CN113441009A - Vitamin C bipolar membrane acidification production process and device - Google Patents

Vitamin C bipolar membrane acidification production process and device Download PDF

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CN113441009A
CN113441009A CN202110691135.7A CN202110691135A CN113441009A CN 113441009 A CN113441009 A CN 113441009A CN 202110691135 A CN202110691135 A CN 202110691135A CN 113441009 A CN113441009 A CN 113441009A
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stage
chamber
conversion
solution
bipolar membrane
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CN113441009B (en
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郑沛尧
赵德胜
陈波
王钰
应俊强
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Heilongjiang Xinhecheng Biotechnology Co ltd
Zhejiang NHU Co Ltd
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Heilongjiang Xinhecheng Biotechnology Co ltd
Zhejiang NHU Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/422—Electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/62—Three oxygen atoms, e.g. ascorbic acid

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Abstract

The invention discloses a bipolar membrane acidification production process and a bipolar membrane acidification production device for vitamin C, wherein the process comprises the following steps: (1) introducing VCNa aqueous solution into a first-stage acid chamber of a bipolar membrane electrodialysis membrane stack connected in series in multiple stages for conversion, introducing the obtained first-stage acid chamber conversion solution into a next-stage acid chamber for continuous conversion, sequentially carrying out conversion to a last-stage acid chamber, and obtaining a product solution rich in vitamin C through the last-stage conversion; (2) introducing water or dilute NaHCO into the first stage alkali chamber corresponding to the first stage acid chamber3The solution is converted, the first stage alkali chamber conversion solution and CO are mixed2After neutralization reaction, the mixture is introduced into a next-stage alkali chamber for continuous conversion, and sequentially carried out to a last-stage alkali chamber, and NaHCO containing a small amount of VCNa is obtained through the last-stage conversion3An aqueous solution. The production process effectively reduces the production cost and the environmental protection pressure, and the deterioration loss of the VC is obviously improved.

Description

Vitamin C bipolar membrane acidification production process and device
Technical Field
The invention belongs to the field of vitamin production, and particularly relates to a bipolar membrane acidification production process and device for vitamin C.
Background
An important link in the production process flow of Vitamin C (VC) is the acidification of sodium salt (VCNa) thereof into VC, and the traditional acidification method is an ion exchange method. However, the resin used in the ion exchange process needs to be regenerated repeatedly, which consumes a large amount of acid and generates a large amount of waste salt, resulting in environmental pressure. The bipolar membrane electrodialysis technique can utilize H generated by in-situ water dissociation+And OH-The organic acid salt is converted into acid and corresponding alkali, and the two are separated by utilizing the selective permeability of the membrane, and the advantages are that: no acid consumption, no waste salt generation, and utilization of the generated by-product base.
Bipolar membrane electrodialysis has been studied and applied for the production of various organic acid hydrochlorides, such as acetic acid, citric acid, amino acids, etc., whereas the application of bipolar membranes to VC has been relatively rare reported. Patent CN109096230A discloses a bipolar membrane acidification method of VCNa, which is substantially identical to the conventional bipolar membrane acidification method of organic acids. Patent CN109232488A discloses a coupling technology of 'activated carbon adsorption + chelate resin adsorption + anion resin adsorption + bipolar membrane electrodialysis', and both pretreatment and aftertreatment are designed, so that the method has high feasibility. However, even in the case where a full flow design such as CN109232488A has been made, VCNa bipolar membrane acidification has not yet seen productive application. The applicant finds that, in addition to the high price of the bipolar membrane, the core problem hindering the popularization of the bipolar membrane is that a part of VC permeates into the NaOH solution, so that the VC is deteriorated to cause loss and reduce the quality of the produced alkali (as shown in fig. 1).
