CN112320828A - Method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string method - Google Patents
Method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string method Download PDFInfo
- Publication number
- CN112320828A CN112320828A CN202011096601.9A CN202011096601A CN112320828A CN 112320828 A CN112320828 A CN 112320828A CN 202011096601 A CN202011096601 A CN 202011096601A CN 112320828 A CN112320828 A CN 112320828A
- Authority
- CN
- China
- Prior art keywords
- acid
- purity
- nano
- aluminum
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
Abstract
The invention discloses a method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string reaction, which belongs to the field of inorganic substance preparation, greatly reduces impurity removal difficulty, improves product purity, and reduces energy consumption and equipment corrosion degree. The invention obtains the soluble aluminum hydroxide by an alkaline purification method, adds hydrochloric acid to prepare high-purity aluminum trichloride solution, then adds high-purity aluminum ingots, utilizes the exothermic polymerization reaction to prepare the high-purity polyaluminum chloride solution, does not need to pressurize and heat, is easy to carry out the polymerization reaction, then adds ammonia water to the generated solution to adjust the pH value, gradually separates out the aluminum hydroxide in the solution, carries out countercurrent washing and liquid-solid separation after the aluminum hydroxide is completely precipitated in the solution, adds SAA in the process, can improve the hydrophobic property of the filtrate, and generates low-density macroporous r spherical active alumina and primary crystal nano alpha-sintering alumina in the subsequent drying and calcining process.
Description
Technical Field
The invention belongs to the field of inorganic substance preparation, and particularly relates to a method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string reaction.
Background
With the progress of modern science and technology, especially emerging industries such as the high-speed development of aerospace technology, the utilization of large-scale atomic energy, ocean development and the like, the industrial production puts forward higher and higher requirements on structural materials. In many respects, conventional metal or alloy materials have been difficult to meet the requirements of practical applications. Alumina is one of basic materials in the high-tech field, and has been widely used in various projects such as aerospace, nuclear energy, metallurgy, electronics, biochemistry, chemical engineering and the like due to its characteristics of high melting point, high hardness, insulation, heat resistance and the like. The high-purity alumina powder becomes a great important branch in advanced inorganic nonmetallic materials, and is one of high-end material industries with large yield, high output value and wide application in the new material industry for 20 th century.
The technology for producing alumina by an acid method is almost the alumina production technology which is proposed in the same period as the Bayer method, but the Bayer method for producing alumina accounts for 95 percent of the productivity in the development of 100 years. The production of alumina by the acid method has been standing for a long time due to a number of problems, but the research of the acid method has never been stopped as a technical reserve for the utilization of non-bauxite resources. The 60's of the last century are the hot tide period of acid process research, typically representing the c.s.i.r.o process and the H + process, the c.s.i.r.o process being a sulfuric acid process with basic aluminum sulfate as an intermediate product proposed by the federal scientific and technological research organization of melbourne, australia; the H + process, which was proposed by Pestzel, France to treat clay and coal shale using a combination of sulfuric and hydrochloric acids and was tested industrially by aluminum industries, Canada, was considered to be the most promising acid process.
In recent years, particularly in 2005, along with the research on the reduction of high-alumina-silica ratio ores and the comprehensive utilization of fly ash, the production of alumina by an acid method is gradually emphasized by people, and a new research heat tide is formed. Patent CN200710010917.X discloses a method for producing alumina by treating bauxite with low aluminum-silicon ratio by a sulfuric acid method combined with a Bayer method; patent CN201010161876.6 discloses a method for producing alumina by using a hydrochloric acid method of fly ash; patent CN201010172151.7 discloses a method for preparing alumina by leaching bauxite with hydrochloric acid and extracting and removing iron; patent CN201110452728.4 discloses a method for the subsequent treatment of aluminum sulfate in the process of extracting alumina from fly ash; patent 201210102803.9 discloses a method for preparing alumina by acid leaching of low-grade bauxite; the process for producing alumina by the acid method disclosed above has the following main problems: (1) the impurity removal of an aluminum salt solution is difficult, the aluminum salt solution is dissolved out under the condition of high temperature and concentrated acid, not only can the aluminum be dissolved out, but also the iron, the potassium, the sodium, the calcium, the magnesium, the lithium, the titanium and part of rare metals are correspondingly dissolved out, and the key is how to economically and effectively remove the impurity; (2) the equipment is corroded and abraded seriously, and particularly, the dissolution tank, the heat exchanger and the evaporator are corroded and abraded to different degrees; (3) the cost is high: the decomposition heat consumption of various aluminum salts (aluminum sulfate, aluminum chloride and aluminum nitrate) is large, and the heat consumption is about 4 times of that of aluminum oxide produced by pyrolyzing aluminum hydroxide by taking aluminum chloride hexahydrate as an example.
