CN101818180B - Method for producing vitamin C by elec-trodialysis with bipolar membrane - Google Patents
Method for producing vitamin C by elec-trodialysis with bipolar membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 151
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 title abstract description 15
- 235000019154 vitamin C Nutrition 0.000 title abstract description 8
- 239000011718 vitamin C Substances 0.000 title abstract description 8
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 title abstract description 6
- 229930003268 Vitamin C Natural products 0.000 title abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 50
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 32
- 235000010378 sodium ascorbate Nutrition 0.000 claims abstract description 26
- 229960005055 sodium ascorbate Drugs 0.000 claims abstract description 26
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims abstract description 26
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 30
- 125000002091 cationic group Chemical group 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 26
- KPHIBLNUVRGOGU-LMVFSUKVSA-N methyl (3s,4r,5s)-3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound COC(=O)C(=O)[C@@H](O)[C@H](O)[C@@H](O)CO KPHIBLNUVRGOGU-LMVFSUKVSA-N 0.000 claims description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 238000005516 engineering process Methods 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 238000000855 fermentation Methods 0.000 claims description 6
- 230000004151 fermentation Effects 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- RGHNJXZEOKUKBD-QTBDOELSSA-N L-gulonic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-QTBDOELSSA-N 0.000 claims description 3
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims 2
- 239000003513 alkali Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 10
- -1 gulonic acid methyl ester Chemical class 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 238000005086 pumping Methods 0.000 abstract 3
- 235000010323 ascorbic acid Nutrition 0.000 abstract 1
- 239000011668 ascorbic acid Substances 0.000 abstract 1
- 229960005070 ascorbic acid Drugs 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000009471 action Effects 0.000 description 25
- 230000005684 electric field Effects 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 21
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 6
- 238000007599 discharging Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
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- 230000004060 metabolic process Effects 0.000 description 1
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- 238000006479 redox reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
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Abstract
The invention discloses a method for producing vitamin C by elec-trodialysis with a bipolar membrane. In the method, the elec-trodialysis with the bipolar membrane is applied to the generation of ascorbic acid in the vitamin C production process. The method comprises the following steps of: a, arranging a module between a pair of electrodes; b, pumping electrolyte into an anode chamber and a cathode chamber, pumping sodium ascorbate into a conversion chamber, and pumping gulonic acid methyl ester into a hydrolysis chamber for circulation; c, applying DC between the anode and the cathode; d, timely removing products according to the change of materials in the hydrolysis chamber, and separating the products to obtain the sodium ascorbate; and e, according to the change of the PH value in the conversion chamber, removing the products of the conversion chamber, and separating the products to obtain the vitamin C. In the method, a byproduct alkali generated in the elec-trodialysis process is fully utilized to complete hydrolyzing the gulonic acid methyl ester, a catalyst in the hydrolysis process is saved, the pH value of the alkali chamber is also reduced, and the service life of the system is prolonged.
Description
Technical field
The present invention relates to a kind of ascorbic working method, particularly a kind of the bipolar membrane electrodialysis method is applied to a kind of technology that methyl 2-keto-L-gulonate changes into dimension C acid.
Background technology
Vitamins C popular name xitix is the catalyzer in cellular oxidation-reduction reaction, has strong activity; Can participate in the multiple metabolism of human body; Can reduce the fragility of capillary vessel, prevent scorbutic generation when increasing the body resistivity, therefore ascorbic application is increasingly extensive.
Produce ascorbic method at present and adopt biological fermentation process usually; Its production process at first is a fermentation production of gulonic acid sodium; With Zeo-karb sodium colombate is changed into ancient dragon acid again, ancient dragon acid generates methyl 2-keto-L-gulonate with the methyl alcohol reaction under acidic conditions, and then adds sodium hydrogencarbonate; Make the methyl 2-keto-L-gulonate hydrolysis generate sodium ascorbate and methyl alcohol, re-use Zeo-karb at last sodium ascorbate is changed into dimension C acid.Twice of whole process uses Zeo-karb that sodium salt is changed into acid, being in great demand of resin, and production unit is also huger, and os is complicated; And the bronsted lowry acids and bases bronsted lowry that regenerative process consumption is a large amount of also can be discharged a large amount of high-salt wastewaters.