VC is very unstable in a strong alkaline solution due to the particularity of VC, and can quickly undergo ring opening and oxidation to deteriorate. At present, the membrane on the market cannot completely prevent the permeation phenomenon, about 1-3% of VC generally permeates, the material loss often exceeds the acceptable range, and the quality of the byproduct NaOH is reduced. None of the above prior art relates to the deterioration problem of the permeated VC, and only the patent CN111138390A focuses on this phenomenon at present, and therefore designs a BP membrane-anode membrane-BP membrane three-compartment structured membrane stack, however, this design only uses the intermediate compartment transition to ensure the quality of the generated alkali, and there is no significant improvement on the deterioration loss of the permeated VC.
Disclosure of Invention
The invention provides a production process and a device of vitamin C, which solve the problems of high cost and high environmental protection pressure in the production of vitamin C by an ion exchange method on one hand and the problem of VC deterioration loss in the conventional bipolar membrane acidification VCNa on the other hand.
The technical scheme of the invention is as follows:
a bipolar membrane acidification production process of vitamin C comprises the following steps:
(1) introducing a VCNa aqueous solution into a first-stage acid chamber (also called a material chamber) in a bipolar membrane electrodialysis membrane stack which is connected in series in a multi-stage manner, promoting hydrogen ions separated by water to combine with VC negative ions left in the first-stage acid chamber under the action of a direct-current electric field to generate vitamin C, introducing the obtained first-stage acid chamber conversion solution into a next-stage acid chamber for continuous conversion, sequentially carrying out the conversion to a last-stage acid chamber, and obtaining a product solution rich in vitamin C through the last-stage conversion;
(2) introducing water or dilute NaHCO into the first stage alkali chamber corresponding to the first stage acid chamber3Under the action of DC electric field, the bipolar membrane promotes the hydroxide ions dissociated from water and the sodium ions migrated from the anode membrane to converge in the alkali chamber to form NaOH water solution, the first-stage alkali chamber conversion solution and CO2After neutralization reaction, the mixture is introduced into a next-stage alkali chamber for continuous conversion, and sequentially carried out to a last-stage alkali chamber, and NaHCO containing a small amount of VCNa is obtained through the last-stage conversion3An aqueous solution.
In the invention, NaOH aqueous solution with a certain concentration needs to be introduced into the polar chamber in advance so as to create a conductive environment.
Because the bipolar membrane stack can not completely isolate non-target ions or molecules from permeating, a small amount of VC can permeate into the alkali chamber and is oxidized in a strong alkaline environmentThe bipolar membrane electrodialysis is designed to be in multistage series connection work, NaOH in each stage of alkali chamber is firstly neutralized and then enters the next stage, so that NaOH is quickly converted into NaHCO3The method reduces the residence time of VCNa in a strong alkaline environment to the maximum extent, reduces deterioration loss, and simultaneously gradually increases the VC/VCNa ratio of each stage of material chamber to finally obtain the VC product.
In the invention, the increase of the number of stages of the bipolar membrane electrodialysis membrane stack is beneficial to reducing the loss of VCNa, and is not too much or too much so as to avoid the increase of the cost, and preferably, the number of stages of the bipolar membrane electrodialysis membrane stack in series is 2-6.
Preferably, the concentration of the VCNa aqueous solution introduced into the first-stage acid chamber is 10 to 35 wt%, preferably 20 to 25 wt%.
In the invention, the first-stage alkali chamber can be filled with water or NaHCO3Solution, preferably NaHCO, introduced into said first stage base chamber3The concentration of the solution is 0.1-2 wt%.
Preferably, NaHCO is added to the alkaline compartment solution after the final neutralization3The concentration is 6-10 wt%.
In the invention, the voltage and current of the bipolar membrane stack can influence the conversion efficiency, in the operation process, different voltages can be applied to all stages of the bipolar membrane electrodialysis, the voltage range is 20-25V, and the current density is controlled to be 40-100 mA/cm2Preferably 40 to 80mA/cm2。
Preferably, each stage of the solution in the acid chamber and the solution in the alkali chamber are operated in a self-circulation mode, and when the NaOH concentration in the alkali chamber reaches 2-3 wt%, the conversion solution in the alkali chamber and CO are mixed2And (3) after neutralization, the solution enters the next stage, and the acid chamber conversion solution directly enters the next stage, so that the decomposition of VC sodium caused by overhigh NaOH concentration in the alkali chamber can be effectively avoided.