Disclosure of Invention
The invention provides a method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string method, which greatly reduces the difficulty of impurity removal, improves the product purity, and reduces the energy consumption and the equipment corrosion degree.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string reaction comprises the following steps:
step S1: purifying by an alkaline method to obtain high-purity easily-soluble aluminum hydroxide, and adding the aluminum hydroxide into acid to prepare an aluminum salt solution;
step S2: adding a high-purity aluminum ingot prepared by a three-layer liquid electrolytic refining method into the aluminum salt solution prepared in the step S1 to react to obtain a high-purity polyaluminum chloride solution;
step S3: slowly adding ammonia water into the high-purity polyaluminum chloride solution prepared in the step S2 to adjust the pH value of the solution, so that aluminum hydroxide in the solution is gradually separated out until the precipitation is complete;
step S4: s3, performing liquid-solid separation after complete precipitation, adding 100Kg of SAA additive in the liquid-solid separation and washing process, improving the hydrophobicity of solid particles and strengthening the washing effect, improving the crystal morphology (pore expansion) of the material, widening the product application (catalyst), and drying the solid after liquid-solid separation;
step S5: and calcining the dried solid in the step S4 at 400-600 ℃ to obtain the nano low-density macroporous spherical gamma-Al 2O3, and calcining at 1250 ℃ to obtain the nano spherical alpha alumina.
In the above steps, the alkaline purification in step S1 includes the following steps:
adding active calcium aluminate (more than 45% of alumina in waste residue discharged from a calcium metal plant and less than 50% of calcium oxide) into the decomposition stock solution of the Bayer process to replace lime for deep desiliconization, wherein the addition is more than 90 g/L, the temperature is more than 170 ℃, the retention time is 20 minutes, the A/S ratio can be more than 3000 after the reaction, obtaining the aluminum hydroxide with the content of the ferrosilicon impurity reduced to less than 50ppm through decomposition, adding water into the product for pulping at 200 ℃, and carrying out autoclaving to reduce sodium and calcium to less than 500 ppm.
The acid is hydrochloric acid with the mass fraction of 29-31%, the concentration of cationic impurities in the aluminum hydroxide reaches the ppm level, the Na < + > is less than or equal to 20ppm, and the Ca2 < + > is less than or equal to 20 ppm;
the high-purity aluminum ingot in the step S2 is obtained by an electrical purification method, and the reaction is carried out by auto-thermal polymerization to obtain a high-purity polyaluminum chloride solution without adding heat from the outside;
in the step S3, when the pH value of the solution is adjusted by ammonia water, the pH value is slowly increased to 6.5 after the pH value is changed from acidity to 6, so that the generation of secondary particle agglomeration caused by rapid alkalization is avoided.
