CN110862326A - Method for preparing high-purity choline from choline chloride - Google Patents
Method for preparing high-purity choline from choline chloride Download PDFInfo
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- CN110862326A CN110862326A CN201810990571.2A CN201810990571A CN110862326A CN 110862326 A CN110862326 A CN 110862326A CN 201810990571 A CN201810990571 A CN 201810990571A CN 110862326 A CN110862326 A CN 110862326A
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- choline
- exchange resin
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- 229960001231 choline Drugs 0.000 title claims abstract description 71
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 title claims abstract description 42
- 235000019743 Choline chloride Nutrition 0.000 title claims abstract description 42
- 229960003178 choline chloride Drugs 0.000 title claims abstract description 42
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 71
- 239000012528 membrane Substances 0.000 claims abstract description 64
- 239000007864 aqueous solution Substances 0.000 claims abstract description 61
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 33
- 238000000909 electrodialysis Methods 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000005341 cation exchange Methods 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 62
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 57
- 239000012498 ultrapure water Substances 0.000 claims description 57
- 239000007788 liquid Substances 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 40
- 239000002585 base Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000010306 acid treatment Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003011 anion exchange membrane Substances 0.000 claims description 10
- -1 hydroxyl ions Chemical class 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229920001429 chelating resin Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940075419 choline hydroxide Drugs 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A method for preparing high purity choline from choline chloride, the method comprising the steps of: 1) pretreating strong-acid cation exchange resin to obtain a pretreated strong-acid cation exchange resin column; 2) enabling the choline chloride aqueous solution to pass through at least one group of pretreated strong-acid cation exchange resin columns to remove cation impurities in the choline chloride aqueous solution; 3) performing electrodialysis treatment on the choline chloride aqueous solution passing through the strong-acid cation exchange column by using a bipolar membrane to obtain a choline aqueous solution and a hydrochloric acid solution; 4) pretreating a strong-base anion exchange resin column to obtain a pretreated strong-base anion exchange resin column; 5) and (3) enabling the choline aqueous solution obtained in the step 3) to pass through at least one group of pretreated strong-base anion exchange resin columns to remove anion impurities in the choline aqueous solution, and then carrying out reduced pressure distillation and concentration on the obtained choline aqueous solution to obtain the ultrapure choline aqueous solution.
Description
(I) technical field
The invention relates to a preparation method of choline, in particular to a method for preparing high-purity choline from choline chloride.
(II) background of the invention
The ultra-clean high-purity reagent is one of key chemical materials in the manufacturing process of a super-large-scale integrated circuit, and is mainly used for cleaning and corroding chips. In recent years, along with the development of the electronics industry, the demand for ultra-clean and high-purity reagents has been increasing, and the purity of the ultra-clean and high-purity reagents has an important influence on the yield and the electrical properties of integrated circuits, so that the requirement for the purity of the ultra-clean and high-purity reagents is increasing.
Choline, hydroxyethyl trimethylamine, is a quaternary ammonium base, a colorless crystalline or colorless bitter water-soluble white slurry, has strong hygroscopicity, and absorbs water quickly when exposed to air. Choline readily reacts with acids to form more stable crystalline salts (e.g., choline chloride), is also unstable under strongly alkaline conditions, but is fairly stable to heat and storage. As an organic strong base, the ionic liquid can be completely ionized in water, and the metal content is low. The chemical characteristics of the choline chloride lead the choline chloride to have wide application in the fields of chemical industry and semiconductors.
Industrially, chemical synthesis, electrolysis and ion exchange resin methods are mainly used for synthesizing choline. The chemical synthesis methods are mainly two, a continuous process for the production of choline hydroxide as disclosed in patent CN104066711, which comprises reacting ethylene oxide, trimethylamine and water in a reaction zone to form a reaction mixture, and extracting heat from the reaction mixture. Subsequently, the reaction mixture was subjected to phase separation to obtain a choline phase and an organic liquid phase containing trimethylamine, and a choline solution was obtained from the choline phase. However, the process is complicated, and ethylene oxide has strong pungent odor and toxicity, and environmental pollution is certainly caused in the production process. Another chemical synthesis method, for example, disclosed in patent CN102731314, is a method for preparing quaternary ammonium hydroxide from quaternary ammonium salt, which comprises contacting choline chloride with alkali metal hydroxide in the presence of an organic solvent, wherein the contacting is carried out in the presence of a precipitation promoter, which is a substance capable of promoting the choline chloride and the alkali metal hydroxide to form alkali metal salt precipitate. According to the method for preparing the choline from the choline chloride, the raw materials are low in price and simple to operate, but the purity of the choline cannot reach the standard of electronic-grade choline.