Preferably, when the conductivity of the last stage acid compartment solution drops to 5mS/cm, indicating that the reaction is substantially complete, the conversion is stopped and the process is run.
Preferably, the CO is2The neutralization equipment can use an absorption kettle or an absorption tower, CO2Molar equivalent ratio to NaOH of1～3：1。
In the present invention, CO used for neutralization2Can be provided in a variety of ways, while taking into account that the previous step of the VCNa acidification process will produce CO2Can be applied to the CO of this step2The process of the invention preferably also comprises a transesterification process of methyl gulonate:
gulonic acid methyl ester and NaHCO3Ester conversion reaction is carried out to generate VCNa and CO2；
Dissolving the generated VCNa, then entering a first-stage acid chamber in the step (1) for conversion, and generating CO2Is used for the neutralization reaction of the step (2).
Preferably, the NaHCO obtained in step (2) contains a small amount of VCNa3And (4) after the aqueous solution is evaporated and crystallized, mechanically applying the aqueous solution to the transesterification process. VCNa is an ester transfer product, so that the subsequent process is not influenced, VC loss is not caused by adopting the operation, and NaHCO can be effectively utilized3By-products.
The invention also provides a bipolar membrane acidification production device of vitamin C, which comprises an anode, a cathode, a polar membrane and a plurality of pairs of double-compartment repeating units which are positioned between the two stages and connected in parallel, wherein each pair of repeating units comprises an acid chamber and an alkali chamber, the acid chamber and the alkali chamber of each pair of repeating units are separated by the anode membrane, and two adjacent repeating units are separated by the bipolar membrane; a polar chamber is arranged between the electrode and the polar film; a pair of positive electrodes, a pair of negative electrodes, a pair of polar membranes and a plurality of pairs of parallel-connected repeated double compartments positioned between two stages form a primary membrane stack;
the acid chamber of each stage of membrane stack is communicated with the acid chamber of the next stage of membrane stack through a pipeline;
the alkali chamber of each stage of membrane stack is communicated with the alkali chamber of the next stage of membrane stack through a pipeline, and a neutralization device is arranged between the two alkali chambers.
Preferably, the series connection stage number of the bipolar membrane stack is 2-6 stages.
Preferably, the bipolar membrane acidification production device for vitamin C further comprises a transesterification device for methyl gulonate, and the transesterification device is provided with CO2Exhaust line of said CO2The exhaust pipeline is connected with the neutralization deviceThe method is simple.
Compared with the prior art, the invention has the beneficial effects that:
1) the existing VCNa is quickly deteriorated in NaOH solution, and the invention adds a neutralization device between every two stages of membrane stacks to quickly convert NaOH into NaHCO3The contact time of VCNa and NaOH is shortened, while in NaHCO3In the solution, even the evaporated solid had no significant deterioration loss.
2) Using NaHCO3CO formed by transesterification2The gas, originally discharged to the outside, is treated, the invention uses the CO2By using, reducing carbon emission and simultaneously generating NaHCO3Can be used indiscriminately.
Drawings
FIG. 1 is a schematic diagram of the principle of acidification of VCNa by bipolar membrane electrodialysis and VC permeation;
FIG. 2 is a schematic view showing the structure of a bipolar membrane acidification step production apparatus for vitamin C of the present invention;
FIG. 3 is a flow chart of the whole production process of the bipolar membrane of vitamin C in the invention.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
Fig. 2 is a schematic structural diagram of a bipolar membrane acidification step production device for vitamin C of the present invention, and as can be seen from fig. 2, the acidification step production device comprises a plurality of bipolar membrane electrodialysis membrane stacks connected in series, and each bipolar membrane electrodialysis membrane stack has the following core structure: - [ bipolar membrane-base compartment-cation exchange membrane-acid compartment]n-bipolar membrane-base chamber configuration, where n is the number of parallel logarithms, each stage of acid chamber being connected to the next stage of acid chamber by a pipe, the VC/VCNa ratio increasing gradually as the number of stages increases. Each stage of alkali chamber is also connected with the next stage of alkali chamber through a pipeline, but a neutralization device is arranged in the middle, and CO is introduced into the neutralization device2Thus, NaOH obtained from each stage of the alkali chamber can be converted into NaHCO in time3The alkalinity intensity is effectively controlled, and the VC in the alkali chamber can not be deteriorated after permeating the membrane.