The SAA additive is S-200 quaternary ammonium salt type neutral cationic surfactant
Has the advantages that: the invention provides a method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string, which adopts a novel acid-base tandem and electrochemical tandem double-string process to try to achieve the purposes of high-quality functional products with purity of more than 4N 5-5N, granularity of nano, controllable crystal forms (amorphous, boehmite, r and alpha) and crystal morphology (pore volume, specific surface and pore structure), has the obvious advantages of low cost, greatly reduces the difficulty of impurity removal and improves the product purity, has short process route and reduced equipment corrosion degree, can release and recycle energy stored in the process of preparing polyaluminium chloride solution by using high-purity aluminum and aluminum salt solution during the polymerization reaction of the process, utilizes self-heating easily-soluble aluminum hydroxide as a raw material to prepare high-purity aluminum trichloride solution with hydrochloric acid, the method realizes a process route for purifying cationic impurities with low cost and short flow, and then realizes normal pressure polymerization reaction of an aluminum salt solution by adding a high-purity aluminum ingot to generate a high-purity polyaluminum chloride solution with high alumina content and high alkalization degree, adding a small amount of ammonia water to precipitate high-purity aluminum hydroxide, and roasting at the low temperature of 400-600 ℃ to generate low-density spherical nano gamma-Al 2O3 for the catalysis field, and also can be used as a raw material of precision electronic ceramics, artificial gems and battery diaphragms by roasting at the temperature of 1250 ℃ to generate high-purity spherical nano alpha alumina.
In the production and preparation process, HCl gas desorbed by drying and roasting heat is an environmental pollutant, and the invention adopts three measures to improve: 1) the polymerization process is enhanced, and the HCl content in the discharged flue gas is reduced while the hydrochloric acid consumption is reduced; 2) facility management of a flue gas closed recovery device in the reinforced baking process; 3) and (3) sending the overflowing HCl gas into an acid dissolving device of aluminum trichloride, and improving the concentration of HCl, the acid dissolving effect and the crystallization process. The reaction of metal aluminum and aluminum salt solution belongs to a neutralization displacement exothermic reaction, in order to reasonably utilize the reaction exothermic, aluminum block reaction is adopted to replace aluminum powder reaction, thus not only saving the powder preparation process and saving the cost, but also avoiding the rapid exothermic violent reaction of the aluminum powder reaction from being difficult to control, the aluminum block reaction releases heat for a long time to avoid heat overflow, the polymerization degree is improved through long-time polymerization, and strict operation rules of starting and stopping the automobile and purging and replacing hydrogen by nitrogen before adding the aluminum block are made in the actual production process.
Drawings
FIG. 1 is a reaction scheme of an embodiment of the present invention;
FIG. 2 is a reaction scheme of an embodiment of the present invention.
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
example 1
As shown in fig. 1, a method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string method comprises the following steps:
step S1: purifying by an alkaline method to obtain high-purity easily soluble aluminum hydroxide, wherein the concentration of cationic impurities in the aluminum hydroxide reaches the ppm level, Na < + > is less than or equal to 20ppm, and Ca2 < + > is less than or equal to 20ppm, and adding the aluminum hydroxide into hydrochloric acid with the mass fraction of 29-31% to prepare an aluminum salt solution;
step S2: adding 4N-5N high-purity aluminum ingots obtained by an electrical purification method into the aluminum salt solution prepared in the step S1, reacting to obtain a high-purity polyaluminum chloride solution by auto-thermal polymerization, without adding heat outside, wherein the polyaluminum chloride solution generated by the reaction has extremely high alumina ion concentration due to high purity and good reaction activity of metallic aluminum, so that the generation of other impurity ions in the aluminum salt solution can be avoided, particularly the AlO +/Cl-ratio is improved, the consumption of process hydrochloric acid is reduced, the ammonia water consumption during subsequent gel deposition is reduced, and multiple effects of reducing the washing water consumption and the discharged flue gas treatment capacity are realized;
step S3: slowly adding ammonia water into the high-purity polyaluminum chloride solution prepared in the step S2 to adjust the pH value of the solution, so that aluminum hydroxide in the solution is gradually separated out until the precipitation is complete, and slowly increasing the pH value to 6.5 after the pH value is changed from acidity to 6, thereby avoiding secondary particle agglomeration caused by rapid alkalization;
step S4: s3, performing liquid-solid separation after complete precipitation, adding 100Kg of SAA additive (S-200 quaternary ammonium salt type neutral cationic surfactant) in each ton of product in the liquid-solid separation and washing process, improving the hydrophobicity of solid particles, strengthening the washing effect, improving the crystal morphology (pore expansion) of the material, widening the product application (catalyst), and drying the solid after liquid-solid separation;
step S5: and calcining the dried solid in the step S4 at 600 ℃ to obtain the nano low-density macroporous spherical gamma-Al 203, and calcining at 1250 ℃ to obtain the nano spherical alpha alumina.
