CN114471167A - Process method for separating and decoloring mixed solution containing oxalic acid and glyoxylic acid - Google Patents

Process method for separating and decoloring mixed solution containing oxalic acid and glyoxylic acid Download PDF

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Publication number
CN114471167A
CN114471167A CN202210075388.6A CN202210075388A CN114471167A CN 114471167 A CN114471167 A CN 114471167A CN 202210075388 A CN202210075388 A CN 202210075388A CN 114471167 A CN114471167 A CN 114471167A
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acid
mixed solution
oxalic acid
solution containing
separating
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张新胜
王锡阳
胡硕真
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East China University of Science and Technology
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East China University of Science and Technology
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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
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
    • 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
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/52—Accessories; Auxiliary operation
    • 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
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/54—Controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention relates to a process method for separating and decoloring mixed solution containing oxalic acid and glyoxylic acid. The method is characterized in that a specific selective ion exchange membrane is introduced into an electrodialysis process, and a mixed solution containing oxalic acid and glyoxylic acid is separated and decolorized. The mixed solution containing oxalic acid and glyoxylic acid is sequentially separated through electrodialysis, and the chromogenic substances cannot permeate through the specific selective ion exchange membrane, so that the separation of oxalic acid and glyoxylic acid is realized, and the decolorization is realized. By the process method provided by the invention, the oxalic acid separation rate of the mixed solution containing oxalic acid and glyoxylic acid and the mixed solution containing the chromogenic substance reaches 99%, the glyoxylic acid separation rate reaches 95%, and the removal rate of the chromogenic substance reaches 98%. The process method separates and decolors the mixed solution containing oxalic acid and glyoxylic acid without adding other chemicals, is clean and pollution-free, has high device popularity, can be used for a long time, has low cost, and is suitable for industrial production.