To this industry present situation, people have attempted many new technologies.The bipolar membrane electrodialysis transformation technology is to utilize Bipolar Membrane under electric field action, water power to be left the reaction that produces hydrogen ion and hydroxide ion; And transporting action and the ion-exchange membrane of inorganic ion under electric field action accomplished the conversion of salt to acid or alkali to the effect of ionic selective permeation.In " membrane science and the technology " fifth phase in 1998; Tsing-Hua University department of chemistry engineering woods likes light, Jiang Weijun, the surplus upright paper of newly delivering " applied research of bipolar membrane electrodialysis technology in production of vitamin C ", specialized in the bipolar membrane electrodialysis technology and has been applied to sodium colombate and is converted into the process that ancient imperial acid and sodium ascorbate are converted into dimension C.Their bipolar membrane electrodialysis method successfully makes sodium ascorbate change into dimension C, and its reaction unit comprises the membrane stack that the Bipolar Membrane that equated by quantity and cationic membrane are arranged alternately, and places the outermost electrode of membrane stack; Whole device is divided into cathode compartment, anolyte compartment, sour chamber and alkali chamber.The principle of this method is: at first sodium ascorbate is charged into sour chamber, then logical direct current between two electrodes; Under the effect of DC electric field; Water in the Bipolar Membrane is dissociated into hydrogen ion and hydroxide ion; The positive layer that hydrogen ion sees through film gets into sour chamber, and hydroxide ion gets into the alkali chamber through the negative layer of film, and the sodium ion in the sour chamber then shifts out sour chamber and sees through anode membrane entering alkali chamber under electric field action.Like this, hydrogen ion combines with Vc acid group in the sodium ascorbate to generate dimension C in sour chamber, and sodium ion and hydroxide ion are combined into sodium hydroxide in the alkali chamber.
Although this method successfully with the bipolar membrane electrodialysis technical application in ascorbic production technique; Replace ion exchange resin, practiced thrift the consumption of soda acid, reduced the discharging of high-salt wastewater; But the higher sodium hydroxide of a large amount of pH values of its by-product is not fully used; Equipment there is certain corrosive nature, and under this high-intensity alkaline condition, the scale deposition of high volence metal ion takes place easily also, influence the operation life of film system.
Summary of the invention
Technical problem to be solved by this invention provides a kind ofly can practice thrift sodium hydrogencarbonate, reduces the pH value of Bipolar Membrane alkali chamber, prolongs the production of vitamin C method of the operation life of system.
For solving the problems of the technologies described above, the technical scheme that the present invention taked is:
A kind of with the ascorbic method of bipolar membrane electrodialysis technology production; Concrete steps are a. fermentation production of gulonic acid sodium; B. sodium colombate is changed into ancient dragon acid; C. ancient dragon acid generates methyl 2-keto-L-gulonate with the methyl alcohol reaction under acidic conditions, d. generates sodium ascorbate and methyl alcohol with the methyl 2-keto-L-gulonate hydrolysis, and e. changes into dimension C acid with sodium ascorbate; Said step b and steps d are based on the bipolar membrane electrodialysis ratio juris; Employing is accomplished by the bipolar membrane electrodialysis device that electrode and the membrane stack between electrode constitute; Said membrane stack comprises many Bipolar Membrane and cationic membrane; Bipolar Membrane is inserted a cationic membrane by the polarity series arrangement between per two adjacent Bipolar Membrane; Said bipolar membrane electrodialysis device is divided into anolyte compartment, cathode compartment, conversion chamber and hydrolysis chamber.
Improvement of the present invention is: the process of said employing bipolar membrane electrodialysis device completing steps b and steps d is undertaken by following operation steps:
A. confirm the quantity of Bipolar Membrane and cationic membrane in the membrane stack according to the production needs, and membrane stack is inserted between the pair of electrodes;
B. electrolytic solution is pumped into anolyte compartment and cathode compartment respectively, sodium colombate pumps into conversion chamber, and methyl 2-keto-L-gulonate pumps into the hydrolysis chamber, circulates respectively, and keeps certain flow rate;
C. as required, between anode and two electrodes of negative electrode, apply suitable direct supply, and the situation of monitoring cathode compartment, anolyte compartment, conversion chamber and hydrolysis chamber;
When D. the pH value of chamber to be transformed reaches certain value, adjust and keep the flow velocity of solution, the solution in the conversion chamber is constantly shifted out together with product separate, obtain ancient dragon acid;
When treating that E. the indoor material of hydrolysis is transformed into certain proportion, the flow velocity of adjustment and maintenance solution, the solution that hydrolysis is indoor constantly shifts out together with product, separates then to obtain sodium ascorbate and methyl alcohol.