In the above steps, the alkaline purification in step S1 includes the following steps: adding active calcium aluminate (more than 45% of alumina in waste residue discharged from a calcium metal plant and less than 50% of calcium oxide) into the decomposition stock solution of the Bayer process to replace lime for deep desiliconization, wherein the addition is more than 90 g/L, the temperature is more than 170 ℃, the retention time is 20 minutes, the A/S ratio can be more than 3000 after the reaction, obtaining the aluminum hydroxide with the content of the ferrosilicon impurity reduced to less than 50ppm through decomposition, adding water into the product for pulping at 200 ℃, and carrying out autoclaving to reduce sodium and calcium to less than 500 ppm.
Comparative example 1
The reaction steps are the same as those of the embodiment 1, but in order to reduce the cost, the method directly selects the commercial common aluminum hydroxide as the raw material to produce the aluminum trichloride solution, and omits the step of obtaining the aluminum salt solution by an alkali method in the step S1, wherein the commercial common aluminum hydroxide has high impurity content of cations (alkali, alkaline earth metals, iron, gallium, zinc and the like), and only can produce 3N products because the impurity removal of the aluminum salt solution does not reach the standard even though the common aluminum hydroxide is oxidized by hydrogen peroxide, adsorbed by resin and extracted organically; due to improper control of decomposition conditions or overlong product standing time, the content of insoluble substances is difficult to reduce by adopting an external heating mode, and insoluble residues discharged by fine filtration are accumulated to influence the environment.
Comparative example 2
The polymerization process of using high-purity aluminum ingots to generate high-purity polyaluminum chloride solution is saved in order to reduce the cost (other steps are the same as the example 1), so that the anions of the product are difficult to clean, the washing water amount is too large, the dosage of hydrochloric acid, ammonia water and aluminum hydroxide of unit products is increased, the cost of the dosage increase greatly exceeds the raw material cost of the high-purity aluminum ingots, and the cost comparison confirms that the polymerization by using the high-purity aluminum ingots is an effective measure for reducing the cost.
Comparative example 3
The step of adding SAA additive is not added in the initial development stage (other steps are the same as the step in the embodiment 1), the produced product can only produce high-purity alpha alumina, the filtering of intermediate colloid materials is difficult, the water washing amount is large, the circulating amount of filtrate is large, the water washing amount is reduced by one third, the pore volume of the product is increased, the density is reduced by adopting the technology of adding SAA, the high-purity nano macroporous low-density gamma-Al 203 (double pores) is generated by low-temperature roasting, the application of the product is widened, and the enterprise benefit is improved.
The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the protection scope of the invention.
Claims (6)
1. A method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string reaction is characterized by comprising the following steps:
step S1: purifying by an alkaline method to obtain high-purity easily-soluble aluminum hydroxide, and adding the aluminum hydroxide into acid to prepare an aluminum salt solution;
step S2: adding a high-purity aluminum ingot into the aluminum salt solution prepared in the step S1 to react to obtain a high-purity polyaluminum chloride solution;
step S3: slowly adding ammonia water into the high-purity polyaluminum chloride solution prepared in the step S2 to adjust the pH value of the solution, so that aluminum hydroxide in the solution is gradually separated out until the precipitation is complete;
step S4: s3, performing liquid-solid separation after complete precipitation, adding 100Kg of SAA additive per ton of product in the process of liquid-solid separation and washing, and drying the solid after liquid-solid separation;
step S5: calcining the dried solid in the step S4 at 400-600 ℃ to obtain the nano low-density macroporous spherical gamma-Al2O3And calcining at 1250 ℃ to obtain the nano spherical alpha alumina.
2. The method for preparing the nano macroporous low-density spherical alumina through the acid-base electrochemical double-string process according to claim 1, wherein the alkaline purification in the step S1 comprises the following steps: adding activated calcium aluminate to replace lime into the Bayer process decomposed stock solution for deep desiliconization, wherein the addition is more than 90 g/L, the temperature is more than 170 ℃, the retention time is 20 minutes, the A/S ratio after reaction can be more than 3000, the content of ferrosilicon impurities is reduced to less than 50ppm of aluminum hydroxide through decomposition, adding water into the product for pulping at 200 ℃, and carrying out autoclaving to reduce sodium and calcium to less than 500 ppm.