A method for preparing hydrogen halide acid by electrolysis method such as short chain quaternary ammonium base four-chamber three-membrane electrolysis disclosed in patent CN107904618A comprises feeding choline chloride into raw material chamber of four-chamber three-membrane electrolytic cell, allowing chloride ions to selectively move to intermediate chamber through anion membrane under the action of electric potential, and combining with hydrogen ions transferred from anode chamber to obtain hydrochloric acid; choline chloride cations in the raw material chamber selectively migrate to the cathode chamber through the cation membrane under the action of potential, and hydroxide anions in the cathode chamber are combined with the choline chloride cations migrated from the raw material chamber to obtain choline product. However, this method generates chlorine gas, which is dissolved in the solution to cause a series of complicated reactions, so that the aqueous choline solution contains a large amount of impurities, and the raw materials and the product are mixed together and are difficult to separate.
Ion exchange resin process as disclosed in patent CN1428330, i.e. a strongly basic anion exchange resin in chlorine form is first treated with NaOH solution to convert it to OH form: the choline chloride dissolved in the solvent is then treated with the resulting resin to obtain the corresponding choline. The method can rapidly, efficiently and massively convert choline chloride into high-purity choline, can obviously reduce the production cost of the choline, but generates a large amount of acid-base wastewater when the resin is cleaned.
Therefore, in view of the problems of economic efficiency and environmental protection, and making the product to meet the electronic grade standard, a new method for preparing high purity choline is required to be opened.
Disclosure of the invention
The invention aims to provide a low-cost, energy-saving and environment-friendly method for preparing high-purity choline from choline chloride, which can provide high-purity choline, has high conversion rate and obvious environmental and economic benefits, and byproducts can be recycled.
The invention is realized by the following technical scheme:
a method for preparing high purity choline from choline chloride, the method comprising the steps of:
1) pretreating strong-acid cation exchange resin, wherein the pretreatment process comprises the following steps: acid treatment, ultrapure water treatment to neutrality, alkali treatment and ultrapure water treatment to neutrality, then repeating the acid treatment/ultrapure water treatment steps for more than two times, and finally washing with a large amount of ultrapure water to obtain a pre-treated strong-acid cation exchange resin column;
2) enabling the choline chloride aqueous solution to pass through at least one group of pretreated strong-acid cation exchange resin columns to remove cation impurities in the choline chloride aqueous solution;
3) performing electrodialysis treatment on the choline chloride aqueous solution passing through the strong-acid cation exchange column by using a bipolar membrane to obtain a choline aqueous solution and a hydrochloric acid solution;
4) pretreating a strong-alkaline anion exchange resin column, wherein the pretreatment process comprises the following steps in sequence: performing alkali treatment, ultrapure water treatment to neutrality, acid treatment and ultrapure water treatment to neutrality, then repeating the alkali treatment/ultrapure water treatment step for more than two times, and finally washing with a large amount of ultrapure water to obtain a pretreated strong-base anion exchange resin column;
5) and (3) enabling the choline aqueous solution obtained in the step 3) to pass through at least one group of pretreated strong-base anion exchange resin columns to remove anion impurities in the choline aqueous solution, and then carrying out reduced pressure distillation and concentration on the obtained choline aqueous solution to obtain the ultrapure choline aqueous solution.
The strong acid cation exchange resin used in the present invention is one commonly referred to as the hydrogen form (H)+) The strongly acidic cation exchange resin is an ion exchange resin having a sulfonic acid group in a styrene-divinylbenzene copolymer, and particularly a WU-64H type cation exchange resin is preferable.
