CN1232091A - Electrolytic bath for pollution-free electrolytic synthesis of L-cysteine hydrochloride and glyoxalic acid - Google Patents
Electrolytic bath for pollution-free electrolytic synthesis of L-cysteine hydrochloride and glyoxalic acid Download PDFInfo
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- CN1232091A CN1232091A CN 98113503 CN98113503A CN1232091A CN 1232091 A CN1232091 A CN 1232091A CN 98113503 CN98113503 CN 98113503 CN 98113503 A CN98113503 A CN 98113503A CN 1232091 A CN1232091 A CN 1232091A
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Abstract
An electrolyzer for synthesizing L-cysteine hydrochloride and glyoxylate by non-pollution electrolysis features that industrial sulfuric acid is used as anode liquid and the L-cysteine hydrochloride, glyoxylate or gluconic acid are generated from cathode while oxygen is released from anode. During electrolysis, pollutant and corrosive chlorine gas are not generated. The electrolyzer is composed of modified metallic anode, perforated plate frame, lead plate as cathode, per-fluoro ion exchange membrane and clamping plates. It features high yield (90% for glyoxylate), high current efficiency (60-95%), and low voltage (3.2-4.0V).
Description
The invention belongs to the organic electrolysis industrial circle.
The present electrolyzer of domestic production L-cysteine hydrochloride, employing be that hydrochloric acid is made anolyte, anode adopts graphite material, emits chlorine in the production process, contaminate environment and etching apparatus.Because electrolytic solution is subjected to the restriction of tank room thickness from the input of tank room side, it is all very little to import and export bore, cause flow of electrolyte very little, thereby mass transfer is poor, and the actuating current during electrolysis just is restricted, so output is less, current efficiency is lower.The external electrolyzer that similar structure is also arranged in salt electrolysis industry, but its trough is only applicable to self-circulation or the less system of flow, there is no the baffling bar that suggested being used to of this groove supported the ionic membrane porous plate and be used to increase flow velocity.Literature search shows that the electrolyzer that does not still have this kind structure both at home and abroad is used for above-mentioned organic electrolysis synthetic patent report.
The present invention relates to a kind of electrolyzer that pollution-free method is produced the L-cysteine hydrochloride that can be used for, specifically it is that a kind of back side input type has sheet frame filter type structure, and adopts modified metal anodic industrialization electrolyzer.Can be used for the electrolysis system that anolyte is a sulphuric acid soln.This system is only emitted the oxygen that does not produce pollution in process of production, thus at big pump circulation flow, big current density, under the higher L-Gelucystine concentration conditions, electrolytic reduction is produced the L-halfcystine.
The object of the present invention is to provide the synthetic of electrolysis of a kind of L-of being applicable to cysteine hydrochloride and oxoethanoic acid, and be suitable for the electrolyzer of suitability for industrialized production.This kind electrolyzer also has a kind of versatility, can be suitable for the electrolytic synthesis (as the electrolytic oxidation of glucose, the electrolytic reduction of oxalic acid etc. and other organic electrolytic process) of multiple organic compound, and to having barrier film or diaphragm-free electrolysis process that good versatility is arranged.
Cell construction pattern of the present invention is the filter press type, has abandoned the pattern of the more unit groove side input of present application, and adopts the pattern of back side input; Simultaneously, electrolyzer is divided into anode unit and cathode electrode unit, thereby can be very conveniently with anode unit and cathode electrode unit combination, as plate-and-frame filter press, form an electrolyzer group, the electrolyzer floor space is significantly reduced, also make electrolysis procedure more concentrated, load and unload easylier, and do not leak.
