CN116791105A - Process for preparing lithium hydroxide by bipolar membrane electrolysis - Google Patents
Process for preparing lithium hydroxide by bipolar membrane electrolysis Download PDFInfo
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- CN116791105A CN116791105A CN202310022262.7A CN202310022262A CN116791105A CN 116791105 A CN116791105 A CN 116791105A CN 202310022262 A CN202310022262 A CN 202310022262A CN 116791105 A CN116791105 A CN 116791105A
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- lithium hydroxide
- brine
- lithium
- bipolar membrane
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 365
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 68
- 239000012528 membrane Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000012267 brine Substances 0.000 claims abstract description 106
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 106
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 44
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 33
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 33
- 239000012535 impurity Substances 0.000 claims abstract description 32
- 239000012266 salt solution Substances 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000909 electrodialysis Methods 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 239000000460 chlorine Substances 0.000 claims description 24
- 229910052801 chlorine Inorganic materials 0.000 claims description 24
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 12
- 239000001103 potassium chloride Substances 0.000 claims description 12
- 235000011164 potassium chloride Nutrition 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 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 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000012141 concentrate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
- C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/012—Preparation of hydrogen chloride from the elements
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The application discloses a process for preparing lithium hydroxide by bipolar membrane electrolysis, which comprises the following steps: treating raw materials; carrying out electrolytic treatment, namely concentrating the purified brine by utilizing electrodialysis to prepare refined brine, and then injecting the prepared refined brine into an electrolytic tank with a bipolar membrane electrodialysis device for electrolytic treatment to obtain lithium hydroxide solution, dilute lithium salt solution and acid liquor; electrolyte treatment; treating gas; and the generated lithium hydroxide product, liquid chlorine product and hydrochloric acid product are respectively collected and stored, so that the subsequent use of the lithium hydroxide product is facilitated. The method has the advantages that the impurity removal and concentration are adopted for multiple treatment, the ion concentration in the brine is strictly controlled, the interference of the impurities is reduced, the preparation purity of lithium hydroxide is ensured, gas and acid liquor generated during electrolysis can be timely recovered, the secondary utilization can be realized, the waste of resources is reduced, the pollution to the environment is reduced, the durability of the battery is higher, and the overall production cost of the lithium hydroxide can be reduced.
Description
Technical Field
The application relates to the field of lithium hydroxide preparation, in particular to a process for preparing lithium hydroxide by bipolar membrane electrolysis.
Background
Lithium hydroxide is an inorganic compound, has a chemical formula of LiOH, is white crystalline powder, is dissolved in water, is slightly dissolved in ethanol, has strong alkalinity, has a pH of 1mol/L solution of about 14 and pKb= -0.04, and is mainly used for preparing lithium salt and lithium-based lubricating grease, electrolyte of an alkaline storage battery, absorption liquid of a lithium bromide refrigerator and the like. The purple litmus solution can be changed into blue, the colorless phenolphthalein solution is changed into red, and the concentrated solution thereof is verified by experiments to be capable of denaturing phenolphthalein and changing the solution from red into colorless (similar to concentrated NaOH).
The existing preparation process has the defects that the impurity removal effect before electrolysis of raw materials is not ideal, the purity of the subsequent lithium hydroxide production is affected, gas and acid liquor are not easy to recycle, resource waste is easy to cause, pollution is caused to the environment, the durability of the battery is insufficient, the purity of the prepared lithium hydroxide cannot meet the requirement of the battery on the use, and the production cost is high. Therefore, a bipolar membrane electrolysis process for preparing lithium hydroxide is proposed to solve the problems.
Disclosure of Invention
The bipolar membrane electrolysis lithium hydroxide preparation process is used for solving the problems that the impurity removal effect of the existing preparation process before electrolysis of raw materials in the prior art is not ideal, the purity of the subsequent lithium hydroxide production is affected, gas and acid liquor are not easy to recycle, waste is easy to cause, pollution is caused to the environment, the durability of a battery is insufficient, the purity of the prepared lithium hydroxide cannot meet the use requirement of the battery, and the production cost is high.