Description

Process method for separating and decoloring mixed solution containing oxalic acid and glyoxylic acid
Technical Field
The invention relates to an electrodialysis technology, belongs to the field of electrochemistry and membrane separation, and particularly relates to a method for carrying out ion separation by using an electrochemistry technology and a membrane separation technology.
Background
The glyoxylate product prepared in the oxalic acid electroreduction process is a mixed solution containing oxalic acid and glyoxylate and a mixed solution of a chromogenic substance, and the recovery of oxalic acid and the removal of the chromogenic substance are necessary requirements for improving the added value of the glyoxylate product. At present, oxalic acid is industrially separated by evaporation crystallization, the method has the disadvantages of high energy consumption, high economic cost and high environmental pressure, and the crystallized oxalic acid contains more impurities and cannot be secondarily utilized as a process raw material. At present, chromogenic substances are adsorbed and removed through ion exchange resin in industry, the method has a common color removal effect, the loss of glyoxylic acid is large during color removal, and the secondary use effect of the ion exchange resin is obviously reduced. The electrodialysis separation of the mixed solution containing oxalic acid and glyoxylic acid and the decolorization have the advantages of simple process flow, low device investment cost, easy popularization of technology and the like. The method is a process technology with green chemical significance from the aspect of environmental benefit, and is an effective measure for improving the resource utilization rate from the aspect of economic benefit.
Disclosure of Invention
The invention aims to provide a process method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid, wherein the oxalic acid is recovered, a chromogenic substance is removed, the glyoxylic acid is refined, the added value of the glyoxylic acid is improved, the application field of the glyoxylic acid is enlarged, and by using the process method, the energy consumption can be saved, the chromogenic substance can be efficiently removed, and a product with high recovery rate and high purity can be obtained.
The invention adopts an electrodialysis process, adopts a four-chamber electrodialysis device as a separation device, and the device is structurally formed by combining an anode plate, a cathode plate and an anion-cation exchange membrane, wherein the ion exchange membrane on the side of the anode plate is a cation exchange membrane, the anion-cation membranes are arranged between the anode plates in an interactive way, and the membranes are separated by a drainage partition plate; the anion exchange membrane is characterized in that polypropylene fibers, polyethylene, polytetrafluoroethylene and the like are used as a support net, functional groups such as quaternary ammonium, benzene rings and ester groups are contained, and the resistance is 1.1-2.31.1 omega-m-2The film thickness is 120 to 150 μm, and the electroosmotic water transport number is 5 to 10 mol water/mol-1Acid radical, wherein the pH tolerance range is 1-14; the cation exchange membrane takes polypropylene fiber, polyethylene, tetrafluoroethylene, polyvinyl chloride and the like as a support net, has functional groups such as sulfonic acid, carboxylic acid, perfluorosulfonic acid, perfluorocarboxylic acid and the like, has high hydrogen ion selective permeability and high organic acid radical anion barrier property, and has the resistance of 0.9-1.8 omega m-2Thickness of the film is 90 to 130 μmThe pH value is 1-12, and the environment stability is very good; the treatment solution is a mixed solution containing oxalic acid and glyoxylic acid and a chromogenic substance.
The invention provides a process method for separating and decoloring mixed solution containing oxalic acid and glyoxylic acid, which comprises the following steps of: firstly, adding sulfuric acid into a polar chamber liquid storage tank (2), adding a mixed solution into a desalting chamber liquid storage tank (6), adding pure water into a concentration chamber liquid storage tank (7), then opening a circulating pump (1) of each liquid storage tank, opening a constant temperature tank (9), starting electrodialysis when the circulating liquid of the system reaches a set temperature, and when the electric flux reaches 0.56 F.mol-1When the solution in the liquid storage tank (7) of the concentration chamber is completely separated, the equal volume of water is quickly supplemented to the liquid storage tank (7) of the concentration chamber after the separation is finished, and the electric flux reaches 1.2 F.mol-1When the solution in the reservoir (7) of the concentration chamber is separated by electrodialysis, the solution is stopped. The anion exchange membrane can permeate acid radical anions with the molecular weight of 50-200; the cation exchange membrane can permeate cations with the molecular weight of 1-300; the chromogenic substance is a mixture of pyruvic acid, glyceric acid and carboxylic acid functional group with the molecular weight of 100-1000; the mass fraction of the oxalic acid is 0.5-8%, and the mass fraction of the glyoxylic acid is 0.5-6%; the mass fraction of the sulfuric acid in the cathode chamber and the anode chamber is 15-25 percent; the constant temperature range is 8-45 ℃; the current density is 10-1000 A.m-2(ii) a The flow of the desalting chamber, the concentration chamber and the cathode and anode chambers is 20-250 m3·h-1。
Drawings
FIG. 1: flow chart of electrodialysis experimental facility. 1 is a circulating pump, 2 is an electrode chamber liquid storage tank, 3 is a desalting chamber liquid storage tank, 4 is a concentration chamber liquid storage tank, 5 is a cathode chamber, 6 is a desalting chamber, 7 is a concentration chamber, 8 is an anode chamber, and 9 is a constant temperature tank.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
