CN104947138A - Method for electrolytic synthesis of butanedioic acid and fixed bed electrochemical reaction device - Google Patents
Method for electrolytic synthesis of butanedioic acid and fixed bed electrochemical reaction device Download PDFInfo
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Abstract
The invention provides a method for electrolytic synthesis of butanedioic acid and a fixed bed electrochemical reaction device. The method comprises the following steps: by taking a maleic anhydride solution with the mass concentration of 5-20% and a sulfuric acid solution with the mass concentration of 3-15% as an electrolyte, introducing the electrolyte into a circulating tank by virtue of a liquid storage tank; inputting the electrolyte into an electrolytic tank by virtue of a magnetic circulating pump; controlling the temperature of the electrolytic tank to be 30-80 DEG C and the current density to be 200-1000A/m<2>, and electrifying for electrolysis; after reaction, discharging the obtained reaction solution from a liquid outlet of a three-way valve, and performing cooling crystallization on the electrolyte, filtration and drying to obtain butanedioic acid; and recovering the filtrate after filtering out butanedioic acid, adding an appropriate amount of raw materials of maleic anhydride and concentrated sulfuric acid to re-prepare the filtrate into an electrolyte for cycle use. The device comprises the electrolytic tank, the liquid storage tank, the circulating tank, the heat exchanger and the magnetic circulating pump. The method and the device provided by the invention have the beneficial effects of improving the productivity and achieving energy conservation and high efficiency.
Description
Technical field
The present invention relates to a kind of method and fixed bed electrochemical reaction appts thereof of electrolytic synthesis of amber acid.
Background technology
Succinic acid (Succinic acid), has another name called succsinic acid, and molecular formula is C
4h
6o
4, be a kind of important organic synthesis raw material, be widely used in the aspects such as medicine, agricultural chemicals, synthesized polymer material, sensitive materials, food-flavoring comps, also can do sanforzing agent, oil-proofing agent, fireproofing agent, dyeing accelerant etc. in textile industry.Succeeding in developing in recent years along with biodegradable plastic poly butylene succinate (PBS), can estimate within the coming years, and the succinic acid demand as PBS main raw material will sharply increase.
Electrochemical reactor, as a kind of special chemical reactor, can be divided three classes according to structure of reactor: the electrochemical reactor of box electrochemical reactor, plate and frame electrolyzer, special construction.Box electrochemical reactor and plate and frame electrolyzer are the electrochemical reactors growing up the earliest and be most widely used, and the shortcoming of this two classes electrochemical reactor is that space-time yield is lower.Consider different electrolytic synthesis requirements, in succession developed again the electrochemical reactor of various special construction afterwards: for capillary gap reactor and the film reactor of low conductivity system; Mass transfer is good, the rotating electrode reactor of homogeneous current distribution and pump suction type reactor; The 3 D electrode reactor etc. that specific electrode surface is high.In recent years, along with the industrial application of electrochemical synthesis constantly increases, have developed some continous way electrolyzers (as CN 201520803) and combined electrolysis bath (as CN 102011136) gradually, thus increase substantially the production efficiency of electrolytic synthesis.In addition, because environmental problem becomes increasingly conspicuous, some new and effective 3 D electrode reactors for the treatment of waste water are progressively subject to the people's attention, such as CN 103910415A and CN 201265045Y, but the related application of 3 D electrode reactor in electrolytic synthesis field and patent actually rare.
So far, the method of industrial production succinic acid most competitive power take MALEIC ANHYDRIDE as the electrochemical hydrogenation method of raw material, and have developed the technology of the multiple electrochemical synthesis succinic acid such as diaphragm process, non membranous and paired electrosynthesis, as CN 2158409Y and CN2651267Y.But industrially at present generally use without diaphragm plate frame electrolyzer, this type of electrolyzer has the shortcomings such as investment of production equipment is high, electrolysis space-time yield is low, weeping is serious, is unfavorable for realizing more massive production.Fixed bed electrochemical reactor is as a kind of 3 D electrode reactor, and current efficiency is high, and space-time yield is high, floor space is little, has prospects for commercial application.If can by the electrolytic synthesis of its successful Application and succinic acid, must improve the production capacity of succinic acid significantly, economic benefit be also very considerable.
Summary of the invention
In order to solve the problems such as investment of production equipment is high, electrolysis space-time yield is low, weeping is serious in current production succinic acid process, the present invention proposes a kind of method and fixed bed electrochemical reaction appts thereof of electrolytic synthesis of amber acid.