According to one aspect of the present application, there is provided a bipolar membrane electrolysis process for preparing lithium hydroxide, comprising the steps of:
(1) Raw material treatment, namely taking a certain amount of brine raw material, mixing the brine raw material with strong acid for reaction, standing for a period of time, utilizing filtering equipment to salvage and separate sediment, removing insoluble impurities in the solution to obtain lithium salt solution, and realizing primary impurity removal of brine;
(2) Carrying out electrolytic treatment, namely concentrating the purified brine by utilizing electrodialysis to prepare refined brine, and then injecting the prepared refined brine into an electrolytic tank with a bipolar membrane electrodialysis device to carry out electrolytic treatment to obtain lithium hydroxide solution, dilute lithium salt solution and acid liquor, wherein the dilute lithium salt solution can be uniformly mixed with the lithium salt solution and then concentrated again, so that the utilization rate of the lithium salt solution is improved;
(3) Treating electrolyte, namely treating lithium hydroxide solution generated in an electrolytic tank, separating water to generate condensed water, and cooling and crystallizing the rest part to generate a lithium hydroxide product;
(4) The method comprises the steps of (1) gas treatment, collecting chlorine generated by solution electrolysis, then performing chlorine treatment, liquefying the treated chlorine, collecting hydrogen generated by electrolysis, and treating and recycling the hydrogen;
(5) And the generated lithium hydroxide product, liquid chlorine product and hydrochloric acid product are respectively collected and stored, so that the subsequent use of the lithium hydroxide product is facilitated.
Further, most of sodium chloride and potassium chloride can be removed in the process of removing impurities from brine in the step (1), and boron, sulfate radical and other ions can be removed by selecting a proper method, so that the mass fraction of anions (excluding chloride ions) is not more than 5%.
Further, after removing impurities from the brine in the step (1), adjusting the pH of the brine to 10.5-11.5, reprecipitating, removing calcium ions and magnesium ions in the brine, and further reducing the total amount of the magnesium ions and the calcium ions to below 0.15mg/L through ion exchange resin.
Further, the step (2) is to continuously concentrate the brine until the mass fraction of lithium ions is 5% -7% (30% -42% in terms of lithium chloride), wherein sodium chloride and potassium chloride are not dissolved in the concentrated brine containing 30% -42% of lithium chloride and are precipitated, so that the total concentration of sodium ions and potassium ions in the brine is controlled below 5% (mass fraction), and refined brine is obtained, and the main component of the refined brine is lithium chloride solution.
Further, during electrolysis in the step (2), cathode and anode materials inside the electrolytic tank are made of highly corrosion-resistant titanium and nickel coatings, so that corrosion damage of lithium chloride solution to the electrode is reduced, normal use of the electrode is ensured, and during electrolysis, refined brine is used as anolyte in the electrolytic tank, and lithium hydroxide solution is used as catholyte.
Further, in the step (2), a cation permselective membrane is provided between the anode compartment and the cathode compartment, allowing Li to be + Through a permeable membrane, cl - Is blocked from passing through, and the electrolysis voltage of the electrolytic cell is controlled to be 3-6V, the current density is 1-100A/dm < 2 >, and the cell temperature is 60-70 ℃.
Further, in the step (2), lithium chloride in the anolyte is converted into lithium hydroxide in the catholyte, and the electrolysis may be continued until the concentration of lithium hydroxide reaches 14% (mass fraction) or near saturation concentration.
In the step (3), the lithium hydroxide solution is concentrated and crystallized to obtain lithium hydroxide-hydrate, and then the lithium hydroxide-hydrate is centrifugally separated, washed and dried to separate water from lithium hydroxide, so that the lithium hydroxide with higher purity is prepared.
And (3) introducing hydrogen in the step (4) into a hydrochloric acid working section through equipment after hydrogen treatment, mixing chlorine gas subjected to chlorine treatment with hydrogen treated by hydrogen in the hydrochloric acid working section, and then mixing the reacted product with acid liquor generated in the step (3) to generate a hydrochloric acid product.
Further, in the step (5), liquid chlorine is stored in a steel bottle and is stored in a dry and ventilated warehouse, and lithium hydroxide and a hydrochloric acid product are respectively stored in the storage process and are stored in a dark place, so that the mutual interference of the lithium hydroxide and the hydrochloric acid is reduced.