FIG. 3 is a flow chart of the whole production process of the bipolar membrane of vitamin C in accordance with the present invention, and the production process of the present invention will be described with reference to specific examples.
Example 1
This example was produced using a production apparatus as shown in FIG. 2, in which a bipolar membrane stack of two compartments was used, each stage having 10 repeating units, and divided into 3 stages in total.
500g of 4 wt% NaOH aqueous solution is introduced into each stage of polar chamber; 500g of 20 wt% aqueous VCNa solution was introduced into the first acid compartment and 400g of 0.1 wt% NaHCO solution into the first base compartment3Aqueous solution, the voltage of the first-stage membrane stack is set to be 25V, and the upper limit of the current density is set to be 80mA/cm2And the acid chamber and the alkali chamber are operated in a self-circulation mode, the NaOH concentration of the alkali chamber is monitored in the process, and when the NaOH concentration of the alkali chamber reaches-2 wt%, the first-stage membrane stack is stopped to obtain 405g of alkali chamber solution and 495g of acid chamber solution.
Transferring the obtained alkali chamber solution to a neutralization kettle, and introducing CO2Neutralizing NaOH with gas to obtain NaHCO3413g of an aqueous solution.
NaHCO after first stage neutralization3The water solution and the first-stage acid chamber solution are respectively introduced into the second-stage membrane stack. The voltage was set to 20V and the upper limit of the current density was set to 80mA/cm2And the acid chamber and the alkali chamber are operated in a self-circulation mode, the NaOH concentration of the alkali chamber is monitored in the process, and when the NaOH concentration of the alkali chamber reaches 2 wt% again, the second-stage membrane stack is stopped, so that 427g of the alkali chamber solution and 482g of the acid chamber solution are obtained.
Transferring the obtained alkali chamber solution to a neutralization kettle, and introducing CO2Neutralizing NaOH with gas to obtain NaHCO3436g of an aqueous solution.
NaHCO after second stage neutralization3And the water solution and the second-stage acid chamber solution are respectively introduced into the third-stage membrane stack. The voltage was set to 25V and the upper limit of the current density was set to 80mA/cm2And the acid chamber and the alkali chamber are operated in a self-circulation mode, the conductivity of the acid chamber is monitored in the process, and when the conductivity of the acid chamber is reduced to 5mS/cm, the third-stage membrane stack is stopped to obtain 467g of alkali chamber solution and 451g of acid chamber solution. Wherein, the VC content of the acid chamber solution is 17.9 wt%, the VCNa content is 1.7 wt%, the acidification conversion rate is 91.3% (the VC in the acid chamber accounts for the total mass of the VC and the VCNa), and the direct yield of the VC/VCNa in the acid chamber is 98.5%.
Transferring the obtained alkali chamber solution to a neutralization kettleIntroduction of CO2Neutralizing NaOH with gas to obtain NaHCO3474g of aqueous solution. Wherein NaHCO3The content was 8.2 wt%, and the content of VCNa was 0.3 wt%.
Evaporating the aqueous solution to dryness to obtain NaHCO341.0g of solid with purity of 95.7%; the content of VCNa was 3.5%. The evaporation process was carried out with 97.7% yield of VCNa passing through. The total yield of VC/VCNa in the whole process is 99.9 percent.