A method for electrolytic synthesis of amber acid, comprises the following steps:
1) the original electrolytic solution in stationary tank is introduced circulation groove post-heating to 30 ~ 40 DEG C, the final concentration of wherein said original electrolytic solution is the mixed solution of the maleic acid anhydride solution of mass concentration 5-20% and the sulphuric acid soln of mass concentration 3-15%;
2) through magnetic force recycle pump by step 1) original electrolytic solution input electrolyzer after the heating that obtains;
3) temperature in electrolyzer is controlled at 30 – 80 DEG C, current density 200 – 1000A/m
2, carry out energising electrolysis to the liquid in electrolyzer, wherein the ratio of cathode and anode current density follows following formula:
J
sun/ J
cloudy=3d
2η/2d
1d (1);
D is cathode tube external diameter (mm), D is anode canister internal diameter (mm), d
1for filling the diameter (mm) of spheroid, η is filling ratio, and the size of filling ratio is relevant with the selection of filling mode; J
sunfor the current density (A/m of anode electrolytic cell
2); J
cloudyfor the current density (A/m of electric tank cathode
2);
4) reheat to 30 ~ 40 DEG C after the incomplete electrolytic solution that electrobath liquid outlet mouth flows out imports circulation groove, and make the electrolytic solution between circulation groove, electrolyzer form circulation loop through magnetic force recycle pump, repeating step 3 while circulation of elecrolyte) electrolysis is carried out to the liquid in electrolyzer, until when the liquid in electrolyzer meets following formula, reaction terminates, and obtains final electrolysis and completes liquid:
t＝0.547m/I (2)
In formula, t is electrolysis time (h), and m is that MALEIC ANHYDRIDE feeds intake quality (g), the electric current passed into when I is actual electrolysis (A);
5) by step 4) electrolysis that obtains complete liquid take out after through crystallisation by cooling, filtration, drying, obtain succinic acid.
The fixed bed electrochemical reaction appts built according to the method described in the present invention, it is characterized in that: comprise electrolyzer, stationary tank, circulation groove, heat exchanger, magnetic force recycle pump, the liquid outlet of described stationary tank is connected with described circulation groove first fluid inlet pipeline, and the liquid outlet of described circulation groove is connected with the fluid inlet pipeline of magnetic force recycle pump; Heat exchanger is arranged on circulation groove outside; The liquid outlet of magnetic force recycle pump is connected with the feed liquor cylinder fluid inlet pipeline of described electrolyzer, and pipeline between magnetic force recycle pump liquid outlet and electrolyzer fluid inlet is furnished with T-valve, and the remaining mouth of pipe of T-valve is as the liquid outlet of tapping; Described electrolyzer comprises anode canister, cathode tube, feed liquor cylinder, goes out fluid cylinder with production well, and it is outside that anode canister is enclosed within cathode tube cylindrical shell, and sealed by insulating washer at the two flange-interface place; Anode canister bottom by flange and feed liquor cylinder affixed, cathode tube top by flange with to go out fluid cylinder affixed; The described liquid outlet going out fluid cylinder is connected with the second fluid inlet pipeline of circulation groove, and is going out on the pipeline between fluid cylinder liquid outlet and described circulation groove to arrange spinner-type flowmeter; The Faradaic current of described electrolyzer is introduced by the flange-interface of anode canister and cathode tube, and conductive electric wire is connected with external power source by the brass screws at flange-interface place.
Described stationary tank is vertical with circulation groove to be placed, the parallel placement of electrolyzer, circulation groove and electrolyzer height is higher than circulation groove height, and the pipeline between stationary tank, electrolyzer, circulation groove all adopts the rubber tubing of resistance to strong acid.
Described anode canister is cylindrical barrel structure or regular polygon tubular structure, and bottom is provided with sieve aperture spreader plate; Described cathode tube is cylindrical barrel structure or regular polygon tubular structure, and cylindrical shell is net barrel structure, and mesh size is according to weighting material size adjustment, is uncovered setting above cathode tube; Fluid inlet is positioned at bottom feed liquor cylinder, and direction is parallel with electrolytic cell body and be at least one; Liquid outlet is opened in going out above fluid cylinder, and direction is parallel with electrolytic cell body and be at least one, goes out fluid cylinder top and is provided with production well and thermometer.
