CN102021604B - Method for preparing succinic acid based on alloy wire mesh-bipolar film combined electrode technology - Google Patents
Method for preparing succinic acid based on alloy wire mesh-bipolar film combined electrode technology Download PDFInfo
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- CN102021604B CN102021604B CN2010105078610A CN201010507861A CN102021604B CN 102021604 B CN102021604 B CN 102021604B CN 2010105078610 A CN2010105078610 A CN 2010105078610A CN 201010507861 A CN201010507861 A CN 201010507861A CN 102021604 B CN102021604 B CN 102021604B
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- succinic acid
- silk screen
- bipolar membrane
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- metal silk
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Abstract
The invention relates to the field of electrochemical synthesis, in particular to design of an anode in an electrolytic bath and a method for preparing succinic acid based on an alloy wire mesh-bipolar film combined electrode technology. In the invention, an alloy wire mesh is used as an anode and is attached to a bipolar film closely to prepare an alloy wire mesh-bipolar film combined electrode; by compressing the space of an anode chamber to zero, zero-polar distance electrolysis is realized and mass transfer impedance in the anode chamber is greatly reduced, thus the voltage of the electrolytic bath is reduced and the effect of energy saving is achieved. In the invention, by using the principle that the bipolar film dissociates water under the action of an electric filed, hydrogen ions and hydroxyl ions generated after water dissociation are respectively led into a cathode chamber and the anode chamber for adjusting the pH value of a reaction medium; in the production process of succinic acid by using the method, no additional acid needs to be added, reaction conditions are moderate and reaction equipment is simple. The method is a novel environmental-friendly energy-saving and emission-reducing process.
Description
Technical field
The present invention relates to a kind of electrochemical synthesis field, be specifically related in the electrolyzer anodic design and a kind ofly prepare the method for Succinic Acid at cathode compartment based on alloyed metal silk screen-Bipolar Membrane combined electrode technology.Adopt this method to have environmental protection, the effect of energy-saving and emission-reduction.
Technical background
Power-saving technology in the electrolysis production is the focus that people pay close attention to always.Electrolytic solution generates heat because of its impedance in mass transfer process in the electrolyzer; Electric energy is converted into heat energy; Not only unnecessarily increase many side reactions; Like liberation of hydrogen, analyse oxygen and increased the generation of non-title product, also increased cooling system in the electrolyzer simultaneously and the unnecessary design and the working cost that bring, thereby increased the cost of product.The present invention is an anode with metal-alloy silk screen; And anode metal-alloy silk screen is close on the Bipolar Membrane, prepare metal-alloy silk screen-Bipolar Membrane combined electrode, the space of anolyte compartment is greatly reduced; Realized zero pole span electrolysis; Subdue the mass transfer impedance in the anolyte compartment, thereby reduced bath voltage, reached energy-conservation effect.
Succinic Acid is a kind of Organic Chemicals with extensive use.Be mainly used in coating, dyestuff, plastics, tackiness agent and medical aspect.Synthesizing succinic acid mainly contains chemical method, biotransformation method and electrolytic process in the industry.At present; Most of industrial Succinic Acid is through chemical method production; Mainly be divided into oxidation style, hydrogenation method and catalysis additive process etc., these method technology comparative maturities, but have more problem; Like the difficult control of side reaction, productive rate is low, purity is not high, the operational condition difficulty high, use that catalyzer costs an arm and a leg etc., and can cause a large amount of pollutions in process of production.In recent years, utilize bacterium or microbial fermentation to obtain Succinic Acid,, become the focus of domestic and international research gradually because the waste material that adopts starch, glucose, cow's milk or other mikrobe to utilize is raw material.But still have a large amount of work to need further research and perfect;, acid production rate low like the product extraction efficiency and transformation efficiency is low, production cost is expensive, the wastewater flow rate big (waste water that every according to estimates production 1t Succinic Acid produces will reach more than the 10t) that produces etc. is difficult to satisfy industrial needs.
