CN114989019A - Acidic ionic liquid recovery method based on bipolar membrane electrodialysis-ultrafiltration - Google Patents
Acidic ionic liquid recovery method based on bipolar membrane electrodialysis-ultrafiltration Download PDFInfo
- Publication number
- CN114989019A CN114989019A CN202210569896.XA CN202210569896A CN114989019A CN 114989019 A CN114989019 A CN 114989019A CN 202210569896 A CN202210569896 A CN 202210569896A CN 114989019 A CN114989019 A CN 114989019A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- ultrafiltration
- acidic ionic
- solution
- bipolar membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- 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
- B01D61/58—Multistep processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of acidic liquid recovery and regeneration, in particular to a bipolar membrane electrodialysis-ultrafiltration-based acidic ionic liquid recovery method, which comprises the following steps: mixing a lignocellulose raw material and an acidic ionic liquid to be treated for hydrothermal reaction; washing the reaction product with ethanol, and concentrating to obtain a concentrated solution; adding water into the concentrated solution to separate out lignin from the concentrated solution to obtain supernatant; removing macromolecular impurities in the supernatant through ultrafiltration, treating ultrafiltration filtrate through electrodialysis, extracting solution in an electrodialysis mixing chamber through diethyl ether to obtain an organic compound part, and removing water from the solution in an electrodialysis acid chamber to obtain an inorganic acid part; mixing the organic compound part and the inorganic acid part to obtain regenerated acidic ionic liquid; the invention can recover different ionic components from the acidic ionic liquid with complex composition in a partitioned manner, thereby improving the recovery rate and the processing speed of the ionic liquid.
Description
Technical Field
The invention relates to the technical field of acidic liquid recovery and regeneration, in particular to a bipolar membrane electrodialysis-ultrafiltration-based acidic ionic liquid recovery method, and particularly relates to a technology for recovering and regenerating acidic ionic liquid used as a solvent and a catalyst in a biomass pretreatment and conversion process.
Background
The outstanding characteristics and excellent solvent performance enable the acidic ionic liquid to become an effective solvent and a catalyst for biomass high-value processes such as biomass processing and conversion. The cost problem and the lack of effective recovery means are main factors for restricting the scale application of the acidic ionic liquid to biomass processing.
Acidic ionic liquids such as triethylammonium hydrogen sulfate ([ TEA)][HSO 4 ]) 1-butyl-3-methylimidazolium hydrogen sulfate ([ Bmim)][HSO 4 ]) And the three ions of organic cation, sulfate ion and hydrogen ion can be ionized in the solution, so that the direct and effective recovery and regeneration of all components are difficult to realize after the biomass processing.
The ultrafiltration technology is widely applied to the processes of industrial wastewater purification, pharmaceutical industry purification, industrial water treatment and the like. The ultrafiltration technology is that different substances in a solution are pushed to pass through an ultrafiltration membrane by pressure difference, and due to the difference of the interception capacities of the ultrafiltration membrane to the substances with different sizes, the substances with specific molecular weight ranges in the solution are intercepted.
The bipolar membrane electrodialysis is widely applied to the fields of environment, chemical industry, biology and the like. The bipolar membrane electrodialyzer membrane stack is formed by arranging a bipolar membrane and an anion-cation membrane in a certain sequence. When voltage is applied to two sides of the membrane stack, the bipolar membrane can dissociate water to obtain hydrogen ions and hydroxyl ions on two sides of the membrane respectively. At the same time, under the action of electric field and ion exchange membrane to selectively transfer ions, the anions and cations in the feed liquid of electrodialyzer can be combined with the hydrogen ions and hydroxyl ions formed by water dissociation. This provides the possibility of recovery of different ions in the salt solution, salt conversion and synthesis of acid and alkali.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a method for recovering acidic ionic liquid based on bipolar membrane electrodialysis-ultrafiltration.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
A method for recovering acidic ionic liquid based on bipolar membrane electrodialysis-ultrafiltration comprises the following steps:
1) mixing a lignocellulose raw material and acidic ionic liquid to be treated for hydrothermal reaction.
2) Washing the obtained reaction product with ethanol, and concentrating to obtain concentrated solution.
3) Adding water into the concentrated solution to separate lignin from the concentrated solution to obtain supernatant.