In the step 1), because the new cation exchange resin contains a small amount of unreacted substances, low molecular weight polymers, impurities such as iron, lead, copper and the like, the new cation exchange resin is easy to transfer into a solution in the reaction process, and the purification effect of the resin is influenced. Therefore, a pretreatment of the strong acid cation exchange resin column is first required. The acid treatment is to input strong acid aqueous solution with a certain multiple of the volume of the cation exchange resin for flow treatment. Further, as the strong acid, a conventionally known strong acid such as hydrochloric acid can be used. The mass concentration of the strong acid contained in the strong acid aqueous solution is 3-4%. The volume of the strong acid aqueous solution used is preferably 5 to 10 times the volume of the resin to be treated. The alkali treatment is that strong alkali aqueous solution with a certain multiple of the volume of the cation exchange resin is input for flow treatment. Further, as the strong base, conventionally known strong bases such as sodium hydroxide and potassium hydroxide can be used. The mass concentration of the strong base contained in the strong base aqueous solution is preferably 3 to 4%, and the volume of the strong base aqueous solution used is preferably 5 to 10 times of the volume of the resin to be treated. The ultrapure water treatment to be neutral is to use ultrapure water flow to clean the ultrapure water to be neutral. The invention repeats the steps of acid treatment/ultrapure water cleaning after acid treatment, ultrapure water treatment, alkali treatment and ultrapure water treatment, circulates for more than 2 times, can promote the shrinkage and expansion of the resin, effectively and uniformly transforms the cation exchange resin, and can clean the inside of the resin. In the preferred acid treatment, ultrapure water treatment and alkali treatment processes of the present invention, the strong acid aqueous solution, the strong alkali aqueous solution and the ultrapure water are passed through the resin at flow rates of 2 to 5BV/h, respectively. Finally, the resin is rinsed with a large amount of ultrapure water, preferably 10 to 20 times the volume of the resin, at a flow rate of 5 to 10BV/h, including upward and downward flow, through the cation exchange resin to complete the pretreatment of the cation exchange resin.
In the step 2), the choline chloride aqueous solution is contacted with at least one group of pretreated strong acid cation exchange resin in a continuous flow method, preferably the choline chloride aqueous solution with the concentration of 0.3-0.6M passes through the strong acid cation exchange resin at the flow rate of 2-5BV/h to remove cation impurities, such as Na+，K+，Mg+And the like. The number of groups of strong-acid cation exchange resins is preferably 1 to 8.
Said step 3) is preferably carried out as follows:
the bipolar membrane electrodialysis device comprises a cathode plate, an anode plate and a membrane stack arranged between the anode plates, wherein the membrane stack consists of one or more groups of electrodialysis units, each unit electrodialysis cell comprises a bipolar membrane, an anion exchange membrane, a cation exchange membrane and a bipolar membrane from the anode to the cathode in sequence, and two adjacent membranes are separated by a partition plate; four membranes sequentially arranged in each unit electrodialysis cell form an acid chamber, a feed liquid chamber and an alkali chamber, and are respectively externally connected with an acid tank, a feed liquid tank and an alkali tank through pipelines to form a loop; an electrode liquid chamber is formed between the cathode plate and the anode plate and the adjacent bipolar membrane respectively, and the electrode liquid chamber is externally connected with an electrode liquid tank through a pipeline to form a loop;
adding a choline chloride aqueous solution passing through a strong acid cation exchange column into a feed liquid tank in a bipolar membrane electrodialysis device, adding 3 wt.% sodium sulfate solution with the same volume into an electrode liquid tank, and adding ultrapure water with the same volume into an acid tank and an alkali tank respectively;
the starting device is used for respectively enabling liquid continuous flow in the feed liquid tank, the polar liquid tank, the acid tank and the alkali tank to enter the feed liquid chamber, the polar liquid chamber, the acid chamber and the alkali chamber, connecting a cathode and an anode of the bipolar membrane electrodialysis device with a cathode and an anode of a direct-current power supply respectively, then starting the power supply, controlling the voltage to be 12.5V-20V, controlling the reaction temperature to be 20-40 ℃, and carrying out electrodialysis treatment, wherein in the treatment process, cations of choline chloride in the feed liquid chamber penetrate through a cation exchange membrane and migrate to the alkali chamber to be combined with hydroxyl ions generated by the bipolar membrane to generate choline, so that a target product is obtained; the chloride ions in the feed liquid chamber migrate to the acid chamber through the anion exchange membrane and combine with hydrogen ions generated by the bipolar membrane to generate hydrochloric acid; when the choline concentration in the alkali chamber does not rise any more and the current tends to be stable, the reaction is stopped, the hydrochloric acid in the acid tank is recovered, and the choline aqueous solution in the alkali tank is taken out.
Further, the anode plate and the cathode plate are titanium ruthenium-plated electrode plates.
Further, the bipolar membrane is bipolar membrane BP-1E (ASTOM Co, Japan), the anion exchange membrane is anion exchange membrane AHA (ASTOM Co, Japan), and the cation exchange membrane is cation exchange membrane CMB (ASTOM Co, Japan).