Described anode is one of lead, lead alloy, titanium, ti-based coating material, wherein selects plumbous as needing interpolation external bracing frame during anode; Lead alloy can select plumbous ternary, quaternary, five yuan of alloys of resistance to strong acid; Ti-based coating material selection ruthenium rhodium coatings, iridium tantalum coating, manganese bioxide coated, tin dioxide coatings etc.; Described negative electrode cylindrical shell is the material of resistance to metal such as titanium, copper, and inner packing material is one of lead, titanium, graphite, and shape is the regular geometric body that area can be regarded as; Feed liquor cylinder with go out fluid cylinder and be insulation acid resisting material.
Described negative electrode adopts net cylinder frame-type ball infill system: (1) free close-packed is filled, and is freely filled by all single obturators, carry out current delivery between single obturator by close contact in tight closely packed mode; (2) string ball or bead string type are filled, and are then freely filled by single obturator wired in series together; (3) stereoscopic graticule cartridge type is filled, and then the three-dimensional dispensing of conductive line of net cylinder inner homogeneous carries out close-packed filling.
The difference of the radius of described anode canister and cathode tube and interpole gap are 1-2mm, are less than traditional plate and frame electrolyzer, suitable with capillary gap reactor.Electrolysis voltage is better than traditional plate and frame electrolyzer equally, thus can reach the object reducing electrolysis energy consumption.
The internal diameter of described anode canister is 20 – 2000mm, and the external diameter of cathode tube is 20 – 2000mm, and the internal diameter of anode canister is greater than cathode tube external diameter, and both differences are less than 5mm; The external diameter of negative electrode packing material is 1 – 20mm; The aperture of anode canister bottom sieve aperture spreader plate and negative electrode cylindrical shell mesh is all less than the external diameter of negative electrode packing material.
Preferably, the internal diameter of described anode canister is 45mm, and the external diameter of cathode tube is 42mm, both differences are 3mm, and cylinder is high is 120mm, and DSA anode selected by anode material, cathode tube selects pure titanium material, and packing material is the titanium ball of diameter 8mm, and filling mode is that stereoscopic graticule cartridge type is filled.
Preferably, step 1) mass concentration of MALEIC ANHYDRIDE in electrolytic solution is 9.8%, h 2 so 4 concentration is the solution of 8%, electrolysis temperature is 50 DEG C, and anodic current density is 1000A/m
2.
When electrochemical reaction appts carries out electrolysis, electrolytic solution introduces circulation groove from the stationary tank of a high position, electrolytic solution reaches default electrolysis temperature carry out heat exchange in circulation groove after, then squeezed in electrolyzer by magnetic force recycle pump and carry out electrolysis, electrolytic solution flows into circulation groove again through spinner-type flowmeter after being flowed out by liquid outlet, realize cyclic electrolysis thus, after electrolysis completes, electrolytic solution is released by T-valve liquid outlet.
The invention has the beneficial effects as follows: the feature of fixed bed electrochemical reactor high space-time yield and high current efficiency is applied in electrolytic synthesis of amber acid by (1), can increase substantially production capacity, reaches energy-conservation, efficient object; (2) anode canister of fixed bed electrochemical reactor and the difference of cathode tube radius and interpole gap can be optimized to 1-2mm, suitable with capillary gap reactor.Average electrolysis voltage is better than traditional plate and frame electrolyzer 0.2-0.3V equally, thus can reach the object reducing electrolysis energy consumption; (3) ratio of the anode and cathode current density of fixed bed electrochemical reactor can change as requested, and this not only can change the mol ratio of cathode hydrogen evolution, Oxygen anodic evolution, ensures safety in production, and can also reduce the generation of side reaction, improves current efficiency.Propose formula a: J
sun/ J
cloudy=3d
2η/2d
1d, can be used for instructing practical application; (4) fixed bed electrochemical reactor is easy to assembly, and negative electrode adopts stereoscopic graticule cartridge type to fill, and both improves cathode utilization rates, and obtains uniform current density; (5) adopt mother liquid recycle technology can effectively improve electrolysis yield and current efficiency, a large amount of discharging of waste liquid can be avoided again.
