CN101817714B - Electrolysis method for hydrolyzing esters - Google Patents
Electrolysis method for hydrolyzing esters Download PDFInfo
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- CN101817714B CN101817714B CN2010101525511A CN201010152551A CN101817714B CN 101817714 B CN101817714 B CN 101817714B CN 2010101525511 A CN2010101525511 A CN 2010101525511A CN 201010152551 A CN201010152551 A CN 201010152551A CN 101817714 B CN101817714 B CN 101817714B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses an electrolysis method for hydrolyzing esters, which adopts an electrolytic hydrolysis device consisting of a cation exchange membrane, an anion exchange membrane and electrodes to perform hydrolysis on the esters. The method comprises the following steps of: a. pumping electrolyte into an anode chamber and a cathode chamber, and pumping ester solution into a hydrolysis chamber to perform circulation; b, applying direct current between a positive electrode and a negative electrode to perform electrolysis on water; and c, hydrolyzing the esters in the hydrolysis chamber by hydrogen ions and hydroxide ions to generate corresponding acids and alcohols. The electrolysis method performs catalysis on the hydrolysis of the esters by electrolyzing the water to directly obtain clear acid and alcohol products without adding any catalysts; besides, the method has a high material utilization ratio, no high-salt wastewater discharge and simple and safe process flows, and can be widely applied to production.
Description
Technical field
The invention belongs to the chemical production field in the chemical industry, be specifically related to a kind of method of ester-type hydrolysis.
Background technology
Ester-type hydrolysis is the important chemical reaction of a class, has very widely in many industries such as petrochemical industry, pharmacy, chemical fibre, agricultural chemicals and uses.At present mostly the mode of ester-type hydrolysis is to be undertaken by catalyzer, and catalyzer commonly used has alkali, amine, salt, enzyme, acid etc.The processes such as the use of catalyzer, regeneration are brought many inconvenience to production, such as complicated, a large amount of generation of waste materials of equipment corrosion, flow process etc., do not meet the requirement of cleaner production recycling economy.
Be that the reaction of 2-KLG and methyl alcohol is generated methyl 2-keto-L-gulonate such as ascorbic production process, and then hydrolysis generate vitamins C and methyl alcohol.In production reality, the hydrolysis of methyl 2-keto-L-gulonate can use sulfuric acid or sodium bicarbonate to make catalyzer at present.When using sulfuric acid to make catalyzer, the conversion of methyl 2-keto-L-gulonate catalytic hydrolysis is obtained vitamins C, but sulfuric acid is very large on quality and the yield impact of product, equipment corrosion is also very serious, removes the process of sulfuric acid and also wants a large amount of vitriol of by-product; And in the acid catalyzed production process speed of response slowly, must in time reaction product be separated, otherwise can cause product yield lower.When using sodium bicarbonate as catalyzer, its product quality, yield, equipment corrosion situation all can be greatly improved, but hydrolysate can only obtain ascorbic sodium salt, need further sodium salt to be changed into acid with the ion conversion, high-salt wastewater is finally discharged in sodium bicarbonate and acid that whole process need consumption is a large amount of.
The catalytic hydrolysis of methyl acetate makes spent ion exchange resin cook solid acid catalyst usually at present, can directly obtain purer acid and pure, and has realized the timely separation of catalyzer.But also there are the filling, regeneration of catalyzer, the problem such as aging, still have a certain amount of discharging of waste liquid, the follow-up manipulation of regeneration that also needs.
Along with the development of science and technology, do not need the direction of people's research of clean hydrolysis process of catalyzer.Gallop etc. such as Zhejiang University's material and pharmaceutical engineering institute of chemical engineering institute deer and in " Non-Catalyzed Hydrolysis of Phenylacetate in High-Temperature Liquid Water reaction kinetics " literary composition of publishing " chemical reaction engineering and technique " in September, 2004, to mention, can be used as catalyzer after water ionizes under High Temperature High Pressure uses, this moment, the ionization constant of water enlarged markedly, hydrogen ion and hydroxide ion quantity also can increase, and have the function of acid-base catalysis; And catalyzer is made in water ionization, can not produce any pollution to environment, thereby be a kind of up-and-coming friendly process.But its processing condition are higher, pressure must more than the 15Mpa, temperature between 152 ℃～216 ℃, all very high to the requirement of equipment and safety, be difficult for being widely used in producing.