4) Removing macromolecular impurities in the supernatant by ultrafiltration to obtain ultrafiltration filtrate.
5) Treating the ultrafiltration filtrate by electrodialysis, extracting the solution in the electrodialysis mixing chamber by diethyl ether to obtain organic compound part, and removing water from the solution in the electrodialysis acid chamber to obtain inorganic acid part.
6) And mixing the organic compound part and the inorganic acid part to obtain the regenerated acidic ionic liquid.
Preferably, in the step 1), distilled water is added into the acidic ionic liquid, and the mass fraction of the acidic ionic liquid in the acidic ionic liquid-distilled water mixture is 45% -95%; the mass ratio of the acidic ionic liquid-distilled water mixture to the lignocellulose raw material is as follows: 1-20:1.
Preferably, the temperature of the hydrothermal reaction is 100-170 ℃, and the reaction time is 10-50 minutes.
Preferably, the ultrafiltration treatment conditions are: the molecular weight cut-off is 1-0.65 Da, the temperature is 10-50 ℃, the transmembrane pressure is 100-700 kPa, the cross flow velocity: 0.1-5.0 ms -1 。
Preferably, the ultrafiltration filtrate is diluted with distilled water to reduce the concentration of organic ions in the ultrafiltration filtrate to 0.01 to 2.0 mol/L.
Preferably, the electrodialysis treatment adopts a three-chamber bipolar membrane electrodialysis device, and the feeding liquid of the electrode chamber is Na 2 SO 4 A solution at a concentration of 1.0-10.0 wt.%; the feed liquid in the mixing chamber is ultrafiltration filtrate, the feed liquid in the acid chamber is dilute sulfuric acid solution, and the concentration of the dilute sulfuric acid solution in the mixing chamber are measured by a flow meterThe feed solution was the same.
Preferably, the initial volume of the solution in each chamber of the three-chamber bipolar membrane electrodialysis device is 0.5-3.0L, and the applied current density is 1-100 mA/cm 2 The flow rate of the solution in each zone is 1.0-30.0L/h.
Further, the ether phase obtained after the ether extraction is subjected to rotary evaporation to separate ether and organic compound parts; and removing water in the acid chamber solution by adopting rotary evaporation to obtain the inorganic acid.
Further, the mixing in the step 6) is to perform mixing reaction on the inorganic acid part and the organic compound part according to the molar ratio of 1:0.5-1: 2.
Further, the acidic ionic liquid to be treated is triethylammonium bisulfate ionic liquid.
Further, the reaction temperature of the hydrothermal reaction in the step 1) is 100-170 ℃, and the reaction time is 10-50 minutes.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention adopts a processing mode based on a membrane separation technology to carry out partition recovery on different ionic components of the acidic ionic liquid with complex composition, thereby improving the recovery rate and the processing speed of the ionic liquid. Meanwhile, the recovery cost of the ionic liquid is reduced.
2) The recovery and regeneration process of acidic ionic liquid with complex composition converts the partitioned recovery of different ionic components, such as triethylammonium bisulfate- [ TEA ] in acidic ionic liquid][HSO 4 ]The triethyl ammonium radical and the sulfate radical in the product are respectively converted into triethylamine and sulfuric acid for recovery. Provides a foundation for the regeneration process of the ionic liquid.
3) The method has the advantages of simple required equipment, simple and convenient process, short treatment time, mild conditions and no additional environmental hazard, and has referential and instructive properties for expanding the practical application of the acidic ionic liquid with complex compositions and electrolytes with similar compositions.
Drawings
Fig. 1 is a schematic view of a bipolar membrane electrodialysis device used in examples 1, 2 and 3 of the present invention.
Fig. 2 is a fourier transform infrared (KBr tabletting) test chart of the regenerated acidic ionic liquid samples obtained in examples 1, 2 and 3 of the present invention.
FIG. 3 is a sample of the regenerated acidic ionic liquid obtained in examples 1, 2 and 3 of the present invention 1 H-NMR nuclear magnetic (DMSO-d 6 is solvent) test chart.
FIG. 4 shows the types and parameters of the ion exchange membranes used in the bipolar membrane electrodialysis employed in the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The technical solution of the present invention is described in detail below with reference to the embodiments and the drawings, but the scope of protection is not limited thereto.