Pretreating the specific selective ion exchange membrane: washing the anion-cation exchange membrane with pure water for several times,then soaking the membrane in 2% hydrochloric acid solution for 24 h, cleaning the anion and cation exchange membranes for a plurality of times by pure water, and soaking the membrane in the pure water to keep the humidity; after an ion exchange membrane is placed into an electrodialysis device for installation, 2L of mixed solution containing 72 g/L of oxalic acid, 60 g/L of glyoxylic acid and 250-degree chroma is placed into a liquid storage tank of a desalting chamber, 2L of pure water is placed into a concentration chamber, and 2L of 20% sulfuric acid is placed into a cathode chamber and an anode chamber respectively; opening the thermostatic bath and the circulating pump, controlling the temperature of each chamber at 25 deg.C and the flow rate at 200 m3·h-1Finally, turning on the power supply to adjust the current density to 150A/m2And after 5 hours of electrodialysis, closing a circulating pump of the concentration chamber, separating liquid in a liquid storage tank of the concentration chamber, wherein the oxalic acid obtained by separation in the process is 71.2 g/L, the recovery rate of the oxalic acid is 99.03%, rapidly supplementing 2L of pure water to the liquid storage tank of the concentration chamber after separation, continuing electrodialysis after turning on the circulating pump again, closing an electrodialysis device after continuing electrodialysis for 3 hours, closing a constant temperature tank and a power supply, separating liquid in the liquid storage tank of the concentration chamber, wherein the glyoxylic acid obtained by separation in the process is 57.1 g/L, the recovery rate of the glyoxylic acid is 95.20%, finally separating liquid in a liquid storage tank of a desalting chamber, wherein the measured chromaticity is 245.1%, and the removal rate of chromogenic substances is 98.04%.
Example 2
Pretreating the specific selective ion exchange membrane: cleaning the anion and cation exchange membranes for several times by using pure water, then soaking the membranes for 24 hours by using 2% hydrochloric acid solution, cleaning the anion and cation exchange membranes for several times by using the pure water, and soaking the membranes in the pure water to keep the humidity; after an ion exchange membrane is placed into an electrodialysis device for installation, 2L of mixed solution containing 72 g/L of oxalic acid, 60 g/L of glyoxylic acid and 250-degree chroma is placed into a liquid storage tank of a desalting chamber, 2L of pure water is placed into a concentration chamber, and 2L of 20% sulfuric acid is placed into a cathode chamber and an anode chamber respectively; the thermostatic bath and the circulating pump are opened, the temperature of each chamber is controlled to be 35 ℃, and the flow rate is controlled to be 230 m3·h-1Finally, turning on the power supply to adjust the current density to 100A/m2Closing a circulating pump of the concentration chamber after electrodialysis for 7.5h, separating liquid in a liquid storage tank of the concentration chamber, obtaining 70.5 g/L oxalic acid after separation in the process, achieving the oxalic acid recovery rate of 98.03%, rapidly supplementing 2L pure water to the liquid storage tank of the concentration chamber after separation, continuing electrodialysis after the circulating pump is turned on again, and continuing electrodialysis after the electrodialysis is continuedAnd after 6 h, closing the electrodialysis device, closing the constant temperature tank and the power supply, separating liquid in a liquid storage tank of the concentration chamber, wherein the glyoxylic acid separated in the process is 56.5 g/L, the recovery rate of the glyoxylic acid is 94.20%, finally separating the liquid in the liquid storage tank of the desalting chamber, the measured chromaticity is 240.8 degrees, and the removal rate of the chromogenic substances reaches 96.34%.
Example 3
Pretreating the specific selective ion exchange membrane: cleaning the anion and cation exchange membranes for several times by using pure water, then soaking the membranes for 24 hours by using 2% hydrochloric acid solution, cleaning the anion and cation exchange membranes for several times by using the pure water, and soaking the membranes in the pure water to keep the humidity; after an ion exchange membrane is placed into an electrodialysis device for installation, 2L of mixed solution containing 72 g/L of oxalic acid, 60 g/L of glyoxylic acid and 250-degree chroma is placed into a liquid storage tank of a desalting chamber, 2L of pure water is placed into a concentration chamber, and 2L of 20% sulfuric acid is placed into a cathode chamber and an anode chamber respectively; opening the thermostatic bath and the circulating pump, controlling the temperature of each chamber at 15 ℃ and the flow at 180 m3·h-1Finally, turning on the power supply to adjust the current density to 400A/m2And after 1.9 h of electrodialysis, closing a circulating pump of the concentration chamber, separating liquid in a liquid storage tank of the concentration chamber, wherein the oxalic acid obtained by separation in the process is 68.2 g/L, the recovery rate of the oxalic acid is 94.73%, quickly supplementing 2L of pure water to the liquid storage tank of the concentration chamber after separation, continuing electrodialysis after re-opening the circulating pump, after 1.7 h of electrodialysis is continued, closing an electrodialysis device, closing a constant temperature tank and a power supply, separating liquid in the liquid storage tank of the concentration chamber, wherein the glyoxylic acid obtained by separation in the process is 54.6 g/L, the recovery rate of the glyoxylic acid is 91.14%, finally separating liquid in a liquid storage tank of a desalting chamber, measuring the chroma to be 237.1%, and the removal rate of chromogenic substances to be 94.84%.
Comparative example 1
After an existing commercially available HF201 type anion exchange membrane and HF-1 type cation exchange membrane are placed in an electrodialysis device for installation, 2L of mixed solution containing 72 g/L of oxalic acid, 60 g/L of glyoxylic acid and 250-degree chroma is placed in a reservoir of a desalting chamber, 2L of pure water is placed in a concentration chamber, and 2L of 20% sulfuric acid is placed in a cathode chamber and an anode chamber respectively; opening the thermostatic bath and the circulating pump, controlling the temperature of each chamber at 25 deg.C and the flow rate at 200 m3·h-1Finally turning on the power supplyThe current density is adjusted to 150A/m2And after 5 hours of electrodialysis, closing a circulating pump of the concentration chamber, separating liquid in a liquid storage tank of the concentration chamber, wherein the oxalic acid obtained by separation in the process is 52.7 g/L, the recovery rate of the oxalic acid is 73.19%, quickly supplementing 2L of pure water to the liquid storage tank of the concentration chamber after separation, continuing electrodialysis after turning on the circulating pump again, closing an electrodialysis device after continuing electrodialysis for 3 hours, closing a constant temperature tank and a power supply, separating liquid in the liquid storage tank of the concentration chamber, wherein the glyoxylic acid obtained by separation in the process is 32.6 g/L, the recovery rate of the glyoxylic acid is 54.34%, finally separating liquid in a liquid storage tank of a desalting chamber, wherein the measured chromaticity is 152.7%, and the removal rate of chromogenic substances is 61.08%.

