CN117358060A - Method for preparing quaternary ammonium base by bipolar membrane electrodialysis - Google Patents
Method for preparing quaternary ammonium base by bipolar membrane electrodialysis Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 91
- 125000001453 quaternary ammonium group Chemical group 0.000 title claims abstract description 46
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000011550 stock solution Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 6
- 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 4
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 4
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- VFHDWENBWYCAIB-UHFFFAOYSA-M hydrogen carbonate;tetramethylazanium Chemical compound OC([O-])=O.C[N+](C)(C)C VFHDWENBWYCAIB-UHFFFAOYSA-M 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- -1 hydrogen ions Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/52—Accessories; Auxiliary operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/54—Controlling or regulating
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
Abstract
The invention discloses a method for preparing quaternary ammonium hydroxide by bipolar membrane electrodialysis. Adding a quaternary ammonium salt solution into a stock solution chamber of a bipolar membrane electrodialysis device, adding pure water into a receiving chamber, and adding a sulfuric acid solution as a polar solution; starting each water pump, regulating the flow, keeping the water pressure of the stock solution chamber and the water pressure of the receiving chamber consistent, turning on a power supply, setting a pressure limit of 27V and a flow limit of 26A; when the operation is carried out until the conductivity of the stock solution chamber rises slowly or no longer, the receiving chamber produces acid recovery solution, and the stock solution chamber obtains quaternary ammonium alkali solution; introducing the obtained quaternary ammonium alkaline solution into alkaline ion exchange resin to obtain high-purity quaternary ammonium alkaline solution; the bipolar membrane electrodialysis device comprises a membrane assembly, wherein the membrane assembly consists of a membrane unit consisting of anode, anode membrane, cathode membrane and cathode which are sequentially distributed; the method has high conversion rate and high purity, and no wastewater is generated.
Description
Technical Field
The invention relates to the technical field of electrodialysis, in particular to a method for preparing quaternary ammonium hydroxide by a bipolar membrane electrodialysis device.
Background
Quaternary ammonium base, a compound with a general formula of R4NOH, wherein R is four identical or different aliphatic hydrocarbon groups or aromatic hydrocarbon groups; common quaternary ammonium bases such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. The organic alkali equivalent to the alkali of sodium hydroxide can be used as organic synthesis reagent, surfactant, catalyst, product purification and developer, and has extremely high value.
Common quaternary ammonium bases, such as tetramethyl ammonium hydroxide, are widely used in industry such as industrial catalysts and electronics. The aqueous solution can be decomposed into trimethylamine gas and methanol gas after heating, does not leave any trace, can be widely applied to the modern electronic industry, and is the most common developing solution used at present; and the cleaning agent has good cleaning effect and no residue.
The production modes of the quaternary ammonium base generally comprise an addition method, a precipitation method, an electrolysis method and an ionic membrane electrolysis method, wherein the common preparation method is the ionic membrane electrolysis method, a two-chamber one-membrane electrolysis tank is formed by using one ionic membrane, quaternary ammonium salt is decomposed into quaternary ammonium root and anions, the quaternary ammonium root is combined with hydroxide generated by a negative electrode to form the quaternary ammonium base, and the anions on the other side are combined with hydrogen ions generated by an anode through the ionic membrane to form acid; the process has the advantages of slower production rate, low production purity, high production cost and lower overall benefit.
Chinese patent CN201710533110.8 proposes a method for preparing quaternary ammonium base of tetramethyl ammonium hydroxide by bipolar membrane; the method comprises the steps that tetramethyl ammonium bicarbonate is used as a raw material, a membrane is a bipolar membrane and a cation selective permeation membrane, the tetramethyl ammonium bicarbonate is decomposed into quaternary ammonium ions and bicarbonate by electric driving force, and meanwhile, the quaternary ammonium ions are combined with hydroxide ions generated on the cathode side of the bipolar membrane through the cation selective permeation membrane to form quaternary ammonium base, and the bicarbonate and hydrogen ions generated on the anode side of the bipolar membrane form water and carbon dioxide; the quaternary ammonium radical is an organic ion, the molecular radius is large, and the membrane is difficult to penetrate through the cation selectivity, so that the production efficiency is reduced, and the economic benefit is poor; meanwhile, the tetramethyl sodium bicarbonate has high price and high raw material cost.
Disclosure of Invention
The invention aims to provide a method for preparing quaternary ammonium hydroxide by bipolar membrane electrodialysis, which has high conversion rate and high purity and does not generate wastewater.