Example 1: a method for recovering and regenerating acidic ionic liquid based on bipolar membrane electrodialysis-ultrafiltration comprises the following specific steps:
1) mixing acidic ionic liquid and distilled water in proportion, wherein the mass fraction of the acidic ionic liquid in the mixed solvent is as follows: 80 percent. After the lignocellulose raw material is crushed and dried, the mixed solvent and the crushed lignocellulose particles are mixed according to the proportion of 5g/1 g. After mixing uniformly, the mixture was reacted in a reaction kettle at 150 ℃ for 30 minutes.
2) After the reaction, the reaction product was washed with hot ethanol and filtered with a buchner funnel, and the filtrate was subjected to rotary evaporation to remove ethanol to obtain a concentrated solution. Adding deionized water into the concentrated solution, standing overnight, then centrifugally separating out lignin, filtering the supernatant through an ultrafiltration membrane with the molecular weight cut-off of 0.65K Da, filtering the pretreated lignin by the ultrafiltration membrane used in ultrafiltration treatment, centrifugally separating to obtain the supernatant, wherein the ultrafiltration treatment conditions are as follows: temperature 25 ℃, transmembrane pressure 400 kPa, cross-flow rate: 2.4 ms -1 。
3) And diluting the filtrate obtained by ultrafiltration with distilled water, wherein the treatment target is that the concentration of the triethylammonium ion in the solution is reduced to 0.1 mol/L.
4) The electrodialysis treatment adopts ｃA BP-A-BP type three-chamber bipolar membrane electrodialysis device, and the electrode chamber feed liquid is NｃA 2 SO 4 Solution, concentration 5.0 wt.%. The feed liquid in the mixing chamber is diluted to obtain ultrafiltration filtrate, and the concentration of the ultrafiltration filtrate is measured by the molar concentration of triethylammonium ions. The acid chamber feeding liquid is a dilute sulfuric acid solution, and the concentration of the dilute sulfuric acid solution is the same as that of the mixing chamber feeding liquid.
5) The initial volume of the solution in each cell of the electrodialyzer was 1.0L, and the current density applied to the electrodialyzer was 25 mA/cm 2 The flow rate of the solution in each zone was 15.0L/h.
6) After the electrodialysis treatment, the cell solution was collected and extracted with 300 ml of ether in three extractions, the ether phases were combined after the extraction was completed and the ether and triethylamine were separated by rotary evaporation. Meanwhile, collecting the acid chamber solution of the electrodialyzer, and removing water in the acid chamber solution by rotary evaporation to obtain concentrated sulfuric acid.
7) And slowly dripping concentrated sulfuric acid into triethylamine, reacting the obtained concentrated sulfuric acid triethylamine in a flask containing a certain amount of deionized water in an ice water bath according to a molar ratio of 1:1, and preserving heat for 3 hours after dripping is finished. Obtaining light yellow liquid, removing water on a rotary evaporator to obtain light yellow acidic ionic liquid triethylammonium bisulfate- [ TEA [ ]][HSO 4 ]。
This example is for acidic ionic liquids [ TEA][HSO 4 ]The recovery rate can reach 93.9 percent, the current efficiency of an electrodialyzer in the recovery process is 87.4 percent, and the recovery energy consumption is 12.4 kwh/kg.
Example 2: a method for recovering and regenerating acidic ionic liquid based on bipolar membrane electrodialysis-ultrafiltration comprises the following specific steps:
1) mixing acidic ionic liquid and distilled water in proportion, wherein the mass fraction of the acidic ionic liquid in the mixed solvent is as follows: 80 percent. After the lignocellulose raw material is crushed and dried, the mixed solvent and the crushed lignocellulose particles are mixed according to the proportion of 5g/1 g. After mixing uniformly, the mixture was reacted in a reaction kettle at 150 ℃ for 30 minutes.
2) After the reaction, the reaction product was washed with ethanol and filtered through a buchner funnel, and the filtrate was subjected to rotary evaporation to remove ethanol to obtain a concentrated solution. Adding deionized water into the concentrated solution, standingAnd (2) centrifuging the separated lignin, filtering the supernatant through an ultrafiltration membrane with the molecular weight cut-off of 0.65K Da, filtering the pretreated lignin by using the ultrafiltration membrane used in the ultrafiltration treatment, centrifuging the pretreated lignin, and obtaining the supernatant, wherein the ultrafiltration treatment conditions are as follows: temperature 25 ℃, transmembrane pressure 400 kPa, cross-flow rate: 2.4 ms -1 。
3) And diluting the filtrate obtained by ultrafiltration with distilled water, wherein the treatment target is that the concentration of the triethylammonium ion in the solution is reduced to 0.2 mol/L.