Electrochemical production Succinic Acid technology has two kinds of diaphragm process and no diaphragm processes.Diaphragm process is many with the barrier film of Nafion monofilm as electrolyzer, and the evolving hydrogen reaction because of cathode compartment when adopting this method makes catholyte be alkalescence, for the generation that guarantees Succinic Acid should add acid catholyte is transferred to acidity; No diaphragm process for the Succinic Acid that prevents negative electrode and generate at the anodic electric polymerization reaction, have potential product safety risk, strict control anode potential, make troubles to operation.The present invention is a raw material with the MALEIC ANHYDRIDE, utilizes the barrier film of Bipolar Membrane as electrolyzer, and MALEIC ANHYDRIDE generates Succinic Acid behind the negative electrode reductive hydrolysis, has prevented that Succinic Acid from the reaction of anodic poly, having guaranteed product gas purity.In addition, the water decomposition in the Bipolar Membrane middle layer goes out H
+See through the cationic exchange layer and arrive the consumption of cathode compartment hydrogen make-up ionic.In electrolytic process, need not to add the sour environment that mineral acid is kept cathode compartment again, practiced thrift production cost, also prevented environmental pollution simultaneously, and had high current efficiency, is a kind of emerging technology of environmental protection.
Summary of the invention
The present invention is an anode with the alloyed metal silk screen; And the anode alloy wire cloth is close on the Bipolar Membrane, prepare alloyed metal silk screen-Bipolar Membrane combined electrode, the space of anolyte compartment is greatly reduced; Realized zero pole span electrolysis; Subdue the mass transfer impedance in the anolyte compartment greatly, thereby reduced bath voltage, reached energy-conservation effect.
Technical scheme of the present invention is a kind of technological based on Bipolar Membrane, is raw material with inexpensive MALEIC ANHYDRIDE, adopts environmental protection, method for saving energy, in cathode compartment, prepares Succinic Acid.Adopt the inventive method, preparation condition is gentle, produces down at 20 ℃～65 ℃, and the current efficiency of cathode compartment is higher than 90%, reaches energy-conservation effect, and not seeing as yet at present has bibliographical information.
For reaching above purpose, the present invention realizes through following technical scheme:
(1) preparation of alloyed metal silk screen-Bipolar Membrane combined electrode:
Cationic exchange rete emulsion flow is prolonged in the alloyed metal grid hole apart from being on the alloy silk screen of 0.1～10mm, treat on anonite membrane, to cover again with the anion exchange membrane facing emulsion when it is closely done, be alloyed metal silk screen-Bipolar Membrane combined electrode after air-dry.
(2) electrolyzer assembling:
With the middle barrier film of Bipolar Membrane as electrolyzer, Bipolar Membrane adopts reverse construction from part, and promptly the cationic exchange membrane aspect in the Bipolar Membrane is to cathode compartment, and anion exchange membrane facing is towards the anolyte compartment; Make anode with the alloyed metal silk screen; Lead electrode is as negative electrode.
(3) electrolytic solution:
Cathode compartment: the aqueous solution of maleic acid, 0.1～3.0molL
-1
Anolyte compartment: 1molL
-1Sulphuric acid soln.
(4) electrolytic condition |:
Current density: 10～100mA/cm
2
Supporting electrolyte: 0.1～1molL
-1Sulphuric acid soln.
Bath voltage: 2～4V;
Electrolyte temperature: 20 ℃～65 ℃.
(5) preparation of Succinic Acid:
MALEIC ANHYDRIDE is hydrolyzed to maleic acid in cathode compartment, generate Succinic Acid behind the electroreduction then, and the reaction equation of preparation Succinic Acid is following in the cathode compartment:
The H that water decomposition in the Bipolar Membrane middle layer generates
+See through the positively charged ion rete and get in the cathode compartment, replenished the maleic acid electroreduction and generated required H in the Succinic Acid process
+, impel reaction forward to carry out.
Described metal alloy is meant: admiro, tin-nickel alloy, Ti-Ni alloy, plumbous nickelalloy, terne metal, titanium ruthenium alloy or plumbic oxide silk screen.