Summary of the invention
The technical problem that the present invention solves provides a kind of method of not bringing any impurity, operating process ester-type hydrolysis simple, that also can be widely used in producing into.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of electrolysis process for ester-type hydrolysis, the method adopts the electrolysis hydrolysis device to finish the hydrolysis of ester class, described electrolysis hydrolysis device comprises electrode and the hydrolysis unit that is arranged alternately and pole plate between electrode, hydrolysis unit comprises cationic exchange membrane and anion-exchange membrane, the work area of electrolysis hydrolysis device comprises anolyte compartment, cathode compartment and hydrolysis chamber, and carries out according to the following steps:
A. electrolytic solution is pumped into respectively anolyte compartment and cathode compartment, ester class solution pump enters to be hydrolyzed the chamber, circulates respectively;
B. behind to be recycled the stablizing, between anode and two electrodes of negative electrode, apply direct supply, carry out the electrolysis of water; Can collect hydrogen and the oxygen of paying product and process this moment;
C. ester by hydrogen ion and hydroxide ion hydrolysis, generates corresponding acid and pure in the hydrolysis chamber, is recycled to device and separates outward, obtains required acid.
The improvement of electrolysis hydrolysis device of the present invention is: described electrolysis hydrolysis device comprises one group of hydrolysis unit and pair of electrodes.Be arranged on two hydrolysis unit between the electrode and can also be two groups or more, be provided with a pole plate between the adjacent hydrolysis unit.
Another kind of structure of the present invention is: the method adopts the electrolysis hydrolysis device to finish the hydrolysis of ester class, described electrolysis hydrolysis device comprises electrode and the cationic exchange membrane that is arranged alternately and pole plate between electrode, the work area of described electrolysis hydrolysis device comprises anolyte compartment and hydrolysis chamber, and the method is carried out according to the following steps:
A. electrolytic solution is pumped into the anolyte compartment, ester class solution pump enters to be hydrolyzed the chamber, circulates;
B. behind to be recycled the stablizing, between anode and two electrodes of negative electrode, apply direct supply, carry out the electrolysis of water;
C. ester by hydrogen ion and hydroxide ion hydrolysis, generates corresponding acid and pure in the hydrolysis chamber.
The improvement of electrolysis hydrolysis device described in the said structure of the present invention is: described electrolysis hydrolysis device comprises a cationic membrane and pair of electrodes.Be arranged on two cationic exchange membranes between the electrode and can also for more than two or two, be provided with a pole plate between the neighboring cation exchange membrane.
The improvement of described electrolytic solution is: described electrolytic solution is any one in water, acid, alkali, the salts solution.
Principle of work of the present invention is as described below:
During electrolysis hydrolysis device work of the present invention, at first electrolytic solution is pumped into anolyte compartment and cathode compartment, ester class solution pump enters to be hydrolyzed the chamber, connects direct supply again between two battery lead plates.This moment, water was become oxygen and hydrogen ion by electrolytic oxidation in the anolyte compartment, and the direct discharger of oxygen, hydrogen ion then enter the hydrolysis chamber by cationic exchange membrane; In cathode compartment, water is become hydrogen and hydroxide ion by electrolytic reduction, and the direct discharger of hydrogen, hydroxide ion then enter the hydrolysis chamber by anion-exchange membrane.Be hydrolyzed indoorly, ester is hydrolyzed under the effect of hydrogen ion and hydroxide ion, generates corresponding acid and pure discharger, carries out subsequent disposal.Must in time the hydrolyzed solution moving-out device be separated in the hydrolytic process, and replenish the indoor ester solution of hydrolysis in good time.
Owing to adopted above technical scheme, the invention technological progress is:
The present invention adopts in the water electrolysis process hydrogen ion that produces respectively in the anode chamber and the cathode chamber and hydroxide ion as catalyzer, promotes the hydrolysis of ester, and the reactive behavior of hydrogen ion and hydroxide ion is far above water molecules.Adopt method of the present invention both to improve hydrolysis reaction speed, can directly obtain required acid again, and do not bring any impurity into.