Claims (9)

1. A method for separating and decoloring mixed solution containing oxalic acid and glyoxylic acid is characterized in that a four-chamber electrodialysis device is adopted as a separation device, the core part of the device is formed by combining an anode plate, a cathode plate, a cation exchange membrane and an anion exchange membrane, the ion exchange membrane on the side of the anode plate is the cation exchange membrane, the cation exchange membrane and the anion exchange membrane are arranged between the anode plates in an interactive way, and the membranes are separated by a drainage clapboard;
the anion exchange membrane takes polypropylene fiber, polytetrafluoroethylene and the like as a support net, has functional groups such as tetrapentylamine group, ethanolamine group and the like, and has the resistance of 1.1-2.31.1 omega-m-2The film thickness is 120 to 150 μm, and the electroosmotic water transport number is 5 to 10 mol water/mol-1Acid radical, wherein the pH tolerance range is 1-14;
the cation exchange membrane takes polypropylene fiber, polyethylene or tetrafluoroethylene-polyvinyl chloride and the like as a support net, has functional groups such as furoic acid, diphenol and the like, and has the resistance of 0.9-1.8 omega-m-2The thickness of the film is 90-130 μm, and the environment stability is very good when the pH value is 1-12; the cation exchange membrane has high selective permeability to hydrogen ions and high barrier property to organic acid radical anions,
the mixed solution contains oxalic acid, glyoxylic acid and a chromogenic substance;
a method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid, comprising the steps of:
a. firstly, sulfuric acid is added into a polar chamber liquid storage tank (2), a mixed solution is added into a desalting chamber liquid storage tank (6), and pure water is added into a concentration chamber liquid storage tank (7)
b. Then the circulating pump (1) of each liquid storage tank is opened, the thermostatic bath (9) is opened, and when the circulating liquid of the system reaches the set temperature
c. Starting the electrodialysis, the electric flux reaches 0.56 F.mol-1Then all the solution in the liquid storage tank (7) of the concentration chamber is separated, the separated solution is the recovered oxalic acid solution, and after the separation is finished, the equal volume of water is quickly supplemented in the liquid storage tank (7) of the concentration chamber
d. When the electric flux reaches 1.2 F.mol-1When the solution in the liquid storage tank (7) of the electrodialysis separation concentration chamber is stopped, the separated solution is recovered glyoxylic acid solution;
e. and separating the solution in a liquid storage tank (6) of the desalting chamber, wherein the solution is a chromogenic substance separation solution.
2. The method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid according to claim 1, wherein the preparation of the cationic and anionic membranes is performed by thermal initiation coupling.
3. The method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid according to claim 1, wherein the anion exchange membrane is permeable to anions having a molecular weight of 50 to 200.
4. The method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid according to claim 1, wherein the cation exchange membrane is permeable to cations having a molecular weight of 1 to 300.
5. The method of claim 1, wherein the chromogenic substance is selected from the group consisting of pyruvic acid, glyceric acid and a mixture having a molecular weight of 100 to 1000 and containing a carboxylic acid functional group.
6. The method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid according to claim 1, wherein the mass fraction of oxalic acid in the mixed solution is 0.5 to 8 percent, and the mass fraction of glyoxylic acid is 0.5 to 6 percent.
7. The method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid according to claim 1, wherein the mass fraction of sulfuric acid in the anode chamber and the cathode chamber is 15 to 25 percent.
8. The method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid according to claim 1, wherein the constant temperature range is 8-45 ℃ and the current density is 10-1000A-m-2。
9. The method for separating and decoloring a mixed solution containing oxalic acid and glyoxylic acid according to claim 1, wherein the flow rates of the desalting chamber, the concentrating chamber and the cathode and anode chambers are 20-250 m3·h-1。
CN202210075388.6A 2022-01-22 2022-01-22 Process method for separating and decoloring mixed solution containing oxalic acid and glyoxylic acid Pending CN114471167A (en)

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