CN114634319A - Treatment method for recycling calcium-containing lepidolite leaching residues - Google Patents
Treatment method for recycling calcium-containing lepidolite leaching residues Download PDFInfo
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- CN114634319A CN114634319A CN202210238873.0A CN202210238873A CN114634319A CN 114634319 A CN114634319 A CN 114634319A CN 202210238873 A CN202210238873 A CN 202210238873A CN 114634319 A CN114634319 A CN 114634319A
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- filtrate
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- ammonia water
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- 238000002386 leaching Methods 0.000 title claims abstract description 107
- 229910052629 lepidolite Inorganic materials 0.000 title claims abstract description 26
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000011575 calcium Substances 0.000 title claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 88
- 238000001035 drying Methods 0.000 claims abstract description 40
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 38
- 238000001914 filtration Methods 0.000 claims abstract description 35
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 22
- DHKHZGZAXCWQTA-UHFFFAOYSA-N [N].[K] Chemical compound [N].[K] DHKHZGZAXCWQTA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003337 fertilizer Substances 0.000 claims abstract description 20
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006229 carbon black Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002893 slag Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 5
- 229910001950 potassium oxide Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- 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
-
- 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
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Pest Control & Pesticides (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a treatment method for recycling calcium-containing lepidolite leaching residues, which is characterized by comprising the following steps of: 1) mixing calcium-containing lepidolite leaching residue with sulfuric acid, leaching in a constant-temperature water bath, filtering to obtain filtrate A and filter residue A, and drying the filter residue A to obtain calcium sulfate; 2) adding ammonia water into the filtrate A, heating and stirring in a constant-temperature water bath, and filtering to obtain filtrate B and filter residue B; 3) continuously adding ammonia water into the filtrate B, stirring and leaching, concentrating, filtering and drying to obtain a nitrogen-potassium fertilizer; 4) adding hydrochloric acid into the filter residue B, heating, stirring, leaching, filtering to obtain a filtrate C and a filter residue C, and washing and drying the filter residue C to obtain white carbon black; 5) and continuously adding ammonia water into the filtrate C, heating and stirring in a constant-temperature water bath, filtering to obtain filtrate D and filter residue D, drying the filter residue D to obtain aluminum hydroxide, and concentrating and drying the filtrate D to obtain ammonium chloride.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a treatment method for recycling calcium-containing lepidolite leaching residues.
Background
In recent years, the lithium battery industry in China is rapidly developed, and the demand and the yield of lithium carbonate are rapidly increased. With the breakthrough of the lithium carbonate extraction technology, the lepidolite ore becomes an important raw material source for preparing lithium carbonate at present. Part of the lepidolite is added with a large amount of calcium salt (such as calcium carbonate and calcium sulfate) in the process of extracting the lithium carbonate so as to enhance the extraction efficiency of the lithium. However, in the process of calcium salt enhanced extraction, a large amount of leaching waste residues are generated, and the leaching waste residues are about 90% of lepidolite concentrate. SiO in lepidolite leaching residue2And Al2O3The content of (A) is about 70%, and a large amount of elements such as calcium and potassium are remained. At present, a large amount of leaching residues are accumulated and stored, so that land is occupied, and the problems of water pollution, soil pollution and the like are caused. Therefore, if the calcium-containing lepidolite leaching residues can be effectively recycled, the environmental problems caused by the leaching residues can be solved, and the valuable resources such as calcium, potassium, silicon, aluminum and the like in the leaching residues can be recycled, so that the healthy development of the lithium battery industry in China is promoted.
The existing lepidolite leaching residue containing calcium has complex components and high alkali metal content, can be only added in a small amount for preparing cement or used as an admixture to be added into building materials such as concrete, cement mortar and the like at present, so valuable elements in the leaching residue, particularly the valuable elements such as calcium, potassium and the like, cannot be recycled, resource waste is caused, and a large amount of leaching residue cannot be utilized and can only be stockpiled due to the difficulty in adding in a large amount in the building industry, and the additional value of the leaching residue is very low.
Disclosure of Invention
The invention aims to solve the technical problem of providing a treatment method for recycling calcium-containing lepidolite leaching residues capable of simultaneously preparing gypsum, nitrogen-potassium fertilizer, ammonium chloride, aluminum hydroxide and white carbon black.