Furthermore, outlets of the anode chamber and the cathode chamber are externally connected with an inlet of an electrode solution tank through pipelines to form a loop, and the pipelines are provided with circulating pumps;
an outlet of the feed liquid chamber is externally connected with an inlet of the feed liquid tank through a pipeline to form a loop, and a circulating pump is arranged on the pipeline;
the outlet of the alkali chamber is externally connected with the inlet of the alkali tank through a pipeline to form a loop, and the pipeline is provided with a circulating pump;
the outlet of the acid chamber is externally connected with the inlet of the acid tank through a pipeline to form a loop, and the pipeline is provided with a circulating pump.
Furthermore, a section of pipeline connected with the liquid inlet of any one of the compartments of the feed liquid compartment, the extreme liquid compartment, the acid compartment and the alkali compartment is a circulating coil pipe, and the circulating coil pipe is placed in ice water, so that the feed liquid in the circulating coil pipe is fully cooled, and the temperature of the feed liquid in the compartment in the electrodialysis process is controlled to be 20-40 ℃.
The invention controls the flow into each compartment by means of a circulating pump, preferably 30L/h.
In the step 4), the strongly basic anion exchange resin used in the invention is hydroxide radical type (OH)-) The strong base anion exchange resin mainly contains strong base groups, such as quaternary ammonium groups, can dissociate OH < - > in water to be strong base, and the positive groups of the resin can be adsorbed and combined with anions in a solution to generate anion exchange action. A preferred strongly basic anion exchange resin is Amberlite IRA-400, USA.
The new strong basic anion exchange resin contains a small amount of unreacted substances, low molecular weight polymers, iron, lead, copper and other impurities, and is easy to transfer into a solution in the reaction process to influence the purification effect of the resin, so the strong basic anion exchange resin is pretreated firstly. The alkali treatment is that strong alkali water solution with a certain multiple of the volume of the strong alkali anion exchange resin is input for flow treatment. Further, as the strong base, conventionally known strong bases such as sodium hydroxide and potassium hydroxide can be used. The concentration of the strong base contained in the strong base aqueous solution is preferably 3 to 4%, and the volume of the strong base aqueous solution used is 5 to 10 times of the volume of the resin to be treated. The acid treatment is that strong acid aqueous solution with a certain multiple of the volume of the strong base anion exchange resin is input for flow treatment. Further, as the strong acid, a conventionally known strong acid such as hydrochloric acid can be used. The strong acid solution contains 3-4% of strong acid. The volume of the strong acid aqueous solution used is 5 to 10 times of the volume of the resin to be treated. The ultrapure water treatment to be neutral is to use ultrapure water flow to clean the ultrapure water to be neutral. The invention repeats the steps of alkali treatment/ultrapure water treatment after alkali treatment, ultrapure water treatment, acid treatment and ultrapure water treatment, circulates for more than 2 times, can promote the shrinkage and expansion of the resin, effectively and uniformly converts the anion exchange resin, and can clean the inside of the resin. In the alkali treatment, the ultrapure water treatment and the acid treatment, the strong alkali aqueous solution, the ultrapure water and the strong acid aqueous solution are preferably respectively passed through the resin at flow rates of 2-5 BV/h. Finally, the resin is rinsed with a large amount of ultrapure water, preferably 10 to 20 times the volume of the resin, at a flow rate of 5 to 10BV/h, including upward and downward flow, through the anion exchange resin to complete the pretreatment of the anion exchange resin.
In said step 5), the aqueous choline solution is preferably contacted with the strongly basic anion exchange resin used in the present invention in a continuous flow method, preferably the aqueous choline solution is passed through the hydroxide type (OH) at a flow rate of 2-5BV/h-) Strong basic anion exchange resin to remove anion impurities in the choline solution, such as chloride, carbonate and the like. Preferably the number of groups of strongly basic anion exchange resins is from 1 to 8.
Through the operation of the invention, the ultrapure choline aqueous solution can be prepared, and the concentration of the removed ionic impurities reaches the standard level of SEMI C12.
Compared with the prior art, the invention has the beneficial effects that: the technology combines the bipolar membrane electrodialysis technology with the ion exchange resin, realizes the preparation of high conversion rate and high purity of choline on the premise of low energy consumption, has the advantages of recyclable by-products and small influence on the environment, not only solves the problems in the traditional preparation process of choline, but also has very high environmental benefit and economic benefit.
(IV) description of the drawings
FIG. 1 is a flow chart of an experiment for preparing high purity choline from choline chloride;
FIG. 2 is a schematic diagram of a membrane stack structure for preparing high-purity choline by bipolar membrane electrodialysis, wherein 1-anode plate, 2-bipolar membrane, 3-partition plate, 4-anion exchange membrane and 5-cation exchange membrane;
FIG. 3 is a diagram of a device for preparing high-purity choline by bipolar membrane electrodialysis;
FIG. 4 is a view of an ion exchange resin column apparatus.