According to the embodiment of the application, the steps of raw material treatment, electrolysis treatment, gas treatment and the like are adopted, so that the problems that the impurity removal effect of the existing preparation process before electrolysis of raw materials is not ideal, the purity of the subsequent lithium hydroxide production is affected, gas and acid liquor are not easy to recycle, waste is easy to cause, pollution is caused to the environment, the durability of the battery is insufficient, the purity of the prepared lithium hydroxide cannot meet the use requirement of the battery, the production cost is high are solved, the impurity removal effect of brine is good, the purity of lithium hydroxide production can be ensured, the gas and the acid liquor can be recycled, the environmental pollution is reduced, the durability of the battery is improved, and the production cost is reduced are solved.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the application, and that other drawings can be obtained from these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a flow chart of the present application;
FIG. 2 is an electrolytic schematic of the present application.
Detailed Description
In order that those skilled in the art will better understand the present application, a technical solution in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present application and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate in order to describe the embodiments of the application herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
In the present application, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal" and the like indicate an azimuth or a positional relationship based on that shown in the drawings. These terms are only used to better describe the present application and its embodiments and are not intended to limit the scope of the indicated devices, elements or components to the particular orientations or to configure and operate in the particular orientations.
Also, some of the terms described above may be used to indicate other meanings in addition to orientation or positional relationships, for example, the term "upper" may also be used to indicate some sort of attachment or connection in some cases. The specific meaning of these terms in the present application will be understood by those of ordinary skill in the art according to the specific circumstances.
Furthermore, the terms "mounted," "configured," "provided," "connected," "coupled," and "sleeved" are to be construed broadly. For example, it may be a fixed connection, a removable connection, or a unitary construction; may be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements, or components. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
Example 1
Referring to fig. 1-2, a process for preparing lithium hydroxide by bipolar membrane electrolysis includes the following steps:
(1) Raw material treatment, namely taking a certain amount of brine raw material, mixing the brine raw material with strong acid for reaction, standing for a period of time, utilizing filtering equipment to salvage and separate sediment, removing insoluble impurities in the solution to obtain lithium salt solution, and realizing primary impurity removal of brine;
(2) Carrying out electrolytic treatment, namely concentrating the purified brine by utilizing electrodialysis to prepare refined brine, and then injecting the prepared refined brine into an electrolytic tank with a bipolar membrane electrodialysis device to carry out electrolytic treatment to obtain lithium hydroxide solution, dilute lithium salt solution and acid liquor, wherein the dilute lithium salt solution can be uniformly mixed with the lithium salt solution and then concentrated again, so that the utilization rate of the lithium salt solution is improved;
(3) Treating electrolyte, namely treating lithium hydroxide solution generated in an electrolytic tank, separating water to generate condensed water, and cooling and crystallizing the rest part to generate a lithium hydroxide product;
(4) The method comprises the steps of (1) gas treatment, collecting chlorine generated by solution electrolysis, then performing chlorine treatment, liquefying the treated chlorine, collecting hydrogen generated by electrolysis, and treating and recycling the hydrogen;
(5) And the generated lithium hydroxide product, liquid chlorine product and hydrochloric acid product are respectively collected and stored, so that the subsequent use of the lithium hydroxide product is facilitated.
Further, most of sodium chloride and potassium chloride can be removed in the process of removing impurities from brine in the step (1), and boron, sulfate radical and other ions can be removed by selecting a proper method, so that the mass fraction of anions (excluding chloride ions) is not more than 5%.
Further, after removing impurities from the brine in the step (1), adjusting the pH of the brine to 10.5, reprecipitating to remove calcium ions and magnesium ions in the brine, and further reducing the total amount of the magnesium ions and the calcium ions to below 0.15mg/L through ion exchange resin.
Further, the step (2) is to continuously concentrate the brine until the mass fraction of lithium ions is 5% -7% (30% -42% in terms of lithium chloride), wherein sodium chloride and potassium chloride are not dissolved in the concentrated brine containing 30% -42% of lithium chloride and are precipitated, so that the total concentration of sodium ions and potassium ions in the brine is controlled below 5% (mass fraction), and refined brine is obtained, and the main component of the refined brine is lithium chloride solution.
