CN1369575A - Process for electrically synthesizing glyoxylic acid by shell-and-tube fixed bed - Google Patents
Process for electrically synthesizing glyoxylic acid by shell-and-tube fixed bed Download PDFInfo
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- CN1369575A CN1369575A CN02102974A CN02102974A CN1369575A CN 1369575 A CN1369575 A CN 1369575A CN 02102974 A CN02102974 A CN 02102974A CN 02102974 A CN02102974 A CN 02102974A CN 1369575 A CN1369575 A CN 1369575A
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Abstract
A process for electrically synthesizing glyoxylic acid by tube-array fixed bed includes loading the over-saturated oxalic acid solution into cathode tank, regulating the temp of cathode tank and cathode chamber to 15-30 deg.C, pumping said solution into cathode chamber by magnetic pump, adding a acid solution to anode tank, pumping it into anode chamber by magnetic pump, regualting cahtode's electric potential until the concentration of glyoxylic acid in cathode liquid is 4-8 wt.%, discharge and crystallizing. Its advantages are high time-spece output rate up to 0.12 Kg/Lh, short reaction time (1.5h), and saving energy.
Description
The present invention relates to a kind of manufacture method of oxoethanoic acid, especially utilize the production technique of electrically synthesizing glyoxylic acid by shell-and-tube fixed bed.
Oxoethanoic acid is the simplest aldehydic acid, has two kinds of character of aldehyde and acid concurrently, is a kind of important chemical material and chemical reagent.Oxoethanoic acid can be used as the intermediate of fine chemical products such as vanillin food grade,1000.000000ine mesh, wallantoin; The linking agent that also is used for water-borne coatings, Polymer Synthesizing process etc.Development along with oxoethanoic acid derived product market, demand to oxoethanoic acid increases, only the present annual requirement of China between 4500～5000t (with 40% oxoethanoic acid densitometer, below all with), and domesticly have only several families chemical plant to produce, ultimate production is about 700t/a, causes the domestic market disparities between supply and demand very outstanding, and price raises up.20% aqueous glyoxylic acid price is 10,000 yuan/t, 30% be 1.6 ten thousand yuan/t, 40% be 2.2 ten thousand yuan/t (once once up to 50,000 yuan/t) thus the production of oxoethanoic acid and application have broad prospects.
Method for preparing glyoxalic acid has chemical method and electrochemical process two big classes at present.Oxalic acid electrochemical reduction legal system oxoethanoic acid, have that raw material is cheap and easy to get, flow process is simple, by product is few, product separate easily, quality height, reaction conditions gentleness, cost are low, do not have characteristics such as " three wastes " pollution, investigator's concern is more rising production method extremely both at home and abroad.
But the defective of oxalic acid electrochemical reduction legal system oxoethanoic acid shows that mainly the equipment space-time yield is low.Theoretically, the solubleness of oxalic acid in water is little, itself is again more weak ionogen, its aqueous conductive ability, so this electrolytic process can't carry out under higher concentration and bigger current density, the equipment space-time yield is low; On technology, the technology tradition of existing industrial production, pilot scale or laboratory study all adopts dull and stereotyped reactor.For example, traditional oxalic acid cathode diaphragm electrolytic process, generally when reaching greater than 4wt% oxoethanoic acid discharging concentration, reaction time consumption 3.5～15h; Someone attempts adding additive in catholyte make moderate progress the equipment space-time yield, but do not tackle the problem at its root.Though pairing electrolytic synthesis energy consumption is low, equipment space-time yield height, its anolyte and catholyte are fled mutually, cause quality product to worsen.
The CN1322859 patent application discloses the method that a kind of paired electrolysis prepares oxoethanoic acid, in electrolytic process, adopt cathode and anode to be the electrolyzer of fixed bed, in electrolytic process, adopt the mode electrolysis of time-dependent current (density) simultaneously according to the content of oxoethanoic acid in the electrolytic solution, fixed bed anode and cathode thickness scope are 4～50mm, optimum thickness range is 10～30mm, the average apparent current density reaches as high as 4500mA/m, and optimum average apparent current density is 1000～3000mA/m.
The present invention is intended on the basis of traditional plate electrode electrosynthesis oxoethanoic acid, developing with gassing porous graphite electrode (or DSA) is double anode, with add between pure lead pipe and/or lead pipe galvanized wire or lead button (also available pure or scribble catalyzer graphite and or carbon tube between add graphite granule) be the electrically synthesizing glyoxylic acid by shell-and-tube fixed bed technology of cathodic electricity reduction oxoethanoic acid.
The present invention adopts calandria type fixed bed device, adopts electrosynthesis technology, and its processing step is:
1) the supersaturation oxalic acid solution is added calandria type fixed bed cathode can;
2) temperature of adjusting cathode can and calandria type fixed bed cathode compartment is 15～30 ℃, is preferably 20～25 ℃;
3) the supersaturation oxalic acid solution in the cathode can is sent into cathode compartment by magnetic drive pump;
4) in anode slot, add the acid solution of 10wt%～36wt%, be preferably 12wt%～20wt%;
5) acid solution in the anode slot is sent into the anolyte compartment by magnetic drive pump;
6) the conditioned reaction cathode potential be-1.2～-1.4V
Discharging when 7) the control electrolysis time makes catholyte oxoethanoic acid concentration reach 4wt%～8wt%;
8) the discharging Crystallization Separation is gone out oxalic acid, promptly get the product glyoxylic acid solution after concentrating.
