CN102912372A - Stepped in-series overflow process succinic acid preparation method on basis of diaphragm-free electrolytic cell - Google Patents
Stepped in-series overflow process succinic acid preparation method on basis of diaphragm-free electrolytic cell Download PDFInfo
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- CN102912372A CN102912372A CN2012104351169A CN201210435116A CN102912372A CN 102912372 A CN102912372 A CN 102912372A CN 2012104351169 A CN2012104351169 A CN 2012104351169A CN 201210435116 A CN201210435116 A CN 201210435116A CN 102912372 A CN102912372 A CN 102912372A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to the field of electrochemical synthesis, in particular to design of an electrolytic cell as well as a stepped in-series overflow process succinic acid preparation method. According to the method, maleic anhydride is hydrolyzed to be maleic acid in a cathode chamber of an electrolytic cell, and then succinic acid is prepared through electrolytic reduction at a cathode. The electrolytic cell is a series overflow cell bank formed by arranging an electrolyte raw material cell, an electrolytic single cell and a product cell in a stepped manner. During preparation, firstly the electrolyte is pumped into the step arranged electrolytic single cell by an infusion pump, electrolysis is started as the power is on, and succinic acid obtained through electrolysis is collected in the product cell. The method has the advantages of simple production process, mild production condition, simple equipment, convenience for operation, energy conservation and emission reduction, and is a green and environmental-friendly, energy-saving and emission-reduction new technology.
Description
Technical field
The present invention relates to a kind of electrochemical synthesis field, be specifically related to the design of electrolyzer and the method that a kind of press over system technology of connecting prepares basic Succinic Acid, it is simple, easy to operate that employing the method has Production Flow Chart, the effect of energy-saving and emission-reduction.
Technical background
The principal reaction principle for preparing Succinic Acid with electrochemical method is:
MALEIC ANHYDRIDE is hydrolyzed to maleic acid in cathode compartment, electroreduction generates Succinic Acid on negative electrode then, and its reaction equation is as follows:
Electrolytic condition |:
Current density: 10～100mAcm
-2
Bath voltage: 2～4V;
Electrolyte temperature: 20 ℃～65 ℃.
Electrolyte quota:
Usually the electrolytic solution that adopts is the aqueous solution of acid maleic acid, and it consists of 0.1～3.0molL
-1The sulphuric acid soln of maleic acid and 0.1～0.5mol/L.
At anode side reaction occurs for fear of the Succinic Acid that generates, the technology of therefore producing Succinic Acid with electrochemical method is divided into again two kinds of diaphragm process and non membranous.Diaphragm process is divided again monofilm method and bipolar embrane method.The food pharmaceutical industries is higher to the Succinic Acid purity requirement of electrosynthesis, is advisable with diaphragm process production.
Succinic Acid is widely used in the aspects such as dyestuff, plastics, coating, tackiness agent as Organic Chemicals in recent years, requirement to the Succinic Acid product purity is relaxed relatively, non membranous electrosynthesis Succinic Acid has obtained faster development because its cell construction is simple, easy to operate.
No matter but diaphragm process and non membranous production Succinic Acid all adopt the batch production mode, be that maleic acid in every batch electrolyzer changes into behind the Succinic Acid must the power failure blowing, after the product Succinic Acid emitted, again add new raw material in electrolyzer again, energising is produced again.The drawback of batch production is apparent.Every batch of start-stop power supply not only is unfavorable for the safety in production of rectifier, and troublesome poeration, and workload is large.
Safety in production is the focus that people pay close attention in the electrolysis production with power-saving technology always.The present invention adopts a kind of series connection press over system technology to produce basic Succinic Acid.It is simple that the method has Production Flow Chart, easy to operate, the effect of energy-saving and emission-reduction.
Particular content of the present invention is that electrolyzer adopts staged to arrange, the electrolytic solution of namely going up an electrolyzer successively overflow continues electrolysis to next electrolyzer, after the electrolytic solution that check reaches regulation finished product Succinic Acid concentration flows out electrolyzer, directly be sent to distillation process, thereby realized the continuous production of Succinic Acid.188 ℃ of the literature values of Succinic Acid fusing point.
Summary of the invention
Technical scheme of the present invention is a kind of based on without membrane technique, and electrolyzer adopts staged to arrange, and electrolytic solution series connection overflow prepares Succinic Acid take inexpensive MALEIC ANHYDRIDE as raw material.Adopt the inventive method, preparation condition is gentle, ℃ lower production the in room temperature～65, and current efficiency is higher than 90%, there is not yet bibliographical information.
