CN112642498A - Electronic grade pyrazole aqueous solution and preparation method thereof - Google Patents
Electronic grade pyrazole aqueous solution and preparation method thereof Download PDFInfo
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- CN112642498A CN112642498A CN202010791952.5A CN202010791952A CN112642498A CN 112642498 A CN112642498 A CN 112642498A CN 202010791952 A CN202010791952 A CN 202010791952A CN 112642498 A CN112642498 A CN 112642498A
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- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 37
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 30
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 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 18
- 239000012528 membrane Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 125000002091 cationic group Chemical group 0.000 claims description 31
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 21
- 239000012498 ultrapure water Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000005086 pumping Methods 0.000 claims description 12
- 239000003729 cation exchange resin Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000005341 cation exchange Methods 0.000 claims description 6
- 229910000575 Ir alloy Inorganic materials 0.000 claims description 4
- ZACYQVZHFIYKMW-UHFFFAOYSA-N iridium titanium Chemical compound [Ti].[Ir] ZACYQVZHFIYKMW-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000003317 industrial substance Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 9
- 238000004140 cleaning Methods 0.000 abstract description 8
- 239000003456 ion exchange resin Substances 0.000 abstract description 8
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000005684 electric field Effects 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000011550 stock solution Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
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- -1 hydrogen ions Chemical class 0.000 description 6
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- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003014 ion exchange membrane Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
Abstract
The invention relates to an electronic-grade pyrazole aqueous solution and a preparation method thereof. Na in the aqueous pyrazole solution+、Mg2+、K+、Ca2+、Cu2+、Zn2+、Ni2+、Cr3+，Al3+、Fe3+The content of the plasma metal ions is lower than 50 ppb, and the content of the pyrazole is more than or equal to 10 percent. The method achieves the purification of the pyrazole aqueous solution by the combined process of ion membrane electrolysis and ion exchange resin, wherein the ion exchange resin is added into an ion membrane electrolysis cell to enhance the conductivity of the solution and assist in removing metal ions. A part of metal ions in the pyrazole stock solution in the anode chamber are transferred from the anode chamber to the cathode chamber under the action of electric field force, and a part of ions are electrifiedAnd adsorbing by using ion resin in the electrolytic bath, and finally obtaining the electronic grade pyrazole aqueous solution in the anode chamber. The electronic grade pyrazole aqueous solution can be used as a solvent of chemical cleaning solution for microelectronic industries such as ultra-large scale integrated circuits or screen displays.
Description
Technical Field
The invention relates to the field of preparation of electronic-grade reagents, in particular to an electronic-grade pyrazole aqueous solution and a preparation method thereof.
Background
Pyrazole is a colorless or white acicular or prismatic crystalline organic cyclic compound, is commonly used as a halogen-containing solvent, a stabilizer of lubricating oil, a chelating agent or an organic synthesis intermediate, and plays an important role in research and development of medicines and pesticides.
The electronic grade pyrazole aqueous solution is an ultra-clean high-purity reagent, and can be used as a cleaning agent for cleaning silicon wafers, substrates and the like in the microelectronic industry such as the integrated circuit and electronic element processing field due to the strong metal ion chelating effect. The key of the ultra-clean high-purity reagent is to control the amount of metal ions contained in the reagent and the content of dust particles in the reagent, and for integrated circuits with small line width, a few metal ions or dust can be enough to scrap the whole circuit. The metal ion content of the pyrazole sold in the market at present is high, so that the pyrazole cannot meet the requirements of the silicon wafer cleaning industry, and the research on the purification preparation process at home and abroad is less. Therefore, it is important to develop a technology capable of reducing the content of metal impurity ions in an aqueous pyrazole solution and to prepare an electronic-grade aqueous pyrazole solution.
