CN101423953B - Method for electrosynthesizing amber acid by organic non-membrane matched pair - Google Patents
Method for electrosynthesizing amber acid by organic non-membrane matched pair Download PDFInfo
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- CN101423953B CN101423953B CN2007100475301A CN200710047530A CN101423953B CN 101423953 B CN101423953 B CN 101423953B CN 2007100475301 A CN2007100475301 A CN 2007100475301A CN 200710047530 A CN200710047530 A CN 200710047530A CN 101423953 B CN101423953 B CN 101423953B
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Abstract
The invention discloses a method for organic diaphragm-free paired electrosynthesis of butane diacid. The method comprises the following steps: as an initial raw material, maleic anhydride is dissolved in water to prepare an aqueous solution containing 15 to 30 weight percent of maleic acid; the aqueous solution is mixed with a mother solution containing 3 to 5 weight percent of sulphuric acid to prepare a solution containing 10 to 20 weight percent of maleic acid; the solution is poured into a multi-pole plate and frame electrolyzer with a 140 to 160 volt DC voltage to carry out a hydrogenation reduction reaction of the maleic acid under conditions of an electrolytic temperature of between 60 and 70 DEG C, conduction time of 5 to 6 hours and a current of 800A at the end of electrolysis and then hot solution is filtered, cooled, and crystallized, and crystals are filtered, washed and dried to obtain the product. The yield is between 99.6 and 99.8 percent, the product purity is between 99.5 and 99.8 percent, and the total current efficiency is between 96 and 98 percent.
Description
One, technical field
The present invention relates to a kind of method of organic no barrier film pairing electrosynthesis Succinic Acid, relate to the method that maleic acid does not have barrier film pairing electrosynthesis Succinic Acid or rather.
Two, background technology
Succinic Acid has another name called succsinic acid, is a kind of Organic Chemicals with extensive use.Be mainly used in food, chemical industry, medicine and other fields, main as souring agent in foodstuffs industry.In chemical industry, be used as pH value when electroplating adjust agent, plastics toughener and be used for that production is sprayed paint, dyestuff, ion exchange resin, agricultural chemicals etc.In pharmaceutical industries, be used for synthetic tranquilizer, diuretic(s), VITAMIN, contraceptive bian and curing cancer drug etc.
Method by the maleic acid synthesizing succinic acid roughly can reduce three kinds of methods, i.e. High Temperature High Pressure catalyzed reaction synthesis method, septate pairing electrosynthesis and aseptate pairing electrosynthesis.Prior art JP02-121946,09.05.1990 discloses: toxilic acid is as the initial feed of preparation Succinic Acid, and toxilic acid is to be hydrolyzed into acid by maleic anhydride is dissolved in the water to make.The toxilic acid aqueous solution of 20～40 weight % is added in the fixed-bed reactor that are filled with the precious metal palladium/carbon catalyst, at 60～150 ℃, logical hydrogen hydrogenation reduction, hydrogen pressure is the 5MPa gauge pressure, the Succinic Acid yield that this method is produced is 99.96～99.99%, by product oxysuccinic acid 100～400PPm, fumaric acid are 10～15PPm.This method can be described as high yield production method cheaply.Yet from the angle of environmental protection, this method also is not the ideal method, and the hydrogenation pressure height is under cover dangerous.
Prior art " fine chemistry industry ", 1997,14,56～57 reports improve the paired electrolysis synthesis technique, in the anolyte compartment, oxalic dialdehyde electrooxidation synthesizing glyoxalic acid, yield is higher than 70%, at cathode compartment, maleic acid electroreduction synthesizing succinic acid, yield can reach 85%.This isolation embrane method is because employed ion-exchange membrane is difficult to satisfy the needs of organic synthesis on performance, cost performance is low, so, gradually by no barrier film electrosynthesis replacement.
Prior art horse Chunan work " organic electrochemistry synthesize introduction " the 12nd chapter " organic electrosynthesis industry and application; " Science Press publishes, the second impression in February, 2003, point out for the 363rd page: the no barrier film electrosynthesis of Succinic Acid is an anode with the lead base plumbic oxide, with the stainless steel is negative electrode, with 1molL
-1Sulfuric acid be supporting electrolyte, the concentration of maleic acid is 1.5molL
-1, under 60～70 ℃ temperature, carry out electrolysis; Can separate out the Succinic Acid crystal after flowing out the electrolytic solution cool to room temperature of electrolyzer, more after filtration, drying obtains product.The Succinic Acid yield is higher than 80%, and total current efficient is greater than 70%, and this method also needs further to improve yield and total current efficient.