For reaching above purpose, the present invention realizes by following technical scheme:
1, arranging of staged series connection overflow groove group:
Staged series connection overflow groove group is comprised of electrolysis list groove and the product groove of the sizes such as electrolytic solution raw material tank, 5～10, the electrolytic solution raw material tank is positioned at foremost, 5～10 the single groove of electrolysis and successively staged arrangements of product groove that wait size, the product groove is positioned at last step, step therein is 100～300mm, be provided with upflow tube between the single groove of upper level electrolysis and next stage electrolysis list groove and the product groove and be connected, be provided with the control valve of Push And Release in the upflow tube; It is inverted "L" shaped that upflow tube is, the single groove liquid level of electrolyte of upper level electrolysis just in time floods upflow tube upper end fluid inlet, upflow tube lower end liquid outlet inserts the nearly bottom of the single groove of next stage electrolysis, thereby the smooth overflow of the electrolytic solution of the upper groove of assurance energy under the state that control valve is opened is to the single groove of next electrolysis; The electrolytic solution raw material tank by infusion pump to the single groove electrolysis of first step electrolysis liquid.
2, staged series connection overflow electrolysis:
After all opening the control valve that arranges in the upflow tube, by infusion pump the electrolytic solution in the electrolytic solution raw material tank is pumped in the single groove of first step electrolysis, overflow is until reach the full-water level of the single groove of last step electrolysis and end step by step, closes infusion pump and whole control valves in the upflow tubes, energising beginning electrolysis.Theoretical according to faraday law, after reaching the electrolysis time of the single groove of each electrolysis that estimates in current efficiency 100% at electrolysis time, open control valve in the upflow tube, provide the electrolytic solution raw material to flow with the stepwise speed of setting by electrolytic solution to the single groove of first step electrolysis incessantly by infusion pump, and in the product groove, collect electrolytic production and send the distillation process condensing crystal to obtain Succinic Acid crystal finished product.The flow velocity of electrolytic solution should be decided according to the size of electrical current, should guarantee in principle when electrolytic solution flows out electrolyzer that the productive rate of Succinic Acid is greater than 90% in the electrolytic solution.
The single groove of electrolysis of the present invention is take graphite as anode, and lead is negative electrode, parallel being staggered, pole span 2mm～20mm.The IR that little pole span is conducive to reduce electrolytic solution falls, and reduces bath voltage, has reached energy-conservation effect.
Implementation result: under ° C of 20C～65, prepare.When current density is 10～100mAcm
-2, the productive rate of Succinic Acid reaches 80～90%, and mean current efficient is 80～90%, and bath voltage＜4V has reached energy-conservation effect.
Description of drawings
Fig. 1 is the staged of the present invention series connection overflow electrolyzer group schematic diagram of arranging.
Embodiment
Among Fig. 1, the 1st, the single groove of electrolysis, the 2nd, control valve, the 3rd, be inverted "L" shaped upflow tube, the 4th, product groove, the 5th, infusion pump, the 6th, electrolytic solution raw material tank.
Embodiment 1
The MALEIC ANHYDRIDE that takes by weighing 1Kg is dissolved in it in water of 10L, and transfers to pH=1 with sulfuric acid, joins in the electrolytic solution raw material tank after its dissolving., control and adjusting: 25 ℃ of electrolyte temperatures, current density 30mAcm
-2, total current 2A.
Behind the control valve 2 that in all opening upflow tube 3, arranges, by infusion pump 5 electrolytic solution in the electrolytic solution raw material tank 6 is pumped in the single groove 1 of first step electrolysis, overflow is until reach the full-water level of the single groove 1 of last step electrolysis and end step by step, close the control valve 2 in infusion pump 5 and the whole upflow tube, energising beginning electrolysis.After the electrolysis 3 hours, open control valve 2 in the upflow tube 3, provide the electrolytic solution raw material to the single groove of the electrolysis of the first step incessantly by infusion pump, the flow velocity that pumps into the electrolytic solution in the single groove 1 of electrolysis of the first step is 8L/min, behind total electrolysis time 4h, send the distillation process condensing crystal to obtain Succinic Acid crystal finished product the Succinic Acid of collecting in the product groove.In the present embodiment, the single groove of electrolysis is undivided cell.
As calculated, the productive rate that generates Succinic Acid is 94.5%, current efficiency 93%; Average electrical bath voltage 2.8V.The fusing point that records the product Succinic Acid is 187 ℃.
Embodiment 2
The preparation treatment process of the raw material of electrolytic solution, electrolytic solution is identical with embodiment 1.
15 ℃ of electrolyte temperatures, electrolytic current density 30mAcm
-2, total current 2A.
Behind electrolysis 3.5h, send the distillation process condensing crystal to obtain Succinic Acid crystal finished product the Succinic Acid of collecting in the product groove.
In the present embodiment, the single groove of electrolysis is appointed and is undivided cell.
Electrolytic process records bath voltage and begins to be followed successively by 2.0V, 2.0V, 2.1V, 2.2V, 2.3V, 2.4V, 2.5V, 2.6V, 2.8V, 3.0V from the single groove of first step electrolysis; The observed yield that generates Succinic Acid is 110%, and current efficiency is 87%; The fusing point that records the product Succinic Acid is 186 ℃.
Embodiment 3
The preparation treatment process of the raw material of electrolytic solution, electrolytic solution is identical with embodiment 1.
45 ℃ of electrolyte temperatures, current density 70mAcm
-215 ℃ of electrolyte temperatures, electrolytic current density 30mAcm
-2, total current 2A.