Disclosure of Invention
In order to prepare the electronic-grade pyrazole aqueous solution, the invention provides a mode of combining ion membrane electrolysis and cation exchange resin, and the electronic-grade pyrazole aqueous solution is prepared at low cost. The specific embodiment is as follows:
an electronic grade pyrazole aqueous solution preparation device is characterized by comprising an ultrapure electrolytic tank (1), an anolyte storage tank (2), an anolyte circulating pump (3), a catholyte storage tank (4) and a catholyte circulating pump (5);
the ultrapure electrolytic cell (1) comprises an anode chamber (6), an anode plate (7), a cathode chamber (8), a cathode plate (9), a cation exchange membrane (10) and an ultrapure electrolytic cell clamp (19);
the anode chamber (6) is separated from the cathode chamber (8) by a cation exchange membrane (10);
cationic exchange resin (11) is respectively filled in the anode chamber (6) and the cathode chamber (8);
the anolyte storage tank (2) and the catholyte storage tank (4) are of a jacket type, and flowing hot water for heat preservation is arranged in the jacket;
the linings of the anolyte storage tank (2) and the catholyte storage tank (4), the plate frame materials of the anode chamber (6) and the cathode chamber (8), the anolyte circulating pump (3) and the catholyte circulating pump (5), and the materials of pipelines, pipes and valves are all fluorine-containing materials with the purity of 99.9-99.999 percent, such as PTFE or PFA or PVDF;
the bottom of the anode chamber (6) is provided with an anode chamber pyrazole aqueous solution inlet (12), and the top is provided with an anode chamber pyrazole aqueous solution outlet (13);
the bottom of the cathode chamber (8) is provided with a cathode chamber pyrazole aqueous solution inlet (14), and the top is provided with a cathode chamber pyrazole aqueous solution outlet (15);
the anode chamber pyrazole aqueous solution inlet (12), the anode chamber pyrazole aqueous solution outlet (13), the cathode chamber pyrazole aqueous solution inlet (14) and the cathode chamber pyrazole aqueous solution outlet (15) are respectively provided with a filter screen (16);
a solution outlet of the anolyte storage tank (2) is connected with an anode chamber pyrazole aqueous solution inlet (12) through an anolyte circulating pump (3) by a pipeline, and an anode chamber pyrazole aqueous solution outlet (13) is connected with a solution inlet of the anolyte storage tank (2); a solution outlet of the catholyte storage tank (4) is connected with a cathode chamber pyrazole aqueous solution inlet (14) through a catholyte circulating pump (5) by a pipeline, and a cathode chamber pyrazole aqueous solution outlet (15) is connected with a solution inlet of the catholyte storage tank (4);
the cathode plate (9) is a titanium electrode, a platinum electrode or a titanium iridium alloy electrode with the purity of 99.9-99.999%, and the anode plate (7) is a platinum electrode or a titanium electrode with the purity of 99.9-99.999%; the distance between the cathode plate (9) and the anode plate (7) is 0.5-3.0 cm.
The material of the cationic exchange resin (11) is 001 x 7 type which is resistant to acid and alkali corrosion and high temperatureThe resin or 2800H type resin or 1500H type resin has a particle size of (0.315-1.25 mm) or more than 95%, or (0.45-1.25 mm) or more than 95%, or (0.71-1.25 mm) or more than 95%, and wet bulk density of 650-850 kg/m3；
The cationic exchange resin (11) is filled in the cathode chamber (8) with the density of 70-95% of the wet bulk density, and is filled in the anode chamber (6) with the density of 80-97% of the wet bulk density.