Three, summary of the invention
Electrosynthesis has many incomparable advantages, for example, cost and facility investment are very low, just can react under normal temperature, the normal pressure, easily control side reaction, can make high purity butylene diacid and mother liquor can recycle, and three-waste pollution is low etc., people call environmentally friendly technology to it, green synthetic engineering.Present inventors combine the relative merits of prior art, and special in no barrier film pairing electrosynthesis Succinic Acid method is improved research, the test of process dedicated experiments has accumulated a large amount of experiences, has proposed complete technical scheme.
Initial feed composition, cell construction, electrode materials are formed in the present invention and deep research has been done in reaction parameter control, has proposed feasible technical scheme.The present invention is the purpose of invention to improve yield and total current efficient.
The method of organic no barrier film pairing electrosynthesis Succinic Acid comprises: MALEIC ANHYDRIDE is dissolved in the water is mixed with the aqueous solution that maleic acid content is 15～30 weight %, what continue is that 3～5 weight % mother liquors mix with sulfuric acid content, finally be mixed with the solution that maleic acid concentration is 10～20 weight %, this solution is added to the hydrogenation reduction that carries out maleic acid in the multipole type plate and frame electrolyzer that volts DS is 140～160V, electrolysis temperature is controlled at 60～70 ℃, 5～6 hours conduction time, electric current was 800A when electrolysis stopped, electrolysis at the end, filtered while hot is removed mechanical impurity, sent in the stirred crystallization still crystallisation by cooling 7 hours, when not being higher than 2 ℃ of coolant water temperatures, the liquid temperature do not filter, the dry product that gets, yield (is basic calculation with the maleic acid) 99.6～99.8%, total current efficient 96～98%.
The used electrolyzer of the present invention is a multipole type plate and frame electrolyzer, and electrolyzer selects for use acrylic plastering sheet material plastic welding to combine, and each trough is made up of 4～10 unit tank rooms, and every unit tank room is separated by the polypropylene plastics flitch; The electrode of electrolyzer uses bipolar connection, two blocks of tip electrodes plates at two ends are received respectively on the positive and negative electrode of power supply, the positive and negative of every electrode plate are respectively positive and negative the two poles of the earth, the total voltage that the passage that the circulation of electrolysis liquid is arranged between battery lead plate and the plate and frame bottom of electrolytic tank, power supply are added on the two end electrodes is the summation of volts lost between each counter electrode.
It is the cathode and anode electrode materials that electrolytic tank electrode is selected lead base cadmium, antimony, silver alloys for use, and weight alloy % consists of that lead is 94.9, cadmium is 2.5, antimony is 2.5, silver is 0.1.
Prepare Succinic Acid according to the invention process, its yield is 99.6～99.8%, and product purity is 99.5～99.8%, and total current efficient is 96～98%, and filtrated stock recovery set usefulness is accomplished zero emission substantially.
Four, description of drawings
Fig. 1 is the structural representation of multipole type plate and frame electrolyzer of the present invention.
Number in the figure is represented: 1-multipole type plate and frame electrolyzer, 2-battery lead plate, 3-tip electrodes plate, 4-electrolytic solution.
Five, embodiment
Illustrate especially exemplified by example in order to implement the present invention better, but be not limitation of the present invention.
Embodiment 1
The 100kg25 weight % maleic acid aqueous solution and sulfuric acid concentration are that the mother liquor 60kg of 4 weight % mixes, be mixed with the maleic acid aqueous solution (sulfur acid 2.4kg) of 15 weight %, be added to volts DS and be the hydrogenation reduction that carries out maleic acid in the multipole type plate and frame electrolyzer of 150V, 65 ℃ of electrolysis temperature controls, switched on 5.5 hours, when treating that current value reaches 800A, close electrolysis power, filtered while hot is removed mechanical impurity, sent in the stirred crystallization still crystallisation by cooling 7 hours, when the liquid temperature is not higher than 2 ℃ of coolant water temperatures, filter, wash the dry Succinic Acid 25.3kg of getting, yield is 99.7%, purity is 99.6%, and total current efficient is 97%.
Above-mentioned multipole type plate and frame electrolyzer [1] selects for use polypropylene plastics flitch plastic welding to combine, and each trough is made up of 6 unit tank rooms, and every unit tank room is separated by the polypropylene plastics plate; The electrode of electrolyzer uses bipolar system to connect, two blocks of tip electrodes plates [3] at two ends are received respectively on the positive and negative electrode of power supply, the positive and negative of every electrode plate [2] are respectively positive and negative the two poles of the earth, the total voltage that the passage that electrolysis liquid [4] circulation is arranged between the bottom of battery lead plate [2] and plate and frame electrolyzer, power supply are added on the two end electrodes is the summation of volts lost between each counter electrode.