Accompanying drawing explanation
Fig. 1 is the specific embodiment of the present invention schematic diagram (arrow represents liquid flow direction);
Fig. 2 is the structural representation of electrolyzer of the present invention;
Fig. 3 is the structural representation of the integral part of electrolyzer of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing
With reference to accompanying drawing 1, Fig. 2 and Fig. 3, a kind of fixed bed electrochemical reaction appts for electrolytic synthesis of amber acid, get electrolyzer 5 as electrolytic cell body, electrolyzer by anode canister 11, cathode tube 10, feed liquor cylinder 12, go out fluid cylinder 9 four part and form, go out fluid cylinder top and be provided with a production well 13, bottom anode canister, be provided with sieve aperture spreader plate 14; Cathode tube to be placed in anode canister then insulated enclosure, and cathode tube inner tight fills spherical titanium ball negative electrode; Described electrolytic cell body passes through fluid cylinder 9 and is connected with spinner-type flowmeter 2, spinner-type flowmeter is connected with circulation groove 4 by rubber tubing, be connected with magnetic force recycle pump 7 by rubber tubing bottom circulation groove, a T-valve 8 is set between magnetic force recycle pump and electrolyzer feed liquor cylinder 12, connects with rubber tubing and form a circulation loop thus.Circulation groove controls electrolyte temperature by heat exchanger 3, and electrolyte temperature carries out Real-Time Monitoring by thermometer 6, and circulation groove is connected with stationary tank 1 by rubber tubing.When described electrolyzer carries out electrolysis, electrolytic solution introduces circulation groove from the stationary tank 1 of a high position, electrolytic solution reaches default electrolysis temperature carry out heat exchange in circulation groove after, then squeezed in electrolyzer by magnetic force recycle pump and carry out electrolysis, electrolytic solution flows into circulation groove again through spinner-type flowmeter after being flowed out by drain pipe, reaches the object of cyclic electrolysis thus.
Embodiment 1 adopts deionized water to prepare 450g electrolytic solution, and the initial composition of electrolytic solution is MALEIC ANHYDRIDE mass concentration 9.8%, h 2 so 4 concentration 8%.Electrolyte temperature controls at 50 DEG C; The diameter that negative electrode fills titanium ball is 8mm; Anodic current density is 1000A/m
2, J
sun/ J
cloudy=4:1; Electrolysis turn on angle is 100% of theoretical capacity.When electrolysis starts, the electrolytic solution prepared is fed to circulation groove by high-order stationary tank, makes electrolytic solution form the loop line of circulation through magnetic force recycle pump, when temperature controls at 50 DEG C, start the electrolysis that is energized.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 38.88g, succinic acid purity 99.68%, fusing point 184.3 DEG C, electrolysis voltage 2.6 – 3.1V, current efficiency is 72.7%, and succinic acid reduction yield is 73.2%.
Embodiment 2:
Electrolyzer, electrolysis process, electrolysis temperature, current density, electrolytic solution initial composition and quality with embodiment 2, the diameter d=10mm of titanium ball negative electrode.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 34.42g, succinic acid purity 99.71%, fusing point 184.6 DEG C, electrolysis voltage 2.7 – 3.1V, current efficiency is 64.4%, and succinic acid reduction yield is 64.8%.
Embodiment 3:
Electrolyzer, electrolysis process, electrolysis temperature, current density, electrolytic solution initial composition and quality with embodiment 2, the diameter d=6mm of titanium ball negative electrode.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 39.38g, succinic acid purity 99.57%, fusing point 184.7 DEG C, electrolysis voltage 2.6 – 3.0V, current efficiency is 73.6%, and succinic acid reduction yield is 74.2%.
Embodiment 4:
Electrolyzer, electrolysis process, electrolysis temperature, titanium ball cathode diameter, electrolytic solution initial composition and quality with embodiment 2, current density, J
sun/ J
cloudy=2:1.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 39.02g, succinic acid purity 99.60%, fusing point 184.7 DEG C, electrolysis voltage 2.6 – 3.2V, current efficiency is 72.9%, and succinic acid reduction yield is 73.5%.
Embodiment 5:
Electrolyzer, electrolysis process, electrolysis temperature, titanium ball cathode diameter, electrolytic solution initial composition and quality with embodiment 2, current density, J
sun/ J
cloudy=3:1.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 38.08g, succinic acid purity 99.76%, fusing point 184.7 DEG C, electrolysis voltage 2.6 – 3.1V, current efficiency is 71.3%, and succinic acid reduction yield is 71.7%.