The method for preparing the electronic-grade pyrazole aqueous solution by using the electronic-grade pyrazole aqueous solution preparation device comprises the following steps of:
A. respectively adding specified amounts of cationic exchange resin (11) into an anode chamber (6) and a cathode chamber (8), respectively adding ultrapure hydrochloric acid aqueous solution for washing into an anode liquid storage tank (2) and a cathode liquid storage tank (4), respectively starting an anode liquid circulating pump (3) and a cathode liquid circulating pump (5), circularly washing each component in an ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then washing with ultrapure water for 6-10 times until the washing liquid is neutral and the content of each metal ion is lower than 5 ppb;
B. adding 10-30% pyrazole aqueous solution raw materials into an anolyte storage tank (2) and a catholyte storage tank (4) at the same time, respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5), and switching on a power supply between a cathode plate and an anode plate to start electrolysis after the pyrazole aqueous solution in the whole device circularly flows to reach a specific temperature;
C. continuously pumping and circulating, continuously reducing metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) to finally obtain an electronic grade pyrazole aqueous solution, and then pumping the pyrazole aqueous solution in the anode chamber (6) and the anolyte storage tank (2) to a product storage tank through a product outlet (17) to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 10-30%; meanwhile, the pyrazole aqueous solution in the cathode chamber (8) and the catholyte storage tank (4) is pumped out through an outlet (18) and can be sold as industrial chemicals;
D. and (3) adding an ultra-pure hydrochloric acid aqueous solution into the anode chamber (6) and the cathode chamber (8), soaking for 5-8 hours for regenerating the cationic resin (11), then fully washing the electronic grade pyrazole aqueous solution preparation device by adopting ultra-pure water, and transferring to the operation step B after the requirements of the step A are met.
And B, the raw material of the pyrazole aqueous solution in the step B is an industrial-grade pyrazole product or a medical-grade pyrazole product, and the pyrazole aqueous solution with the required concentration is obtained after the pyrazole aqueous solution is dissolved by adding water.
And in the step B, the voltage of the cathode and anode plates is 15-50V, and the flow velocity of the solution in the anode chamber (6) and the cathode chamber (8) is 0.5-2.0 m/min through pumping of the anolyte circulating pump (3) and the catholyte circulating pump (5).
And the electrolysis temperature in the step B is 25-50 ℃.
And D, the content of various metal ions in the electronic grade pyrazole aqueous solution product obtained in the step C is lower than 50 ppb, and the mass percentage content of pyrazole is more than or equal to 10%.
The purity of the ultra-pure hydrochloric acid aqueous solution in the steps A and D is 99.9-99.999%, and the concentration is 10-30%.
Compared with the prior art, the method for preparing the electronic grade pyrazole aqueous solution by combining the ionic membrane electrolysis and the cation exchange resin has the following outstanding effects and advantages:
(1) in the process of solution circulation and electrolysis, a part of metal ions in the solution in the anode chamber are driven by electric field force to migrate from the anode chamber to the cathode chamber through the middle cation exchange membrane (9), and the other part of metal ions exchange with hydrogen ions on the cation type resin (11) and are adsorbed on the cation type resin (11); under the combined action of the driving of an electrolytic electric field of an ionic membrane electrolysis method and the adsorption action of cation exchange resin, the concentration of metal ions in the pyrazole aqueous solution is greatly reduced.
(2) Cation exchange resin is added into the electrolytic cell, and the conductivity of the pyrazole aqueous solution which is not conductive originally is greatly increased by means of the conductivity of the cation exchange resin, so that the efficiency of the electrolytic cell is obviously improved.
(3) The process provided by the method is simple to operate and low in cost.
Drawings
FIG. 1 is a schematic view of a plate-and-frame type ionic membrane electrolytic circulation device
FIG. 2 is a schematic view of the inside of a plate and frame type electrolytic cell;
the parts in the figure illustrate:
1-ultrapure electrolytic tank, 2-anolyte storage tank, 3-anolyte circulating pump, 4-catholyte storage tank, 5-catholyte circulating pump, 6-anode chamber, 7-anode plate, 8-cathode chamber, 9-cathode plate, 10-cation exchange membrane, 11-cation exchange resin, 12-anode chamber pyrazole aqueous solution inlet, 13-anode chamber pyrazole aqueous solution outlet, 14-cathode chamber pyrazole aqueous solution inlet, 15-cathode chamber pyrazole aqueous solution outlet, 16-filter screen, 17-anolyte storage tank product outlet, 18-catholyte storage tank outlet, 19-ultrapure electrolytic tank clamp
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Example 1
In the used ultra-pure electrolytic tank (1), a cathode plate (9) is a titanium electrode (with the purity of 99.99 percent), and an anode plate (7) is a platinum electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 0.8 cm. The cationic exchange resin (11) used in the anode chamber (6) and the cathode chamber (8) is 001 x 7 type cationic exchange resin, the particle size range is that the particle size is (0.315-1.25 mm) is not less than 95 percent, and the wet bulk density is 800 kg/m3The cathode chamber (8) is packed at a density of 80% of its wet bulk density, and the anode chamber (6) is packed at a density of 85% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 10% is obtained by dissolving the industrial grade pyrazole product in water.