(V) detailed description of the preferred embodiments
For a better understanding of the principles of the experiment and the efficacy of the invention, the invention will now be further described with reference to the drawings and specific examples.
Example 1
As shown in fig. 1, fig. 2, fig. 3, and fig. 4, the implementation process of the present invention is as follows:
1) pretreating the cation exchange resin in the WU-64H type according to the following steps: 3% hydrochloric acid having a volume 5 times the volume of the resin to be treated was passed through the resin at a flow rate of 2BV/H, ultrapure water was passed through the resin at a flow rate of 2BV/H until the resin was washed to neutrality, 3% NaOH having a volume 5 times the volume of the resin to be treated was passed through the resin at a flow rate of 2BV/H, ultrapure water was passed through the resin at a flow rate of 2BV/H until the resin was washed to neutrality, then the 3% hydrochloric acid treatment/ultrapure water treatment step was repeated 2 times, and finally ultrapure water having a volume 10 times the volume of the resin to be treated was passed through (including upward and downward flow through) the resin at a flow rate of 5BV/H, completing the pretreatment of the WU-64H type cation exchange resin.
2) A0.5M choline chloride solution was prepared and passed through a series of cation exchange resin columns type WU-64H at a flow rate of 2 BV/H.
3) The bipolar membrane electrodialysis device comprises a cathode plate 1, an anode plate 1 and a membrane stack arranged between the plates. The anode plate and the cathode plate are titanium ruthenium-plated electrode plates, and the anode plate and the cathode plate are respectively connected with the positive electrode and the negative electrode of a direct-current power supply; the membrane stack is formed by connecting 5 unit electrodialysis cells in series, the assembly sequence of each unit electrodialysis cell from the anode to the cathode is bipolar membrane BP-1E (ASTOM Co, Japan)2, anion exchange membrane AHA (ASTOM Co, Japan)4, cation exchange membrane CMB (ASTOM Co, Japan)5, bipolar membrane BP-1E (ASTOM Co, Japan), and the effective area of a single membrane is 189cm2And two adjacent membranes are separated by a separator 3; an anode chamber and a cathode chamber are respectively formed between the anode plate and the cathode plate and between the adjacent bipolar membranes, and in each unit electrodialysis cell, four membranes which are sequentially arranged form an acid chamber, a feed liquid chamber and an alkali chamber which are respectively externally connected with an acid tank, a feed liquid tank and an alkali tank. The anode chamber, the cathode chamber, the feed liquid chamber, the alkali chamber,The acid chambers are provided with a liquid inlet and a liquid outlet;
outlets of the anode chamber and the cathode chamber are externally connected with an inlet of an electrode solution tank through a pipeline to form a loop, and the pipeline is provided with a circulating pump 6; one section of pipeline connected with the liquid inlets of the cathode chamber and the anode chamber is a circulating coil pipe, and the circulating coil pipe is placed in ice water, so that the liquid in the circulating coil pipe is fully cooled;
an outlet of the feed liquid chamber is externally connected with an inlet of the feed liquid tank through a pipeline to form a loop, and a circulating pump 7 is arranged on the pipeline;
the outlet of the alkali chamber is externally connected with the inlet of the alkali tank through a pipeline to form a loop, and the pipeline is provided with a circulating pump 8;
the outlet of the acid chamber is externally connected with the inlet of the acid tank through a pipeline to form a loop, and the pipeline is provided with a circulating pump 9;
adding 500mL of choline chloride aqueous solution passing through cation exchange resin into a material liquid tank, preparing 0.5L of 3 wt.% sodium sulfate solution, adding the 3 wt.% sodium sulfate solution into a polar liquid tank, adding 0.5L of ultrapure water into an alkali tank and an acid tank, opening a circulating pump of each compartment, adjusting the flow of each compartment to be 20L/h, and placing a circulating coil pipe in ice water to cool the material liquid in the pipe; and starting a direct current power supply, controlling the voltage to be 15V, reacting for 60 minutes at the reaction temperature of 24.5 ℃ in the compartment, and obtaining the choline in the alkali tank.
Taking out 1mL of alkali liquor from the alkali chamber every 10min, taking phenolphthalein as an indicator, titrating with hydrochloric acid standard solution, and measuring the choline concentration at the moment until the alkali concentration does not rise any more, the current is basically stable, and the reaction reaches the end point. The hydrochloric acid (concentration: 0.36M) in the acid tank was recovered, and the choline solution in the base tank was taken out.
