CN111410202B - Method for preparing pyrophyllite from spodumene lithium extraction waste residues - Google Patents
Method for preparing pyrophyllite from spodumene lithium extraction waste residues Download PDFInfo
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- CN111410202B CN111410202B CN202010233861.XA CN202010233861A CN111410202B CN 111410202 B CN111410202 B CN 111410202B CN 202010233861 A CN202010233861 A CN 202010233861A CN 111410202 B CN111410202 B CN 111410202B
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- 239000002699 waste material Substances 0.000 title claims abstract description 66
- 229910052903 pyrophyllite Inorganic materials 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 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 title claims abstract description 36
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 36
- 238000000605 extraction Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 27
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 19
- 239000012065 filter cake Substances 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910019093 NaOCl Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 5
- 238000004061 bleaching Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 18
- 239000003365 glass fiber Substances 0.000 description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical group [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for preparing pyrophyllite by utilizing spodumene extracted lithium waste residues uses final solid waste residues obtained in the process of extracting lithium by water after spodumene sulfuric acid roasting as raw materials, and the pyrophyllite is prepared by two processes of impurity removal, bleaching and calcination. Firstly, mixing waste residue and water according to the mass ratio of 1:3-8, adding H whose mass is 3% -5% of waste residue into the mixture 2 O 2 Reacting the solution at normal temperature for 1-2 h; adding sodium sulfoxylate accounting for 2.5 to 4.5 percent of the mass of the waste residue and oxalic acid accounting for 2 to 5 percent of the mass of the waste residue into the waste residue, reacting for 1 to 2 hours at the temperature of 55 to 95 ℃, filtering and washing to obtain a filter cake. And (3) adding bauxite into the filter cake according to the mass ratio of 1:0.2-0.5 after drying, and calcining the filter cake for 1-2 hours at 600-950 ℃ to obtain the pyrophyllite. The method fully utilizes the main components in the residual waste residues in the lithium extraction process of spodumene, changes waste into valuable, increases economic benefits, and can effectively solve the problem of solid waste environmental compatibility in the existing ore lithium processing industry.
Description
Technical Field
The invention belongs to the technical field of industrial solid waste recycling, and particularly relates to a method for preparing pyrophyllite by utilizing spodumene lithium extraction waste residues.
Background
Pyrophyllite has two polytypes. Monoclinic (2M) is more common. The space group is C 6 2h -C2/c；a 0 ＝0.515nm，b 0 ＝0.892nm，c 0 =1.895 nm, β=99.55 °; z=2. Triclinic system (1 Tc), C 1 i -P1；a 0 ＝0.5173nm，b 0 ＝0.8960nm，c 0 =0.9360 nm, α=91.2°, β=100.4°, γ=90°, z=2. Theoretical chemical composition (w) B ％)：Al 2 O 3 28.3％，SiO 2 66.7％，H 2 O5.0%. The structural unit layer is formed by sandwiching a layer of an octahedral layer of aluminum hydroxide between two layers of silicon oxygen tetrahedral layers to form a 2:1 layered structure. 2/3 of the octahedra are coated with Al 3+ Occupancy (M) 1 ) The other 1/3 of the octahedral sites are vacancies (M 2 ). The pyrophyllite has good chemical stability and insulation, and canFor ceramic materials and refractory materials. Meanwhile, the pyrophyllite has low hardness, slidability, good covering power and adsorptivity, and is used for filling materials and carriers in the industries of papermaking, rubber, paint, chemical industry, pesticide coating and the like.
Pyrophyllite is the main raw material in the glass fiber industry, and the cost of the pyrophyllite is about 50% of the raw material in the glass fiber industry. The demand of the domestic glass fiber enterprises for pyrophyllite raw materials is increased to more than 200 ten thousand tons in 2018, but the high-quality medium-quality aluminum pyrophyllite is tense in resources, and the method becomes a main reason for restricting the cost control of the glass fiber industry.
Spodumene is a main raw material of battery-grade lithium carbonate and lithium hydroxide, and the main processing technology is a sulfuric acid roasting method. The process flow is as follows:
the sulfuric acid roasting method needs to use 20% -40% of excessive sulfuric acid, and the excessive sulfuric acid needs to be neutralized after roasting. According to the different neutralization modes, the components of the lithium extraction waste residues are different. The main stream sulfuric acid roasting process in industry is to reduce cost, and calcium carbonate is selected as neutralizer, so that the lithium extraction waste residue also contains 10% -20% of calcium sulfate. Because of the presence of calcium sulfate, the industrial waste residue is difficult to be utilized by other industries even if the residue is subjected to iron and impurity removal treatment subsequently. The main reason is that the calcium sulfate generates acidic SO after high-temperature roasting 2 The gas is difficult to treat, so the waste residue treatment is also a difficult problem for spodumene processing enterprises at present.