First, prescribed amounts of 001 x 7 type cationic exchange resin (11) were added to the anode chamber (6) and cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.9%, concentration 10%) was added to the anolyte tank (2) and catholyte tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.
Adding a 10% pyrazole aqueous solution raw material into an anolyte storage tank (2) and a catholyte storage tank (4) at the same time, and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of solutions in an anode chamber (6) and a cathode chamber (8) to be 1.0 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 25 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 20V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 10%, wherein the specific content of each metal ion is shown in table 1.
After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.
Pyrazole products treated by a combination of ion-exchange resin and membrane electrolysis processes, wherein Na is present+、Mg2+、K+、Ca2+、Cu2+、Zn2+、Ni2+、Cr3+、Al3+、Fe3+The total content is less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 10 percent, thereby achieving the standard of the electronic grade pyrazole cation impurity content.
Example 2
The cathode plate (9) of the used ultra-pure electrolytic tank (1) is a platinum electrode (with the purity of 99.99 percent), and the anode plate (7) is a titanium electrode (with the purity of 99.99 percent); a cathode plate (9) and an anodeThe distance between the plates (7) was 1.0 cm. The cationic exchange resin (11) used in the anode chamber (6) and the cathode chamber (8) is 2800H type cationic exchange resin, the particle size range is that the particle size is (0.315-1.25 mm) is not less than 95%, and the wet bulk density is 810 kg/m3The cathode chamber (8) was packed at a density of 81% of its wet bulk density, and the anode chamber (6) was packed at a density of 87% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 10% is obtained by dissolving the industrial grade pyrazole product in water.
First, a prescribed amount of 2800H type cationic exchange resin (11) was added to the anode chamber (6) and the cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.99%, concentration 20%) was added to the anolyte tank (2) and the catholyte tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.
Adding a 10% pyrazole aqueous solution raw material into an anolyte storage tank (2) and a catholyte storage tank (4) at the same time, and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of solutions in an anode chamber (6) and a cathode chamber (8) to be 1.2 m/min. The feed amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 30 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 25V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 10%, wherein the specific content of each metal ion is shown in table 1.
After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.
Pyrazole products treated by a combination of ion-exchange resin and membrane electrolysis processes, wherein Na is present+、Mg2+、K+、Ca2+、Cu2+、Zn2+、Ni2+、Cr3+、Al3+、Fe3+The total content is less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 10 percent, thereby achieving the standard of the electronic grade pyrazole cation impurity content.
Example 3
The cathode plate (9) of the used ultra-pure electrolytic tank (1) is a titanium iridium alloy electrode (with the purity of 99.99 percent), and the anode plate (7) is a platinum electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 1.5 cm. The cationic exchange resin (11) used in the anode chamber (6) and the cathode chamber (8) is 2800H type cationic exchange resin, the particle size range is that the particle size is (0.45-1.25 mm) is not less than 95%, and the wet bulk density is 780 kg/m3The cathode chamber (8) was packed at a density of 84% of its wet bulk density, and the anode chamber (6) was packed at a density of 89% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 20 percent is obtained by dissolving the industrial grade pyrazole product in water.
First, a prescribed amount of 2800H type cationic exchange resin (11) was added to the anode chamber (6) and the cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.99%, concentration 20%) was added to the anolyte tank (2) and the catholyte tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.