Further, during electrolysis in the step (2), cathode and anode materials inside the electrolytic tank are made of highly corrosion-resistant titanium and nickel coatings, so that corrosion damage of lithium chloride solution to the electrode is reduced, normal use of the electrode is ensured, and during electrolysis, refined brine is used as anolyte in the electrolytic tank, and lithium hydroxide solution is used as catholyte.
Further, in the step (2), a cation permselective membrane is provided between the anode compartment and the cathode compartment, allowing Li to be + Through a permeable membrane, cl - Is blocked from passing through, and the electrolysis voltage of the electrolytic cell is controlled to be 3V, the current density is 1-100A/dm < 2 >, and the cell temperature is 70 ℃.
Further, in the step (2), lithium chloride in the anolyte is converted into lithium hydroxide in the catholyte, and the electrolysis may be continued until the concentration of lithium hydroxide reaches 14% (mass fraction) or near saturation concentration.
In the step (3), the lithium hydroxide solution is concentrated and crystallized to obtain lithium hydroxide-hydrate, and then the lithium hydroxide-hydrate is centrifugally separated, washed and dried to separate water from lithium hydroxide, so that the lithium hydroxide with higher purity is prepared.
And (3) introducing hydrogen in the step (4) into a hydrochloric acid working section through equipment after hydrogen treatment, mixing chlorine gas subjected to chlorine treatment with hydrogen treated by hydrogen in the hydrochloric acid working section, and then mixing the reacted product with acid liquor generated in the step (3) to generate a hydrochloric acid product.
Further, in the step (5), liquid chlorine is stored in a steel bottle and is stored in a dry and ventilated warehouse, and lithium hydroxide and a hydrochloric acid product are respectively stored in the storage process and are stored in a dark place, so that the mutual interference of the lithium hydroxide and the hydrochloric acid is reduced.
The method is suitable for the bipolar membrane electrolysis process for preparing lithium hydroxide with lower pH of brine, higher temperature of an electrolytic tank and lower voltage.
Example 2
Referring to fig. 1-2, a process for preparing lithium hydroxide by bipolar membrane electrolysis includes the following steps:
(1) Raw material treatment, namely taking a certain amount of brine raw material, mixing the brine raw material with strong acid for reaction, standing for a period of time, utilizing filtering equipment to salvage and separate sediment, removing insoluble impurities in the solution to obtain lithium salt solution, and realizing primary impurity removal of brine;
(2) Carrying out electrolytic treatment, namely concentrating the purified brine by utilizing electrodialysis to prepare refined brine, and then injecting the prepared refined brine into an electrolytic tank with a bipolar membrane electrodialysis device to carry out electrolytic treatment to obtain lithium hydroxide solution, dilute lithium salt solution and acid liquor, wherein the dilute lithium salt solution can be uniformly mixed with the lithium salt solution and then concentrated again, so that the utilization rate of the lithium salt solution is improved;
(3) Treating electrolyte, namely treating lithium hydroxide solution generated in an electrolytic tank, separating water to generate condensed water, and cooling and crystallizing the rest part to generate a lithium hydroxide product;
(4) The method comprises the steps of (1) gas treatment, collecting chlorine generated by solution electrolysis, then performing chlorine treatment, liquefying the treated chlorine, collecting hydrogen generated by electrolysis, and treating and recycling the hydrogen;
(5) And the generated lithium hydroxide product, liquid chlorine product and hydrochloric acid product are respectively collected and stored, so that the subsequent use of the lithium hydroxide product is facilitated.
Further, most of sodium chloride and potassium chloride can be removed in the process of removing impurities from brine in the step (1), and boron, sulfate radical and other ions can be removed by selecting a proper method, so that the mass fraction of anions (excluding chloride ions) is not more than 5%.
Further, after removing impurities from the brine in the step (1), adjusting the pH of the brine to 11.5, reprecipitating to remove calcium ions and magnesium ions in the brine, and further reducing the total amount of the magnesium ions and the calcium ions to below 0.15mg/L through ion exchange resin.