Present method combines the advantage of acid catalysis and base catalysis in the situation of not adding catalyzer, directly obtain required acid product, production process is simple and safe, has not only saved the consumption of soda acid, but also need not follow-up waste treatment stream journey, greatly save production cost, simplified technical process.And can implement the present invention at normal temperatures and pressures, its material utilization is high, and without any pollutant emission, the technique environmental protection can be widely used in producing, and meets the idea of development of recycling economy.
Description of drawings
Fig. 1 is the structural representation of electrolysis hydrolysis device in the embodiment of the invention 1;
Fig. 2 is the structural representation of electrolysis hydrolysis device in the embodiment of the invention 2.
Wherein: 1. positive plate, 2. negative plate, 3. cationic exchange membrane, 4. anion-exchange membrane, 5. anolyte compartment, 6. hydrolysis chamber, 7. cathode compartment.
Embodiment
Below in conjunction with specific embodiment the present invention is described in more detail.
The present invention is applied to ascorbic production, and the electrolysis hydrolysis device comprises cationic exchange membrane 3, anion-exchange membrane 4 and pair of electrodes, and it arranges order and is followed successively by positive plate 1, cationic exchange membrane 3, anion-exchange membrane 4 and negative plate 2; Three conversion zones are arranged: anolyte compartment 5, cathode compartment 7 and hydrolysis chamber 6 in this electrolysis hydrolysis device; Being anolyte compartment 5 between positive plate 1 and the cationic exchange membrane 3 wherein, is cathode compartment 7 between negative plate 2 and the anion-exchange membrane 4, and the zone between the anion and cation exchange membrane is hydrolysis chamber 6.
After whole plant installs, at first water is pumped in anolyte compartment and the cathode compartment, methyl 2-keto-L-gulonate pumps into the hydrolysis chamber, connects direct supply behind to be recycled the stablizing between two battery lead plates.This moment, water was become oxygen and hydrogen ion by electrolytic oxidation in the anolyte compartment, and the direct discharger of oxygen, hydrogen ion then enter the hydrolysis chamber by cationic exchange membrane; In cathode compartment, water is become hydrogen and hydroxide ion by electrolytic reduction, and the direct discharger of hydrogen, hydroxide ion then enter the hydrolysis chamber by anion-exchange membrane; Under hydrogen ion and hydroxide ion effect, finish hydrolysis at the indoor methyl 2-keto-L-gulonate of hydrolysis, directly generate vitamins C and methyl alcohol, then with the circulation discharger, carry out subsequent disposal.
Adopt present method not only to avoid using sodium bicarbonate, and omitted follow-up ascorbic ion exchange process that sodium ascorbate is changed into, omitted resin, and the bronsted lowry acids and bases bronsted lowry used of resin regeneration; Also reduced simultaneously the discharging of high-salt wastewater, reached simplification of flowsheet, saved the purpose of cost, environmental protection.
The present embodiment difference from Example 1 is that pumping into the indoor solution of hydrolysis is methyl acetate, and methyl acetate is hydrolyzed under the effect of hydrogen ion and hydroxide ion and generates acetic acid and methyl alcohol.
Its hydrolysis electrolyzer as shown in Figure 2.The present invention is used for the hydrolysis of methyl-formiate, its electrolysis hydrolysis device comprises a cationic exchange membrane 3 and pair of electrodes, it arranges order and is followed successively by positive plate 1, cationic exchange membrane 3 and negative plate 2, the work area of this electrolysis hydrolysis device is anolyte compartment 5 and hydrolysis chamber 6, be to be anolyte compartment 5 between positive plate 1 and the cationic exchange membrane 3, be hydrolysis chamber 6 between negative plate 2 and the cationic exchange membrane 3.
After equipment installs, water is pumped into the anolyte compartment, the methyl-formiate solution pump enters to be hydrolyzed the chamber, behind to be recycled the stablizing, applies direct supply between anode and two electrodes of negative electrode.This moment, water was become oxygen and hydrogen ion by electrolytic oxidation in the anolyte compartment, and the direct discharger of oxygen, hydrogen ion then enter the hydrolysis chamber by cationic exchange membrane; Indoor in hydrolysis, because negative plate is applied with voltage, water can be electrolyzed to produce hydrogen and hydroxide ion, and the direct discharger of hydrogen, methyl-formiate then are hydrolyzed under hydroxide ion and hydrionic effect, generates formic acid and methyl alcohol.