To achieve the above object, the present invention provides a method for preparing quaternary ammonium base by bipolar membrane electrodialysis, characterized in that the preparation steps include:
s1, adding a quaternary ammonium salt solution into a stock solution chamber of a bipolar membrane electrodialysis device, adding pure water into a receiving chamber, and adding a sulfuric acid solution as a polar solution;
s2, starting each water pump, adjusting flow, keeping the water pressure of the stock solution chamber and the water pressure of the receiving chamber consistent, turning on a power supply, setting pressure limiting 27V and current limiting 26A;
s3, when the conductivity of the stock solution chamber rises slowly or does not rise any more, the receiving chamber outputs acid recovery solution, and the stock solution chamber obtains quaternary ammonium alkali solution;
s4, introducing the obtained quaternary ammonium alkaline solution into alkaline ion exchange resin to obtain high-purity quaternary ammonium alkaline solution;
the bipolar membrane electrodialysis device comprises a membrane assembly, wherein the membrane assembly comprises sequentially distributed anodes, anode membranes, membrane units consisting of cathode membrane sandwich bipolar membranes, cathode membranes and cathodes; the anode and the anode film form an anode chamber, the cathode film and the cathode form a cathode chamber, the anode surface of the bipolar film and the cathode surface of the cathode film close to the anode form a stock solution chamber, and the cathode surface of the bipolar film and the anode surface of the cathode film close to the cathode form a receiving chamber.
Further, the quaternary ammonium salt solution includes, but is not limited to, tetramethyl ammonium chloride, tetramethyl ammonium bicarbonate, tetraethyl ammonium chloride, triethyl methyl ammonium chloride, benzyl trimethyl ammonium chloride, tetrapropyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide.
Further, the concentration of the quaternary ammonium salt solution is 5-30%.
Further, the concentration of the sulfuric acid solution is 2-8%.
Further, the initial liquid volume ratio of the stock solution chamber and the receiving chamber is 1:1-5.
Further, in the bipolar membrane electrodialysis device, the flow rates of the stock solution chamber, the receiving chamber and the electrode solution are independently 100-400L/h, and the water pressures of the stock solution chamber, the receiving chamber and the electrode solution are controlled to be basically the same.
Further, in the bipolar membrane electrodialysis device, the number of the membrane units is 5-150, and adjacent membrane units are overlapped;
the membrane sizes of the anode membrane, the cathode membrane and the bipolar membrane in the membrane unit are 200mm x 400mm, 100mm x 300mm,400mm x 800mm and 1200mm x 600mm, which are mutually independent;
further, in the bipolar membrane electrodialysis device, the current density is 10-800A/m < 2 > during operation, and the operation voltage is set to be 1.5-2.5V/group.
Further, in the bipolar membrane electrodialysis device, the temperature of the solution is controlled to be 15-35 ℃ during operation.
The anode is the positive electrode, the cathode is the positive and negative electrodes, and the negative film is the anion permselective film.
The concentration of the quaternary ammonium salt solution is 5-30%. Too low a concentration can result in low solution conductivity, thereby resulting in low system efficiency; too high a concentration may result in a sticky liquid. The effect is best when the content is 5-30%.
The concentration of the sulfuric acid solution is 2-8%. The sulfuric acid solution is used as the polar liquid, the concentration is too low, the conductivity is poor, and the concentration is too high, so that the ion leakage can be caused. The inventors of the present invention found that when the concentration of the sulfuric acid solution is 2 to 8%, the conductivity is good and no leakage of ions is caused.
In the bipolar membrane electrodialysis device, the flow rates of the stock solution chamber, the receiving chamber and the electrode solution are independently 100-400L/h, and the water pressures of the stock solution chamber, the receiving chamber and the electrode solution are controlled to be basically the same. Flow rates below or above 100-400L/h can result in inefficiency in the device. The inlet water pressure is the same in order to ensure that ion permeation due to pressure is prevented.
In bipolar membrane electrodialysis devices, too high or too low a voltage (current) during operation can result in increased material loss rates. Therefore, the current density is selected to be 10-800A/m 2, and the operation voltage is set to be 1.5-2.5V/group.
In the bipolar membrane electrodialysis device, the temperature of the solution is controlled to be 15-35 ℃ during operation. Too low temperature, low ionic activity and low efficiency; the temperature is too high, which is easy to cause equipment damage. The inventor of the invention discovers that when the temperature of the solution is 15-35 ℃, the ion activity is good and the efficiency is high; and will not cause equipment damage.