The technical scheme adopted by the invention for solving the technical problems is as follows: a treatment method for recycling calcium-containing lepidolite leaching residues comprises the following steps:
(1) mixing calcium-containing lepidolite leaching residue with sulfuric acid, leaching in a constant-temperature water bath, filtering the leaching solution to obtain filtrate A and filter residue A, and drying the filter residue A to obtain calcium sulfate; the sulfuric acid can react with aluminosilicate minerals in the leaching residue to convert potassium, aluminum, silicon and other elements into soluble sulfate and silicic acid, and the calcium element is converted into calcium sulfate which is slightly soluble in water;
(2) adding ammonia water into the filtrate A, heating and stirring the filtrate added with the ammonia water in a constant-temperature water bath, and filtering to obtain filtrate B and filter residue B; the ammonia water can convert aluminum and silicon in the filtrate into precipitate, so that the precipitate is separated from the filtrate A, and most of sulfuric acid in the filtrate A can be converted into ammonium sulfate by the ammonia water;
(3) continuously adding ammonia water into the filtrate B, stirring and leaching, concentrating, filtering and drying the leachate to obtain a nitrogen-potassium fertilizer; the ammonia water can convert the redundant sulfuric acid in the filtrate B into ammonium sulfate;
(4) adding hydrochloric acid into the filter residue B, heating, stirring and leaching, filtering the leaching solution to obtain a filtrate C and a filter residue C, washing and drying the filter residue C to obtain white carbon black, wherein the filtrate C is an aluminum chloride solution; hydrochloric acid can convert water-insoluble aluminum hydroxide into water-soluble aluminum chloride;
(5) and continuously adding ammonia water into the filtrate C, heating and stirring the filtrate added with the ammonia water in a constant-temperature water bath, filtering to obtain filtrate D and filter residue D, drying the filter residue D to obtain aluminum hydroxide, and concentrating and drying the filtrate D to obtain ammonium chloride. Ammonia can convert aluminum chloride to aluminum hydroxide precipitate and water-soluble ammonium chloride.
Preferentially, the concentration of the sulfuric acid in the step (1) is 3-12mol/l, and the liquid-solid mass ratio is 1-10: 1, the leaching temperature is 30-90 ℃, and the leaching time is 60-720 min.
Preferentially, the adding amount of the ammonia water in the step (2) is adjusted to adjust the pH value of the filtrate A to be 5-8, the heating temperature is 70-95 ℃, and the time is 10-60 min.
Preferentially, the adding amount of the ammonia water in the step (3) is to adjust the pH value of the filtrate B to be 5-9, the leaching temperature is 10-80 ℃, and the leaching time is 20-120 min.
Preferentially, the concentration of the hydrochloric acid in the step (4) is 3-12mol/L, and the solid-liquid ratio is 2-8: 1, the leaching temperature is 20-90 ℃, and the leaching time is 30-180 min.
Preferentially, the ammonia water is added in the step (5) in an amount of adjusting the pH value of the filtrate C to be 8-11, the heating temperature is 10-70 ℃, and the time is 30-240 min.
Compared with the prior art, the invention has the advantages that
1. Compared with the existing method for building materials, the method for preparing the leaching slag has the advantages that only a small amount of leaching slag can be added into the building materials such as cement and the like, the added value of the leaching slag is very low, the leaching slag can be used for preparing the gypsum, the added value of the leaching slag is obviously increased, the prepared gypsum can be widely applied to industries such as buildings and the like, and the treatment capacity of the leaching slag is greatly increased.
2. The method can be used for recovering valuable elements in the leaching slag which cannot be recovered for building materials, and can be used for recovering elements such as aluminum, silicon, calcium, potassium and the like in the leaching slag to prepare calcium sulfate, nitrogen-potassium fertilizer, ammonium chloride, white carbon black and aluminum hydroxide, so that the valuable resources in the leaching slag are recycled, and the additional value of the leaching slag is also obviously improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
SiO in lepidolite leaching residue2、Al2O3、K2The O and CaO contents were 48.20%, 26.41%, 7.26% and 5.96%, respectively. Adding 7mol/L sulfuric acid solution into the leached residues, wherein the solid-to-liquid ratio is 5:1, the leaching time is 120min, the leaching temperature is 70 ℃, filtering after leaching to obtain filtrate A and filter residue A, and drying the filter residue A to obtain white calcium sulfate (gypsum). Adding ammonia water into the filtrate A, adjusting the pH value of the filtrate to 7, leaching at 85 ℃ for 40mAnd in, filtering to obtain filtrate B and filter residue B. And continuously adding ammonia water into the filtrate B, adjusting the pH value to be 8, leaching for 30min at the leaching temperature of 50 ℃, and concentrating and drying the solution to obtain the nitrogen-potassium fertilizer, wherein the nitrogen content in the nitrogen-potassium fertilizer is 17.83 percent, and the potassium oxide content in the nitrogen-potassium fertilizer is 12.1 percent. Adding 8mol/L hydrochloric acid into the filter residue B, adjusting the solid-liquid ratio to be 3:1, leaching for 90min at 30 ℃, and filtering to obtain filter residue C and filtrate C. Washing and drying the filter residue C to obtain white carbon black and SiO in the white carbon black2The content of (B) was 99.1%. And continuously adding ammonia water into the filtrate C, adjusting the pH value to 9, leaching at 50 ℃ for 60min, and filtering to obtain filter residue D and filtrate D. And washing and drying the filter residue D to obtain aluminum hydroxide powder, wherein the content of the aluminum hydroxide is 97.2%. And concentrating and drying the filtrate D to obtain ammonium chloride powder, wherein the content of ammonium chloride is 99.8%.
Example 2
SiO in lepidolite leaching residue2、Al2O3、K2The O and CaO contents were 45.32%, 27.33%, 7.62%, and 9.23%, respectively. Adding 8mol/L sulfuric acid solution into the leached residues, wherein the solid-liquid ratio is 4:1, the leaching time is 150min, the leaching temperature is 70 ℃, filtering after leaching to obtain filtrate A and filter residue A, and drying the filter residue A to obtain white calcium sulfate. Adding ammonia water into the filtrate A, adjusting the pH value of the filtrate to 7, leaching at 80 ℃ for 40min, and filtering to obtain filtrate B and filter residue B. And continuously adding ammonia water into the filtrate B, adjusting the pH value to 7, leaching for 30min at the leaching temperature of 30 ℃, and concentrating and drying the solution to obtain the nitrogen-potassium fertilizer, wherein the nitrogen content in the nitrogen-potassium fertilizer is 17.06 percent, and the potassium oxide content in the nitrogen-potassium fertilizer is 17.17 percent. Adding 10mol/L hydrochloric acid into the filter residue B, adjusting the solid-to-liquid ratio to be 3:1, leaching for 30min at 50 ℃, and filtering to obtain filter residue C and filtrate C. Washing and drying the filter residue C to obtain white carbon black and SiO in the white carbon black2The content of (B) was 99.3%. And continuously adding ammonia water into the filtrate C, adjusting the pH value to 10, leaching at 50 ℃ for 60min, and filtering to obtain filter residue D and filtrate D. And washing and drying the filter residue D to obtain aluminum hydroxide powder with the aluminum hydroxide content of 96.2%. And concentrating and drying the filtrate D to obtain ammonium chloride powder, wherein the content of ammonium chloride is 99.9%.
Example 3
SiO in lepidolite leaching residue2、Al2O3、K2The O and CaO contents were 40.56%, 24.13%, 8.23%, and 10.36%, respectively. Adding 5mol/L sulfuric acid solution into the leached residues, wherein the solid-liquid ratio is 7:1, the leaching time is 150min, the leaching temperature is 80 ℃, filtering after leaching to obtain filtrate A and filter residues A, and drying the filter residues A to obtain white calcium sulfate. Adding ammonia water into the filtrate A, adjusting the pH value of the filtrate to 6, leaching at 80 ℃ for 30min, and filtering to obtain filtrate B and filter residue B. And continuously adding ammonia water into the filtrate B, adjusting the pH value to be 5, leaching for 30min at the leaching temperature of 50 ℃, and concentrating and drying the solution to obtain the nitrogen-potassium fertilizer, wherein the nitrogen content in the nitrogen-potassium fertilizer is 18.57 percent, and the potassium oxide content in the nitrogen-potassium fertilizer is 12.03 percent. Adding 5mol/L hydrochloric acid into the filter residue B, adjusting the solid-to-liquid ratio to be 6:1, leaching for 30min at 60 ℃, and filtering to obtain filter residue C and filtrate C. Washing and drying the filter residue C to obtain white carbon black and SiO in the white carbon black2The content of (D) is 98.7%. And continuously adding ammonia water into the filtrate C, adjusting the pH value to 11, leaching at 60 ℃ for 30min, and filtering to obtain filter residue D and filtrate D. And washing and drying the filter residue D to obtain aluminum hydroxide powder with the aluminum hydroxide content of 95.9%. And concentrating and drying the filtrate D to obtain ammonium chloride powder, wherein the content of ammonium chloride is 99.9%.
Example 4
SiO in lepidolite leaching residue2、Al2O3、K2The O and CaO contents were 45.32%, 27.33%, 7.62%, and 9.23%, respectively. Adding 3mol/L sulfuric acid solution into the leached residues, wherein the solid-to-liquid ratio is 10:1, the leaching time is 720min, the leaching temperature is 30 ℃, filtering after leaching to obtain filtrate A and filter residue A, and drying the filter residue A to obtain white calcium sulfate. Adding ammonia water into the filtrate A, adjusting the pH value of the filtrate to 5, leaching at 70 ℃ for 60min, and filtering to obtain filtrate B and filter residue B. And continuously adding ammonia water into the filtrate B, adjusting the pH value to be 5, leaching for 120min at the leaching temperature of 10 ℃, and concentrating and drying the solution to obtain the nitrogen-potassium fertilizer, wherein the nitrogen content in the nitrogen-potassium fertilizer is 15.41 percent, and the potassium oxide content in the nitrogen-potassium fertilizer is 22.32 percent. Adding 3mol/L hydrochloric acid into the filter residue B,adjusting the solid-liquid ratio to be 8:1, leaching for 180min at 20 ℃, and filtering to obtain filter residue C and filtrate C. Washing and drying the filter residue C to obtain white carbon black and SiO in the white carbon black2The content of (B) was 99.4%. And continuously adding ammonia water into the filtrate C, adjusting the pH value to 8, leaching at 10 ℃ for 240min, and filtering to obtain filter residue D and filtrate D. And washing and drying the filter residue D to obtain aluminum hydroxide powder with the aluminum hydroxide content of 96.5%. And concentrating and drying the filtrate D to obtain ammonium chloride powder, wherein the content of ammonium chloride is 99.8%.
Example 5
SiO in lepidolite leaching residue2、Al2O3、K2The O and CaO contents were 40.56%, 24.13%, 8.23%, and 10.36%, respectively. Adding 12mol/L sulfuric acid solution into the leached residues, wherein the solid-to-liquid ratio is 3:1, the leaching time is 60min, the leaching temperature is 90 ℃, filtering after leaching to obtain filtrate A and filter residue A, and drying the filter residue A to obtain white calcium sulfate. Adding ammonia water into the filtrate A, adjusting the pH value of the filtrate to 8, leaching at 95 ℃ for 10min, and filtering to obtain filtrate B and filter residue B. And continuously adding ammonia water into the filtrate B, adjusting the pH value to 9, leaching for 20min at the leaching temperature of 80 ℃, and concentrating and drying the solution to obtain the nitrogen-potassium fertilizer, wherein the nitrogen content in the nitrogen-potassium fertilizer is 18.37 percent, and the potassium oxide content in the nitrogen-potassium fertilizer is 11.21 percent. Adding 12mol/L hydrochloric acid into the filter residue B, adjusting the solid-to-liquid ratio to be 3:1, leaching for 180min at 20 ℃, and filtering to obtain filter residue C and filtrate C. Washing and drying the filter residue C to obtain white carbon black and SiO in the white carbon black2The content of (A) was 98.9%. And continuously adding ammonia water into the filtrate C, adjusting the pH value to 11, leaching at 70 ℃ for 30min, and filtering to obtain filter residue D and filtrate D. And washing and drying the filter residue D to obtain aluminum hydroxide powder with the aluminum hydroxide content of 95.7%. And concentrating and drying the filtrate D to obtain ammonium chloride powder with the ammonium chloride content of 99.5%.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (6)
1. A treatment method for recycling calcium-containing lepidolite leaching residues is characterized by comprising the following steps:
(1) mixing calcium-containing lepidolite leaching residue with sulfuric acid, leaching in a constant-temperature water bath, filtering the leaching solution to obtain filtrate A and filter residue A, and drying the filter residue A to obtain calcium sulfate;
(2) adding ammonia water into the filtrate A, heating and stirring the filtrate added with the ammonia water in a constant-temperature water bath, and filtering to obtain filtrate B and filter residue B;
(3) continuously adding ammonia water into the filtrate B, stirring and leaching, concentrating, filtering and drying the leachate to obtain a nitrogen-potassium fertilizer; the ammonia water can convert the redundant sulfuric acid in the filtrate B into ammonium sulfate;
(4) adding hydrochloric acid into the filter residue B, heating, stirring and leaching, filtering the leaching solution to obtain a filtrate C and a filter residue C, washing and drying the filter residue C to obtain white carbon black, wherein the filtrate C is an aluminum chloride solution;
(5) and continuously adding ammonia water into the filtrate C, heating and stirring the filtrate added with the ammonia water in a constant-temperature water bath, filtering to obtain filtrate D and filter residue D, drying the filter residue D to obtain aluminum hydroxide, and concentrating and drying the filtrate D to obtain ammonium chloride.
2. The treatment method for recycling calcium-containing lepidolite leaching residues according to claim 1, characterized in that: the concentration of the sulfuric acid in the step (1) is 3-12mol/l, and the liquid-solid mass ratio is 1-10: 1, the leaching temperature is 30-90 ℃, and the leaching time is 60-720 min.
3. The treatment method for recycling calcium-containing lepidolite leaching residues according to claim 1, characterized in that: and (3) adjusting the adding amount of the ammonia water in the step (2) until the pH value of the filtrate A is 5-8, heating the filtrate A at 70-95 ℃ for 10-60 min.
4. The treatment method for recycling calcium-containing lepidolite leaching residues according to claim 1, characterized in that: and (4) adjusting the pH value of the filtrate B to 5-9, the leaching temperature to 10-80 ℃, and the leaching time to 20-120min by the ammonia water added in the step (3).
5. The treatment method for recycling calcium-containing lepidolite leaching residues according to claim 1, characterized in that: the concentration of the hydrochloric acid in the step (4) is 3-12mol/L, and the solid-liquid ratio is 2-8: 1, the leaching temperature is 20-90 ℃, and the leaching time is 30-180 min.
6. The treatment method for recycling calcium-containing lepidolite leaching residues according to claim 1, characterized in that: and (3) adding the ammonia water in the step (5) in an amount of adjusting the pH value of the filtrate C to be 8-11, heating the filtrate C to be 10-70 ℃ and keeping the heating time to be 30-240 min.
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| CN110015855A (en) * | 2019-04-01 | 2019-07-16 | 中国地质科学院郑州矿产综合利用研究所 | Treatment method of lithium slag |
| CN112898073A (en) * | 2021-01-14 | 2021-06-04 | 襄阳泽东化工集团有限公司 | Method for preparing NPK compound fertilizer by using phosphate tailings and potassium feldspar |
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| CN104445212A (en) * | 2013-09-16 | 2015-03-25 | 贵阳铝镁设计研究院有限公司 | Method for processing fly ash used for circulating fluidized bed |
| CN110015855A (en) * | 2019-04-01 | 2019-07-16 | 中国地质科学院郑州矿产综合利用研究所 | Treatment method of lithium slag |
| CN112898073A (en) * | 2021-01-14 | 2021-06-04 | 襄阳泽东化工集团有限公司 | Method for preparing NPK compound fertilizer by using phosphate tailings and potassium feldspar |
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