3. The method for preparing the nano macroporous low-density spherical alumina through the acid-base electrochemical double-string reaction according to claim 1, wherein the acid is hydrochloric acid with the mass fraction of 29-31%, and the concentration of cationic impurities in the aluminum hydroxide reaches the ppm level.
4. The method for preparing the nano macroporous low-density spherical alumina through the acid-base electrochemical double-string process according to claim 1, wherein the high-purity aluminum ingot in the step S2 is obtained through an electrical purification method.
5. The method for preparing the nano macroporous low-density spherical alumina through the acid-base electrochemical double-string process according to claim 1 or 4, wherein the high-purity aluminum ingot is reacted with the aluminum salt solution in the step S2 to obtain the high-purity polyaluminum chloride solution through the auto-thermal polymerization reaction without adding heat from the outside.
6. The method for preparing the nano macroporous low-density spherical alumina through the acid-base electrochemical double-string in the claim 1, wherein the pH value of the solution is slowly increased to 6.5 after the pH value is changed from acidity to 6 when the pH value is adjusted by ammonia water in the step S3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011096601.9A CN112320828A (en) | 2020-10-14 | 2020-10-14 | Method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011096601.9A CN112320828A (en) | 2020-10-14 | 2020-10-14 | Method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112320828A true CN112320828A (en) | 2021-02-05 |
Family
ID=74313528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011096601.9A Pending CN112320828A (en) | 2020-10-14 | 2020-10-14 | Method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112320828A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5419500A (en) * | 1977-07-14 | 1979-02-14 | Taki Chem Co Ltd | Method of producing aluminium hydroxide |
| JPS553340A (en) * | 1978-06-20 | 1980-01-11 | Sumitomo Alum Smelt Co Ltd | Production of readily soluble aluminum hydroxide compound and aluminum salt |
| JPS63123811A (en) * | 1986-11-10 | 1988-05-27 | Honshu Paper Co Ltd | Production of highly basic aluminum polychloride solution in high concentration |
| CN1594095A (en) * | 2004-06-18 | 2005-03-16 | 中国铝业股份有限公司 | Process for producing soluble aluminum hydroxide |
| CN101108740A (en) * | 2006-07-19 | 2008-01-23 | 中国科学院过程工程研究所 | Technique for processing bauxite to produce hydroted alumina with sodium hydroxide molten salt growth method |
| CN102602969A (en) * | 2012-04-23 | 2012-07-25 | 长安大学 | Method for extracting aluminum oxide from fluidized bed coal ash |
| CN102838151A (en) * | 2012-09-20 | 2012-12-26 | 金刚新材料股份有限公司 | Preparation method of ultralow-sodium non-mineralized alpha alumina powder |
| CN103663516A (en) * | 2012-09-26 | 2014-03-26 | 中国科学院过程工程研究所 | Method for preparing aluminum hydroxide by utilizing high-alumina coal ash |
| CN107778016A (en) * | 2017-11-06 | 2018-03-09 | 陕西盛迈石油有限公司 | The method that alumina sol infusion process prepares alumina fibre |
| CN111017971A (en) * | 2019-12-26 | 2020-04-17 | 山东鲁阳浩特高技术纤维有限公司 | Alumina sol and preparation method thereof |
-
2020
- 2020-10-14 CN CN202011096601.9A patent/CN112320828A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5419500A (en) * | 1977-07-14 | 1979-02-14 | Taki Chem Co Ltd | Method of producing aluminium hydroxide |
| JPS553340A (en) * | 1978-06-20 | 1980-01-11 | Sumitomo Alum Smelt Co Ltd | Production of readily soluble aluminum hydroxide compound and aluminum salt |
| JPS63123811A (en) * | 1986-11-10 | 1988-05-27 | Honshu Paper Co Ltd | Production of highly basic aluminum polychloride solution in high concentration |
