quantitative method comprises the following steps: external standard curve.
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 introduction volume: 10 mu L of the solution; the quantitative method comprises the following steps: external standard curve method.
Example 1
The erythritol is prepared by using a net-shaped Ti/Pt as an anode zero-polar distance electrolytic tank one-pot method.
Adopting a zero polar distance electrolytic tank, selecting a mesh 316L stainless steel electrode as a cathode, and enabling the effective areas of the anode and the cathode to be 75cm 2 Nafion 427 was selected as the cation exchange membrane.
100g of acetonitrile, 400mL of water and 12g of sodium bromide are respectively added into an anolyte storage tank and a catholyte storage tank, and the mass flow of 1, 3-butadiene is adjusted to be 0.065g/min, the current is 7.5A, and the current density is 1000A/m 2 The current efficiency is 90 percent, the voltage is 3.6V, and the anolyte continuously enters a cathode liquid storage tank by a peristaltic pump with the mass flow of 0.11g/min for alkaline hydrolysis saponification cyclization. After the cathode electrolytic reaction liquid is rolled out, 1,2,3,4The aqueous solution of diepoxybutane is alkaline and has a pH value of 12, and 68% hydrobromic acid by mass fraction is added at a mass flow rate of 0.83g/min by using a peristaltic pump, keeping the pH stable at 1. And (3) carrying out reduced pressure distillation on the reaction liquid subjected to acidification and ring opening to remove excessive acid and water, carrying out freeze crystallization, drying to obtain white crystal erythritol, and carrying out chromatographic characterization, wherein the total yield is 87%, and the electrolysis energy consumption is 4986 kWh/t.
Example 2
The acetonitrile/water ratio is changed, potassium bromide halide is used as electrolyte, and reticular Ti/Pt is used as an anode, and the one-pot method of the zero-polar-distance electrolytic tank is used for preparing the erythritol.
A zero-polar-distance electrolytic cell is adopted, the acetonitrile/water ratio is adjusted to be 1:2, namely 167g of acetonitrile, 333g of water and 10g of potassium bromide are used as reaction liquid, Nafion 115 is used as a cation exchange membrane, and other conditions are as in example 1.
After 1,2,3, 4-diepoxybutane is synthesized by pair electrolysis, the reaction solution is subjected to acidolysis ring-opening, freezing crystallization and drying to obtain white crystal erythritol, the electrolysis current and the current density are kept unchanged, the current efficiency is 87%, the voltage is 4.1V, the total yield is 80%, and the electrolysis energy consumption is 5874 kWh/t.
Example 3
The erythritol is prepared by changing the ratio of acetonitrile to water, adopting 1,3, 5-hexatriene conjugated olefin as a raw material and adopting a net-shaped Ti/Pt as an anode zero-polar distance electrolytic tank one-pot method.
A zero-polar-distance electrolytic cell is adopted, the ratio of acetonitrile/water is adjusted to be 1:3, namely 125g of acetonitrile, 375g of water and 11.25g of sodium bromide are used as reaction liquid, Nafion 117 is used as a cation exchange membrane, and other conditions are as in example 1.
After 1,2,3, 4-diepoxybutane is synthesized by pair electrolysis, the reaction solution is subjected to acidolysis ring-opening, freezing crystallization and drying to obtain white crystal erythritol, the electrolysis current and the current density are kept unchanged, the current efficiency is 80%, the voltage is 3.8V, the total yield is 76%, and the electrolysis energy consumption is 5921 kWh/t.
Example 4
The one-pot method is used for preparing the erythritol by changing the acetonitrile/water ratio and the halide/water ratio and using the net-shaped Ti/Pt as an anode in a zero-polar distance electrolytic tank.
A zero-polar-distance electrolytic cell was used, the acetonitrile/water ratio was adjusted to 1:6, the halide/water ratio was adjusted to 4:100, that is, 71.4g of acetonitrile, 428.6g of water, and 17.14g of sodium bromide were used as reaction solutions, and Nafion 551 was used as a cation exchange membrane, and the other conditions were as in example 1.
After 1,2,3, 4-diepoxybutane is synthesized by pair electrolysis, the reaction solution is subjected to acidolysis ring-opening, freezing crystallization and drying to obtain white crystal erythritol, the electrolysis current and the current density are kept unchanged, the current efficiency is 75%, the voltage is 3.4V, the total yield is 78%, and the electrolysis energy consumption is 5651 kWh/t.