Further improvement of the present invention is: said membrane stack comprises two Bipolar Membrane and a cationic membrane, and wherein cationic membrane places between two Bipolar Membrane.
The improvement of electrolytic solution according to the invention is: said electrolytic solution is any one in water, acid, alkali or the salts solution.
Another embodiment of the invention is: adopt the process of bipolar membrane electrodialysis device completing steps d and step e, undertaken by following operation steps:
A. confirm the quantity of Bipolar Membrane and cationic membrane in the membrane stack according to the production needs, and membrane stack is inserted between the pair of electrodes;
B. electrolytic solution is pumped into anolyte compartment and cathode compartment respectively, sodium ascorbate pumps into conversion chamber, and methyl 2-keto-L-gulonate pumps into the hydrolysis chamber, circulates respectively, and keeps certain flow rate;
C. as required, between anode and two electrodes of negative electrode, apply suitable direct supply, and the situation of monitoring cathode compartment, anolyte compartment, conversion chamber and hydrolysis chamber;
When treating that D. the indoor material of hydrolysis is transformed into certain proportion, the flow velocity of adjustment and maintenance solution, the solution that hydrolysis is indoor constantly shifts out together with product, separates then to obtain sodium ascorbate and methyl alcohol;
When E. the pH value of chamber to be transformed reaches certain value, adjust and keep the flow velocity of solution, the solution in the conversion chamber is constantly shifted out together with product separate, obtain tieing up C acid.
The principle of work of bipolar membrane electrodialysis device of the present invention is described below:
Membrane stack and the pair of electrodes that comprises that many Bipolar Membrane, cationic membrane constitute according to the invention, membrane stack is between electrode; Wherein Bipolar Membrane is inserted a cationic membrane by the polarity series arrangement between per two adjacent Bipolar Membrane, and the outermost layer of membrane stack is Bipolar Membrane; Between positive plate and the adjacent Bipolar Membrane is the anolyte compartment; Between negative plate and the adjacent Bipolar Membrane is cathode compartment; Be conversion chamber between the Bipolar Membrane of cationic membrane and anode side, be the hydrolysis chamber between the Bipolar Membrane of cationic membrane and cathode side, hydrolysis chamber and conversion chamber are alternately arranged.
In the anolyte compartment, water becomes hydrogen ion and hydroxide ion in the Bipolar Membrane internal ionization under electric field action, and hydroxide ion is moved by the electric field action anode, and the cavity block layer that sees through Bipolar Membrane gets into the anolyte compartment, discharges with the anolyte circulation; Hydrogen ion sees through the anode membrane layer entering conversion chamber of Bipolar Membrane under electric field action simultaneously.At cathode compartment, water becomes hydrogen ion and hydroxide ion in the Bipolar Membrane internal ionization under electric field action, and hydrogen ion is moved to negative electrode by electric field action, and the anode membrane layer that sees through Bipolar Membrane gets into cathode compartment, discharges with the catholyte circulation; Hydroxide ion sees through the cavity block layer entering hydrolysis chamber of Bipolar Membrane under electric field action simultaneously.
In conversion chamber, the sodium ion in the sodium colombate solution passes cationic membrane and gets into the hydrolysis chamber under electric field action, and ancient imperial acid ion and hydrogen ions generate ancient dragon acid, accomplish the conversion of sodium salt to acid.
In the hydrolysis chamber, methyl 2-keto-L-gulonate gets into the hydrolysis chamber with certain flow rate, under the effect of hydroxide ion, is hydrolyzed, and combines to generate sodium ascorbate and methyl alcohol with sodium ion, accomplishes hydrolytic process.
Owing to adopted above technical scheme, institute of the present invention acquisition of technology progress is:
The present invention adopts the bipolar membrane electrodialysis method, makes water under the Bipolar Membrane effect, directly be dissociated into stronger hydrogen ion of reactive behavior and hydroxide ion.It is indoor directly methyl 2-keto-L-gulonate to be passed into the hydrolysis of by-product alkali in the device in present method; Carry out ester reaction, utilize the hydroxide ion of by-product to replace sodium hydrogencarbonate to carry out the catalysis of ester reaction, do not need to add in addition catalyzer; Simplify technical process greatly, practiced thrift production cost.