| CN1594095A (en) * | 2004-06-18 | 2005-03-16 | 中国铝业股份有限公司 | Process for producing soluble aluminum hydroxide |
| CN101108740A (en) * | 2006-07-19 | 2008-01-23 | 中国科学院过程工程研究所 | Technique for processing bauxite to produce hydroted alumina with sodium hydroxide molten salt growth method |
| CN102602969A (en) * | 2012-04-23 | 2012-07-25 | 长安大学 | Method for extracting aluminum oxide from fluidized bed coal ash |
| CN102838151A (en) * | 2012-09-20 | 2012-12-26 | 金刚新材料股份有限公司 | Preparation method of ultralow-sodium non-mineralized alpha alumina powder |
| CN103663516A (en) * | 2012-09-26 | 2014-03-26 | 中国科学院过程工程研究所 | Method for preparing aluminum hydroxide by utilizing high-alumina coal ash |
| CN107778016A (en) * | 2017-11-06 | 2018-03-09 | 陕西盛迈石油有限公司 | The method that alumina sol infusion process prepares alumina fibre |
| CN111017971A (en) * | 2019-12-26 | 2020-04-17 | 山东鲁阳浩特高技术纤维有限公司 | Alumina sol and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| ZHAO CHANGWEI ET AL.: "Preparation and characterization of γ-Al2O3 by polyaluminum chloride with high Al13 content", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》 * |
| 元炯亮等: "铝酸钠溶液添加铝酸钙脱硅过程研究", 《有色金属》 * |
| 杨立新等: "均匀碱化制备高纯聚合氯化铝的形态特征", 《湘潭大学自然科学学报》 * |
| 王磊等: "拜耳法生产易溶氢氧化铝的工艺技术", 《有色冶金节能》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106830030B (en) | A kind of method using the safe and efficient production sandy alumina of aluminium ash | |
| CN112441572B (en) | Method for recovering waste lithium iron phosphate anode material | |
| CN113684369A (en) | Method for treating waste industrial lithium-containing aluminum electrolyte | |
| CN110627095B (en) | Method for extracting lithium and preparing battery-grade lithium carbonate from alumina production process | |
| CN102251119B (en) | Method for recycling vanadium extraction tailings | |
| CN102634673B (en) | Method for deeply removing iron ions from chromium-containing waste residue pickle liquor | |
| CN105132720B (en) | Method for recovering rare earth in ion adsorption type rare earth ore leaching solution through fractional precipitation | |
| CN113896211B (en) | Treatment method for funding waste lithium iron phosphate battery | |
| CN103693665B (en) | A kind of coal ash for manufacturing is for the method for high purity aluminium oxide | |
| CN102828025B (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN103395796B (en) | Comprehensive utilization method of serpentine and device used by method | |
| CN101235440A (en) | Method of comprehensively utilizing serpentine | |
| CN111348669B (en) | Preparation method of sodium hexafluoroaluminate | |
| CN106517621A (en) | Process of recycling wastewater containing ammonia chloride | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN112093814A (en) | Method for preparing aluminum oxide by using aluminum ash without slagging | |
| CN113120938B (en) | Method for preparing calcium fluoride by using fluorine-containing wastewater | |
| CN114751434A (en) | Comprehensive recycling method of sedimentary lithium resource | |
| CN104760980A (en) | Preparation technology of highly-pure ultrafine alumina powder | |
| CN111041204B (en) | Comprehensive utilization method of magnesium and/or calcium-containing waste liquid in rare earth smelting separation process | |
| CN104724740A (en) | Preparation method of high-purity ultra-fine aluminum hydroxide powder | |
| CN112320828A (en) | Method for preparing nano macroporous low-density spherical alumina by acid-base electrochemical double-string method | |
| CN114560767B (en) | Method for preparing ferrous oxalate by siderite | |
| CN113896214A (en) | Method for preparing high-purity lithium carbonate by adsorbing and carbonizing lithium sulfate solution | |
| CN101880771A (en) | Method for recovering magnesium from magnesium-contained waste liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210205 |