Under the action of an electric field, acid radical ions in the stock solution chamber enter the receiving chamber through the anion selective permeation membrane and are combined with hydrogen ions generated on the positive surface of the bipolar membrane to form acid; simultaneously, hydroxyl generated on the cathode surface of the quaternary ammonium ion bipolar membrane in the stock solution chamber is combined to form quaternary ammonium base.
The invention prepares the quaternary ammonium base by the common quaternary ammonium salt. Meanwhile, the energy consumption required by the prior art is reduced, the raw materials with low cost are replaced, and the economic benefit of production is improved; for example, tetramethylammonium hydroxide can be prepared using tetramethylammonium chloride.
Drawings
FIG. 1 is a schematic diagram of a bipolar membrane electrodialysis system according to the invention;
figure 2 is a schematic diagram of the piping connections of a bipolar membrane electrodialysis system.
The device comprises a 1-receiving liquid outlet, a 2-stock liquid outlet, a 3-stock liquid inlet, a 4-receiving liquid inlet, a 5-polar liquid outlet, a 6-polar liquid inlet, a 7-receiving liquid flowmeter, an 8-receiving liquid valve, a 9-receiving liquid pump, a 10-stock liquid flowmeter, an 11-stock liquid valve and a 12-stock liquid pump, wherein the two parts are respectively provided with a first inlet, a second inlet, a third inlet and a fourth inlet; 13-pole liquid flowmeter, 14-pole liquid valve, 15-pole liquid water pump.
Description of the embodiments
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1: preparation of quaternary ammonium bases
Reference is made to fig. 1 and 2.
1. Preparing water for solid tetramethyl ammonium chloride into 10% tetramethyl ammonium chloride water solution;
2. the solution is passed into a bipolar membrane electrodialysis system for treatment: 2L of 10% tetramethyl ammonium chloride aqueous solution is taken and added into a stock solution chamber, 4L of pure water is added into a receiving chamber, and 3% sulfuric acid solution is added into polar solution;
3. the bipolar membrane electrodialysis system related by the process is adopted for preparing quaternary ammonium base, wherein the electrodialysis device comprises 10 membrane units, the specification of the membranes is 200mm multiplied by 400mm, the membranes are selected from homogeneous bipolar membranes and anion permselective membranes (also can be directly commercially available) which are independently researched and produced by Fujian Huntingrun corporation, the effective area of each membrane is 0.0527m2, and the total effective area of the 10 membrane units is 0.527m2; the thickness of the separator is 0.075cm, the effective width of the separator is 17cm, and the separator is made of polypropylene material; the cathode and the anode are titanium ruthenium-coated iridium electrodes; the polar liquid is sulfuric acid solution with the concentration of 3 percent;
4. starting each water pump, regulating the flow, keeping the water pressure of the stock solution chamber and the water pressure of the receiving chamber consistent, turning on a power supply, setting pressure limiting 27V and current limiting 26A;
5. the operation is carried out until the conductivity of the stock solution chamber rises slowly or no longer, the receiving chamber produces hydrochloric acid recovery solution, and the stock solution chamber obtains tetramethyl ammonium hydroxide solution;
6. and introducing the quaternary ammonium alkali solution into alkaline ion exchange resin to obtain high-purity tetramethylammonium hydroxide solution.
According to experimental data and detection data, the average running voltage of each membrane unit of the example is calculated to be 1.5V, the average running current density is 470A/m < 2 >, the conversion rate is over 96%, the purity of the quaternary ammonium base is 95%, the acid production concentration is 0.85mol/L, the unit treatment energy consumption of raw salt (including the treatment of other parts about the energy consumption) is 502.5kwh/t, and the unit treatment capacity of the raw salt is 1.40 kg/(m < 2 >. H).
Example 2: preparation of quaternary ammonium bases
The quaternary ammonium alkali solution is tetramethyl ammonium chloride, and the concentration of the raw material solution is 15%. The procedure is as in example 1.
The average running current density is 628A/m < 2 >, the average running voltage is 2.0V per unit, the conversion rate is 95%, the purity of the quaternary ammonium base is 92%, the acid production concentration is 1.0mol/L, the unit treatment energy consumption of crude salt is 698kwh/t, and the crude salt treatment capacity is 1.80 kg/(m < 2 >. H).
