CN109134317B - Method for preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis - Google Patents
Method for preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis Download PDFInfo
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- CN109134317B CN109134317B CN201811049436.4A CN201811049436A CN109134317B CN 109134317 B CN109134317 B CN 109134317B CN 201811049436 A CN201811049436 A CN 201811049436A CN 109134317 B CN109134317 B CN 109134317B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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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
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Abstract
The invention discloses a method for preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis, which comprises the steps of adopting a bipolar membrane electrodialysis device, firstly introducing an L-10-camphorsulfonic acid ammonium solution into a salt chamber in a bipolar membrane electrodialysis membrane stack, respectively introducing deionized water into an acid chamber and an alkali chamber in the bipolar membrane electrodialysis membrane stack, and respectively introducing a strong electrolyte solution into an anode chamber and a cathode chamber in the bipolar membrane electrodialysis membrane stack; and then applying direct current to two ends of the bipolar membrane electrodialysis membrane stack to realize the preparation of the L-10-camphorsulfonic acid by converting the L-10-camphorsulfonic acid ammonium. In the bipolar membrane electrodialysis conversion process, the conversion rate of the L-10-camphorsulfonic acid ammonium can reach more than 98%, and the purity of the obtained product L-10-camphorsulfonic acid can reach more than 99%. The preparation method is simple to operate, does not need to consume any chemical reagent, and avoids the problems of consumption of a large amount of chemical reagents and generation of secondary pollutants caused by regeneration of ion exchange resin after the ion exchange method in the traditional process is used.
Description
Technical Field
The invention relates to a method for preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis, belonging to the technical field of organic acid production.
Background
The camphorsulfonic acid is a derivative of camphor, has a chiral counterpart structure, can be divided into a left-handed structure and a right-handed structure according to the chemical characteristics of the camphor sulfonic acid, wherein the levo-camphorsulfonic acid (L-10-camphorsulfonic acid) is widely applied to the industries of medicine, light industry, daily chemicals and the like. At present, the chemical synthesis of L-10-camphorsulfonic acid is mainly to synthesize a solution of ammonium camphorsulfonate, then obtain the solution of L-10-camphorsulfonate by resolution, and then obtain the solution of L-10-camphorsulfonic acid by continuous ion exchange through a fixed bed. The process often has the production cycle long, and the overall yield is relatively lower, and product purity is relatively poor, still needs further separation and purification, and in addition, resin after the ion exchange still need be regenerated, need consume a large amount of reagents, can produce a large amount of waste water simultaneously, causes secondary pollution to the environment.
In view of the above problems, chinese patent CN105461596A proposes a clean production process for converting ammonium camphorsulfonate into camphorsulfonic acid, which comprises the following steps: (1) filtering the raw material solution by a ceramic membrane to obtain dialysate; (2) the ceramic membrane dialysate enters a continuous ion exchange system for ion exchange to obtain a camphorsulfonic acid solution; (3) carrying out reverse osmosis concentration on the camphorsulfonic acid solution to obtain a concentrated solution; (4) and carrying out MVR concentration on the camphorsulfonic acid concentrated solution, and then crystallizing to obtain the camphorsulfonic acid crystal. However, the ion exchange system is still used in the clean production process, and the above problems cannot be solved.
Bipolar membrane electrodialysis, as a green, environment-friendly and energy-saving membrane separation technology, can dissociate water into H under low voltage+And OH-Therefore, organic and inorganic salts can be converted into corresponding acid and alkali in one step, no chemical reagent is consumed in the process, and no by-product is generated. However, at present, L-10-camphorsulfonic acid is not prepared by converting L-10-camphorsulfonic acid ammonium salt by bipolar membrane electrodialysis methodThe report of (1).