Further, the step (2) is to continuously concentrate the brine until the mass fraction of lithium ions is 5% -7% (30% -42% in terms of lithium chloride), wherein sodium chloride and potassium chloride are not dissolved in the concentrated brine containing 30% -42% of lithium chloride and are precipitated, so that the total concentration of sodium ions and potassium ions in the brine is controlled below 5% (mass fraction), and refined brine is obtained, and the main component of the refined brine is lithium chloride solution.
Further, during electrolysis in the step (2), cathode and anode materials inside the electrolytic tank are made of highly corrosion-resistant titanium and nickel coatings, so that corrosion damage of lithium chloride solution to the electrode is reduced, normal use of the electrode is ensured, and during electrolysis, refined brine is used as anolyte in the electrolytic tank, and lithium hydroxide solution is used as catholyte.
Further, in the step (2), a cation permselective membrane is provided between the anode compartment and the cathode compartment, allowing Li to be + Through a permeable membrane, cl - Is blocked from passing through, and the electrolysis voltage of the electrolytic cell is controlled to be 5V, the current density is 1-100A/dm < 2 >, and the cell temperature is 65 ℃.
Further, in the step (2), lithium chloride in the anolyte is converted into lithium hydroxide in the catholyte, and the electrolysis may be continued until the concentration of lithium hydroxide reaches 14% (mass fraction) or near saturation concentration.
In the step (3), the lithium hydroxide solution is concentrated and crystallized to obtain lithium hydroxide-hydrate, and then the lithium hydroxide-hydrate is centrifugally separated, washed and dried to separate water from lithium hydroxide, so that the lithium hydroxide with higher purity is prepared.
And (3) introducing hydrogen in the step (4) into a hydrochloric acid working section through equipment after hydrogen treatment, mixing chlorine gas subjected to chlorine treatment with hydrogen treated by hydrogen in the hydrochloric acid working section, and then mixing the reacted product with acid liquor generated in the step (3) to generate a hydrochloric acid product.
Further, in the step (5), liquid chlorine is stored in a steel bottle and is stored in a dry and ventilated warehouse, and lithium hydroxide and a hydrochloric acid product are respectively stored in the storage process and are stored in a dark place, so that the mutual interference of the lithium hydroxide and the hydrochloric acid is reduced.
The method is suitable for the bipolar membrane electrolysis process for preparing lithium hydroxide with high brine PH, high electrolytic tank temperature and low voltage.
Example 3
Referring to fig. 1-2, a process for preparing lithium hydroxide by bipolar membrane electrolysis includes the following steps:
(1) Raw material treatment, namely taking a certain amount of brine raw material, mixing the brine raw material with strong acid for reaction, standing for a period of time, utilizing filtering equipment to salvage and separate sediment, removing insoluble impurities in the solution to obtain lithium salt solution, and realizing primary impurity removal of brine;
(2) Carrying out electrolytic treatment, namely concentrating the purified brine by utilizing electrodialysis to prepare refined brine, and then injecting the prepared refined brine into an electrolytic tank with a bipolar membrane electrodialysis device to carry out electrolytic treatment to obtain lithium hydroxide solution, dilute lithium salt solution and acid liquor, wherein the dilute lithium salt solution can be uniformly mixed with the lithium salt solution and then concentrated again, so that the utilization rate of the lithium salt solution is improved;
(3) Treating electrolyte, namely treating lithium hydroxide solution generated in an electrolytic tank, separating water to generate condensed water, and cooling and crystallizing the rest part to generate a lithium hydroxide product;
(4) The method comprises the steps of (1) gas treatment, collecting chlorine generated by solution electrolysis, then performing chlorine treatment, liquefying the treated chlorine, collecting hydrogen generated by electrolysis, and treating and recycling the hydrogen;
(5) And the generated lithium hydroxide product, liquid chlorine product and hydrochloric acid product are respectively collected and stored, so that the subsequent use of the lithium hydroxide product is facilitated.