Remove the mother liquor 67kg that adds the 100kg30 weight % maleic acid aqueous solution and sulfuric acid concentration 3 weight %, be mixed with the 20 weight % maleic acid aqueous solution (sulfur acid 2kg), volts DS 160V, 60 ℃ of electrolysis temperatures, outside switching on 5 hours, other processing step and embodiment 1 are just the same, the result gets Succinic Acid 25.3kg, yield is 99.6%, and purity is 99.8%, total current efficient 98%.
Remove the mother liquor 67kg that adds the 100kg15 weight % maleic acid aqueous solution and sulfuric acid concentration 5 weight %, prepare the 10 weight % maleic acid aqueous solution (sulfur acid 3.4kg), volts DS 140V, 70 ℃ of electrolysis temperatures, outside switching on 6 hours, other processing step and embodiment 1 are just the same, the result gets Succinic Acid 25.35kg, yield is 99.8%, and purity is 99.5%, and total current efficient is 96%.
Claims (3)
1. the method for organic no barrier film pairing electrosynthesis Succinic Acid, it is characterized in that MALEIC ANHYDRIDE is dissolved in the water and be mixed with the aqueous solution that maleic acid content is 15～30 weight %, what continue is that 3～5 weight % mother liquors mix with sulfuric acid content, finally be mixed with the solution that maleic acid concentration is 10～20 weight %, be delivered to volts DS and be the hydrogenation reduction that carries out maleic acid in the multipole type plate and frame electrolyzer of 140～160V, electrolysis temperature is controlled at 60～70 ℃, 5～6 hours conduction time, when electrolysis stops, electric current is 800A, electrolysis at the end, filtered while hot is removed mechanical impurity, send in the stirred crystallization still, crystallisation by cooling 7 hours when the liquid temperature is not higher than 2 ℃ of coolant water temperatures, filters, the dry product that gets, with the maleic acid is basic calculation, the product yield is 99.6～99.8%, and product purity 99.5～99.8%, total current efficient are 96～98%.
2. the method for organic no barrier film pairing electrosynthesis Succinic Acid according to claim 1, it is characterized in that described electrolyzer is a multipole type plate and frame electrolyzer, electrolyzer selects for use acrylic plastering sheet material plastic welding to combine, each trough is made up of 4～10 unit tank rooms, and every unit tank room is separated by the polypropylene plastics flitch; The electrode of electrolyzer uses bipolar system to connect, two blocks of tip electrodes plates at two ends are received respectively on the positive and negative electrode of power supply, the positive and negative of every electrode plate are respectively positive and negative the two poles of the earth, the total voltage that the passage that the circulation of electrolysis liquid is arranged between battery lead plate and the plate and frame bottom of electrolytic tank, power supply are added on the two end electrodes is the summation of volts lost between each counter electrode.
3. the method for organic no barrier film pairing electrosynthesis Succinic Acid according to claim 2, it is characterized in that it is the anode and cathode electrode materials that described electrolytic tank electrode is selected lead base cadmium, antimony, silver alloys for use, weight alloy % consists of that lead is 94.9, cadmium is 2.5, antimony is 2.5, silver is 0.1.
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| CN101792913B (en) * | 2010-04-01 | 2012-11-14 | 浙江工业大学 | Paired electrolytic synthesis method for producing butanedioic acid and sulfuric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2158409Y (en) * | 1993-02-25 | 1994-03-09 | 上海化工高等专科学校 | Electrolytic prodn. of butane diacid and the apparatus therefor |
| CN2517752Y (en) * | 2002-01-11 | 2002-10-23 | 孙金和 | Synthetized butanedioic acid bipolar type electrolyzer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2158409Y (en) * | 1993-02-25 | 1994-03-09 | 上海化工高等专科学校 | Electrolytic prodn. of butane diacid and the apparatus therefor |
| CN2517752Y (en) * | 2002-01-11 | 2002-10-23 | 孙金和 | Synthetized butanedioic acid bipolar type electrolyzer |
Non-Patent Citations (2)
| Title |
|---|
| 马淳安.有机电化学合成导论 1.科学出版社,2002,363. |
| 马淳安.有机电化学合成导论 1.科学出版社,2002,363. * |
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