Accompanying drawing 1 is for electrolyzer profile and electrode solution flow to synoptic diagram, and accompanying drawing 2 has the inside assembly drawing of barrier film coventional type electrolyzer, accompanying drawing 3, coventional type anode unit and cathode electrode unit, accompanying drawing 4, energy-saving anode unit, among the accompanying drawing 1-4, each numeral: 1,1 ' external splint, 2 inner splints, 4 negative plates, 4 ' positive plate, 5 energy-saving no porous board slot frames, 6 coventional types have porous board slot frame pattern I, and 6 ' coventional type has porous board slot frame pattern II, 7 catholyte liquid collecting ducts, 7 ' anolyte liquid collecting duct, 8 anolytes shunting duct, 8 ' catholyte shunting duct, 9 support the baffling bar, and 10 have the porous plate tank room, 10 ' no porous plate tank room, 11 shunting grooves, 11 ' liquid collecting groove, 13 anolytes inlet, the outlet of 13 ' anolyte, 14 pads, 15 ion-exchange membranees, 16 catholyte imports, the outlet of 16 ' catholyte.
Cell construction such as following
Anode unit: dual mode, a kind of is the middle groove frame (5) that is, shell tool, clamp with positive plate (4 ') outside, is Energy-saving, be characterized in that positive plate can to greatest extent near ionic membrane, reduce groove and press; Another kind places for positive plate (4 ') The centre, shell tool, clamp with groove frame (6,6 ') outside, is plain edition, and it is better that it is suitable for cathode and anode liquid electric conductivity Situation.
Cathode electrode unit: the centre is minus plate (4), shell tool, and clamp with groove frame (6,6 ') on both sides.
The unitary combination of cathode and anode is very simple, to septate electrolyzer, isolate the cathode and anode unit with the ionic membrane that has pad to clamp, i.e. combination is finished, be: anode unit-ion-exchange membrane-cathode electrode unit-ion-exchange membrane-anode unit ...-anode unit, tightly clamp with clamping plate the outside again, promptly forms an ion-exchange membrane electrolyzer group.For undivided cell, then simpler, clamp an energy-saving framework (5) with a positive plate and a negative plate, it is positive plate-energy-saving framework-negative plate-energy-saving framework ...-positive plate, equally, outermost is tightly clamped with clamping plate, promptly forms a undivided cell.
Electrolyzer of the present invention adopts the back side I/O mode of electrolytic solution.This kind mode can increase groove electrolyte inside flow to greatest extent, electrolytic solution flow velocity on electrode is increased, can not only make the turbulence of electrolytic solution bigger, improve the mass transfer situation, the polarization of minimizing on electrode, and make and can be had more by electrolysis raw material thing that multimachine can carry out effective collision with electrode, thereby improve current efficiency, reduce side reaction and take place.
Electrolytic solution is imported, output is as described below:
To diaphragm sell is arranged: anolyte is extracted out from the anode circulation groove with pump, squeeze into external splint (1 ') inlet, enter anode electrolytic cell liquid shunting duct (8), through groove frame (6,6 ') ingress enters the anolyte compartment, enter anolyte liquid collecting duct (7 ') through the baffling passage from groove frame (6,6 ') exit, flow back in the anode circulation groove through external splint (1 ') exit by the liquid collecting duct again.
Catholyte is extracted out from the negative electrode circulation groove by pump, squeeze into electrolyzer inner cathode shunting duct (8 ') via external splint (1) inlet, through groove frame (6,6 ') entering the mouth enters cathode compartment, flow through the baffling passage from groove frame (6,6 ') exit leaves cathode compartment and enter catholyte liquid collecting duct (7), after the catholyte circulation groove is flowed back in external splint (1) outlet.
To undivided cell: because this kind electrolyzer need not barrier film, then only an import and an outlet need be arranged, promptly with pump by extracting electrolytic solution in the circulation groove out, enter shunting duct (8 ') in the groove from external splint (1) ingress, enter tank room through groove frame (5) ingress, enter liquid collecting duct (7) through the baffling passage from groove frame (5) outlet again, after circulation groove is got back in external splint (1) outlet.