Obtained NaHCO3For the conversion of methyl gulonate, 68g of methyl gulonate were dissolved in 340g of methanol at 67 ℃ and 30g of the resulting NaHCO were added in 5 portions for 1.5h3Continuing the heat preservation reaction for 3h, filtering and drying to obtain CO with the VCNa apparent yield of 99.4 percent2The gas can be applied to the neutralization kettle.
Example 2
The equipment and the membrane stack adopted in the embodiment are the same as those in the embodiment 1, and the total number is 2.
500g of 4 wt% NaOH aqueous solution is introduced into each stage of polar chamber; 500g of 20 wt% aqueous VCNa solution was introduced into the first acid compartment and 400g of 0.5 wt% NaHCO solution into the first base compartment3Aqueous solution, the voltage of the first-stage membrane stack is set to be 20V, and the upper limit of the current density is set to be 80mA/cm2And the acid chamber and the alkali chamber are operated in a self-circulation mode, the NaOH concentration of the alkali chamber is monitored in the process, and when the NaOH concentration of the alkali chamber reaches-3 wt%, the first-stage membrane stack is stopped, so that 420g of alkali chamber solution and 480g of acid chamber solution are obtained.
Transferring the obtained alkali chamber solution to a neutralization kettle, and introducing CO2Neutralizing NaOH with gas to obtain NaHCO3435g of aqueous solution.
NaHCO after first stage neutralization3The water solution and the first-stage acid chamber solution are respectively introduced into the second-stage membrane stack. The voltage was set to 25V and the upper limit of the current density was set to 80mA/cm2And the acid chamber and the alkali chamber are operated in a self-circulation mode, the conductivity of the acid chamber is monitored in the process, and when the conductivity of the acid chamber is reduced to 5mS/cm, the second-stage membrane stack is stopped to obtain 459g of alkali chamber solution and 456g of acid chamber solution. Wherein, the VC content of the acid chamber solution is 17.7 wt%, the VCNa content is 1.7 wt%, and the acidification conversion rate is 91.2%. The direct yield of VC/VCNa in the acid chamber is 98.5 percent.
Transferring the obtained alkali chamber solution to a neutralization kettle, and introducing CO2Neutralization of gasesNaOH to obtain NaHCO3468g of aqueous solution. Wherein NaHCO3The content was 8.7 wt%, and the content of VCNa was 0.3 wt%.
Evaporating the aqueous solution to dryness to obtain NaHCO340.1g of solid with purity of 95.5%; the VCNa content was 3.4%. The evaporation process was carried out with 97.1% yield of VCNa through a portion. The total yield of VC/VCNa in the whole process is 99.9 percent.
Obtained NaHCO3For the conversion of methyl gulonate, 68g of methyl gulonate were dissolved in 340g of methanol at 67 ℃ and 30g of the resulting NaHCO were added in 5 portions for 1.5h3Continuing the heat preservation reaction for 3h, filtering and drying to obtain CO with the VCNa apparent yield of 99.2 percent2The gas can be applied to the neutralization kettle.
Example 3
The equipment adopted in the embodiment is the same as that of the embodiment 1, but the bipolar membrane stack is different in type and is divided into 2 grades.
500g of 4 wt% NaOH aqueous solution is introduced into each stage of polar chamber; 500g of 20 wt% aqueous VCNa solution was introduced into the first acid compartment and 400g of 0.5 wt% NaHCO solution into the first base compartment3Aqueous solution, the voltage of the first-stage membrane stack is set to be 20V, and the upper limit of the current density is set to be 80mA/cm2And the acid chamber and the alkali chamber are operated in a self-circulation mode, the NaOH concentration of the alkali chamber is monitored in the process, and when the NaOH concentration of the alkali chamber reaches-3 wt%, the first-stage membrane stack is stopped to obtain 429g of alkali chamber solution and 471g of acid chamber solution.
Transferring the obtained alkali chamber solution to a neutralization kettle, and introducing CO2Neutralizing NaOH with gas to obtain NaHCO3446g of aqueous solution.