Further, most of sodium chloride and potassium chloride can be removed in the process of removing impurities from brine in the step (1), and boron, sulfate radical and other ions can be removed by selecting a proper method, so that the mass fraction of anions (excluding chloride ions) is not more than 5%.
Further, after removing impurities from the brine in the step (1), adjusting the pH of the brine to 11.5, reprecipitating to remove calcium ions and magnesium ions in the brine, and further reducing the total amount of the magnesium ions and the calcium ions to below 0.15mg/L through ion exchange resin.
Further, the step (2) is to continuously concentrate the brine until the mass fraction of lithium ions is 5% -7% (30% -42% in terms of lithium chloride), wherein sodium chloride and potassium chloride are not dissolved in the concentrated brine containing 30% -42% of lithium chloride and are precipitated, so that the total concentration of sodium ions and potassium ions in the brine is controlled below 5% (mass fraction), and refined brine is obtained, and the main component of the refined brine is lithium chloride solution.
Further, during electrolysis in the step (2), cathode and anode materials inside the electrolytic tank are made of highly corrosion-resistant titanium and nickel coatings, so that corrosion damage of lithium chloride solution to the electrode is reduced, normal use of the electrode is ensured, and during electrolysis, refined brine is used as anolyte in the electrolytic tank, and lithium hydroxide solution is used as catholyte.
Further, in the step (2), a cation permselective membrane is provided between the anode compartment and the cathode compartment, allowing Li to be + Through a permeable membrane, cl - Is blocked from passing through, and the electrolysis voltage of the electrolytic cell is controlled to be 6V, the current density is 1-100A/dm < 2 >, and the cell temperature is 60 ℃.
Further, in the step (2), lithium chloride in the anolyte is converted into lithium hydroxide in the catholyte, and the electrolysis may be continued until the concentration of lithium hydroxide reaches 14% (mass fraction) or near saturation concentration.
In the step (3), the lithium hydroxide solution is concentrated and crystallized to obtain lithium hydroxide-hydrate, and then the lithium hydroxide-hydrate is centrifugally separated, washed and dried to separate water from lithium hydroxide, so that the lithium hydroxide with higher purity is prepared.
And (3) introducing hydrogen in the step (4) into a hydrochloric acid working section through equipment after hydrogen treatment, mixing chlorine gas subjected to chlorine treatment with hydrogen treated by hydrogen in the hydrochloric acid working section, and then mixing the reacted product with acid liquor generated in the step (3) to generate a hydrochloric acid product.
Further, in the step (5), liquid chlorine is stored in a steel bottle and is stored in a dry and ventilated warehouse, and lithium hydroxide and a hydrochloric acid product are respectively stored in the storage process and are stored in a dark place, so that the mutual interference of the lithium hydroxide and the hydrochloric acid is reduced.
The method is suitable for preparing lithium hydroxide by bipolar membrane electrolysis with higher pH of brine, lower temperature of an electrolytic tank and higher voltage.
Example 4
Referring to fig. 1-2, a process for preparing lithium hydroxide by bipolar membrane electrolysis includes the following steps:
(1) Raw material treatment, namely taking a certain amount of brine raw material, mixing the brine raw material with strong acid for reaction, standing for a period of time, utilizing filtering equipment to salvage and separate sediment, removing insoluble impurities in the solution to obtain lithium salt solution, and realizing primary impurity removal of brine;
(2) Carrying out electrolytic treatment, namely concentrating the purified brine by utilizing electrodialysis to prepare refined brine, and then injecting the prepared refined brine into an electrolytic tank with a bipolar membrane electrodialysis device to carry out electrolytic treatment to obtain lithium hydroxide solution, dilute lithium salt solution and acid liquor, wherein the dilute lithium salt solution can be uniformly mixed with the lithium salt solution and then concentrated again, so that the utilization rate of the lithium salt solution is improved;
(3) Treating electrolyte, namely treating lithium hydroxide solution generated in an electrolytic tank, separating water to generate condensed water, and cooling and crystallizing the rest part to generate a lithium hydroxide product;
(4) The method comprises the steps of (1) gas treatment, collecting chlorine generated by solution electrolysis, then performing chlorine treatment, liquefying the treated chlorine, collecting hydrogen generated by electrolysis, and treating and recycling the hydrogen;
(5) And the generated lithium hydroxide product, liquid chlorine product and hydrochloric acid product are respectively collected and stored, so that the subsequent use of the lithium hydroxide product is facilitated.