Example 3: preparation of quaternary ammonium bases
The quaternary ammonium alkali solution is tetrapropylammonium bromide, and the concentration of the raw material solution is 6%. The procedure is as in example 1.
The average running current density is 420A/m < 2 >, the average running voltage is 2.0V per unit, the conversion rate is 98%, the purity of the quaternary ammonium base is 97%, the acid production concentration is 0.7mol/L, the unit treatment energy consumption of raw salt is 268kwh/t, and the unit treatment capacity of the raw salt is 3.13 kg/(m < 2 >. H).
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (9)
1. A method for preparing quaternary ammonium base by bipolar membrane electrodialysis, which is characterized by comprising the following preparation steps:
s1, adding a quaternary ammonium salt solution into a stock solution chamber of a bipolar membrane electrodialysis device, adding pure water into a receiving chamber, and adding a sulfuric acid solution as a polar solution;
s2, starting each water pump, adjusting flow, keeping the water pressure of the stock solution chamber and the water pressure of the receiving chamber consistent, turning on a power supply, setting pressure limiting 27V and current limiting 26A;
s3, when the conductivity of the stock solution chamber rises slowly or does not rise any more, the receiving chamber outputs acid recovery solution, and the stock solution chamber obtains quaternary ammonium alkali solution;
s4, introducing the obtained quaternary ammonium alkaline solution into alkaline ion exchange resin to obtain high-purity quaternary ammonium alkaline solution;
the bipolar membrane electrodialysis device comprises a membrane assembly, wherein the membrane assembly consists of an anode, an anode membrane, a membrane unit consisting of a cathode membrane sandwich bipolar membrane, a cathode membrane and a cathode which are sequentially distributed; the anode and the anode film form an anode chamber, the cathode film and the cathode form a cathode chamber, the anode surface of the bipolar film and the cathode surface of the cathode film close to the anode form a stock solution chamber, and the cathode surface of the bipolar film and the anode surface of the cathode film close to the cathode form a receiving chamber.
2. The method of preparing a quaternary ammonium base by bipolar membrane electrodialysis according to claim 1 wherein the quaternary ammonium salt solution includes, but is not limited to, tetramethyl ammonium chloride, tetramethyl ammonium bicarbonate, tetraethyl ammonium chloride, triethyl methyl ammonium chloride, benzyl trimethyl ammonium chloride, tetrapropyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide.
3. The method for preparing quaternary ammonium base by bipolar membrane electrodialysis according to claim 1, wherein the concentration of the quaternary ammonium salt solution is 5-30%.
4. The method for preparing quaternary ammonium base by bipolar membrane electrodialysis according to claim 1, characterized in that the concentration of the sulfuric acid solution is 2-8%.
5. The method for preparing quaternary ammonium hydroxide according to claim 1, wherein the initial liquid volume ratio of the stock solution chamber to the receiving chamber is 1:1-5.
6. The method for preparing quaternary ammonium hydroxide according to claim 1, wherein in the bipolar membrane electrodialysis device, the flow rates of the stock solution chamber, the receiving chamber and the electrode solution are independently 100 to 400L/h, and the water pressures of the stock solution chamber, the receiving chamber and the electrode solution are controlled to be substantially the same.
7. The method for preparing quaternary ammonium hydroxide by bipolar membrane electrodialysis according to claim 1, wherein in the bipolar membrane electrodialysis device, the number of the membrane units is 5-150 groups, and adjacent membrane units are arranged in a superposition manner;
the membrane sizes of the anode membrane, the cathode membrane and the bipolar membrane in the membrane unit are 200mm x 400mm, 100mm x 300mm,400mm x 800mm and 1200mm x 600mm, which are mutually independent.
8. The method for preparing quaternary ammonium base by bipolar membrane electrodialysis according to claim 1, wherein the current density in the bipolar membrane electrodialysis device is 10-800A/m during operation 2 The operation voltage is set to be 1.5-2.5V/group.
9. The method for preparing quaternary ammonium base by bipolar membrane electrodialysis according to claim 1, wherein the temperature of the solution in the bipolar membrane electrodialysis device is controlled to be 15-35 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311374492.6A CN117358060A (en) | 2023-10-23 | 2023-10-23 | Method for preparing quaternary ammonium base by bipolar membrane electrodialysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311374492.6A CN117358060A (en) | 2023-10-23 | 2023-10-23 | Method for preparing quaternary ammonium base by bipolar membrane electrodialysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
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