4) Pretreating Amberlite IRA-400 anion exchange resin according to the following steps: 3% NaOH having a volume 5 times the volume of the resin to be treated was passed through the resin at a flow rate of 2BV/h, ultrapure water was passed through the resin at a flow rate of 2BV/h until the resin was washed neutral, 3% hydrochloric acid having a volume 5 times the volume of the resin to be treated was passed through the resin at a flow rate of 2BV/h, ultrapure water was passed through the resin at a flow rate of 2BV/h until the resin was washed neutral, then the 3% NaOH alkaline treatment/ultrapure water treatment step was repeated 2 times, and finally, ultrapure water having a volume 10 times the volume of the resin to be treated was passed through (including upward and downward flow-through) the anion exchange resin at a flow rate of 5BV/h, completing the pretreatment of the Amberlite IRA-400 anion exchange resin.
5) The choline solution was passed through a series of Amberlite IRA-400 anion exchange resin columns at a flow rate of 2 BV/h.
The final choline yield is 81.30%, the product is distilled under reduced pressure and concentrated to 25.08%, the content of impurities in the product is detected by sampling, and the detection result of the sample 1 is shown in a table.
Example 2
Referring to the procedure of example 1, a 0.3M choline chloride solution was prepared and passed through a series of columns of a strongly acidic cation exchange resin type WU-64H. Stacking 5 groups of bipolar membrane electrodialysis membrane stacks with the BP-1E/AHA/CMB/BP-1E configuration and the size of 9cm multiplied by 21cm, adding 500mL of choline chloride solution passing through cation exchange resin into a feed liquid tank, wherein the reaction temperature in the compartments is 23.7 ℃, reacting for 50 minutes under the same conditions as in example 1, and obtaining choline in an alkali tank. Then taking out the choline solution in the alkali tank and passing through a group of Amberlite IRA-400 anion exchange resin columns. The final choline yield was 77.22%, 0.21M hydrochloric acid solution was obtained in the acid chamber, the obtained choline was distilled under reduced pressure and concentrated to 24.94%, the content of impurities contained therein was measured by sampling, and the measurement results of sample 2 are shown in the table.
Example 3
In a procedure of example 1, a 0.3M choline chloride solution was prepared and passed through a series of cation exchange resin columns of WU-64H type. 5 groups of bipolar membrane electrodialysis membrane stacks of BP-1E/AHA/CMB/BP-1E configuration with dimensions of 9cm × 21cm were stacked, and the voltage was adjusted to 10V, at which the reaction temperature in the compartment was 23.9 deg.C, and the same conditions as in example 1 were applied for 130 minutes, and choline was obtained in an alkaline tank. Then taking out the choline solution in the alkali tank and passing through a group of Amberlite IRA-400 anion exchange resin columns. The final choline yield was 78.43%, and the acid compartment obtained a 0.38M hydrochloric acid solution. And (3) carrying out reduced pressure distillation on the obtained choline, concentrating to 25.05%, sampling, and detecting the content of impurities in the choline, wherein the detection result of the sample 3 is shown in a table.
And (3) detecting the product, wherein anions are analyzed by adopting an ion chromatograph, cation impurities are analyzed by adopting ICP-MS, and the result is shown in table 1:
TABLE 1
| Detecting items | Unit of | | Sample | 1 | |
|
| Content (wt.) | ％ | 25±0.1 | 25.08 | 24.94 | 25.05 | |
| Carbonate salt | ppb | 100 | 66 | 45 | 32 | |
| Chloride compound | ppb | 100 | 74 | 48 | 55 | |
| Lithium ion source | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Sodium salt | ppb | 0.1 | 0.07 | 0.05 | 0.08 | |
| Magnesium alloy | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Aluminium | ppb | 0.1 | 0.06 | 0.08 | 0.05 | |
| Potassium salt | ppb | 0.1 | 0.04 | 0.05 | 0.02 | |
| Calcium carbonate | ppb | 0.1 | 0.06 | 0.05 | 0.05 | |
| Chromium (III) | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Manganese oxide | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Iron | ppb | 0.1 | 0.05 | 0.07 | 0.03 | |
| Nickel (II) | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Cobalt | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Copper (Cu) | ppb | 0.1 | 0.02 | 0.01 | 0.02 | |
| Zinc | ppb | 0.1 | 0.01 | 0.03 | 0.01 | |
| Molybdenum (Mo) | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Cadmium (Cd) | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Lead (II) | ppb | 0.1 | Not detected out | Not detected out | Not detected out | |
| Silver (Ag) | ppb | 0.1 | Not detected out | Not detected out | Not detected out |
It should be understood that the above-described embodiments are merely examples for clearly illustrating the present invention, and no limitation is set on the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art upon the basis of the present invention. All obvious modifications which are equivalent or which are obvious on the basis of the technical solutions proposed by the present invention are within the scope of protection of the present invention.