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis, so as to realize a low-energy-consumption, green and environment-friendly production process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method for preparing the L-10-camphorsulfonic acid by bipolar membrane electrodialysis comprises the following steps:
adopting a bipolar membrane electrodialysis device, firstly introducing an L-10-camphorsulfonic acid ammonium solution into a salt chamber in a bipolar membrane electrodialysis membrane stack, respectively introducing deionized water into an acid chamber and an alkali chamber in the bipolar membrane electrodialysis membrane stack, and respectively introducing strong electrolyte solutions into an anode chamber and a cathode chamber in the bipolar membrane electrodialysis membrane stack; then applying direct current to two ends of the bipolar membrane electrodialysis membrane stack to realize the preparation of L-10-camphorsulfonic acid by converting L-10-camphorsulfonic acid ammonium, namely H generated by bipolar membrane dissociation in an acid chamber under the action of direct current+Combined with L-10-camphorsulfonic acid anion migrating from the salt compartment to the acid compartment to form L-10-camphorsulfonic acid, and OH produced by bipolar membrane dissociation in the base compartment-And combines with ammonium ions migrating from the salt chamber to the alkali chamber to generate ammonia water.
The arrangement mode of the membrane stack in the bipolar membrane electrodialysis device is sequentially set as anode electrode-anode chamber-bipolar membrane- [ acid chamber-anion exchange membrane-salt chamber-cation exchange membrane-alkali chamber-bipolar membrane]nCathode compartment-cathode electrode, the number of repeating units n, n being from 1 to 1000.
The content of the L-10-camphorsulfonic acid ammonium in the L-10-camphorsulfonic acid ammonium solution which is introduced into the salt room is 10-200 g/L.
The strong electrolyte solution which is introduced into the anode chamber and the cathode chamber is sodium sulfate or sodium nitrate solution, and the concentration is 0.01-1.0 mol/L. The anode chamber and the cathode chamber are connected in series, so that the total amount of cations and the total amount of anions in the two polar chambers are kept unchanged, and the balance of anions and cations in the electrolyte is maintained.
The anode electrode and the cathode electrode are made of corrosion-resistant titanium ruthenium coating; the compartments between adjacent ion exchange membranes, including the acid chamber, the alkali chamber and the salt chamber, are all formed by gaskets with flow channels and grids, and the thickness of each gasket is 0.8 mm.
In the operation process, the feed liquid of each compartment is circulated for 5-30 minutes by a peristaltic pump, and air bubbles in the membrane stack are discharged.
In the operation process, the peristaltic pump is used for controlling the linear flow velocity of the flowing solutions of the anode chamber, the cathode chamber, the acid chamber, the alkali chamber and the salt chamber to be 3-10cm/s, so that the concentration polarization phenomenon is avoided.
In the operation process, the operation is carried out at constant voltage, and the upper limit of the current density is set to be 10-100mA/cm2。
After the bipolar membrane electrodialysis conversion, the conductivity of the L-10-camphor ammonium sulfonate solution can be reduced to be below 500 mu S/cm.
In the bipolar membrane electrodialysis conversion process, the conversion rate of the L-10-camphorsulfonic acid ammonium can reach more than 98%, and the purity of the obtained product L-10-camphorsulfonic acid can reach more than 99%.
Compared with the prior art, the invention has the beneficial effects that:
the invention firstly applies bipolar membrane electrodialysis to convert the L-10-camphorsulfonic acid ammonium solution to prepare the L-10-camphorsulfonic acid, and the bipolar membrane can be used for directly dissociating water to generate H in the process+And OH-The method has the advantages that the L-10-camphorsulfonic acid ammonium is converted into the L-10-camphorsulfonic acid ammonium and ammonia water by a one-step method, and the obtained product has higher purity. The method avoids the method of using ion exchange resin to carry out ion exchange in the traditional process, thereby also avoiding the problems of large amount of chemical reagent consumption and secondary pollutant generation caused by resin regeneration after ion exchange. Therefore, the preparation of the L-10-camphorsulfonic acid by converting the L-10-camphorsulfonic acid ammonium solution through the bipolar membrane is an economic, green and environment-friendly production method and has important industrial application value.