The present invention utilizes the hydrolysis of the base catalysis ester of by-product, not only combine the advantage of acid catalysis and base catalysis, has also kept bipolar membrane electrodialysis techniques save resin, reduces acid and alkali consumption, has reduced discharging the advantage of high-salt wastewater; And in whole hydrolytic process, do not add any catalyzer, do not bring other metals ion into, reduced the discharging of production process refuse; Also greatly reduce the pH value of system simultaneously, alleviated the fouling tendency of high volence metal ion, reduced, help system's long-time running corrosion on Equipment.
Description of drawings
Fig. 1 is structure of the present invention and principle of work synoptic diagram.
Wherein, 1, anode, 2, the anolyte compartment, 3, Bipolar Membrane, 4, anode membrane, 5, cavity block, 6, conversion chamber, 7, the hydrolysis chamber, 8, cathode compartment.
Embodiment
To combine specific embodiment that the present invention is carried out further detailed explanation below.
Embodiment 1
Include a cover bipolar membrane electrodialysis device in the present embodiment, the bipolar membrane electrodialysis device is to be made up of two Bipolar Membrane, cationic membrane and pair of electrodes, and this device is followed successively by positive plate, Bipolar Membrane, cationic membrane, Bipolar Membrane and negative plate from left to right.This structures shape four work areas of this bipolar membrane electrodialysis device be: anolyte compartment, conversion chamber, hydrolysis chamber and cathode compartment.By the zone that constitutes between positive plate and the adjacent Bipolar Membrane is the anolyte compartment, and the cathode side and the positive plate of this Bipolar Membrane are oppositely arranged; By the zone that constitutes between negative plate and the adjacent Bipolar Membrane is cathode compartment, and the anode side and the negative plate of this Bipolar Membrane are oppositely arranged; Being a cationic membrane between the adjacent Bipolar Membrane, is conversion chamber between the Bipolar Membrane of cationic membrane and anode side, is the hydrolysis chamber between the Bipolar Membrane of cationic membrane and cathode side.
When the bipolar membrane electrodialysis method is produced vitamins C, carry out according to the following steps:
1) fermentation generates sodium colombate,
2) make the bipolar membrane electrodialysis device according to aforesaid way,
3) 4% NaOH solution is pumped into the anolyte compartment according to certain flow velocity and cathode compartment circulates; The methyl 2-keto-L-gulonate of treating hydrolysis is pumped into the hydrolysis chamber with certain flow rate to circulate; Sodium colombate solution is pumped into conversion chamber to circulate;
4) stable back to be recycled applies direct supply between two battery lead plates;
At this moment, in the anolyte compartment, water becomes hydrogen ion and hydroxide ion in the Bipolar Membrane internal ionization under electric field action, and hydroxide ion is moved by the electric field action anode, and the cavity block layer that sees through Bipolar Membrane gets into the anolyte compartment, discharges with the anolyte circulation; Hydrogen ion sees through the anode membrane layer entering conversion chamber of Bipolar Membrane under electric field action simultaneously.At cathode compartment, water becomes hydrogen ion and hydroxide ion in the Bipolar Membrane internal ionization under electric field action, and hydrogen ion is moved to negative electrode by electric field action, and the anode membrane layer that sees through Bipolar Membrane gets into cathode compartment, discharges with the catholyte circulation; Hydroxide ion sees through the cavity block layer entering hydrolysis chamber of Bipolar Membrane under electric field action simultaneously.
5) in conversion chamber, the sodium ion in the sodium colombate solution passes cationic membrane and gets into the hydrolysis chamber under electric field action, and dimension C acid ion and hydrogen ions generate ancient dragon acid;
6) ancient dragon acid generates methyl 2-keto-L-gulonate with the methyl alcohol reaction under acidic conditions;
7) in the hydrolysis chamber, methyl 2-keto-L-gulonate gets into the hydrolysis chamber with certain flow rate, under the effect of hydroxide ion, is hydrolyzed, and combines to generate sodium ascorbate and methyl alcohol with sodium ion, accomplishes hydrolytic process, product is shifted out separate then;
8) adopt Zeo-karb, the sodium ascorbate that the hydrolysis chamber is generated transforms generation dimension C acid.
The ancient imperial acid solution that methanol solution that the hydrolysis chamber generates in the present embodiment and switch room generate carries out esterification and obtains methyl 2-keto-L-gulonate.