Behind electrolysis 6.5h, send the distillation process condensing crystal to obtain Succinic Acid crystal finished product the Succinic Acid of collecting in the product groove.
Record bath voltage and be followed successively by 2.2V, 2.3V, 2.4V, 2.5V, 2.6V, 2.7V, 2.8V, 2.9V, 3.1V, 3.3V; The observed yield that generates Succinic Acid is 105%, and current efficiency is 80%; The fusing point that records the product Succinic Acid is 185 ℃.
Observed yield is fully air-dry Succinic Acid productive rate of end.
Claims (5)
1. the staged series connection press over system based on undivided cell prepares the Succinic Acid method, with MALEIC ANHYDRIDE at the indoor maleic acid that is hydrolyzed to of electric tank cathode, then on negative electrode take current density as 10～100mA.cm-2 electrolytic reduction prepares Succinic Acid, it is characterized in that:
Described electrolyzer, to rearrange series connection overflow groove group by the single groove of the electrolysis of the sizes such as electrolytic solution raw material tank, 5～10 and product groove staged, wherein the electrolytic solution raw material tank is positioned at foremost, the single groove of electrolysis and product groove successively staged are arranged, the product groove is positioned at last step, is provided with upflow tube between the single groove of upper level electrolysis and next stage electrolysis list groove and the product groove and is connected;
Staged series connection overflow electrolysis:
Described electrolytic reduction prepares Succinic Acid, at first electrolytic solution pumped in the single groove of electrolysis of staged arrangement by infusion pump, and energising beginning electrolysis, and in the product groove, collect the Succinic Acid that electrolysis obtains.
2. a kind of staged series connection press over system based on undivided cell according to claim 1 prepares the Succinic Acid method, it is characterized in that the single groove of described electrolysis and the arrangement of product groove staged, and drop is 100～300mm between ladder.
3. a kind of staged series connection press over system based on undivided cell according to claim 1 prepares the Succinic Acid method, it is characterized in that described upflow tube, be inverted "L" shaped, the single groove liquid level of electrolyte of upper level electrolysis just in time floods upflow tube upper end fluid inlet, and upflow tube lower end liquid outlet inserts the nearly bottom of the single groove of next stage electrolysis.
4. a kind of staged series connection press over system based on undivided cell according to claim 1 prepares the Succinic Acid method, when it is characterized in that described infusion pump pumps into electrolytic solution in the single groove of electrolysis that staged arranges, only to the single groove electrolysis of first step electrolysis liquid.
5. a kind of staged series connection press over system based on undivided cell according to claim 1 prepares the Succinic Acid method, it is characterized in that the single groove of described electrolysis is take graphite as anode, and lead is negative electrode, parallel being staggered, pole span 2mm～20mm.
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| CN2012104351169A CN102912372A (en) | 2012-11-02 | 2012-11-02 | Stepped in-series overflow process succinic acid preparation method on basis of diaphragm-free electrolytic cell |
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| CN2012104351169A CN102912372A (en) | 2012-11-02 | 2012-11-02 | Stepped in-series overflow process succinic acid preparation method on basis of diaphragm-free electrolytic cell |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107794550A (en) * | 2017-09-07 | 2018-03-13 | 浙江工业大学 | A kind of method that accessory substance fumaric acid content is reduced during electrolytic synthesis of amber acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508291A (en) * | 2002-12-18 | 2004-06-30 | 吴建国 | Method for preparing perchlorate by electrolysis of chlorate |
| CN2651267Y (en) * | 2003-11-04 | 2004-10-27 | 马世金 | Non-diaphragm continuous electrolytic succinic acid producing apparatus |
| CN101100758A (en) * | 2007-06-30 | 2008-01-09 | 浙江工业大学 | Technique and device for non-membrane electrolytic synthesis of butanedioic acid |
| CN101225524A (en) * | 2007-09-30 | 2008-07-23 | 浙江工业大学 | Novel method for non-membrane intermittent environment-friendly electrosynthesis of succinic acid |
-
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- 2012-11-02 CN CN2012104351169A patent/CN102912372A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508291A (en) * | 2002-12-18 | 2004-06-30 | 吴建国 | Method for preparing perchlorate by electrolysis of chlorate |
| CN2651267Y (en) * | 2003-11-04 | 2004-10-27 | 马世金 | Non-diaphragm continuous electrolytic succinic acid producing apparatus |
| CN101100758A (en) * | 2007-06-30 | 2008-01-09 | 浙江工业大学 | Technique and device for non-membrane electrolytic synthesis of butanedioic acid |
| CN101225524A (en) * | 2007-09-30 | 2008-07-23 | 浙江工业大学 | Novel method for non-membrane intermittent environment-friendly electrosynthesis of succinic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107794550A (en) * | 2017-09-07 | 2018-03-13 | 浙江工业大学 | A kind of method that accessory substance fumaric acid content is reduced during electrolytic synthesis of amber acid |
| CN107794550B (en) * | 2017-09-07 | 2019-04-09 | 浙江工业大学 | A method of reducing by-product fumaric acid content during electrolytic synthesis of amber acid |
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Application publication date: 20130206 |