Embodiment 6:
Electrolyzer, electrolysis process, electrolysis temperature, titanium ball cathode diameter, electrolytic solution initial composition and quality with embodiment 2, current density, J
sun/ J
cloudy=5:1.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 39.14g, succinic acid purity 99.61%, fusing point 184.7 DEG C, electrolysis voltage 2.6 – 3.2V, current efficiency is 73.1%, and succinic acid reduction yield is 73.7%.
Embodiment 7:
Electrolyzer, electrolysis process, electrolysis temperature, titanium ball cathode diameter, electrolytic solution initial composition and quality with embodiment 2, current density, J
sun/ J
cloudy=6:1.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 35.09g, succinic acid purity 99.70%, fusing point 184.7 DEG C, electrolysis voltage 2.8 – 3.3V, current efficiency is 65.6%, and succinic acid reduction yield is 67.1%.
Embodiment 8:
Recycling Mother Solution applies mechanically test:
(1) first time mother liquid recycle electrolysis: in Example 2, the filtrate of the complete succinic acid of suction filtration is as mother liquor, adds MALEIC ANHYDRIDE 44.1g, and sulfuric acid 3g adds deionized water quantitatively to 450g, prepared electrolytic solution thus.The diameter of electrolyzer, electrolysis process, titanium ball negative electrode, current density, electrolysis temperature are with embodiment 2.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 48.12g, succinic acid purity 99.33%, fusing point 184.6 DEG C, electrolysis voltage 2.7 – 3.1V, current efficiency is 89.7%, and succinic acid reduction yield is 90.6%.
(2) second time mother liquid recycle electrolysis: the filtrate of getting first time mother liquid recycle electrolysis, as mother liquor, is added MALEIC ANHYDRIDE 44.1g, sulfuric acid 3g, added deionized water quantitatively to 450g, prepared electrolytic solution thus.The diameter of electrolyzer, electrolysis process, titanium ball negative electrode, current density, electrolysis temperature are with embodiment 1.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 49.32g, succinic acid purity 99.42%, fusing point 185.1 DEG C, electrolysis voltage 2.6-3.1V, current efficiency is 92.0%, and succinic acid reduction yield is 92.9%.
(3) third time mother liquid recycle electrolysis: the filtrate of getting the electrolysis of second time mother liquid recycle, as mother liquor, is added MALEIC ANHYDRIDE 44.1g, sulfuric acid 3g, added deionized water quantitatively to 450g, prepared electrolytic solution thus.The diameter of electrolyzer, electrolysis process, titanium ball negative electrode, current density, electrolysis temperature are with embodiment 2.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 49.49g, succinic acid purity 99.15%, fusing point 184.8 DEG C, electrolysis voltage 2.7 – 3.2V, current efficiency is 92.1%, and succinic acid reduction yield is 93.2%.
(4) the 4th mother liquid recycle electrolysis: the filtrate of getting third time mother liquid recycle electrolysis, as mother liquor, is added MALEIC ANHYDRIDE 44.1g, sulfuric acid 3g, added deionized water quantitatively to 450g, prepared electrolytic solution thus.The diameter of electrolyzer, electrolysis process, titanium ball negative electrode, current density, electrolysis temperature are with embodiment 1.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 51.35g, succinic acid purity 99.12%, fusing point 185.5 DEG C, electrolysis voltage 2.7 – 3.0V, current efficiency is 95.5%, and succinic acid reduction yield is 96.7%.
(5) the 5th mother liquid recycle electrolysis: the filtrate of getting the 4th mother liquid recycle electrolysis, as mother liquor, adds MALEIC ANHYDRIDE 44.1g, and sulfuric acid 3g adds deionized water quantitatively to 450g, prepared electrolytic solution thus.The diameter of electrolyzer, electrolysis process, titanium ball negative electrode, current density, electrolysis temperature are with embodiment 1.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 52.34g, succinic acid purity 99.21%, fusing point 185.0 DEG C, electrolysis voltage 2.6 – 3.0V, current efficiency is 97.4%, and succinic acid reduction yield is 98.6%.