Embodiment 2
The bipolar membrane electrodialysis device of using in the present embodiment is identical with embodiment 1, but when being applied to ascorbic production, carries out according to the following steps:
1) fermentation generates sodium colombate,
2) adopt Zeo-karb that sodium colombate is changed into ancient dragon acid,
3) ancient dragon acid generates methyl 2-keto-L-gulonate with the methyl alcohol reaction under acidic conditions,
4) make the bipolar membrane electrodialysis device according to aforesaid way,
5) 4% NaOH solution is pumped into the anolyte compartment according to certain flow velocity and cathode compartment circulates; The methyl 2-keto-L-gulonate of treating hydrolysis is pumped into the hydrolysis chamber with certain flow rate to circulate; Sodium ascorbate solution is pumped into conversion chamber to circulate;
6) stable back to be recycled applies direct supply between two battery lead plates;
At this moment, in the anolyte compartment, water becomes hydrogen ion and hydroxide ion in the Bipolar Membrane internal ionization under electric field action, and hydroxide ion is moved by the electric field action anode, and the cavity block layer that sees through Bipolar Membrane gets into the anolyte compartment, discharges with the anolyte circulation; Hydrogen ion sees through the anode membrane layer entering conversion chamber of Bipolar Membrane under electric field action simultaneously.At cathode compartment, water becomes hydrogen ion and hydroxide ion in the Bipolar Membrane internal ionization under electric field action, and hydrogen ion is moved to negative electrode by electric field action, and the anode membrane layer that sees through Bipolar Membrane gets into cathode compartment, discharges with the catholyte circulation; Hydroxide ion sees through the cavity block layer entering hydrolysis chamber of Bipolar Membrane under electric field action simultaneously.
7) in the hydrolysis chamber, methyl 2-keto-L-gulonate gets into the hydrolysis chamber with certain flow rate, under the effect of hydroxide ion, is hydrolyzed, and combines to generate sodium ascorbate and methyl alcohol with sodium ion, accomplishes hydrolytic process, product is shifted out separate then;
8) in conversion chamber, the sodium ion in the sodium ascorbate solution passes cationic membrane and gets into the hydrolysis chamber under electric field action, and dimension C acid ion and hydrogen ions generate dimension C acid, accomplish the conversion of sodium salt to acid.
Sodium ascorbate and methanol solution are through after separating, reclaiming in the present embodiment, and sodium ascorbate solution can pump into and carry out the conversion of salt to acid in the conversion chamber; The ancient imperial acid solution that methanol solution that the hydrolysis chamber generates and switch room generate carries out esterification and obtains methyl 2-keto-L-gulonate.
Claims (3)
1. produce ascorbic method with bipolar membrane electrodialysis technology for one kind; Its key step comprises a. fermentation production of gulonic acid sodium; B. sodium colombate is changed into ancient dragon acid; C. ancient dragon acid generates methyl 2-keto-L-gulonate with the methyl alcohol reaction under acidic conditions, d. generates sodium ascorbate and methyl alcohol with the methyl 2-keto-L-gulonate hydrolysis, and e. changes into dimension C acid with sodium ascorbate;
It is characterized in that: said step b and steps d are based on the bipolar membrane electrodialysis ratio juris; Employing is accomplished by the bipolar membrane electrodialysis device that electrode and the membrane stack between electrode constitute; Said membrane stack comprises many Bipolar Membrane and cationic membrane; Bipolar Membrane is inserted a cationic membrane by the polarity series arrangement between per two adjacent Bipolar Membrane; The zone that constitutes between said positive plate and the adjacent Bipolar Membrane is the anolyte compartment, and the cathode side and the positive plate of this Bipolar Membrane are oppositely arranged; By the zone that constitutes between negative plate and the adjacent Bipolar Membrane is cathode compartment, and the anode side and the negative plate of this Bipolar Membrane are oppositely arranged; Being a cationic membrane between the adjacent Bipolar Membrane, is conversion chamber between the Bipolar Membrane of cationic membrane and anode side, is the hydrolysis chamber between the Bipolar Membrane of cationic membrane and cathode side;
Said step b and steps d are undertaken by following operation steps:
A. confirm the quantity of Bipolar Membrane and cationic membrane in the membrane stack according to the production needs, and membrane stack is inserted between the pair of electrodes;
B. electrolytic solution is pumped into anolyte compartment and cathode compartment respectively, sodium colombate pumps into conversion chamber, and methyl 2-keto-L-gulonate pumps into the hydrolysis chamber, circulates respectively, and keeps certain flow rate;
C. as required, between anode and two electrodes of negative electrode, apply suitable direct supply, and the situation of monitoring cathode compartment, anolyte compartment, conversion chamber and hydrolysis chamber;
When D. the pH value of chamber to be transformed reaches certain value, adjust and keep the flow velocity of solution, the solution in the conversion chamber is constantly shifted out together with product separate, obtain ancient dragon acid;
When treating that E. the indoor material of hydrolysis is transformed into certain proportion, the flow velocity of adjustment and maintenance solution, the solution that hydrolysis is indoor constantly shifts out together with product, separates then to obtain sodium ascorbate and methyl alcohol.