The present invention is owing to utilized and add the electrode particle between electrode tube or electrode tube and be negative electrode, and directly with tubulation control reaction electrode temperature, the electrosynthesis oxoethanoic acid technology under thereby the realization high current density is apparent, improve electrosynthesis oxoethanoic acid space-time yield greatly, shortened the reaction times, the general only about 0.03Kg/Lh of the average space-time yield of one pole parallel plate reactor, reach 4wt% with top discharge concentration, electrolysis time 3.5～15h, and this reactor can reach 0.12Kg/Lh, reach the only about 1.5h of the required electrolysis time of discharging concentration, make continuous industry production become possibility; Compare with traditional dull and stereotyped reactor, but do not increase the volume of electrolyzer; Because use tubulation control reaction temperature, tubulation itself is again electrode, thereby can make things convenient for temperature of reaction on the control electrode, with the maintenance electrode surface than low reaction temperatures, in time remove reaction heat, thereby guaranteed current efficiency; In addition, the present invention has made full use of low-temperature receiver, and promptly the temperature of catholyte needn't be controlled too lowly in the cathode can, has increased the temperature of electrolytic solution, can reduce groove and press, thereby reach energy-conservation effect.
Accompanying drawing is an electrically synthesizing glyoxylic acid by shell-and-tube fixed bed process unit embodiment synoptic diagram.
Embodiment 1: as shown in the figure, the present invention can adopt 2 two kinds of electrolyzers of calandria type fixed bed cathode compartment 3 of polyvinyl chloride panel system and double anode chamber.Be separated with strong-acid type cation exchange membrane 4 in the middle of the chamber, yin, yang the two poles of the earth.Cathode material: adopt pure lead pipe and or lead pipe between add galvanized wire or lead button, also available pure or scribble catalyzer carbon tube and or carbon tube between add graphite granule.Anode material: adopt gassing porous graphite plate or DSA.The cathode can 9 supersaturation oxalic acid solution of packing into can be respectively 25 and 20 ℃ by the temperature that temperature controlling system 10 is regulated cathode can 9 and calandria type fixed bed cathode compartment 3, and the supersaturation oxalic acid solution is sent into cathode compartment 3 by magnetic drive pump 5.Adorn the hydrochloric acid soln of 14Wt% in the anode slot 6, and send into the anolyte compartment by magnetic drive pump 15; When using hydrochloric acid soln, available absorption liquid bottle 8 absorbs chlorine by gas-liquid separator 7 alkali lye.Temperature of reaction is shown that by thermopair 14 electric current of reaction cathode potential and reaction is regulated by salt bridge 11, saturated KC1 solution bottle 12 by reference mercurous chloride electrode 13, and the reaction cathode potential transfers to-1.3V.Discharging when the catholyte oxoethanoic acid reaches 5.5wt% concentration, electrolysis time 1.5h, Crystallization Separation goes out oxalic acid, obtains about 20wt% glyoxylic acid solution after concentrating, and product is slightly yellow.
Embodiment 2: technology is identical with embodiment 1, its difference is that acid solution also can adopt sulphuric acid soln, and concentration is 20wt%, and the temperature of cathode can and calandria type fixed bed cathode compartment is adjusted to 20 and 25 ℃ respectively, the reaction cathode potential transfers to-1.4V, can adopt absorption liquid bottle and gas-liquid separator.Discharging when the catholyte oxoethanoic acid reaches 6wt% concentration, electrolysis time is about 2h.
Claims (4)
1, the production technique of electrically synthesizing glyoxylic acid by shell-and-tube fixed bed adopts calandria type fixed bed device, it is characterized in that its processing step is:
1) the supersaturation oxalic acid solution is added calandria type fixed bed cathode can;
2) temperature of adjusting cathode can and calandria type fixed bed cathode compartment is 15～30 ℃;
3) the supersaturation oxalic acid solution in the cathode can is sent into cathode compartment by magnetic drive pump;
4) in anode slot, add the acid solution of 10wt%～36wt%;
5) acid solution in the anode slot is sent into the anolyte compartment by magnetic drive pump;
6) the conditioned reaction cathode potential be-1.2～-1.4V;
Discharging when 7) the control electrolysis time makes catholyte oxoethanoic acid concentration reach 4wt%～8wt%;
8) the discharging Crystallization Separation is gone out oxalic acid, promptly get the product glyoxylic acid solution after concentrating.
2, the production technique of electrically synthesizing glyoxylic acid by shell-and-tube fixed bed as claimed in claim 1, the temperature that it is characterized in that regulating cathode can and calandria type fixed bed cathode compartment is 20～25 ℃.
3, the production technique of electrically synthesizing glyoxylic acid by shell-and-tube fixed bed as claimed in claim 1, the acid solution that it is characterized in that adding in the anode slot is 12wt%～20wt%.
4, the production technique of electrically synthesizing glyoxylic acid by shell-and-tube fixed bed as claimed in claim 1 is characterized in that the acid solution that adds is hydrochloric acid soln or sulphuric acid soln in anode slot.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021029741A CN1238564C (en) | 2002-02-09 | 2002-02-09 | Process for electrically synthesizing glyoxylic acid by shell-and-tube fixed bed |
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| CNB021029741A CN1238564C (en) | 2002-02-09 | 2002-02-09 | Process for electrically synthesizing glyoxylic acid by shell-and-tube fixed bed |
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| CN1369575A true CN1369575A (en) | 2002-09-18 |
| CN1238564C CN1238564C (en) | 2006-01-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947138A (en) * | 2015-05-19 | 2015-09-30 | 浙江工业大学 | Method for electrolytic synthesis of butanedioic acid and fixed bed electrochemical reaction device |
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2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104947138A (en) * | 2015-05-19 | 2015-09-30 | 浙江工业大学 | Method for electrolytic synthesis of butanedioic acid and fixed bed electrochemical reaction device |
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