(6) the 6th mother liquid recycle electrolysis: the filtrate of getting the 5th mother liquid recycle electrolysis, as mother liquor, adds MALEIC ANHYDRIDE 44.1g, and sulfuric acid 3g adds deionized water quantitatively to 450g, prepared electrolytic solution thus.The diameter of electrolyzer, electrolysis process, titanium ball negative electrode, current density, electrolysis temperature are with embodiment 2.After electrolysis terminates, electrolysis completes liquid and is placed in refrigerator, crystallization 75min under 0 DEG C of condition, filters, drying can obtain succinic acid crystal 49.72g, succinic acid purity 99.17%, fusing point 185.8 DEG C, electrolysis voltage 2.6 – 3.0V, current efficiency is 92.5%, and succinic acid reduction yield is 93.6%.
Above-mentioned seven electrolysis, the average result of six recycled electrolysis is: succinic acid purity 99.23%, fusing point 185.1 DEG C, bath voltage 2.6 – 3.0V, and current efficiency is 93.2%, and succinic acid reduction yield is 94.3%.Be not difficult to draw by above data analysis: after adopting recycled electrolysis, the quality product of succinic acid does not have obvious decline, electrolysis voltage still can maintain 2.6 – about 3.0V, current efficiency and electrolytic reduction yield all improve a lot, wherein apply mechanically yield and can reach about 95% especially, very there is prospects for commercial application.
Content described in this specification sheets embodiment is only enumerating the way of realization of inventive concept; protection scope of the present invention should not be regarded as being only limitted to the specific form that embodiment is stated, protection scope of the present invention also comprises those skilled in the art and conceives the equivalent technologies means that can expect according to the present invention.
Claims (10)
1. a method for electrolytic synthesis of amber acid, comprises the following steps:
1) the original electrolytic solution in stationary tank is introduced circulation groove post-heating to 30 ~ 40 DEG C, the final concentration of wherein said original electrolytic solution is the mixed solution of the maleic acid anhydride solution of mass concentration 5-20% and the sulphuric acid soln of mass concentration 3-15%;
2) through magnetic force recycle pump by step 1) original electrolytic solution input electrolyzer after the heating that obtains;
3) temperature in electrolyzer is controlled at 30 – 80 DEG C, current density 200 – 1000A/m
2, carry out energising electrolysis to the liquid in electrolyzer, the ratio of cathode and anode current density follows following formula:
J
sun/ J
cloudy=3d
2η/2d
1d (1)
Wherein, d is cathode tube external diameter (mm), D is anode canister internal diameter (mm), d
1for filling the diameter (mm) of spheroid, η is filling ratio, and the size of filling ratio is relevant with the selection of filling mode; J
sunfor the current density (A/m of anode electrolytic cell
2); J
cloudyfor the current density (A/m of electric tank cathode
2);
4) reheat to 30 ~ 40 DEG C after the liquid that electrobath liquid outlet mouth flows out imports circulation groove, and make the electrolytic solution between circulation groove, electrolyzer form circulation loop through magnetic force recycle pump, repeating step 3 while circulation of elecrolyte) electrolysis is carried out to the liquid in electrolyzer, until when the liquid in electrolyzer meets following formula, reaction terminates to obtain final electrolysis and completes liquid:
t＝0.547m/I (2)
In formula, t is electrolysis time (h), and m is that MALEIC ANHYDRIDE feeds intake quality (g), the electric current passed into when I is actual electrolysis (A);
5) by step 4) electrolysis that obtains complete liquid take out after through crystallisation by cooling, filtration, drying, obtain succinic acid.
2. the fixed bed electrochemical reaction appts built in accordance with the method for claim 1, it is characterized in that: comprise electrolyzer, stationary tank, circulation groove, heat exchanger, magnetic force recycle pump, the liquid outlet of described stationary tank is connected with described circulation groove first fluid inlet pipeline, and the liquid outlet of described circulation groove is connected with the fluid inlet pipeline of magnetic force recycle pump; Heat exchanger is arranged on circulation groove outside; The liquid outlet of magnetic force recycle pump is connected with the feed liquor cylinder fluid inlet pipeline of described electrolyzer, and pipeline between magnetic force recycle pump liquid outlet and electrolyzer fluid inlet is furnished with T-valve, and the remaining mouth of pipe of T-valve is as the liquid outlet of tapping; Described electrolyzer comprises anode canister, cathode tube, feed liquor cylinder, goes out fluid cylinder with production well, and it is outside that anode canister is enclosed within cathode tube cylindrical shell, and sealed by insulating washer at the two flange-interface place; Anode canister bottom by flange and feed liquor cylinder affixed, cathode tube top by flange with to go out fluid cylinder affixed; The described liquid outlet going out fluid cylinder is connected with the second fluid inlet pipeline of circulation groove, and is going out on the pipeline between fluid cylinder liquid outlet and described circulation groove to arrange spinner-type flowmeter; The Faradaic current of described electrolyzer is introduced by the flange-interface of anode canister and cathode tube, and conductive electric wire is connected with external power source by the brass screws at flange-interface place.