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FIG. 1 is a schematic diagram of the principle of preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis according to the present invention.
Detailed Description
The following examples further illustrate the preparation of L-10-camphorsulfonic acid by bipolar membrane electrodialysis.
Example 1:
this example uses a bipolar membrane electrodialysis device as shown in FIG. 1, and the membrane stack arrangement is anode electrode-anode chamber-bipolar membrane- [ acid chamber-anion exchange membrane-salt chamber-cation exchange membrane-alkali chamber-bipolar membrane]nCathode compartment-cathode electrode, the number of repeating units n being 5. The anode and cathode in the membrane stack are made of corrosion-resistant titanium ruthenium-coated, and the compartments between adjacent ion exchange membranes comprise acid chambers and alkali chambers and are formed by gaskets with flow channels and grids, wherein the thickness of each gasket is 0.8 mm. The cation exchange membrane, anion exchange membrane and bipolar membrane used in the membrane stack are CJMC-3, CJMA-3 and CJBPM-2 produced by combined fertilizer technology Polymer materials science and technology Limited, and the effective area of a single membrane is 189cm2(9cm×21cm)。
The anode chamber and the cathode chamber are connected in series, and 500mL of 0.3mol/L Na is introduced2SO4And (3) introducing 1000mL of 100 g/L-10-camphorsulfonic acid ammonium solution (the conductivity is 13mS/cm) into a salt chamber in the bipolar membrane electrodialysis membrane stack by taking the aqueous solution as strong electrolyte, and introducing 800mL of deionized water into an acid chamber and an alkali chamber in the bipolar membrane electrodialysis membrane stack respectively. During the experiment, the linear flow rate of the solution in each compartment flowing in the membrane stack is 4cm/s, the membrane stack is operated at constant voltage, the voltage of the membrane stack is set to be 20V, and the upper limit of the current density is set to be 50mA/cm2。
The experiment was run until the conductivity of the salt compartment dropped to 500. mu.S/cm and was stopped, the conversion of L-10-camphorsulfonic acid ammonium salt was 96.2%, and the L-10-camphorsulfonic acid product obtained in the acid compartment was tested by liquid phase and had a purity as high as 99.8%, indicating that L-10-camphorsulfonic acid ammonium salt could be efficiently converted to L-10-camphorsulfonic acid by bipolar membrane electrodialysis.
Example 2:
the bipolar membrane electrodialysis apparatus used in this example was the same as in example 1.
The anode chamber and the cathode chamber are connected in series, and 500mL of 0.3mol/L Na is introduced2SO4And (3) introducing 1000mL of 200 g/L-10-camphorsulfonic acid ammonium solution (the conductivity is 26mS/cm) into a salt chamber in the bipolar membrane electrodialysis membrane stack, and introducing 800mL of deionized water into an acid chamber and an alkali chamber in the bipolar membrane electrodialysis membrane stack respectively. In the experimental processThe linear flow rate of the solution in each compartment flowing in the membrane stack was 4cm/s, the operation was carried out at constant voltage, the membrane stack voltage was set to 15V, and the upper limit of the current density was set to 50mA/cm2。
The experiment was run until the conductivity of the salt compartment dropped to 500. mu.S/cm and was stopped, the conversion of L-10-camphorsulfonic acid ammonium salt was 98.1%, and the L-10-camphorsulfonic acid product obtained in the acid compartment was tested by liquid phase and had a purity as high as 99.5%, indicating that L-10-camphorsulfonic acid ammonium salt could be efficiently converted to L-10-camphorsulfonic acid by bipolar membrane electrodialysis.
Example 3:
the bipolar membrane electrodialysis apparatus used in this example was the same as in example 1.