NaHCO after first stage neutralization3The water solution and the first-stage acid chamber solution are respectively introduced into the second-stage membrane stack. The voltage was set to 25V and the upper limit of the current density was set to 80mA/cm2And the acid chamber and the alkali chamber are operated in a self-circulation mode, the conductivity of the acid chamber is monitored in the process, and when the conductivity of the acid chamber is reduced to 5mS/cm, the second-stage membrane stack is stopped to obtain 473g of alkali chamber solution and 444g of acid chamber solution. Wherein, the VC content of the acid chamber solution is 17.8 wt%, the VCNa content is 1.8 wt%, and the acidification conversion rate is 90.8%. The direct yield of VC/VCNa in the acid chamber is 96.9 percent.
Transferring the obtained alkali chamber solution to a neutralization kettle, and introducing CO2Gas neutralization of NaOH, obtaining NaHCO3482g of aqueous solution. Wherein NaHCO3The content was 8.2 wt%, and the content of VCNa was 0.6 wt%.
Evaporating the aqueous solution to dryness to obtain NaHCO340.7g of solid with purity 91.7%; VCNa content 7.3%. The evaporation process was carried out with 97.8% yield of VCNa passing through. The total yield of VC/VCNa in the whole process is 99.9 percent.
Obtained NaHCO3For the conversion of methyl gulonate, 68g of methyl gulonate were dissolved at 67 ℃ in 340g of methanol and 30g of the resulting NaHCO were added in 5 portions for 1.5h3Continuing the heat preservation reaction for 3h, filtering and drying to obtain CO with the VCNa apparent yield of 98.9 percent2The gas can be applied to the neutralization kettle.
Comparative example 1
The comparative example apparatus, membrane stack, was the same as example 1, but without fractionation and without the use of CO2Neutralizing the alkali liquor.
500g of 4 wt% NaOH aqueous solution was introduced into the cell; 500g of 20 wt% VCNa aqueous solution was introduced into the acid chamber, 400g of pure water was introduced into the alkali chamber, the voltage of the stack was set to 25V, and the upper limit of the current density was set to 80mA/cm2And the acid chamber and the alkali chamber solutions are operated in a self-circulation mode, the conductivity of the acid chamber is monitored in the process, and when the conductivity of the acid chamber is reduced to 5mS/cm, the bipolar membrane electrodialysis is stopped to obtain 442g of the alkali chamber solution and 458g of the acid chamber solution.
Wherein, the VC content in the acid chamber is 17.7 wt%, the VCNa content is 1.6 wt%, the acidification conversion rate is 91%, and the direct yield of VC/VCNa in the acid chamber is 98.5%.
The NaOH content in the alkaline chamber was 4.2 wt.%, the VCNa content was 0.25 wt.% measured immediately after the end of the run, 0.18 wt.% measured after 4h, 0.06 wt.% measured after 24h, and could not be measured after 48 h. The color of the solution in the alkaline chamber is changed from light yellow to light powder to colorless in turn. NaOH alkali liquor cannot be directly used for converting gulonic acid methyl ester, and VC penetrating into an alkali chamber is finally and completely lost. The total yield of VC/VCNa in the whole process is 98.5 percent.
The results of examples 1-3 and comparative example 1 show that the production process is carried out in a multistage manner, and the solution in the alkaline chamber is first treated with CO2Neutralization and then entering the next stage reaction, thus basically avoiding the loss of VC/VCNa in the alkali chamber; and since the transesterification product is VCNa, NaHCO obtained in the base compartment3Can be straightenedFollowed by transesterification for methyl gulonate, NaHCO3The small amount of VCNa contained in the product is directly utilized.