Claims (4)
1. electrolysis process that is used for ester-type hydrolysis, it is characterized in that: the method adopts the electrolysis hydrolysis device to finish the hydrolysis of ester class, described electrolysis hydrolysis device comprises electrode and the hydrolysis unit that is arranged alternately and pole plate between electrode, hydrolysis unit comprises cationic exchange membrane and anion-exchange membrane, the work area of described electrolysis hydrolysis device comprises anolyte compartment, cathode compartment and hydrolysis chamber, and the method is carried out according to the following steps
A. water is pumped into anolyte compartment and cathode compartment, ester class solution pump enters to be hydrolyzed the chamber, circulates respectively;
B. between anode and two electrodes of negative electrode, apply direct supply, carry out the electrolysis of water;
C. ester is entered hydrogen ion and the hydroxide ion hydrolysis that is hydrolyzed the chamber from anolyte compartment and cathode compartment in the hydrolysis chamber, generates corresponding acid and pure.
2. a kind of electrolysis process for ester-type hydrolysis according to claim 1, it is characterized in that: described electrolysis hydrolysis device comprises one group of hydrolysis unit and pair of electrodes.
3. electrolysis process that is used for ester-type hydrolysis, it is characterized in that: the method adopts the electrolysis hydrolysis device to finish the hydrolysis of ester class, described electrolysis hydrolysis device comprises electrode and the cationic exchange membrane that is arranged alternately and pole plate between electrode, the work area of described electrolysis hydrolysis device comprises anolyte compartment and hydrolysis chamber, and the method is carried out according to the following steps
A. water is pumped into the anolyte compartment, ester class solution pump enters to be hydrolyzed the chamber, circulates;
B. between anode and two electrodes of negative electrode, apply direct supply, carry out the electrolysis of water;
C. ester enters the hydrogen ion hydrolysis of hydrolysis chamber by hydroxide ion with from the anolyte compartment in the hydrolysis chamber, generates corresponding acid and pure.
4. a kind of electrolysis process for ester-type hydrolysis according to claim 3, it is characterized in that: described electrolysis hydrolysis device comprises a cationic exchange membrane and pair of electrodes.
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| CN2010101525511A CN101817714B (en) | 2010-04-22 | 2010-04-22 | Electrolysis method for hydrolyzing esters |
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| CN2010101525511A CN101817714B (en) | 2010-04-22 | 2010-04-22 | Electrolysis method for hydrolyzing esters |
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| CN101817714B true CN101817714B (en) | 2013-04-03 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261817A (en) * | 1997-06-30 | 2000-08-02 | 电合成公司 | Electrochemical methods for recovery of ascorbic acid |
| CN1618784A (en) * | 2004-06-28 | 2005-05-25 | 烟台大学 | Method of producing formic acid using packed bed electrodialysis |
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- 2010-04-22 CN CN2010101525511A patent/CN101817714B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261817A (en) * | 1997-06-30 | 2000-08-02 | 电合成公司 | Electrochemical methods for recovery of ascorbic acid |
| CN1618784A (en) * | 2004-06-28 | 2005-05-25 | 烟台大学 | Method of producing formic acid using packed bed electrodialysis |
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Address after: 050099 No. 6, middle Mill Road, circular chemical industry park, Hebei, Shijiazhuang Patentee after: HEBEI XIETONG ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Address before: 050035 No. 55 Kunlun street, hi tech Development Zone, Hebei, Shijiazhuang Patentee before: Shijiazhuang Development Zone Desai Chemical Technology Co., Ltd. |
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Effective date of registration: 20200214 Address after: 050099, No. 6, Shek Lian street, circular chemical industry park, Shijiazhuang, Hebei Patentee after: Hebei Cooperative Environment Technology Co., Ltd. Address before: 050099 No. 6, middle Mill Road, circular chemical industry park, Hebei, Shijiazhuang Patentee before: HEBEI XIETONG ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. |