The groove mount structure of electrolyzer of the present invention is achieved the systemic circulation flow.Now be described below:
The profile of groove frame is a rectangle, and its internal structure pattern is divided into two kinds, and a kind of for porous board slot frame (6,6 ') is arranged, another kind then is no porous board slot frame (5).Two BODY WITH SQUARE APERTURE (7 ', 7) are arranged at the top of groove frame, are respectively the liquid collecting duct of anolyte, catholyte; Two BODY WITH SQUARE APERTURE (8,8 ') are also arranged at the bottom, are respectively the shunting duct of anolyte, catholyte.Groove frame middle part constitutes tank room for square groove; To the groove frame of porous plate is arranged, a side of its tank room one side of film (promptly by) be porous (10), it mainly plays a supportive role to film, and simultaneously also for ion migration provides passage, it is hollow that tank room leans on a side of electrode, in baffling bar (9) is arranged; The baffling bar plays a supportive role to porous one side on the one hand, also plays guide functions on the other hand, and it is faster that electrolytic solution is flowed in tank room.Liquid collecting duct, the communication of shunting duct (8,8 ', 7,7 ') and tank room are that the groove (11,11 ') between passing hole channel and tank room is realized; The position that groove is opened has two kinds, and a kind of is the ditch of slotting between shunting duct, lower-left and tank room and upper right liquid collecting duct and tank room, and another kind is between shunting duct, bottom right and tank room and the ditch of slotting between upper left liquid collecting duct and tank room.So just cathode and anode liquid separately unlikelyly can be scurried mutually, simultaneously since groove can open broad, just provide a unimpeded passage for electrolytic solution, provide reliable assurance for big flow circulates.
To the groove frame of no porous plate, its middle part tank room (10 ') is penetrating rectangle, baffling bar (9) water conservancy diversion is arranged, its groove (11,11 ') and the same the opening of groove frame that porous plate is arranged.It is used in energy-saving anode unit or the undivided cell.
The profile of electrode (4,4 ') is to add a conducting plates in groove frame rectangle side, and is same, and respectively there are two liquid collecting ducts and shunting duct in its top and the bottom.The middle part of positive plate (4 ') have one with the onesize mesh electrode of groove frame tank room, it is the nidus of anode electrolysis; Negative electrode (4) middle part then is dull and stereotyped.
Elastomeric pad (14) realizes by adding in the sealing of electrolyzer.Between groove frame and electrode, between groove frame and the film, between electrode and inner splint, between inner splint and the external splint, with the identical pad of groove shaped as frame shape, clamp external splint on the pad, pad and electrode, groove frame, film, inside and outside clamping plate are fitted reach the purpose of sealing.The pattern of pad has two kinds, and first kind, upper and lower respectively have two liquid collecting ducts and a shunting duct, and the middle part is a hollow, and it had both made liquid collecting, shunting smooth road, duct, and positive and negative utmost point liquid is string mutually, guarantees also that positive and negative utmost point liquid does not leak outside simultaneously; Second kind is then had only two ducts, i.e. lower-left and upper right, position are positioned at the centre in the corresponding liquid collecting of groove frame, shunting duct, and circle is for sun (or cloudy) utmost point liquid turnover electrolyzer provides passage and sealing.
The effect of the inside and outside clamping plate of electrolyzer mainly is to be used for entirely clamping slot frame and electrode, makes pad sealed electrolytic cell effectively, makes it into as a wholely, and provides big traffic channel.
The shape of inner splint (2,2 '), size, structure are the same with the second sharp pad, and profile is a rectangle, in the lower-left with upper right a circular duct (13,13 ') arranged respectively.