Implementation result: 20 ℃～65 ℃ preparations down.When current density is 10～100mA/cm
2, in the cathode compartment, the productive rate of Succinic Acid reaches 80～90%, and mean current efficient is 75～85%, and bath voltage＜4V has reached energy-conservation effect.
Embodiment
Embodiment 1
PREPARATIOM OF BIPOLAR MEMBRANE.
5g SBS (styrene-butadiene-styrene block copolymer) is dissolved in 40mL toluene and the dioxane mixing solutions (V/V=3/1), adds 10～60% new vinylformic acid (AA) and the 1.0%BPO (Lucidol is in the AA quality) that steam.In the nitrogen atmosphere, 80 ℃ of isothermal reaction 3h, the cooling termination reaction promptly gets SBS-g-PAA cationic exchange rete emulsion.
5g SBS is dissolved in 20mL toluene and the 20mL dioxane mixing solutions, and adds 3g N, TMSDMA N dimethylamine base ethyl propenoate (DMAEMA) and 1.0%BPO (in the DMAEMA quality).In the nitrogen atmosphere, 80 ℃ of isothermal reaction 3h.Must contain tertiary amine group SBS-g-DMAEMA graft copolymer, be SBS-g-DMAEMA anion exchange membrane facing emulsion.
SBS-g-PAA cationic exchange rete emulsion flow is prolonged on the Zn-Ni alloy silk screen of smooth aperture 0.3mm, treat to cover again with SBS-g-DMAEMA anion exchange membrane facing emulsion when it is closely done, be Zn-Ni alloy wire cloth-Bipolar Membrane combined electrode after air-dry.
With the middle barrier film of Zn-Ni alloy wire cloth-Bipolar Membrane combined electrode, be 0.5molL in anolyte compartment and the cathode compartment as electrolyzer
-1Sulfuric acid, at 10mA/cm
2Work under the current density, bath voltage is less than 2V.
Embodiment 2
The Bipolar Membrane of preparing with example 1 is the barrier film of negative and positive two Room.The MALEIC ANHYDRIDE that takes by weighing 10g is dissolved in it in water of 100mL, and transfers to every liter of mixed solution sulfur acid 0.5mol with the sulfuric acid of 1mol, treats to join in the cathode compartment after its dissolving.20 ℃ of electrolyte temperatures, current density 30mAcm
-2, total current 2A, electrolysis time are 3.5h.Recording bath voltage is 2.8V; The apparent productive rate that generates Succinic Acid in the cathode compartment is 110%, and current efficiency is 87%; The fusing point that records the product Succinic Acid is 188 ℃, and is identical with literature value, shows that its purity is high.
Embodiment 3
The Bipolar Membrane of preparing with example 1 is the barrier film of negative and positive two Room.25 ℃ of electrolyte temperatures, current density 70mA/cm
2
The MALEIC ANHYDRIDE that takes by weighing 10g is dissolved in it in water of 100mL, and transfers to every liter of mixed solution sulfur acid 0.5mol with sulfuric acid, treats to join in the cathode compartment after its dissolving.Total current 2A, electrolysis time are 4h.The apparent productive rate that generates Succinic Acid in the cathode compartment is 105%, and current efficiency is 79%; Bath voltage 3.2V.
Embodiment 4
45 ℃ of electrolyte temperatures, current density 70mA/cm
2With the barrier film of Nafion monofilm as electrolyzer.
The electrolytic solution of anolyte compartment, cathode compartment is formed all identical with embodiment 3 with processing condition.Total current 2A, electrolysis time are 5h.The apparent productive rate that generates Succinic Acid in the cathode compartment is 94%, bath voltage 5.1V.
With the Nafion monofilm during as the barrier film of electrolyzer; Cathode compartment is alkalescence because of liberation of hydrogen, and the anolyte compartment is acid because of analysing oxygen, according to reaction formula 2; In cathode compartment; Forward reaction must carry out in acid atmosphere, and the alkalescence in the cathode compartment has blocked the generation of Succinic Acid, so productive rate and the current efficiency of resultant is all low when using Bipolar Membrane in example 2, the example 3 in negative and positive two Room.