4) The electrodialysis treatment adopts ｃA BP-A-BP type three-chamber bipolar membrane electrodialysis device, and the feed liquid of the electrode chamber is NｃA 2 SO 4 Solution, concentration 5.0 wt.%. The feed liquid in the mixing chamber is diluted to obtain ultrafiltration filtrate, and the concentration of the ultrafiltration filtrate is measured by the molar concentration of triethylammonium ions. The acid chamber feeding liquid is a dilute sulfuric acid solution, and the concentration of the dilute sulfuric acid solution is the same as that of the mixing chamber feeding liquid.
5) The initial volume of the solution in each cell of the electrodialyzer was 1.0L, and the current density applied to the electrodialyzer was 25 mA/cm 2 The flow rate of the solution in each zone was 15.0L/h.
6) After the electrodialysis treatment, the cell solution was collected and extracted with 300 ml of ether in three extractions, the ether phases were combined after the extraction was completed and the ether and triethylamine were separated by rotary evaporation. Meanwhile, collecting the acid chamber solution of the electrodialyzer, and removing water in the acid chamber solution by rotary evaporation to obtain concentrated sulfuric acid.
7) And (3) slowly dripping concentrated sulfuric acid into triethylamine, reacting the obtained concentrated sulfuric acid and triethylamine in a flask containing a certain amount of deionized water in an ice-water bath according to a molar ratio of 1:1, and preserving heat for 3 hours after dripping is finished. Obtaining light yellow liquid, removing water on a rotary evaporator to obtain light yellow acidic ionic liquid triethylammonium bisulfate- [ TEA [ ]][HSO 4 ]。
This example is for acidic ionic liquids [ TEA][HSO 4 ]The recovery rate can reach 95.4 percent, the current efficiency of the electrodialyzer in the recovery process is 89.4 percent, and the recovery energy consumption is 26.8 kwh/kg.
Example 3: a method for recovering and regenerating acidic ionic liquid based on bipolar membrane electrodialysis-ultrafiltration comprises the following specific steps:
1) mixing acidic ionic liquid and distilled water in proportion, wherein the mass fraction of the acidic ionic liquid in the mixed solvent is as follows: 80 percent. After the lignocellulose raw material is crushed and dried, the mixed solvent and the crushed lignocellulose particles are mixed according to the proportion of 5g/1 g. After mixing uniformly, the mixture was reacted in a reaction kettle at 150 ℃ for 30 minutes.
2) After the reaction, the reaction product was washed with ethanol and filtered through a buchner funnel, and the filtrate was subjected to rotary evaporation to remove ethanol to obtain a concentrated solution. Adding deionized water into the concentrated solution, standing overnight, then centrifugally separating out lignin, filtering the supernatant through an ultrafiltration membrane with the molecular weight cut-off of 0.65K Da, filtering the pretreated lignin by the ultrafiltration membrane used in ultrafiltration treatment, centrifugally separating to obtain the supernatant, wherein the ultrafiltration treatment conditions are as follows: temperature 25 ℃, transmembrane pressure 400 kPa, cross-flow rate: 2.4 ms -1 。
3) And diluting the filtrate obtained by ultrafiltration with distilled water, wherein the treatment target is that the concentration of the triethylammonium ion in the solution is reduced to 0.3 mol/L.
4) The electrodialysis treatment adopts ｃA BP-A-BP type three-chamber bipolar membrane electrodialysis device, and the feed liquid of the electrode chamber is NｃA 2 SO 4 Solution, concentration 5.0 wt.%. The feed liquid in the mixing chamber is diluted to obtain ultrafiltration filtrate, and the concentration of the ultrafiltration filtrate is measured by the molar concentration of triethylammonium ions. The acid chamber feeding liquid is a dilute sulfuric acid solution, and the concentration of the acid chamber feeding liquid is the same as that of the mixing chamber feeding liquid.
5) The initial volume of the solution in each cell of the electrodialyzer was 1.0L, and the current density applied to the electrodialyzer was 20 mA/cm 2 The flow rate of the solution in each zone was 15.0L/h.