The profile of external splint (1,1 ') is similar to inner splint, is rectangle, but its size is bigger, and because of it needs could clamp electrolyzer with the bolt pulling, so need leave bolt hole, this hole is beyond groove frame periphery, and electrolyzer is assembled in unlikely influence.Two mouths of pipe (16 are arranged on the external splint, 16 '), one in the lower-left, one upper right, its position size is the same with second kind of pad, it constitutes: the external splint inboard in the lower-left, upper rightly respectively open a circular groove, perforate in the middle of the groove, other has two flanged (FLGD) pipes, and the thickness of ring flange is consistent with the circular groove degree of depth, and diameter is consistent with groove diameter, the external diameter of straight tube is consistent with groove intermediary hole internal diameter on the flange, this pipe is inserted in from a side of external splint groove, stretches to the external splint outside, this mouth of pipe is the import and export of electrolytic solution (anolyte or catholyte).Need to strengthen in the outside of external splint with channel-section steel, smooth to guarantee external splint.
Electrolytic solution is owing to there is severe corrosive, and the corrosion resistance nature of its groove frame, electrode, pad, ion-exchange membrane must be very strong.Explore through long-term, we have adopted the sheet material of polypropylene, polyvinyl chloride, and integral body mills out the groove frame on milling machine, gets porous with drilling machine at groove frame central slot place again.Pad has adopted good springiness, terpolymer EP rubber that corrosion resistance nature is splendid or chloroprene rubber.Electrode then adopts modified metal anode and lead electrode respectively.Ion-exchange membrane then adopts home-made sulfonic acid type perfluorinated ion-exchange membrane.
Embodiment 1. electrolysis production L-cysteine hydrochlorides, catholyte is L-cystine salt solution 150～200g/l, anolyte is 0.1～1.8NH
2SO
4Solution, electrode distance 0.6～2.0cm, energising area (monofilm) 22.8dm
2, current density 5～10A/dm
2, bath voltage 3.2～4.0V, pump circulation, positive and negative utmost point flow velocity＞0.5m/s in the groove, 40～45 ℃ of temperature, positive plate is the modified metal anode, negative electrode is 2
#Stereotype, homemade sulfonic acid type perfluorinated ion-exchange membrane.Faradaic current efficient 95%, L-cysteine hydrochloride yield 1.37～1.39.Treatment capacity 11.6kg (Gelucystine)/monofilm day, single groove (16 films) 50 tons/year of processing poweies (Gelucystine), unit consumption 0.58 degree/kg.
Embodiment 3. diaphragm-free electrolysis are produced Sunmorl N 60S, electrolytic solution: 2M grape+0.2M NaBr solution, energising area 22.8dm
2, pump circulation, groove electrolyte inside linear velocity＞0.5m/s, current density 5A/dm
2, bath voltage 4V, temperature is 45 ℃ in the electrode distance 1cm, groove, control electrolytic solution pH7, anode is the modified metal anode, negative electrode is 2
#Stereotype, then product yield 85%, current efficiency 80%.
Claims (5)
1. one kind is used for the industrialization electrolyzer that anolyte is the electrolytic synthesis L-cysteine hydrochloride that does not produce pollution of sulfuric acid system, it is characterized in that adopting back side input type pump circulation plate frame structure electrolyzer.Anode adopts the modified metal anode of ability oxygen, and negative electrode is a stereotype, and anolyte is the H of 0.1～1.8N
2SO
4, catholyte is the L-cystine hydrochloride of 150～200g/l, cathode and anode distance 0.6～2.0cm, and barrier film is the sulfonic acid type perfluorinated ion-exchange membrane, actuating current 5-10A/dm
2, groove is pressed 3.2-4.0V, 40～45 ℃ of temperature, and solution is at electrode surface flow velocity＞0.5m/s.
2. electrolyzer according to claim 1 and condition, it is characterized in that having two kinds of anolyte compartment's array modes: a kind of is energy-saving type: the combination of electrode and groove frame: electrode (4 ')-groove frame (5)-electrode (4 '), this mode lower electrode is apart from 0.6cm, and groove is pressed 3.0～3.2V.A kind of is plain type: the combination of electrode and groove frame: groove frame (6)-electrode (4 ')-groove frame (6 '), this mode lower electrode are apart from 2cm, and groove is pressed 3.5～4.0V.