Embodiment 5
The Bipolar Membrane of preparing with example 1 is the barrier film of negative and positive two Room.50 ℃ of electrolyte temperatures, current density 10mAcm-2.The electrolytic solution of anolyte compartment, cathode compartment is formed all identical with embodiment 2 with other processing condition.Total current 2A, electrolysis time are 3.5h.The apparent productive rate that generates Succinic Acid in the cathode compartment is 101%, and current efficiency is 83%, bath voltage 2.5V.
Current density is 10mA/cm
2The time, bath voltage is low, and liberation of hydrogen analyses that the side reaction of oxygen is little, and the current efficiency of title product is higher, but long reaction time, productive rate is lower.Apparent productive rate is an end air-dry Succinic Acid productive rate fully.
Claims (4)
1. one kind prepares the method for Succinic Acid based on alloyed metal silk screen-Bipolar Membrane technology, it is characterized in that:
(1) preparation of alloyed metal silk screen-Bipolar Membrane combined electrode
Cationic exchange rete emulsion flow is prolonged on the alloyed metal silk screen, treat on anonite membrane, to cover again with the anion exchange membrane facing emulsion when it is closely done, be alloyed metal silk screen-Bipolar Membrane combined electrode after air-dry;
(2) electrolyzer assembling
With the middle barrier film of Bipolar Membrane as electrolyzer, Bipolar Membrane adopts the cationic exchange membrane aspect to cathode compartment, and anion exchange membrane facing is made anode towards the reverse construction from part of anolyte compartment with the alloyed metal silk screen, and lead electrode is as negative electrode;
(3) electrolytic solution
Cathode compartment: the aqueous solution of maleic acid, anolyte compartment: 1molL
-1Sulphuric acid soln;
(4) electrolytic condition
Current density: 10～100mA/cm
2, supporting electrolyte: 0.1～1molL
-1Sulphuric acid soln, bath voltage: 2～4V, electrolyte temperature: 20 ℃～65 ℃.
2. according to claim 1 based on the technological method for preparing Succinic Acid of alloyed metal silk screen-Bipolar Membrane, it is characterized in that described alloyed metal is: admiro, tin-nickel alloy, Ti-Ni alloy, plumbous nickelalloy, terne metal or titanium ruthenium alloy.
3. according to claim 1 based on the technological method for preparing Succinic Acid of alloyed metal silk screen-Bipolar Membrane, the pitch-row that it is characterized in that described alloyed metal silk screen is 0.1～10mm.
4. according to claim 1 based on the technological method for preparing Succinic Acid of alloyed metal silk screen-Bipolar Membrane, it is characterized in that the aqueous solution of described maleic acid, its content is 0.1～3.0molL
-1
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| CN101967653A (en) * | 2010-11-08 | 2011-02-09 | 福建师范大学 | Alloying metal net-two pole film composite electrode |
| CN105177620B (en) * | 2015-05-14 | 2018-05-11 | 山东飞扬化工有限公司 | The diaphragm electrolysis device for synthesizing succinic acid and method of a kind of zero pole span |
| US11339483B1 (en) | 2021-04-05 | 2022-05-24 | Alchemr, Inc. | Water electrolyzers employing anion exchange membranes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101187034A (en) * | 2007-09-06 | 2008-05-28 | 浙江工业大学 | Bipolar type diaphragm-free type electrolysis device for synthesizing succinic acid |
| CN101486637A (en) * | 2009-02-09 | 2009-07-22 | 常茂生物化学工程股份有限公司 | Method for extracting amber acid from fermentation liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101187034A (en) * | 2007-09-06 | 2008-05-28 | 浙江工业大学 | Bipolar type diaphragm-free type electrolysis device for synthesizing succinic acid |
| CN101486637A (en) * | 2009-02-09 | 2009-07-22 | 常茂生物化学工程股份有限公司 | Method for extracting amber acid from fermentation liquor |
Non-Patent Citations (1)
| Title |
|---|
| 谢鸿芳等.双极膜技术在电合成中的应用.《化学世界》.2009,(第11期),693-696. * |
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