The anode chamber and the cathode chamber are connected in series, and 500mL of 0.3mol/L Na is introduced2SO4And (3) introducing 1000mL of 200 g/L-10-camphorsulfonic acid ammonium solution (the conductivity is 26mS/cm) into a salt chamber in the bipolar membrane electrodialysis membrane stack, and introducing 800mL of deionized water into an acid chamber and an alkali chamber in the bipolar membrane electrodialysis membrane stack respectively. During the experiment, the linear flow rate of the solution in each compartment flowing in the membrane stack is 4cm/s, the membrane stack is operated at constant voltage, the voltage of the membrane stack is set to be 20V, and the upper limit of the current density is set to be 50mA/cm2。
The experiment was run until the conductivity of the salt compartment dropped to 300. mu.S/cm, the conversion of L-10-camphorsulfonic acid ammonium salt was 98.8%, and the L-10-camphorsulfonic acid product obtained in the acid compartment was tested by liquid phase and had a purity as high as 99.4%, indicating that L-10-camphorsulfonic acid ammonium salt could be efficiently converted to L-10-camphorsulfonic acid by bipolar membrane electrodialysis.
Claims (4)
1. A method for preparing L-10-camphorsulfonic acid by bipolar membrane electrodialysis is characterized by comprising the following steps: adopting a bipolar membrane electrodialysis device, firstly introducing an L-10-camphorsulfonic acid ammonium solution into a salt chamber in a bipolar membrane electrodialysis membrane stack, respectively introducing deionized water into an acid chamber and an alkali chamber in the bipolar membrane electrodialysis membrane stack, and respectively introducing strong electrolyte solutions into an anode chamber and a cathode chamber in the bipolar membrane electrodialysis membrane stack; then applying direct current to two ends of the bipolar membrane electrodialysis membrane stack to realize the preparation of L-10-camphorsulfonic acid by the conversion of the L-10-camphorsulfonic acid ammonium;
in the operation process, the peristaltic pump is used for controlling the linear flow velocity of the flowing solutions of the anode chamber, the cathode chamber, the acid chamber, the alkali chamber and the salt chamber to be 3-10cm/s, so that the concentration polarization phenomenon is avoided;
the arrangement mode of the membrane stack in the bipolar membrane electrodialysis device is sequentially set as anode electrode-anode chamber-bipolar membrane- [ acid chamber-anion exchange membrane-salt chamber-cation exchange membrane-alkali chamber-bipolar membrane]nCathode compartment-cathode electrode, the number of repeating units n, n being 5;
the cation exchange membrane, anion exchange membrane and bipolar membrane used in the membrane stack are CJMC-3, CJMA-3 and CJBPM-2;
the content of the L-10-camphorsulfonic acid ammonium in the L-10-camphorsulfonic acid ammonium solution which is introduced into the salt room is 100g/L or 200 g/L; the anode electrode and the cathode electrode are made of corrosion-resistant titanium ruthenium coating;
the strong electrolyte solution which is introduced into the anode chamber and the cathode chamber is sodium sulfate solution, and the concentration is 0.01-1.0 mol/L.
2. The method of claim 1, wherein: in the operation process, the feed liquid of each compartment is circulated for 5-30 minutes by a peristaltic pump, and air bubbles in the membrane stack are discharged.
3. The method of claim 1, wherein: in the running process, the operation is carried out at constant voltage, and the current density is set to be 10-100 mA/cm.
4. The method of claim 1, wherein: after the conversion by bipolar membrane electrodialysis, the conductivity of the L-10-camphorsulfonic acid ammonium solution is less than or equal to 500 mu S/cm.
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| CN114672830A (en) * | 2020-12-24 | 2022-06-28 | 江苏优士化学有限公司 | Preparation method of organic acid |
| CN114288857B (en) * | 2021-12-31 | 2023-03-10 | 中国科学技术大学 | Method for preparing ultrahigh-concentration acid and alkali through overflow type-saturated feeding bipolar membrane electrodialysis |
| CN114506961A (en) * | 2022-03-21 | 2022-05-17 | 青岛职业技术学院 | Method for extracting thioglycollic acid from tail liquid of thiourethane production |
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