And (3) simultaneously adding a pyrazole aqueous solution raw material with the concentration of 20% into an anolyte storage tank (2) and a catholyte storage tank (4), and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of the solutions in the anode chamber (6) and the cathode chamber (8) to be 1.4 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 35 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 30V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 20%, wherein the specific content of each metal ion is shown in table 1.
After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.
Pyrazole products treated by a combination of ion-exchange resin and membrane electrolysis processes, wherein Na is present+、Mg2+、K+、Ca2+、Cu2+、Zn2+、Ni2+、Cr3+、Al3+、Fe3+Are all less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 20 percent, thereby reaching the standard of the electronic grade pyrazole cation impurity content.
Example 4
In the used ultra-pure electrolytic tank (1), a cathode plate (9) is a titanium electrode (with the purity of 99.99 percent), and an anode plate (7) is a platinum electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 2.2 cm. The cationic exchange resin (11) used in the anode chamber (6) and the cathode chamber (8) is 001 x 7 type cationic exchange resin, the particle size range is that the particle size is (0.45-1.25 mm) is not less than 95%, and the wet bulk density is 750 kg/m3The cathode chamber (8) is packed at a density of 90% of its wet bulk density, and the anode chamber (6) is packed at a density of 93% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 30% is obtained by dissolving the industrial grade pyrazole product in water.
First, prescribed amounts of 001 x 7 type cationic exchange resin (11) were added to the anode chamber (6) and cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.99%, concentration 30%) was added to the anolyte tank (2) and catholyte tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.
And (3) simultaneously adding a pyrazole aqueous solution raw material with the concentration of 30% into an anolyte storage tank (2) and a catholyte storage tank (4), and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of the solutions in the anode chamber (6) and the cathode chamber (8) to be 1.0 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 40 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 35V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 30%, wherein the specific content of each metal ion is shown in table 1.
After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.
Pyrazole products treated by a combination of ion-exchange resin and membrane electrolysis processes, wherein Na is present+、Mg2+、K+、Ca2+、Cu2+、Zn2+、Ni2+、Cr3+、Al3+、Fe3+Are all less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 30 percent, thereby reaching the standard of the electronic grade pyrazole cation impurity content.
Example 5
In the used ultra-pure electrolytic tank (1), a cathode plate (9) is a titanium electrode (with the purity of 99.99 percent), and an anode plate (7) is a titanium electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 1.8 cm. Cationic exchange resins (11) used in the anode compartment (6) and cathode compartment (8)Is 1500H type cationic exchange resin with particle size of 0.71-1.25 mm or more than 95% and wet bulk density of 680 kg/m3The cathode chamber (8) was packed at a density of 93% of its wet bulk density, and the anode chamber (6) was packed at a density of 95% of its wet bulk density. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 30% is obtained by dissolving the industrial grade pyrazole product in water.
Firstly, prescribed amounts of 1500H type cationic exchange resin (11) are added to an anode chamber (6) and a cathode chamber (8), respectively, and ultrapure hydrochloric acid for washing (purity 99.99%, concentration 20%) is added to an anode liquid storage tank (2) and a cathode liquid storage tank (4), respectively. Starting an anolyte circulating pump (3) and a catholyte circulating pump (5), circularly washing each component in the ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then cleaning with ultrapure water to ensure that the ultrapure water meets the purification requirement.
And (3) simultaneously adding a pyrazole aqueous solution raw material with the concentration of 30% into an anolyte storage tank (2) and a catholyte storage tank (4), and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of the solutions in the anode chamber (6) and the cathode chamber (8) to be 0.7 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 45 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 40V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain an electronic grade pyrazole aqueous solution product with the mass concentration of 30%, wherein the specific content of each metal ion is shown in table 1.
After the electrolysis is finished, the cation type resin (11) in the anode chamber (6) and the cathode chamber (8) is regenerated by high-purity hydrochloric acid and is washed by ultrapure water for recycling.