6) After the electrodialysis treatment, the cell solution was collected and extracted with 300 ml of ether in three extractions, the ether phases were combined after the extraction was completed and the ether and triethylamine were separated by rotary evaporation. Meanwhile, collecting the acid chamber solution of the electrodialyzer, and removing water in the acid chamber solution by rotary evaporation to obtain concentrated sulfuric acid.
7) And (3) slowly dripping concentrated sulfuric acid into triethylamine, reacting the obtained concentrated sulfuric acid and triethylamine in a flask containing a certain amount of deionized water in an ice-water bath according to a molar ratio of 1:1, and preserving heat for 3 hours after dripping is finished. Obtaining light yellow liquidRemoving water on a rotary evaporator to obtain light yellow acidic ionic liquid triethylammonium bisulfate- [ TEA [ ]][HSO 4 ]。
This example is for acidic ionic liquids [ TEA][HSO 4 ]The recovery rate can reach 95.8 percent, the current efficiency of the electrodialyzer in the recovery process is 90.3 percent, and the recovery energy consumption is 43.4 kwh/kg.
As can be seen from FIG. 1, acidic ionic liquids such as [ TEA ]][HSO 4 ]TEA is ionized in the solution + (Triethylammonium radical), H + 、SO 4 2- Three ions. Byproduct biomass-based cation C after biomass processing X+ And biomass-based anion A X- And TEA + 、SO 4 2- And H + Together maintain the charge balance of the solution. By means of a three-compartment bipolar membrane electrodialysis device as shown in FIG. 1, SO in the feed solution of the mixing compartment is obtained after application of an electric field across the stack 4 2- Transferring to an acid chamber (right chamber) through an anion exchange membrane under the action of an electric field, and reacting with H generated in the acid chamber + A sulfuric acid solution is formed. While mixing the OH generated in the chamber (left chamber) - Will successively neutralize H in the solution + And TEA + Water and Triethylamine (TEA) are formed and the main reactions taking place in the mixing chamber are shown below. Then triethylamine is separated by means of ethyl ether extraction, distillation and the like, and reacts with sulfuric acid to generate [ TEA][HSO 4 ]An aqueous solution of (a). Further removing excess water to obtain [ TEA][HSO 4 ]。
OH - +H + →H 2 O （1）
OH - +TEA + →H 2 O+ TEA （2）
As can be seen from FIG. 2, the regenerated acidic ionic liquid [ TEA ] recovered in examples 1, 2 and 3 of the present invention][HSO 4 ]Sample and original [ TEA][HSO 4 ]The positions of the absorption peaks of the infrared spectrums of the samples are matched. Illustrative examples 1-3 recovered regenerated acidic ionic liquid samples have characteristic functional groups consistent with the original ionic liquid samples. As can be seen from FIG. 3, the regenerated acidic ionic liquid [ TEA ] recovered in examples 1, 2 and 3 of the present invention][HSO 4 ]Nuclei of samplesMagnetic hydrogen spectrum liquid and original [ TEA][HSO 4 ]The peak positions of the nuclear magnetic hydrogen spectra of the samples are consistent, further explaining that the recovery of the samples can keep the original chemical structure and composition, namely, the recovery and regeneration method of the acidic ionic liquid based on the bipolar membrane electrodialysis-ultrafiltration can realize the acidic ionic liquid [ TEA][HSO 4 ]And (3) effectively recovering and regenerating the sample.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for recovering acidic ionic liquid based on bipolar membrane electrodialysis-ultrafiltration is characterized by comprising the following steps:
1) mixing a lignocellulose raw material and an acidic ionic liquid to be treated for hydrothermal reaction;
2) washing the obtained reaction product with ethanol, and concentrating to obtain a concentrated solution;
3) adding water into the concentrated solution to separate out lignin from the concentrated solution to obtain supernatant;
4) removing macromolecular impurities in the supernatant through ultrafiltration to obtain ultrafiltration filtrate;
5) treating the ultrafiltration filtrate by electrodialysis, extracting the solution in the electrodialysis mixing chamber by diethyl ether to obtain an organic compound part, and removing water from the solution in the electrodialysis acid chamber to obtain an inorganic acid part;
6) and mixing the organic compound part and the inorganic acid part to obtain the regenerated acidic ionic liquid.