3. fixed bed electrochemical reaction appts as claimed in claim 2, it is characterized in that: described stationary tank is vertical with circulation groove to be placed, the parallel placement of electrolyzer, circulation groove and electrolyzer height is higher than circulation groove height, and the pipeline between stationary tank, electrolyzer, circulation groove all adopts the rubber tubing of resistance to strong acid.
4. fixed bed electrochemical reaction appts as claimed in claim 2, is characterized in that: described anode canister is cylindrical barrel structure or regular polygon tubular structure, and bottom is provided with sieve aperture spreader plate; Described cathode tube is cylindrical barrel structure or regular polygon tubular structure, and cylindrical shell is net barrel structure, and mesh size is according to weighting material size adjustment, is uncovered setting above cathode tube; Fluid inlet is positioned at bottom feed liquor cylinder, and direction is parallel with electrolytic cell body and be at least one; Liquid outlet is opened in going out above fluid cylinder, and direction is parallel with electrolytic cell body and be at least one, goes out fluid cylinder top and is provided with production well and thermometer.
5. fixed bed electrochemical reaction appts as claimed in claim 4, is characterized in that: described anode is one of lead, lead alloy, titanium, ti-based coating material, wherein selects plumbous as needing interpolation external bracing frame during anode; Lead alloy selects plumbous ternary, quaternary, five yuan of alloys of resistance to strong acid; Ti-based coating material selection ruthenium rhodium coatings, iridium tantalum coating, manganese bioxide coated, tin dioxide coatings; Described negative electrode cylindrical shell is titanium, the copper material of resistance to metal, and inner packing material is one of lead, titanium, graphite, and shape is the regular geometric body that area can be regarded as; Feed liquor cylinder with go out fluid cylinder and be insulation acid resisting material.
6. fixed bed electrochemical reaction appts as claimed in claim 4, is characterized in that: described negative electrode adopts net cylinder frame-type ball infill system.
7. fixed bed electrochemical reaction appts as claimed in claim 4, is characterized in that: the difference of the radius of described anode canister and cathode tube and interpole gap are 1-3mm.
8. fixed bed electrochemical reaction appts as claimed in claim 7, it is characterized in that: the internal diameter of described anode canister is 20 – 2000mm, the external diameter of cathode tube is 20 – 2000mm, and the internal diameter of anode canister is greater than cathode tube external diameter, and both differences are less than 5mm; The external diameter of negative electrode packing material is 1 – 20mm; The aperture of anode canister bottom sieve aperture spreader plate and negative electrode cylindrical shell mesh is all less than the external diameter of negative electrode packing material.
9. fixed bed electrochemical reaction appts as claimed in claim 8, it is characterized in that: the internal diameter of described anode canister is 45mm, the external diameter of cathode tube is 42mm, both differences are 3mm, cylinder is high is 120mm, and DSA anode selected by anode material, and cathode tube selects pure titanium material, packing material is the titanium ball of diameter 8mm, and filling mode is that stereoscopic graticule cartridge type is filled.
10. fixed bed electrochemical reaction appts as claimed in claim 1, it is characterized in that: step 1) mass concentration of MALEIC ANHYDRIDE in electrolytic solution is 9.8%, h 2 so 4 concentration is the solution of 8%, electrolysis temperature is 50 DEG C, and anodic current density is 1000A/m
2.