3. according to claim 1 and 2 described electrolyzers, it is characterized in that the one or both sides of film adopt porous plate to support, in establish the baffling bar with the increase solution flow rate.
4. according to claim 1 and 2,3 described electrolyzers, it is characterized in that the UNICOM in tank room and shunting, liquid collecting duct adopts the mode of groove (11,11 ') to realize.
5. according to claim 1,2,3,4 described electrolyzers, it is characterized in that can be used for other has film or does not have film organic electrolysis process, electrolytic reduction as glucose electrolytic oxidation and oxalic acid is produced gluconic acid and salt and oxoethanoic acid, and other organic electrolytic process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98113503 CN1232091A (en) | 1998-04-13 | 1998-04-13 | Electrolytic bath for pollution-free electrolytic synthesis of L-cysteine hydrochloride and glyoxalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98113503 CN1232091A (en) | 1998-04-13 | 1998-04-13 | Electrolytic bath for pollution-free electrolytic synthesis of L-cysteine hydrochloride and glyoxalic acid |
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| Publication Number | Publication Date |
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| CN1232091A true CN1232091A (en) | 1999-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98113503 Pending CN1232091A (en) | 1998-04-13 | 1998-04-13 | Electrolytic bath for pollution-free electrolytic synthesis of L-cysteine hydrochloride and glyoxalic acid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839383A (en) * | 2012-09-24 | 2012-12-26 | 山东东岳高分子材料有限公司 | Method for preparing organic acid by electrolyzing organic acid salt on basis of chlor-alkali perfluor ion exchange membrane |
| CN105401166A (en) * | 2015-11-19 | 2016-03-16 | 宁波市远发生物工程有限公司 | Method for preparing L-cysteine hydrochloride anhydrous substances |
| CN108330507A (en) * | 2018-05-17 | 2018-07-27 | 邓剑军 | A kind of diaphragm cell |
| CN110158116A (en) * | 2019-05-31 | 2019-08-23 | 凯莱英医药集团（天津）股份有限公司 | Electrolysis unit and electrolysis system |
| CN111394729A (en) * | 2020-04-26 | 2020-07-10 | 江苏地一环保科技有限公司 | Electrolytic device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof |
| CN113430546A (en) * | 2021-06-09 | 2021-09-24 | 苏州至善化学有限公司 | Preparation method of homocysteine thiolactone hydrochloride |
-
1998
- 1998-04-13 CN CN 98113503 patent/CN1232091A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839383A (en) * | 2012-09-24 | 2012-12-26 | 山东东岳高分子材料有限公司 | Method for preparing organic acid by electrolyzing organic acid salt on basis of chlor-alkali perfluor ion exchange membrane |
| CN102839383B (en) * | 2012-09-24 | 2015-03-18 | 山东东岳高分子材料有限公司 | Method for preparing organic acid by electrolyzing organic acid salt on basis of chlor-alkali perfluor ion exchange membrane |
| CN105401166A (en) * | 2015-11-19 | 2016-03-16 | 宁波市远发生物工程有限公司 | Method for preparing L-cysteine hydrochloride anhydrous substances |
| CN108330507A (en) * | 2018-05-17 | 2018-07-27 | 邓剑军 | A kind of diaphragm cell |
| CN110158116A (en) * | 2019-05-31 | 2019-08-23 | 凯莱英医药集团（天津）股份有限公司 | Electrolysis unit and electrolysis system |
| CN111394729A (en) * | 2020-04-26 | 2020-07-10 | 江苏地一环保科技有限公司 | Electrolytic device and printed board acid etching waste liquid regeneration and copper recovery equipment thereof |
| CN113430546A (en) * | 2021-06-09 | 2021-09-24 | 苏州至善化学有限公司 | Preparation method of homocysteine thiolactone hydrochloride |
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