2. The bipolar membrane electrodialysis-ultrafiltration-based acidic ionic liquid recovery method according to claim 1, wherein in the step 1), distilled water is added into the acidic ionic liquid, and the mass fraction of the acidic ionic liquid in the acidic ionic liquid-distilled water mixture is 45% -95%; the mass ratio of the acidic ionic liquid-distilled water mixture to the lignocellulose raw material is as follows: 1-20:1.
3. The method for recovering the acidic ionic liquid based on the bipolar membrane electrodialysis-ultrafiltration as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 100-170 ℃ and the reaction time is 10-50 minutes.
4. The method for recovering the acidic ionic liquid based on the bipolar membrane electrodialysis-ultrafiltration as claimed in claim 1, wherein the ultrafiltration treatment conditions are as follows: the molecular weight cut-off is 1-0.65 Da, the temperature is 10-50 ℃, the transmembrane pressure is 100-700 kPa, the cross flow velocity: 0.1-5.0 ms -1 。
5. The method for recovering the acidic ionic liquid based on bipolar membrane electrodialysis-ultrafiltration as claimed in claim 1, wherein the ultrafiltration filtrate is diluted with distilled water to reduce the concentration of the organic ions in the ultrafiltration filtrate to 0.01-2.0 mol/L.
6. The bipolar membrane electrodialysis-ultrafiltration-based acidic ionic liquid recovery method according to claim 1, wherein the electrodialysis treatment adopts a three-chamber bipolar membrane electrodialysis device, and the feeding liquid of a chamber is Na 2 SO 4 A solution at a concentration of 1.0-10.0 wt.%; the feed liquid in the mixing chamber is ultrafiltration filtrate, and the feed liquid in the acid chamber is dilute sulfuric acid solution, and the concentration of the dilute sulfuric acid solution is the same as that of the feed liquid in the mixing chamber.
7. The bipolar membrane electrodialysis-ultrafiltration-based acidic ionic liquid recovery method according to claim 6, wherein the initial volume of each compartment solution of the three-compartment bipolar membrane electrodialysis device is 0.5-3.0L, and the applied current density is 1-100 mA/cm 2 The flow rate of the solution in each zone is 1.0-30.0L/h.
8. The method for recovering the acidic ionic liquid based on the bipolar membrane electrodialysis-ultrafiltration as claimed in claim 1, wherein the diethyl ether phase obtained after the diethyl ether extraction is subjected to rotary evaporation to separate diethyl ether and organic compound parts; and removing water in the acid chamber solution by adopting rotary evaporation to obtain the inorganic acid.
9. The bipolar membrane electrodialysis-ultrafiltration-based acidic ionic liquid recovery method according to claim 1, wherein the mixing in step 6) is a mixing reaction of inorganic acid part and organic compound part in a molar ratio of 1:0.5-1: 2.
10. The bipolar membrane electrodialysis-ultrafiltration-based acidic ionic liquid recovery method according to claim 1, wherein the acidic ionic liquid to be treated is triethylammonium bisulfate ionic liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210569896.XA CN114989019A (en) | 2022-05-24 | 2022-05-24 | Acidic ionic liquid recovery method based on bipolar membrane electrodialysis-ultrafiltration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210569896.XA CN114989019A (en) | 2022-05-24 | 2022-05-24 | Acidic ionic liquid recovery method based on bipolar membrane electrodialysis-ultrafiltration |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114989019A true CN114989019A (en) | 2022-09-02 |
Family
ID=83026343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210569896.XA Pending CN114989019A (en) | 2022-05-24 | 2022-05-24 | Acidic ionic liquid recovery method based on bipolar membrane electrodialysis-ultrafiltration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114989019A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118184517A (en) * | 2024-05-14 | 2024-06-14 | 山东海化集团有限公司 | Method for recycling triethylamine through vinylene carbonate byproduct triethylamine hydrochloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073131A (en) * | 2012-12-28 | 2013-05-01 | 中国环境科学研究院 | Process for treating amantadine bromination waste water and mineral acid and alkali recycling through bipolar membrane electrodialysis process |