Example 5
Changing the halide/water ratio, adopting 1, 4-pentadiene isolated olefin as a raw material, adopting halide ammonium bromide as an electrolyte, and adopting a net-shaped Ti/Pt as an anode zero-polar distance electrolytic tank one-pot method to prepare the erythritol.
A zero-polar-distance electrolytic cell was used, the halide/water ratio was adjusted to 2:100, i.e., 100g acetonitrile, 400g water and 20g ammonium bromide were used as the reaction solution, Nafion 211 was used as the cation exchange membrane, and the other conditions were as in example 1.
After 1,2,3, 4-diepoxybutane is synthesized by pair electrolysis, the reaction solution is subjected to acidolysis ring-opening, freezing crystallization and drying to obtain white crystal erythritol, the electrolysis current and the current density are kept unchanged, the current efficiency is 88 percent, the voltage is 4V, the total yield is 85 percent, and the electrolysis energy consumption is 5666 kWh/t.
Example 6
By changing the anode type, using a mesh Ti/RuO 2 The erythritol is prepared by a one-pot method by using the erythritol as an anode and an electrolytic cell with zero polar distance.
Adopting a zero polar distance electrolytic tank, and adjusting the anode to be a net-shaped Ti/RuO 2 100g of acetonitrile, 400g of water and 12g of sodium bromide were added as a reaction solution, and Nafion 211 was used as a cation exchange membrane, and other conditions were as in example 1.
After 1,2,3, 4-diepoxybutane is synthesized by pair electrolysis, the reaction liquid is subjected to acidolysis ring-opening, freezing crystallization and drying to obtain white crystal erythritol, the electrolysis current and the current density are kept unchanged, the current efficiency is 86%, the voltage is 4.2V, the total yield is 88%, and the electrolysis energy consumption is 6088 kWh/t.
Example 7
1,3, 7-octatriene isolated olefin is used as a raw material, halide potassium chloride is used as an electrolyte, the type of an anode is changed, and reticular Ti/RuO is used 2 The erythritol is prepared by a one-pot method by using the erythritol as an anode and an electrolytic cell with zero polar distance.
A zero-polar-distance electrolytic cell is adopted, the ratio of halide to water is adjusted, 100g of acetonitrile, 400g of water and 40g of sodium bromide are added as reaction liquid, Nafion 427 is selected as a cation exchange membrane, and other conditions are as shown in example 1.
After 1,2,3, 4-diepoxybutane is synthesized by pair electrolysis, the aqueous solution is alkaline, the pH value is 11, hydrobromic acid with the mass fraction of 68 percent is added by a peristaltic pump at the mass flow rate of 0.84g/min, and the pH value is kept stable at 2. Acidolysis ring-opening is carried out on the reaction solution, and the white crystal erythritol is obtained after freezing crystallization and drying, the electrolysis current and the current density are kept unchanged, the current efficiency is 78%, the voltage is 3.3V, the total yield is 85%, and the electrolysis energy consumption is 5274 kWh/t.
Comparative example 1
In the prior art, plate-shaped graphite is generally used as an anode, sodium bromide is used as an electrocatalyst, the inter-polar distance is larger than or equal to 3mm, the plate-shaped graphite is used as the anode in the comparative example, and a non-zero inter-polar distance electrolytic tank with the inter-polar distance of 3mm is used for preparing the erythritol by a one-pot method.
The ratio of halide to water was adjusted by adding 100g of acetonitrile, 400g of water and 12g of sodium bromide as reaction solution, and selecting Nafion 427 as cation exchange membrane, and other conditions were as in comparative example 1.
After 1,2,3, 4-diepoxybutane is synthesized by pair electrolysis, the reaction solution is subjected to acidolysis ring-opening, freezing crystallization and drying to obtain white crystal erythritol, the electrolysis current and the current density are kept unchanged, the current efficiency is 48%, the voltage is 6.7V, the total yield is 64%, and the electrolysis energy consumption is 10440 kWh/t.
Comparative example 2
The existing technology for electrochemically synthesizing erythritol mainly comprises glucose oxygen oxidation and electrochemical oxidation reduction, erythritol is prepared by using a non-zero polar distance diaphragm electrolytic cell with a polar distance of 3mm, and plate-shaped graphite is used as an anode for electrolysis. Adding 1500g 10% aqueous solution of grape acid into a stainless steel autoclave, maintaining the rotation speed at 1000rpm, heating to 45 deg.C, displacing with oxygen for 2 times, and adjusting the pressure in the autoclave to 2 bar. 242g of 50% potassium hydroxide solution is dripped at the speed of 142.4g/h per hour, the heat preservation reaction is carried out for 5h after 1.7h of dripping, and the yield is 89%. 0.066g of sodium ribonate was dissolved in 20mL of water, the pH was lowered from 6.8 to 3.5 using a cation exchange resin, and the resin was removed by filtration. 25mL of the reaction solution was transferred to an electrolytic cell for electrolysis. The electrolytic current is 0.5A, the voltage is 6.5V, and after the 2F electricity is introduced, the total yield of the two steps is 72 percent.