2. according to claim 1 a kind of with the ascorbic method of bipolar membrane electrodialysis technology production, it is characterized in that: said membrane stack comprises two Bipolar Membrane and a cationic membrane, and wherein cationic membrane places between two Bipolar Membrane.
3. according to claim 1 a kind of with the ascorbic method of bipolar membrane electrodialysis technology production, it is characterized in that: adopt the process of bipolar membrane electrodialysis device completing steps d and step e, undertaken by following operation steps:
A. confirm the quantity of Bipolar Membrane and cationic membrane in the membrane stack according to the production needs, and membrane stack is inserted between the pair of electrodes;
B. electrolytic solution is pumped into anolyte compartment and cathode compartment respectively, sodium ascorbate pumps into conversion chamber, and methyl 2-keto-L-gulonate pumps into the hydrolysis chamber, circulates respectively, and keeps certain flow rate;
C. as required, between anode and two electrodes of negative electrode, apply suitable direct supply, and the situation of monitoring cathode compartment, anolyte compartment, conversion chamber and hydrolysis chamber;
When treating that D. the indoor material of hydrolysis is transformed into certain proportion, the flow velocity of adjustment and maintenance solution, the solution that hydrolysis is indoor constantly shifts out together with product, separates then to obtain sodium ascorbate and methyl alcohol;
When E. the pH value of chamber to be transformed reaches certain value, adjust and keep the flow velocity of solution, the solution in the conversion chamber is constantly shifted out together with product separate, obtain tieing up C acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| US9339765B2 (en) | 2011-09-16 | 2016-05-17 | General Electric Company | Electrodialysis method and apparatus for passivating scaling species |
| CN102382084B (en) * | 2011-09-21 | 2014-03-19 | 石家庄开发区德赛化工有限公司 | Method for producing vitamin C |
| CN104313633B (en) * | 2014-07-22 | 2016-09-07 | 宜宾丝丽雅集团有限公司 | A kind of Bipolar Membrane method prepares the production technology of gluconic acid |
| CN106186466A (en) * | 2016-09-30 | 2016-12-07 | 淄博格瑞水处理工程有限公司 | A kind of sodium chloride waste water Zero-discharge treating process producing aluminium oxide generation |
| CN108774125A (en) * | 2018-05-28 | 2018-11-09 | 苏州澄江环境科技有限公司 | A kind of technique recycling raw material from gulonic acid mother solution |
| CN109096230A (en) * | 2018-09-10 | 2018-12-28 | 合肥科佳高分子材料科技有限公司 | One kind preparing ascorbic method by bipolar membrane electrodialysis |
| CN109232488A (en) * | 2018-10-26 | 2019-01-18 | 山东鲁维制药有限公司 | A kind of high ascorbic environment-friendly production process of industrialization level |
| CN114368864A (en) * | 2021-12-30 | 2022-04-19 | 嘉兴诚毅环保科技有限责任公司 | Industrial sewage treatment device |
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| BR9810227A (en) * | 1997-06-30 | 2000-08-08 | Electrosynthesis Co Inc | Processes for the production of ascorbic acid, a base co-product and a methoxide salt co-product |
| CN1198812C (en) * | 2002-12-09 | 2005-04-27 | 东北制药总厂 | Process of preparing coarse vitamin C with glulconic acid |
| CN101284824A (en) * | 2008-06-06 | 2008-10-15 | 郑州拓洋实业有限公司 | Preparation method of cenolate |
| CN101643408A (en) * | 2009-08-31 | 2010-02-10 | 厦门世达膜科技有限公司 | Production method of gulonic acid in production of vitamin C |
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