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| 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 |
| CN110141969A (en) * | 2019-05-27 | 2019-08-20 | 常茂生物化学工程股份有限公司 | A kind of two compartment method electrolytic separation of Bipolar Membrane anode membrane continuously prepares L-TARTARIC ACID method |
| CN113430549A (en) * | 2021-05-28 | 2021-09-24 | 浙江工业大学 | Laminated electrochemical reactor and application thereof in electrolytic synthesis of succinic acid |
| CN114836771A (en) * | 2022-04-29 | 2022-08-02 | 浙江工业大学 | Cylindrical embedded electrochemical reactor, electrolysis system and application |
| CN114959752A (en) * | 2022-04-29 | 2022-08-30 | 浙江工业大学 | Electrochemical reactor, electrochemical system and application of electrochemical reactor and system in electrolytic synthesis of 2, 6-dichlorobenzonitrile |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083871A (en) * | 1993-05-31 | 1994-03-16 | 华东化工学院 | Frame type fixed bed electrode electrolyzer and industrial application thereof |
| JPH0693484A (en) * | 1992-09-14 | 1994-04-05 | Mitsui Toatsu Chem Inc | Electrolytic reduction method |
| RU2135458C1 (en) * | 1997-12-23 | 1999-08-27 | Государственный научный центр Российской Федерации "НИОПИК" | Method of synthesis of succinic acid |
| CN1369575A (en) * | 2002-02-09 | 2002-09-18 | 厦门大学 | Process for electrically synthesizing glyoxylic acid by shell-and-tube fixed bed |
| 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 |
| CN201087216Y (en) * | 2007-09-06 | 2008-07-16 | 浙江工业大学 | Complex pole type non diaphragm device for electrolysis synthesizing succinic 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 |
| CN101407923A (en) * | 2008-10-31 | 2009-04-15 | 浙江工业大学 | Method for electrolytic synthesis of amber acid by using electrochemistry pipe reactor |
| CN101736357A (en) * | 2009-12-31 | 2010-06-16 | 浙江工业大学 | Method for continuous electrolytic synthesis of butanedioic acid |
-
2015
- 2015-05-19 CN CN201510256796.1A patent/CN104947138B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0693484A (en) * | 1992-09-14 | 1994-04-05 | Mitsui Toatsu Chem Inc | Electrolytic reduction method |
| CN1083871A (en) * | 1993-05-31 | 1994-03-16 | 华东化工学院 | Frame type fixed bed electrode electrolyzer and industrial application thereof |
| RU2135458C1 (en) * | 1997-12-23 | 1999-08-27 | Государственный научный центр Российской Федерации "НИОПИК" | Method of synthesis of succinic acid |
| CN1369575A (en) * | 2002-02-09 | 2002-09-18 | 厦门大学 | Process for electrically synthesizing glyoxylic acid by shell-and-tube fixed bed |
| 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 |
| CN201087216Y (en) * | 2007-09-06 | 2008-07-16 | 浙江工业大学 | Complex pole type non diaphragm device for electrolysis synthesizing succinic 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 |
| CN101407923A (en) * | 2008-10-31 | 2009-04-15 | 浙江工业大学 | Method for electrolytic synthesis of amber acid by using electrochemistry pipe reactor |
| CN101736357A (en) * | 2009-12-31 | 2010-06-16 | 浙江工业大学 | Method for continuous electrolytic synthesis of butanedioic acid |
Non-Patent Citations (2)
| Title |
|---|
| 叶志勇: "固定床三维电极电催化氧化深度处理氨氮废水", 《矿产综合利用》 * |
| 赵峰鸣等: "固定床电化学反应器内电解合成丁二酸的研究", 《高校化学工程学报》 * |
Cited By (8)
| 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 |
| CN110141969A (en) * | 2019-05-27 | 2019-08-20 | 常茂生物化学工程股份有限公司 | A kind of two compartment method electrolytic separation of Bipolar Membrane anode membrane continuously prepares L-TARTARIC ACID method |
| CN113430549A (en) * | 2021-05-28 | 2021-09-24 | 浙江工业大学 | Laminated electrochemical reactor and application thereof in electrolytic synthesis of succinic acid |
| CN114836771A (en) * | 2022-04-29 | 2022-08-02 | 浙江工业大学 | Cylindrical embedded electrochemical reactor, electrolysis system and application |
| CN114959752A (en) * | 2022-04-29 | 2022-08-30 | 浙江工业大学 | Electrochemical reactor, electrochemical system and application of electrochemical reactor and system in electrolytic synthesis of 2, 6-dichlorobenzonitrile |
| CN114959752B (en) * | 2022-04-29 | 2024-02-13 | 浙江工业大学 | Electrochemical reactor, system and application thereof in electrolytic synthesis of 2, 6-dichlorobenzonitrile |
| CN114836771B (en) * | 2022-04-29 | 2024-03-26 | 浙江工业大学 | Cylindrical embedded electrochemical reactor, electrolysis system and application |
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