As can be seen from the comparison between the above examples and comparative examples, the method for preparing erythritol by using 1, 3-butadiene as a raw material has the advantages of wide raw material source, simple steps, high atom economy, less three wastes, low energy consumption and low cost.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (9)
1. A method for preparing erythritol by a paired electrolysis one-pot method, which is characterized by comprising the following steps of:
s1: introducing 1, 3-butadiene into a halide-containing solution in an anode chamber of an electrolytic cell to obtain a halohydrin compound;
s2: allowing the anolyte to pass through a cathode chamber of an electrolytic cell to carry out saponification reaction to obtain 1,2,3, 4-diepoxybutane;
s3: acidifying 1,2,3, 4-diepoxybutane, and performing epoxy hydrolysis ring-opening reaction to obtain erythritol;
wherein the electrolytic bath in S1 and S2 is a zero-polar-distance chamber electrolytic bath with a diaphragm.
2. The method according to claim 1, characterized in that the cells of S1 and S2 are composed of an anode, a diaphragm, a cathode;
preferably, the electrolytic cell forms a zero-polar distance sandwich structure through a mesh anode, a diaphragm and a mesh cathode;
preferably, the anode material is one or more of titanium-plated platinum, titanium-based noble metal oxide coated electrode, pure platinum, coated electrode with high polymer material as matrix and graphite, preferably titanium-plated platinum and/or titanium-based noble metal oxide coated layer, more preferably titanium-based noble metal oxide coated layer;
preferably, the membrane is a cation exchange membrane, preferably one or more of Nafion 117, Nafion 115, Nafion 212, Nafion 427, and Nafion 551, more preferably Nafion 427;
preferably, the cathode material is one or more of stainless steel, platinum and graphite, preferably 316L stainless steel mesh and/or porous graphite plate, more preferably 316L stainless steel mesh.
3. The method of claim 1 or 2, wherein the halide in S1 comprises but is not limited to one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide, and ammonium bromide, preferably sodium bromide and/or potassium bromide, more preferably sodium bromide;
preferably, the addition amount of the halide is a catalyst amount, and the mass ratio of the halide to water is preferably 1:100-4:100, more preferably 2:100-3: 100;
and/or, the solution is an aqueous solution;
and/or adding a cosolvent acetonitrile into the solution;
preferably, the ratio of acetonitrile to water is from 1:1 to 1:6, preferably from 1:2 to 1: 4.
4. The method according to claim 1 or 2, wherein water in the catholyte in S2 is subjected to hydrogen evolution reaction, and free hydroxide ions are involved in saponification cyclization reaction.
5. The method for preparing a catalyst according to any one of claims 1 to 4, wherein the electrolysis cells in S1 and S2 have a voltage of 3.3V to 4.2V and a current efficiency of 75% to 90%.
6. The aqueous solution of diepoxybutane according to claim 1, characterized in that the aqueous solution of 1,2,3, 4-diepoxybutane in S3 is basic with a pH value of 10-14, preferably a pH value of 11-12;
and/or, using sulfuric acid and/or hydrobromic acid as a neutralizing agent;
and/or, the ring-opening reaction is carried out under strong acidic condition, and the pH value is 1-3, preferably 1-2.
7. An erythritol product produced by the production method according to any one of claims 1 to 6.
8. The erythritol product according to claim 7, wherein the erythritol comprises, but is not limited to, one or more of D- (-) -meso-erythritol, (D) -erythritol, (L) -erythritol.
9. Use of a pair-wise electrolytic one-pot process for the preparation of alcohols according to any one of claims 1 to 6, when a conjugated olefin containing two or more double bonds or an isolated olefin containing two or more double bonds is used as starting material, for the preparation of an epoxide of a diene or a di-alcoholate of a diene, preferably for the preparation of any one of erythritol, 1, 4-dichloro-2, 3-dihydroxybutane, epoxybutene, 1,2,3, 4-diepoxybutane, 3-butene-1, 2-diol, 3, 4-diepoxy-1, 2-butanediol.
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