Pyrazole products treated by a combined process of ion-exchange resin and membrane electrolysis, processes for their preparation and their useIn Na+、Mg2+、K+、Ca2+、Cu2+、Zn2+、Ni2+、Cr3+、Al3+、Fe3+Are all less than 50 ppb, and the mass fraction of the pyrazole aqueous solution is 30 percent, thereby reaching the standard of the electronic grade pyrazole cation impurity content.
Control group 1
The cathode plate (9) of the used ultra-pure electrolytic tank (1) is a titanium iridium alloy electrode (with the purity of 99.99 percent), and the anode plate (7) is a platinum electrode (with the purity of 99.99 percent); the distance between the cathode plate (9) and the anode plate (7) is 1.5 cm. The anode chamber (6) and the cathode chamber (8) are free of cation exchange resin. The raw material of the pyrazole aqueous solution is an industrial grade pyrazole product, and the pyrazole aqueous solution with the mass concentration of 20 percent is obtained by dissolving the industrial grade pyrazole product in water.
Ultrapure water for washing is added into the anode liquid storage tank (2) and the cathode liquid storage tank (4) respectively. And starting the anolyte circulating pump (3) and the catholyte circulating pump (5) to circularly wash each part in the ultrapure electrolytic tank (1) so as to meet the purification requirement.
And (3) simultaneously adding a pyrazole aqueous solution raw material with the concentration of 20% into an anolyte storage tank (2) and a catholyte storage tank (4), and respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5) to enable the flow rates of the solutions in the anode chamber (6) and the cathode chamber (8) to be 1.4 m/min. The feeding amounts of jacket heating media of the anolyte tank (2) and the anolyte tank (4) were adjusted so that the temperature of the ultrapure electrolytic cell (1) was maintained at 35 ℃. After the pyrazole aqueous solution in the whole device circularly flows and reaches a constant temperature, a power supply between the cathode plate and the anode plate is switched on, and the voltage is controlled to be 30V. And after continuous pumping circulation, metal ions in the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) are continuously reduced, and after the reaction is finished, the pyrazole solution in the anode chamber (6) and the anolyte storage tank (2) is pumped to a product storage tank to obtain a pyrazole aqueous solution product with the mass concentration of 20%, wherein the specific content of each metal ion is shown in table 1.
Control group 2
The raw material of the used pyrazole aqueous solution is an industrial grade pyrazole product which is dissolved by adding water,to obtain a pyrazole aqueous solution with the mass concentration of 20%. The cation exchange resin is 2800H type cation exchange resin, the particle size range is that the particle size is more than or equal to 95% (0.45-1.25 mm), and the wet bulk density is 780 kg/m3. The ion exchange resin column was packed at a density of 84% of its wet bulk density. The cation exchange resin is washed by ultrapure hydrochloric acid (purity 99.9%, concentration 10%), and then washed by ultrapure water to meet the purification requirements. A 20% aqueous pyrazole solution was slowly added to the ion exchange column and controlled to flow through the resin at a 1-fold bed volume flow rate. When the pyrazole outflow concentration is close to 20%, the product starts to be collected, and the specific content of each metal ion in the product is shown in the table 1.