Further, most of sodium chloride and potassium chloride can be removed in the process of removing impurities from brine in the step (1), and boron, sulfate radical and other ions can be removed by selecting a proper method, so that the mass fraction of anions (excluding chloride ions) is not more than 5%.
Further, after removing impurities from the brine in the step (1), adjusting the pH of the brine to 10.5, reprecipitating to remove calcium ions and magnesium ions in the brine, and further reducing the total amount of the magnesium ions and the calcium ions to below 0.15mg/L through ion exchange resin.
Further, the step (2) is to continuously concentrate the brine until the mass fraction of lithium ions is 5% -7% (30% -42% in terms of lithium chloride), wherein sodium chloride and potassium chloride are not dissolved in the concentrated brine containing 30% -42% of lithium chloride and are precipitated, so that the total concentration of sodium ions and potassium ions in the brine is controlled below 5% (mass fraction), and refined brine is obtained, and the main component of the refined brine is lithium chloride solution.
Further, during electrolysis in the step (2), cathode and anode materials inside the electrolytic tank are made of highly corrosion-resistant titanium and nickel coatings, so that corrosion damage of lithium chloride solution to the electrode is reduced, normal use of the electrode is ensured, and during electrolysis, refined brine is used as anolyte in the electrolytic tank, and lithium hydroxide solution is used as catholyte.
Further, in the step (2), a cation permselective membrane is provided between the anode compartment and the cathode compartment, allowing Li to be + Through a permeable membrane, cl - Is blocked from passing through, and the electrolysis voltage of the electrolytic cell is controlled to be 6V, the current density is 1-100A/dm < 2 >, and the cell temperature is 60 ℃.
Further, in the step (2), lithium chloride in the anolyte is converted into lithium hydroxide in the catholyte, and the electrolysis may be continued until the concentration of lithium hydroxide reaches 14% (mass fraction) or near saturation concentration.
In the step (3), the lithium hydroxide solution is concentrated and crystallized to obtain lithium hydroxide-hydrate, and then the lithium hydroxide-hydrate is centrifugally separated, washed and dried to separate water from lithium hydroxide, so that the lithium hydroxide with higher purity is prepared.
And (3) introducing hydrogen in the step (4) into a hydrochloric acid working section through equipment after hydrogen treatment, mixing chlorine gas subjected to chlorine treatment with hydrogen treated by hydrogen in the hydrochloric acid working section, and then mixing the reacted product with acid liquor generated in the step (3) to generate a hydrochloric acid product.
Further, in the step (5), liquid chlorine is stored in a steel bottle and is stored in a dry and ventilated warehouse, and lithium hydroxide and a hydrochloric acid product are respectively stored in the storage process and are stored in a dark place, so that the mutual interference of the lithium hydroxide and the hydrochloric acid is reduced.
The method is suitable for the bipolar membrane electrolysis process for preparing lithium hydroxide with lower PH of brine, lower temperature of an electrolytic tank and higher voltage.