Claims (10)

1. The bipolar membrane acidification production process of vitamin C is characterized by comprising the following steps:
(1) introducing a VCNa aqueous solution into a first-stage acid chamber of a multistage series-connected bipolar membrane electrodialysis membrane stack, promoting hydrogen ions separated by water to combine with VC negative ions left in the bipolar membrane electrodialysis membrane stack under the action of a direct-current electric field to generate vitamin C, introducing the obtained first-stage acid chamber conversion solution into a next-stage acid chamber for continuous conversion, sequentially carrying out the conversion to a last-stage acid chamber, and obtaining a product solution rich in vitamin C through the last-stage conversion;
(2) introducing water or dilute NaHCO into the first stage alkali chamber corresponding to the first stage acid chamber3The solution is prepared by converging hydroxide ions obtained by water dissociation promoted by the bipolar membrane and sodium ions migrated from the anode membrane into NaOH aqueous solution in an alkali chamber under the action of a direct current electric field to obtain a first-stage alkali chamber conversion solution and CO2After neutralization reaction, the mixture is introduced into a next-stage alkali chamber for continuous conversion, and sequentially carried out to a last-stage alkali chamber, and NaHCO containing a small amount of VCNa is obtained through the last-stage conversion3An aqueous solution.
2. The bipolar membrane acidification production process of vitamin C, according to claim 1, characterized in that the number of series connection stages of bipolar membrane electrodialysis membrane stacks is 2-6.
3. The bipolar membrane acidification production process of vitamin C in claim 1, wherein the concentration of VCNa aqueous solution introduced into the first-stage acid chamber is 10-35 wt%.
4. Bipolar membrane acidification production process of vitamin C according to claim 1, characterized in that NaHCO fed into said first stage alkaline chamber3The concentration of the solution is 0.1-2 wt%.
5. According to the rightThe bipolar membrane acidification production process of vitamin C, according to claim 1, characterized in that the voltage used by the bipolar membrane electrodialysis membrane stack is 20-25V, and the current density is 40-100 mA/cm2Preferably 40 to 80mA/cm2。
6. The bipolar membrane acidification production process of vitamin C, according to claim 1, wherein each stage of the acid chamber and the alkali chamber solution self-circulation operation is performed, and when the NaOH concentration in the alkali chamber reaches 2-3 wt%, the alkali chamber conversion solution and CO are mixed together2After neutralization, the acid chamber enters the next stage, and the acid chamber conversion solution directly enters the next stage.
7. The bipolar membrane acidification production process of vitamin C, according to claim 1, characterized in that when the conductivity of the last stage acid chamber solution drops to 5mS/cm, the conversion is stopped, followed by deep acidification by ion exchange resin.
8. The bipolar membrane acidification production process of vitamin C according to claim 1, characterized in that it further comprises a transesterification process of methyl gulonate:
gulonic acid methyl ester and NaHCO3Ester conversion reaction is carried out to generate VCNa and CO2；
Dissolving the generated VCNa, then entering a first-stage acid chamber in the step (1) for conversion, and generating CO2Is used for the neutralization reaction of the step (2).
9. Bipolar membrane acidification production process of vitamin C according to claim 8, characterized in that the NaHCO with low content of VCNa obtained in step (2)3And after the aqueous solution is evaporated and crystallized, mechanically applying the aqueous solution to the transesterification process.
10. A bipolar membrane acidification production device of vitamin C is characterized by comprising an anode electrode, a cathode electrode, a polar membrane and a plurality of pairs of parallel double-compartment repeating units positioned between two stages, wherein each pair of repeating units comprises an acid chamber and a base chamber, the acid chamber and the base chamber of each pair of repeating units are separated by the anode membrane, and two adjacent repeating units are separated by the bipolar membrane; a polar chamber is arranged between the electrode and the polar film; a pair of positive electrodes, a pair of negative electrodes, a pair of polar membranes and a plurality of pairs of parallel-connected repeated double compartments positioned between two stages form a primary membrane stack;
the acid chamber of each stage of membrane stack is communicated with the acid chamber of the next stage of membrane stack through a pipeline;
the alkali chamber of each stage of membrane stack is communicated with the alkali chamber of the next stage of membrane stack through a pipeline, and a neutralization device is arranged between the two alkali chambers.
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