Claims (10)
1. A method for preparing high purity choline from choline chloride, the method comprising the steps of:
1) pretreating strong-acid cation exchange resin, wherein the pretreatment process comprises the following steps: acid treatment, ultrapure water treatment to neutrality, alkali treatment and ultrapure water treatment to neutrality, then repeating the acid treatment/ultrapure water treatment steps for more than two times, and finally washing with a large amount of ultrapure water to obtain a pre-treated strong-acid cation exchange resin column;
2) enabling the choline chloride aqueous solution to pass through at least one group of pretreated strong-acid cation exchange resin columns to remove cation impurities in the choline chloride aqueous solution;
3) performing electrodialysis treatment on the choline chloride aqueous solution passing through the strong-acid cation exchange column by using a bipolar membrane to obtain a choline aqueous solution and a hydrochloric acid solution;
4) pretreating a strong-alkaline anion exchange resin column, wherein the pretreatment process comprises the following steps in sequence: performing alkali treatment, ultrapure water treatment to neutrality, acid treatment and ultrapure water treatment to neutrality, then repeating the alkali treatment/ultrapure water treatment step for more than two times, and finally washing with a large amount of ultrapure water to obtain a pretreated strong-base anion exchange resin column;
5) and (3) enabling the choline aqueous solution obtained in the step 3) to pass through at least one group of pretreated strong-base anion exchange resin columns to remove anion impurities in the choline aqueous solution, and then carrying out reduced pressure distillation and concentration on the obtained choline aqueous solution to obtain the ultrapure choline aqueous solution.
2. The method of claim 1, wherein: the strong-acid cation exchange resin is a WU-64H type cation exchange resin.
3. The method of claim 1 or 2, wherein: in the step (1), the acid treatment is a flow treatment of a strong acid aqueous solution which is input into the cation exchange resin and has a volume 5-10 times of that of the cation exchange resin, wherein the strong acid is hydrochloric acid with a mass concentration of 3-4%; the alkali treatment is that strong alkali aqueous solution with the volume 5-10 times of that of the cation exchange resin is input for flow treatment, the strong alkali is sodium hydroxide or potassium hydroxide, and the mass concentration of the strong alkali in the strong alkali aqueous solution is preferably 3-4%; in the acid treatment, ultrapure water treatment and alkali treatment processes, respectively passing a strong acid aqueous solution, a strong base aqueous solution and ultrapure water through cation exchange resin at flow rates of 2-5 BV/h; the ultrapure water treatment to be neutral is to use ultrapure water flow to clean the ultrapure water to be neutral; finally, ultrapure water 10-20 times the volume of the resin is used for washing through the cation exchange resin at the flow rate of 5-10BV/h, so as to complete the pretreatment of the cation exchange resin.
4. The method of claim 1 or 2, wherein: in the step 2), the choline chloride aqueous solution is contacted with at least one group of pretreated strong acid cation exchange resin in a continuous flow method, wherein the concentration of the choline chloride aqueous solution is 0.3-0.6M, and the choline chloride aqueous solution passes through the strong acid cation exchange resin at the flow rate of 2-5BV/h to remove cation impurities.