TABLE 1 Metal ion content scale (ppb) in the electronic grade pyrazole aqueous solution products of the examples
| Pyrazole concentration | Na + | Mg 2+ | K + | Ca 2+ | Cu 2+ | Zn2+ | Ni2+ | Cr3+ | Al3+ | Fe3+ | |
| Example 1 | 10% | 8.2 | 10.5 | 0 | 15.6 | 12.3 | 5.6 | 19.6 | 13.6 | 35.0 | 46.2 |
| Example 2 | 10% | 0 | 3.5 | 0 | 6.5 | 8.5 | 0 | 15.6 | 13.6 | 30.2 | 35.6 |
| Example 3 | 20% | 10.2 | 6.5 | 0 | 12.5 | 13.4 | 10.2 | 15.6 | 13.6 | 40.2 | 38 |
| Example 4 | 30% | 15.2 | 15.5 | 3.2 | 12.5 | 13.4 | 10.2 | 25.6 | 13.6 | 39.8 | 47.5 |
| Example 5 | 30% | 20.3 | 16.3 | 5.8 | 20.5 | 16.7 | 10.2 | 25.6 | 27.6 | 46.3 | 47.5 |
| Control group 1 | 20% | 340.3 | 243.6 | 354.6 | 208.4 | 108.5 | 132.8 | 284.7 | 103.6 | 463.5 | 485.8 |
| Control group 2 | 20% | 89.6 | 69.3 | 79.5 | 56.9 | 45.8 | 42.6 | 54.7 | 43.8 | 49.2 | 43.2 |
Claims (9)
1. An electronic grade pyrazole aqueous solution preparation device is characterized by comprising an ultrapure electrolytic tank (1), an anolyte storage tank (2), an anolyte circulating pump (3), a catholyte storage tank (4) and a catholyte circulating pump (5);
the ultrapure electrolytic cell (1) comprises an anode chamber (6), an anode plate (7), a cathode chamber (8), a cathode plate (9), a cation exchange membrane (10) and an ultrapure electrolytic cell clamp (19);
the anode chamber (6) is separated from the cathode chamber (8) by a cation exchange membrane (10);
cationic exchange resin (11) is respectively filled in the anode chamber (6) and the cathode chamber (8);
the anolyte storage tank (2) and the catholyte storage tank (4) are of a jacket type, and flowing hot water for heat preservation is arranged in the jacket;
the linings of the anolyte storage tank (2) and the catholyte storage tank (4), the plate frame materials of the anode chamber (6) and the cathode chamber (8), the anolyte circulating pump (3) and the catholyte circulating pump (5), and the materials of pipelines, pipes and valves are all fluorine-containing materials with the purity of 99.9-99.999 percent, such as PTFE or PFA or PVDF;
the bottom of the anode chamber (6) is provided with an anode chamber pyrazole aqueous solution inlet (12), and the top is provided with an anode chamber pyrazole aqueous solution outlet (13);
the bottom of the cathode chamber (8) is provided with a cathode chamber pyrazole aqueous solution inlet (14), and the top is provided with a cathode chamber pyrazole aqueous solution outlet (15);
the anode chamber pyrazole aqueous solution inlet (12), the anode chamber pyrazole aqueous solution outlet (13), the cathode chamber pyrazole aqueous solution inlet (14) and the cathode chamber pyrazole aqueous solution outlet (15) are respectively provided with a filter screen (16);
a solution outlet of the anolyte storage tank (2) is connected with an anode chamber pyrazole aqueous solution inlet (12) through an anolyte circulating pump (3) by a pipeline, and an anode chamber pyrazole aqueous solution outlet (13) is connected with a solution inlet of the anolyte storage tank (2); and a solution outlet of the catholyte storage tank (4) is connected with a cathode chamber pyrazole aqueous solution inlet (14) through a pipeline by a catholyte circulating pump (5), and a cathode chamber pyrazole aqueous solution outlet (15) is connected with a solution inlet of the catholyte storage tank (4).
2. The electronic grade pyrazole aqueous solution preparation device according to claim 1, wherein the cathode plate (9) is a titanium electrode, a platinum electrode or a titanium iridium alloy electrode with the purity of 99.9-99.999%, and the anode plate (7) is a platinum electrode or a titanium electrode with the purity of 99.9-99.999%; the distance between the cathode plate (9) and the anode plate (7) is 0.5-3.0 cm.
3. The apparatus for preparing electronic grade pyrazole aqueous solution according to claim 1, wherein the cation exchange resin (11) is acid, alkali, and high temperature resistant 001 x 7 type resin, 2800H type resin, or 1500H type resin, and has a particle size of (0.315-1.25 mm) or more than 95%, or (0.45-1.25 mm) or more than 95%, or (0.71-1.25 mm) or more than 95%, and a wet bulk density of 650-850 kg/m3；
The cationic exchange resin (11) is filled in the cathode chamber (8) with the density of 70-95% of the wet bulk density, and is filled in the anode chamber (6) with the density of 80-97% of the wet bulk density.