The application has the advantages that:
the ion concentration in the brine is strictly controlled by adopting the processes of impurity removal and concentration for multiple times, the interference of the impurities is reduced, the preparation purity of the lithium hydroxide is ensured, the subsequent lithium hydroxide is beneficial to meeting the use requirement of a battery, gas and acid liquor generated during electrolysis can be timely recovered and can be reused after the process, the dilute lithium salt solution can be concentrated and recovered, the waste of resources is reduced, the pollution to the environment is reduced, the durability of the battery is higher, and the whole production cost of the lithium hydroxide can be reduced.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A bipolar membrane electrolysis process for preparing lithium hydroxide is characterized in that: the bipolar membrane electrolysis lithium hydroxide preparation process comprises the following steps:
(1) Raw material treatment, namely taking a certain amount of brine raw material, mixing the brine raw material with strong acid for reaction, standing for a period of time, utilizing filtering equipment to salvage and separate sediment, removing insoluble impurities in the solution to obtain lithium salt solution, and realizing primary impurity removal of brine;
(2) Carrying out electrolytic treatment, namely concentrating the purified brine by utilizing electrodialysis to prepare refined brine, and then injecting the prepared refined brine into an electrolytic tank with a bipolar membrane electrodialysis device to carry out electrolytic treatment to obtain lithium hydroxide solution, dilute lithium salt solution and acid liquor, wherein the dilute lithium salt solution can be uniformly mixed with the lithium salt solution and then concentrated again, so that the utilization rate of the lithium salt solution is improved;
(3) Treating electrolyte, namely treating lithium hydroxide solution generated in an electrolytic tank, separating water to generate condensed water, and cooling and crystallizing the rest part to generate a lithium hydroxide product;
(4) The method comprises the steps of (1) gas treatment, collecting chlorine generated by solution electrolysis, then performing chlorine treatment, liquefying the treated chlorine, collecting hydrogen generated by electrolysis, and treating and recycling the hydrogen;
(5) And the generated lithium hydroxide product, liquid chlorine product and hydrochloric acid product are respectively collected and stored, so that the subsequent use of the lithium hydroxide product is facilitated.
2. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: in the step (1), most sodium chloride and potassium chloride can be removed in the process of removing impurities from brine, and boron, sulfate radical and other ions can be removed by selecting a proper method, so that the mass fraction of anions (excluding chloride ions) is not more than 5%.
3. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: and (3) removing impurities from the brine in the step (1), adjusting the pH of the brine to 10.5-11.5, reprecipitating, removing calcium ions and magnesium ions in the brine, and further reducing the total amount of the magnesium ions and the calcium ions to below 0.15mg/L through ion exchange resin.
4. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: and (2) continuously concentrating the brine until the mass fraction of lithium ions is 5% -7% (30% -42% in terms of lithium chloride), wherein sodium chloride and potassium chloride are not dissolved in the concentrated brine containing 30% -42% of lithium chloride and are precipitated, so that the total concentration of sodium ions and potassium ions in the brine is controlled below 5% (mass fraction), and refined brine is obtained, and the main component of the refined brine is lithium chloride solution.
5. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: and (2) during electrolysis, cathode and anode materials in the electrolytic tank are made of highly corrosion-resistant titanium and nickel coatings so as to reduce corrosion damage of lithium chloride solution to the electrode and ensure normal use of the electrode, and during electrolysis, refined brine is used as anolyte and lithium hydroxide solution is used as catholyte in the electrolytic tank.
6. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: in the step (2), a cation permselective membrane is disposed between the anode and cathode compartments, allowing Li to flow + Through a permeable membrane, cl - Is blocked from passing through, and the electrolysis voltage of the electrolytic cell is controlled to be 3-6V, the current density is 1-100A/dm < 2 >, and the cell temperature is 60-70 ℃.
7. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: the lithium chloride in the anolyte in step (2) is converted into lithium hydroxide in the catholyte, and the electrolysis may be continued until the concentration of lithium hydroxide reaches 14% (mass fraction) or near saturation concentration.
8. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: in the step (3), the lithium hydroxide solution is concentrated and crystallized to obtain lithium hydroxide-hydrate, and then the lithium hydroxide-hydrate is centrifugally separated, washed and dried to separate water from lithium hydroxide, so that the lithium hydroxide with higher purity is prepared.
9. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: and (3) introducing hydrogen in the step (4) into a hydrochloric acid working section through equipment after hydrogen treatment, mixing chlorine gas subjected to chlorine treatment with hydrogen treated by hydrogen in the hydrochloric acid working section, and then mixing the reacted product with acid liquor generated in the step (3) to generate a hydrochloric acid product.
10. The process for preparing lithium hydroxide by bipolar membrane electrolysis according to claim 1, wherein the process comprises the following steps: and (5) storing the liquid chlorine in a steel bottle, storing in a dry and ventilated warehouse, and storing lithium hydroxide and a hydrochloric acid product respectively in the storage process, and storing in a dark place, so that the mutual interference of the lithium hydroxide and the hydrochloric acid is reduced.
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