| CN107285534A (en) * | 2017-07-08 | 2017-10-24 | 华东理工大学 | A kind of process for handling the organic wastewater containing free acid and quaternary ammonium salt |
| CN111848409A (en) * | 2020-06-30 | 2020-10-30 | 浙江工业大学 | Method for preparing tetraethyl ammonium tetrafluoroborate by bipolar membrane electrodialysis assistance |
-
2022
- 2022-05-24 CN CN202210569896.XA patent/CN114989019A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073131A (en) * | 2012-12-28 | 2013-05-01 | 中国环境科学研究院 | Process for treating amantadine bromination waste water and mineral acid and alkali recycling through bipolar membrane electrodialysis process |
| CN107285534A (en) * | 2017-07-08 | 2017-10-24 | 华东理工大学 | A kind of process for handling the organic wastewater containing free acid and quaternary ammonium salt |
| CN111848409A (en) * | 2020-06-30 | 2020-10-30 | 浙江工业大学 | Method for preparing tetraethyl ammonium tetrafluoroborate by bipolar membrane electrodialysis assistance |
Non-Patent Citations (2)
| Title |
|---|
| XIAOCONG LIANG ET AL.: "Accurately-controlled recovery and regeneration of protic ionic liquid after Ionosolv pretreatment via bipolar membrane electrodialysis with ultrafiltration", BIORESOURCE TECHNOLOGY, vol. 318, pages 124255 - 1 * |
| XIAOCONG LIANG ET AL.: "Recovery of ionic liquid via a hybrid methodology of electrodialysis with ultrafiltration after biomass pretreatment", BIORESOURCE TECHNOLOGY, vol. 220, pages 289 - 296, XP029734771, DOI: 10.1016/j.biortech.2016.08.092 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118184517A (en) * | 2024-05-14 | 2024-06-14 | 山东海化集团有限公司 | Method for recycling triethylamine through vinylene carbonate byproduct triethylamine hydrochloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102597253B (en) | Process for economically manufacturing xylose from hydrolysate using electrodialysis and direct recovery method | |
| CN110644014B (en) | Preparation method of tetraethyl ammonium hydroxide | |
| WO2012051774A1 (en) | Process for salting out and extracting organic acid from fermentation broth | |
| CN101033241B (en) | Method of preparing high-purity humic acid | |
| CN102267919A (en) | Preparation method of L-dopa from Mucuna pruriens | |
| CN114989019A (en) | Acidic ionic liquid recovery method based on bipolar membrane electrodialysis-ultrafiltration | |
| CN108793204B (en) | Method and system for preparing lithium carbonate from lithium-containing feed liquid | |
| CN105061607A (en) | Lithium-ion imprinted polymer and preparation method thereof | |
| CN103203187B (en) | A preparation method for solid film dip-coated with a novel chiral recognition agent | |
| Li et al. | A cascade electro-dehydration process for simultaneous extraction and enrichment of uranium from simulated seawater | |
| CN103304677B (en) | A kind of method of separation and purification Rhizoma amorphophalli glucomannan | |
| CN104093485B (en) | The method that pentose is extracted from lignocellulosic matrix | |
| CN106018632B (en) | A kind of method of nitrosamine precursor in enriching and purifying water based on ion exchange technique | |
| CN107532221B (en) | Process for recovering acid from acid/sugar solution | |
| CN114797795A (en) | By using GMA/H 3 PO 4 Method for treating uranium-containing wastewater by using modified natural fibers | |
| CN108129328B (en) | Preparation method of methyl triethyl ammonium chloride | |
| CN105712841B (en) | A kind of method of the propane diols of the separation and Extraction from zymotic fluid 1,3 | |
| CN104291501A (en) | Method of treating ammonium nitrate wastewater by adoption of integrated membrane technology | |
| CN115536588A (en) | Hydroxy glycine functional ionic liquid, preparation method thereof and application thereof in iodine extraction | |
| CN102311379A (en) | Method for preparing 1-deoxynojirimycin by membrane separation technology | |
| CN105237786A (en) | Method for preparing quaternization polyphenyl ether anion exchange membrane | |
| CN111574735B (en) | Polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film and preparation and application thereof | |
| CN110387279B (en) | Recovery method of hydrophilic ionic liquid for removing sulfur in coal | |
| CN102952008A (en) | Method for extracting succinic acid from anaerobic fermentation broth | |
| CN111392783A (en) | Method for removing vanadium ions from high-acid iron-and vanadium-containing nickel sulfate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |