CN114988484A - Gypsum tailing treatment method of solid lithium ore neutralization process - Google Patents
Gypsum tailing treatment method of solid lithium ore neutralization process Download PDFInfo
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- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 57
- 239000010440 gypsum Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 42
- 239000007787 solid Substances 0.000 title claims abstract description 36
- 238000006386 neutralization reaction Methods 0.000 title claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 87
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 10
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims 3
- 238000001354 calcination Methods 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 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
- 238000011084 recovery Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 229910052629 lepidolite Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 235000019640 taste Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- -1 aluminum and iron Chemical class 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/468—Purification of calcium sulfates
-
- 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
- C01F7/021—After-treatment of oxides or hydroxides
-
- 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
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
-
- 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
- C01F7/46—Purification of aluminium oxide, aluminium hydroxide or aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Organic Chemistry (AREA)
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- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a gypsum tailing treatment method of a solid lithium ore neutralization process, which comprises the following steps: step 1, mixing gypsum tailing powder with a strong acid solution and then reacting; step 2, carrying out solid-liquid separation on the product obtained after the reaction in the step 1 to obtain a filtrate and a filter cake; step 3, drying the filter cake obtained in the step 2 to obtain high-strength gypsum; step 4, adding a strong alkali solution into the filtrate obtained in the step 2, adjusting the pH value, and then carrying out solid-liquid separation to obtain an aluminum-containing solution and an iron hydroxide precipitate; step 5, roasting the ferric hydroxide precipitate to obtain ferric oxide solid; step 6, adding a weak alkaline solution into the aluminum-containing solution, carrying out solid-liquid separation after the pH value of the solution is reached, and obtaining aluminum hydroxide filter residues; and 7, roasting the aluminum hydroxide filter residue to obtain the high-purity aluminum oxide. The method can separate high-strength gypsum, aluminum oxide and ferric oxide products with high added values from the gypsum tailings, is environment-friendly, and improves the environmental protection of the solid lithium ore treatment process.
Description
Technical Field
The invention relates to the field of tailing treatment methods of lithium ore neutralization processes, in particular to a gypsum tailing treatment method of a solid lithium ore neutralization process.
Background
With the development of social economy, the contradiction between supply and demand of global petroleum resources is increasingly prominent, and the demand of global lithium carbonate is greatly increased by the pulling of lithium battery markets of hybrid power and electric automobiles when main economic entities popularize and popularize electric automobiles. The external dependency degree of 2011-2015 in China, which belongs to the import country of lithium resources at present, reaches 80 percent, the search for new lithium resources becomes the urgent affairs of China, the dependence of the lithium resources of China on the outside can be fundamentally solved, and the energy safety of China is ensured. Also, solid lithium minerals should be used more efficiently and economically as an auxiliary resource to meet the growing demand for lithium and lithium salts.
The main occurrence modes of the global lithium ore resource resources comprise salt lake brine, spodumene and lepidolite, the yield of the world lithium salt pair in 2017 is 60 percent by extracting lithium from 23.54 million tons of brine and 40 percent by extracting lithium from ores in terms of equivalent of lithium carbonate. Many domestic enterprises, such as the southern group, the nine-ridge new energy and other enterprises, are focused on the process of producing lithium carbonate from ores, but acid tailing waste residues generated in the process of producing lithium carbonate are difficult to treat, and the problem of limiting large-scale mass production is solved. Especially for lepidolite ore and lithium-containing bauxite, the impurities are more, and if the acid tailing waste residue of the lepidolite ore and the lithium-containing bauxite cannot be properly and cost-effectively treated, the normal operation and further production expansion of the lithium extraction process can be restricted, so that the comprehensive utilization of the tailing waste residue becomes one of the important problems in the lithium salt industry.
At present, after solid lithium ore is treated by a neutralization process, more gypsum filter residues exist, the storage space is large, if the solid lithium ore is directly discharged, environmental pollution and resource waste can be caused, so that the neutralization filter residues need to be subjected to advanced treatment, and the utilization efficiency of resources is improved. However, in the prior art, no suitable method is available for high-value utilization, so that a method with high efficiency, environmental protection and low cost is needed for further processing the solid lithium ore neutralization tailings so as to realize comprehensive utilization of the solid lithium ore neutralization tailings.
Disclosure of Invention
The invention aims to provide a gypsum tailing treatment method for a solid lithium ore neutralization process, which aims to solve the problem that the prior art does not have an effective treatment method for gypsum tailings obtained by neutralizing solid lithium ores, and realize the recovery of high-strength gypsum, aluminum and iron after the gypsum tailings are treated.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the gypsum tailing treatment method of the solid lithium ore neutralization process comprises the following steps:
step 1, crushing and drying gypsum tailings obtained after the solid lithium ores are subjected to neutralization process treatment to obtain gypsum tailing powder.
One or more of sulfuric acid, hydrochloric acid, nitric acid and perchloric acid are selected and mixed according to any proportion to obtain a strong acid solution, wherein the mass fraction of the strong acid solution is required to be 30-80%.
After mixing the gypsum tailing powder and the strong acid solution according to the solid-liquid mass mixing ratio of 1: 1-1: 5, reacting for 30-90 minutes at the temperature of 30-80 ℃.
And 2, carrying out solid-liquid separation on the product obtained after the reaction in the step 1 to respectively obtain a filtrate and a filter cake.
And 3, drying the filter cake obtained in the step 2 for 3-5 hours at the temperature of 50-100 ℃ to obtain the high-strength gypsum. Through the step, the high-strength gypsum can be recovered from the gypsum tailings.
And 4, optionally selecting one from ammonia water solution, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution and ammonium carbonate solution or optionally mixing several solutions according to any proportion to obtain strong alkali solution, wherein the required concentration of the strong alkali solution is 2-5 mol/L.
And (3) adding the strong alkali solution into the filtrate obtained in the step (2) at a dropping speed of 5-20 rpm until the pH value of the filtrate is adjusted to 3.0-4.0, and then carrying out solid-liquid separation to obtain an aluminum-containing solution and ferric hydroxide precipitates.
And 5, roasting the ferric hydroxide precipitate obtained in the step 4 at the temperature of 400-800 ℃ for 3-6 h to obtain ferric oxide solid. Iron can be recovered from the gypsum tailings by this step and is recovered as ferric oxide solids.
And 6, optionally selecting one of ammonia water, sodium carbonate and potassium carbonate or optionally mixing several of the ammonia water, the sodium carbonate and the potassium carbonate according to any proportion to obtain a weak alkaline solution, wherein the required concentration of the weak alkaline solution is 0.5-3.5 mol/L.
And (4) adding a weak alkaline solution into the aluminum-containing solution obtained in the step (4) until the pH value of the aluminum-containing solution is adjusted to 4.0-6.0, and then carrying out solid-liquid separation to obtain the aluminum hydroxide filter residue.
And 7, roasting the aluminum hydroxide filter residue obtained in the step 6 at the temperature of 800-1500 ℃ for 3-6 h to obtain the high-purity aluminum oxide. Aluminum can be recovered from the gypsum tailings by this step and is recovered as alumina.
The leaching solution of the clay lithium ore sulfuric acid method contains a large amount of impurity ions such as aluminum and iron, and the impurity ions need to be separated in order to obtain a lithium-containing solution with simple components. In order to achieve the purpose, 35% of calcium carbonate in mass fraction is added into sulfuric acid leaching solution to adjust the pH =6, then the leaching solution after the pH adjustment is filtered, the filtrate is lithium-containing neutralization solution for removing aluminum and iron, and the filter residue is calcium sulfate containing aluminum and iron. In order to reasonably utilize filter residues as resources, the experiment explores the influence of different sulfuric acid concentrations, different solid-to-liquid ratios, different reaction temperatures and different reaction times on the leaching of the aluminum and the iron. The invention takes place the following reactions:
2Al(OH) 3 +3H 2 SO 4 =Al 2 (SO 4 ) 3 +6H2O
2Fe(OH) 3 +3H 2 SO 4 =Fe 2 (SO4) 3 +6H 2 O
Fe 2 (SO 4 ) 3 +6NaOH=2Fe(OH) 3 +3Na 2 SO 4
Al 2 (SO4) 3 +6NaOH=2Al(OH) 3 +3Na 2 SO 4
Al(OH) 3 +NaOH=NaAlO 2 +2H 2 O
the invention provides a method for treating gypsum tailings containing aluminum and iron obtained by a solid lithium ore neutralization process, which comprises the steps of treating the gypsum tailings with acid and alkali, and separating solid from liquid for multiple times to obtain high-strength gypsum, aluminum oxide and ferric oxide products with high added values. The process disclosed by the invention is green and environment-friendly, the environmental protection of the solid lithium ore treatment process is further improved, and the specific high practical value is achieved.
Drawings
FIG. 1 is a block flow diagram of the method of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to specific data. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
The process of the present invention for comprehensively utilizing the waste slag containing aluminum and iron gypsum by an acid method will be described below by way of specific examples, but those skilled in the art will understand that the following examples are only specific examples of the preparation method of the present invention and are not intended to limit the entirety thereof.
Embodiment 1, as shown in fig. 1, this embodiment includes the following steps:
(1) and obtaining gypsum tailings left after the solid lithium ore neutralization process, crushing the gypsum tailings into powder, and drying the powder for 5 hours at the temperature of 60 ℃ to obtain gypsum tailing powder.
Selecting sulfuric acid from sulfuric acid, hydrochloric acid, nitric acid and perchloric acid as a required strong acid solution, and preparing the strong acid solution with the mass fraction of 30% of sulfuric acid.
Mixing the gypsum tailing powder with a strong acid solution according to the solid-liquid mass mixing ratio of 1:2, and reacting for 30 minutes at the temperature of 30 ℃.
(2) And (2) filtering the product obtained in the step (1) to realize solid-liquid separation, and respectively obtaining a filtrate and a filter cake.
(3) And (3) drying the filter cake obtained in the step (2) at the temperature of 50 ℃ for 3 hours to obtain the high-strength gypsum.
(4) Selecting a sodium hydroxide solution from an ammonia water solution, a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution and an ammonium carbonate solution as a required strong alkali solution, and preparing the sodium hydroxide solution to enable the concentration of the sodium hydroxide solution to be 2 mol/L.
Sodium hydroxide solution was added to the filtrate obtained in step (2) at a dropping rate of 5rpm until the pH of the filtrate was adjusted to 3.0. Then filtering to realize solid-liquid separation, and obtaining an aluminum-containing solution and ferric hydroxide precipitates.
(5) And (5) roasting the ferric hydroxide precipitate obtained in the step (4) at the temperature of 400 ℃ for 3 hours to obtain ferric oxide solid.
(6) Selecting ammonia water from ammonia water, sodium carbonate and potassium carbonate as a needed weak alkaline solution, and preparing the ammonia water to enable the concentration of the ammonia water to be 3.5 mol/L.
And (4) adding an ammonia water solution dropwise into the aluminum-containing solution obtained in the step (4) until the pH value of the aluminum-containing solution is adjusted to 4.0, and then carrying out solid-liquid separation to obtain the aluminum hydroxide filter residue.
(7) And (4) roasting the aluminum hydroxide filter residue obtained in the step (6) at the temperature of 1500 ℃ for 3 hours to obtain the high-purity aluminum oxide.
In this example, the obtained high-strength gypsum, ferric oxide, and alumina had tastes of about 91%, 75%, and 83%/80%, respectively, and the recovery rates were 89%, 80%, and 83%/82%, respectively.
Embodiment 2, this embodiment includes the following steps:
(1) and obtaining the gypsum tailings left after the solid lithium ore neutralization process, crushing the gypsum tailings into powder, and drying the powder for 5 hours at the temperature of 60 ℃ to obtain the gypsum tailing powder.
Selecting sulfuric acid from sulfuric acid, hydrochloric acid, nitric acid and perchloric acid as a required strong acid solution, and preparing the strong acid solution with the mass fraction of 30% of sulfuric acid.
Mixing the gypsum tailing powder with a strong acid solution according to the solid-liquid mixing mass ratio of 1:5, and reacting for 30 minutes at the temperature of 30 ℃.
(2) And (2) filtering the product obtained in the step (1) to realize solid-liquid separation, and respectively obtaining a filtrate and a filter cake.
(3) And (3) baking the filter cake obtained in the step (2) for 3 hours at the temperature of 50 ℃ to obtain the high-strength gypsum.
(4) Selecting a sodium hydroxide solution from an ammonia water solution, a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution and an ammonium carbonate solution as a required strong alkali solution, and preparing the sodium hydroxide solution to enable the concentration of the sodium hydroxide solution to be 2 mol/L.
Sodium hydroxide solution was added to the filtrate obtained in step (2) at a dropping rate of 5rpm until the pH of the filtrate was adjusted to 4.0. Then filtering to realize solid-liquid separation, and obtaining an aluminum-containing solution and ferric hydroxide precipitates.
(5) And (5) roasting the ferric hydroxide precipitate obtained in the step (4) at the temperature of 400 ℃ for 6 hours to obtain ferric oxide solid.
(6) And selecting ammonia water from ammonia water, sodium carbonate and potassium carbonate as a required weak alkaline solution, and preparing the ammonia water to ensure that the concentration of the ammonia water is 2.0 mol/L.
And (5) adding an ammonia water solution dropwise into the aluminum-containing solution obtained in the step (4) until the pH value of the aluminum-containing solution is adjusted to 6.0, and then carrying out solid-liquid separation to obtain the aluminum hydroxide filter residue.
(7) And (4) roasting the aluminum hydroxide filter residue obtained in the step (6) at the temperature of 800 ℃ for 2 hours to obtain the high-purity aluminum oxide.
The high strength gypsum, ferric oxide, and alumina obtained in this example had tastes of about 94%, 81%, and 87%/85%, respectively, and the recovery rates were 93%, 84%, and 87%/85%, respectively.
Example 3:
(1) and obtaining gypsum tailings left after the solid lithium ore neutralization process, crushing the gypsum tailings into powder, and drying the powder for 10 hours at the temperature of 90 ℃ to obtain gypsum tailing powder.
Selecting sulfuric acid from sulfuric acid, hydrochloric acid, nitric acid and perchloric acid as a required strong acid solution, and preparing the strong acid solution with the mass fraction of 60% of sulfuric acid.
Mixing the gypsum tailing powder and the strong acid solution according to the solid-liquid mixing mass ratio of 1:3, and reacting for 30 minutes at the temperature of 30 ℃.
(2) And (2) filtering the product obtained in the step (1) to realize solid-liquid separation, and respectively obtaining a filtrate and a filter cake.
(3) And (3) baking the filter cake obtained in the step (2) at the temperature of 50 ℃ for 3 hours to obtain the high-strength gypsum.
(4) Selecting a sodium hydroxide solution from an ammonia water solution, a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution and an ammonium carbonate solution as a required strong alkali solution, and preparing the sodium hydroxide solution to enable the concentration of the sodium hydroxide solution to be 3.5 mol/L.
Sodium hydroxide solution was added to the filtrate obtained in step (2) at a dropping rate of 5rpm until the pH of the filtrate was adjusted to 4.0. Then filtering to realize solid-liquid separation to obtain an aluminum-containing solution and ferric hydroxide precipitates.
(5) And (5) roasting the ferric hydroxide precipitate obtained in the step (4) at the temperature of 400 ℃ for 6 hours to obtain ferric oxide solid.
(6) Selecting ammonia water from ammonia water, sodium carbonate and potassium carbonate as a needed weak alkaline solution, and preparing the ammonia water to enable the concentration of the ammonia water to be 2.0 mol/L.
And (4) adding an ammonia water solution dropwise into the aluminum-containing solution obtained in the step (4) until the pH value of the aluminum-containing solution is adjusted to 6.0, and then carrying out solid-liquid separation to obtain the aluminum hydroxide filter residue.
(7) And (5) roasting the aluminum hydroxide filter residue obtained in the step (6) at the temperature of 800 ℃ for 2 hours to obtain the high-purity aluminum oxide.
The high strength gypsum, ferric oxide, and alumina obtained in this example had tastes of about 90%, 83%, 85%/83%, respectively, and recovery rates of 95%, 85%, 90%/88%, respectively.
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the limitation of the concept and scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall into the protection scope of the present invention, and the technical content of the present invention which is claimed is fully set forth in the claims.
Claims (9)
1. The gypsum tailings treatment method of the solid lithium ore neutralization process is characterized by comprising the following steps of:
step 1, mixing gypsum tailing powder and a strong acid solution according to a solid-liquid mass mixing ratio of 1: 1-1: 5, and reacting for 30-90 minutes at a temperature of 30-80 ℃;
step 2, carrying out solid-liquid separation on the product obtained after the reaction in the step 1 to respectively obtain filtrate and filter cakes;
step 3, drying the filter cake obtained in the step 2 to obtain high-strength gypsum;
step 4, adding a strong alkali solution into the filtrate obtained in the step 2 until the pH value of the filtrate is adjusted to 3.0-4.0, and then carrying out solid-liquid separation to obtain an aluminum-containing solution and an iron hydroxide precipitate;
step 5, roasting the ferric hydroxide precipitate obtained in the step 4 to obtain ferric oxide solid;
step 6, adding a weak alkaline solution into the aluminum-containing solution obtained in the step 4 until the pH value of the aluminum-containing solution is adjusted to 4.0-6.0, and then carrying out solid-liquid separation to obtain aluminum hydroxide filter residue;
and 7, roasting the aluminum hydroxide filter residue obtained in the step 6 to obtain high-purity aluminum oxide.
2. The method for treating the gypsum tailings in the solid lithium ore neutralization process according to claim 1, wherein the gypsum tailing powder in the step 1 is obtained by crushing and pulverizing gypsum tailings, and drying at 60-100 ℃ for 5-12 hours.
3. The method for treating the gypsum tailings of the solid lithium ore neutralization process according to claim 1, wherein the mass fraction of the strong acid solution used in the step 1 is 30-80%, and the strong acid solution is one of sulfuric acid, hydrochloric acid, nitric acid and perchloric acid or a mixture of the sulfuric acid, the hydrochloric acid, the nitric acid and the perchloric acid in any proportion.
4. The method for treating the gypsum tailings in the solid lithium ore neutralization process according to claim 1, wherein the drying temperature in the step 3 is 50-100 ℃, and the drying time is 3-5 hours.
5. The method for treating the gypsum tailings of the solid lithium ore neutralization process according to claim 1, wherein the concentration of the strong alkali solution used in the step 4 is 2-5 mol/L, and the strong alkali solution is any one of an ammonia solution, a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution and an ammonium carbonate solution or a mixture of the solutions in any proportion.
6. The method for treating the gypsum tailings in the solid lithium ore neutralization process according to claim 1, wherein the strong alkali solution is added into the filtrate at a dropping speed of 5 rpm-20 rpm in the step 4.
7. The method for treating gypsum tailings of the solid lithium ore neutralization process according to claim 1, wherein the calcination temperature in step 5 is 400 ℃ to 800 ℃.
8. The method for treating the gypsum tailings in the solid lithium ore neutralization process according to claim 1, wherein the concentration of the weak alkaline solution used in the step 6 is 0.5-3.5 mol/L, and the weak alkaline solution is any one of ammonia water, sodium carbonate and potassium carbonate or a mixture of the ammonia water, the sodium carbonate and the potassium carbonate in any proportion.
9. The method for treating gypsum tailings of the solid lithium ore neutralization process according to claim 1, wherein the calcination temperature in step 7 is 800-1500 ℃.
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| CN104528798A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院青海盐湖研究所 | Method for purifying low-grade natural gypsum or gypsum tailings by recrystallization |
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| CN113060752A (en) * | 2021-03-23 | 2021-07-02 | 力上资源科技开发有限公司 | Recycling method of fluorite flotation tailings |
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