4. The method for preparing the electronic-grade pyrazole aqueous solution by using the electronic-grade pyrazole aqueous solution preparation device as claimed in claim 1, comprising the following steps of:
A. respectively adding specified amounts of cationic exchange resin (11) into an anode chamber (6) and a cathode chamber (8), respectively adding ultrapure hydrochloric acid aqueous solution for washing into an anode liquid storage tank (2) and a cathode liquid storage tank (4), respectively starting an anode liquid circulating pump (3) and a cathode liquid circulating pump (5), circularly washing each component in an ultrapure electrolytic tank (1) and the cationic exchange resin (11), and then washing with ultrapure water for 6-10 times until the washing liquid is neutral and the content of each metal ion is lower than 5 ppb;
B. adding 10-30% pyrazole aqueous solution raw materials into an anolyte storage tank (2) and a catholyte storage tank (4) at the same time, respectively starting an anolyte circulating pump (3) and a catholyte circulating pump (5), and switching on a power supply between a cathode plate and an anode plate to start electrolysis after the pyrazole aqueous solution in the whole device circularly flows to reach a specific temperature;
C. continuously pumping and circulating, continuously reducing metal ions in the pyrazole aqueous solution in the anode chamber (6) and the anolyte storage tank (2) to finally obtain an electronic-grade pyrazole aqueous solution, and then pumping the pyrazole aqueous solution in the anode chamber (6) and the anolyte storage tank (2) to a product storage tank through a product outlet (17) to obtain an electronic-grade pyrazole aqueous solution product with the mass concentration of 10-30%; meanwhile, the pyrazole aqueous solution in the cathode chamber (8) and the catholyte storage tank (4) is pumped out through an outlet (18) and can be sold as industrial chemicals;
D. and (3) adding an ultra-pure hydrochloric acid aqueous solution into the anode chamber (6) and the cathode chamber (8), soaking for 5-8 hours for regenerating the cationic resin (11), then fully washing the electronic grade pyrazole aqueous solution preparation device by adopting ultra-pure water, and transferring to the operation step B after the requirements of the step A are met.
5. The method for preparing the electronic grade pyrazole aqueous solution according to claim 4, wherein the pyrazole aqueous solution in the step B is prepared from an industrial grade pyrazole product or a pharmaceutical grade pyrazole product by adding water to dissolve the pyrazole aqueous solution to obtain the pyrazole aqueous solution with the required concentration.
6. The method for preparing the electronic-grade pyrazole aqueous solution according to claim 4, wherein in the step B, the voltage of the cathode and anode plates is 15-50V, and the flow rate of the solution in the anode chamber (6) and the cathode chamber (8) is 0.5-2.0 m/min through pumping of the anolyte circulating pump (3) and the catholyte circulating pump (5).
7. The method for preparing an electronic grade pyrazole aqueous solution according to claim 4, wherein the electrolysis temperature in the step B is 25-50 ℃.
8. The method for preparing the electronic-grade pyrazole aqueous solution according to claim 4, wherein the content of various metal ions in the electronic-grade pyrazole aqueous solution product obtained in the step C is less than 50 ppb, and the mass percentage of pyrazole is more than or equal to 10%.
9. The method of claim 4, wherein the ultra-pure hydrochloric acid in steps A and D has a purity of 99.9-99.999% and a concentration of 10-30%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896361A (en) * | 2021-10-18 | 2022-01-07 | 中南大学 | Method for cleaning and disposing stainless steel pickling acid waste liquid and recycling resources |
| CN115160225A (en) * | 2022-09-01 | 2022-10-11 | 阜新泽程化工有限责任公司 | Industrial production method of electronic pure pyrazole |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896361A (en) * | 2021-10-18 | 2022-01-07 | 中南大学 | Method for cleaning and disposing stainless steel pickling acid waste liquid and recycling resources |
| CN115160225A (en) * | 2022-09-01 | 2022-10-11 | 阜新泽程化工有限责任公司 | Industrial production method of electronic pure pyrazole |
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