5. The method of claim 1, wherein: the step 3) is implemented as follows:
the bipolar membrane electrodialysis device comprises a cathode plate, an anode plate and a membrane stack arranged between the anode plates, wherein the membrane stack consists of one or more groups of electrodialysis units, each unit electrodialysis cell comprises a bipolar membrane, an anion exchange membrane, a cation exchange membrane and a bipolar membrane from the anode to the cathode in sequence, and two adjacent membranes are separated by a partition plate; four membranes sequentially arranged in each unit electrodialysis cell form an acid chamber, a feed liquid chamber and an alkali chamber, and are respectively externally connected with an acid tank, a feed liquid tank and an alkali tank through pipelines to form a loop; an electrode liquid chamber is formed between the cathode plate and the anode plate and the adjacent bipolar membrane respectively, and the electrode liquid chamber is externally connected with an electrode liquid tank through a pipeline to form a loop;
adding a choline chloride aqueous solution passing through a strong acid cation exchange column into a feed liquid tank in a bipolar membrane electrodialysis device, adding 3 wt.% sodium sulfate solution with the same volume into an electrode liquid tank, and adding ultrapure water with the same volume into an acid tank and an alkali tank respectively;
the starting device is used for respectively enabling liquid continuous flow in the feed liquid tank, the polar liquid tank, the acid tank and the alkali tank to enter the feed liquid chamber, the polar liquid chamber, the acid chamber and the alkali chamber, connecting a cathode and an anode of the bipolar membrane electrodialysis device with a cathode and an anode of a direct-current power supply respectively, then starting the power supply, controlling the voltage to be 12.5V-20V, controlling the reaction temperature to be 20-40 ℃, and carrying out electrodialysis treatment, wherein in the treatment process, cations of choline chloride in the feed liquid chamber penetrate through a cation exchange membrane and migrate to the alkali chamber to be combined with hydroxyl ions generated by the bipolar membrane to generate choline, so that a target product is obtained; the chloride ions in the feed liquid chamber migrate to the acid chamber through the anion exchange membrane and combine with hydrogen ions generated by the bipolar membrane to generate hydrochloric acid; when the choline concentration in the alkali chamber does not rise any more and the current tends to be stable, the reaction is stopped, the hydrochloric acid in the acid tank is recovered, and the choline aqueous solution in the alkali tank is taken out.
6. The method of claim 5, wherein: in the bipolar membrane electrodialysis device, a bipolar membrane BP-1E is adopted as the bipolar membrane, an anion exchange membrane AHA is adopted as the anion exchange membrane, and a cation exchange membrane CMB is adopted as the cation exchange membrane.
7. The method of claim 1, wherein: in the step 4), the strong-base anion exchange resin is Amberlite IRA-400 in the United states.
8. The method of claim 1 or 7, wherein: in the step (5), the acid treatment is to input strong acid aqueous solution with 5-10 times of the volume of the anion exchange resin for flow treatment, and the strong acid is hydrochloric acid with the mass concentration of 3-4%; the alkali treatment is to input strong alkali aqueous solution with the volume 5-10 times of that of the anion exchange resin for flow treatment, the strong alkali is sodium hydroxide or potassium hydroxide, and the mass concentration of the strong alkali in the strong alkali aqueous solution is preferably 3-4%; in the acid treatment, ultrapure water treatment and alkali treatment processes, respectively passing the strong acid aqueous solution, the strong base aqueous solution and ultrapure water through anion exchange resin at the flow rate of 2-5 BV/h; the ultrapure water treatment to be neutral is to use ultrapure water flow to clean the ultrapure water to be neutral; finally, ultrapure water with the volume 10-20 times of the resin is used for washing through the anion exchange resin at the flow rate of 5-10BV/h so as to complete the pretreatment of the anion exchange resin.
9. The method of claim 1 or 7, wherein: in the step 5), the choline aqueous solution is contacted with at least one group of strongly basic anion exchange resins in a continuous flow method, wherein the choline aqueous solution passes through the strongly basic anion exchange resins at a flow rate of 2-5BV/h to remove anionic impurities in the choline solution.
10. The method of claim 1, wherein: the number of groups of the strong acid cation exchange resin column and the strong base anion exchange resin column is 1-8 groups respectively.
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| ES2133306T3 (en) * | 1991-10-08 | 1999-09-16 | Conoco Inc | PROCEDURE FOR THE MONITORING AND CONTROL OF A PROCESS OF REACTION OF ALCANOLAMINA. |
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| ES2133306T3 (en) * | 1991-10-08 | 1999-09-16 | Conoco Inc | PROCEDURE FOR THE MONITORING AND CONTROL OF A PROCESS OF REACTION OF ALCANOLAMINA. |
| JP2010215592A (en) * | 2009-03-18 | 2010-09-30 | Kurita Engineering Co Ltd | Method for regenerating amine liquid |
| CN102976454A (en) * | 2012-10-29 | 2013-03-20 | 中国科学院过程工程研究所 | Method for separating cations of NH4<+> and Mg<2+> with same electric properties in fermentation wasterwater by using packed bed electrodialyzer |
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| JIANGNAN SHEN等: "Synthesis of quaternary ammonium hydroxidefrom its halide salt by bipolar membraneelectrodialysis (BMED): effect of molecularstructure of ammonium compoundson the process performance", 《J.CHEM.TECHNOL.BIOTECHNOL》 * |
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