Disclosure of Invention
The invention provides a method for preparing pyrophyllite by utilizing spodumene lithium extraction waste residues, which comprises the steps of impurity removal and purification of the waste residues, and then synthesizing the pyrophyllite by taking bauxite as a raw material and adopting a high-temperature roasting method. The method has the advantages of simple and easy process, high resource utilization rate, no three-waste discharge, waste recycling, higher added value and good economic benefit.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing pyrophyllite by utilizing spodumene lithium extraction waste residues comprises the following steps:
I. uniformly mixing the dried spodumene lithium extraction waste residue with water according to the mass ratio of 1:3-8 to prepare slurry;
II, adding H accounting for 3 to 5 percent of the mass of the waste residue into the slurry 2 O 2 Reacting for 1-2 h under normal temperature;
heating the reacted slurry to 55-95 ℃, adding sodium sulfoxylate accounting for 2.5-4.5% of the mass of waste residue and oxalic acid accounting for 2-5% of the mass of the waste residue, keeping the temperature, reacting for 1-2 h, and filtering, washing and drying to obtain a filter cake after impurity removal;
IV, adding bauxite into the filter cake according to the mass ratio of 1:0.1-0.5, and calcining for 1-2 h at 600-950 ℃ to obtain the pyrophyllite.
The method for producing pyrophyllite by using spodumene extraction lithium waste residues as described above, preferably, the method comprises the following steps of 2 O 3 The content is more than 15 percent.
The method for producing pyrophyllite by utilizing spodumene extraction lithium waste residues as described above, preferably, H in the step II 2 O 2 The mass percentage concentration of the solution is 25-50%, and the reaction time at normal temperature is 1.5-2 hours.
The method for producing pyrophyllite by utilizing spodumene extraction lithium waste residues as described above, preferably, H in the step II 2 O 2 Can be replaced by NaOCl 0.5-2% by mass.
In the method for producing pyrophyllite by utilizing the spodumene extraction lithium waste residues, the reaction temperature in the step III is preferably 60-90 ℃ and the reaction time is preferably 1.5-2 hours.
The method for producing pyrophyllite by utilizing spodumene extraction lithium waste residues, which is described above, is preferred to carry out co-grinding and uniform mixing before calcining the filter cake and bauxite in the step IV, wherein the granularity is more than 90% of 80 meshes.
The method for producing pyrophyllite by utilizing spodumene extraction lithium waste residues as described above, preferably comprises the step IV of carrying out Al in bauxite 2 O 3 The content is more than 40 percent.
In the method for producing pyrophyllite by utilizing the spodumene lithium extraction waste residues, preferably, the calcination temperature in the step IV is 650-850 ℃ and the calcination time is 1.5-2 hours.
The method for producing pyrophyllite by utilizing spodumene extraction lithium waste residues as described above, preferably, the bauxite in the step IV can use Al (OH) with the same aluminum oxide content as the bauxite 3 Or Al 2 O 3 Instead of.
The spodumene lithium extraction waste residue can be solid waste residue obtained in the process of leaching lithium by water after roasting spodumene sulfuric acid, and the residual lithium waste residue after neutralization by sodium hydroxide is amorphous aluminum silicon residue, contains a small amount of ferric oxide components, and is additionally adsorbed soluble sodium sulfate, lithium sulfate and the like. The alumina and silica contained in the waste residue can supplement an aluminum source, and pyrophyllite is synthesized by a roasting method. The basic reaction is as follows:
Al 2 O 3 ·nSiO 2 (aluminum silicon slag) +Al 2 O 3 ·3H 2 O (bauxite) →Al 2 [Si 2 O 10 ](OH) 2 (pyrophyllite)
The pyrophyllite is the main raw material of glass fiber enterprises. Therefore, the method can solve the problem of waste residue utilization of ore lithium processing enterprises and bring remarkable economic benefit. More importantly, the technique is possible.
The method has the beneficial effects that the method effectively utilizes the waste residues of ore lithium processing enterprises, obtains the pyrophyllite product through a high-temperature roasting one-step method after impurity removal, effectively solves the solid waste problem of the ore lithium processing lithium industry, changes waste into valuables, improves the economic benefit, and effectively relieves the current situation of high-quality pyrophyllite resource shortage caused by rapid development of the glass fiber industry in China. The pyrophyllite synthesized by the method has good quality and low cost, can be used as a raw material of glass fiber enterprises and reduces the production cost, thereby having remarkable economic benefit and better application prospect.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of lithium extraction waste residue.
FIG. 2 is an X-ray powder diffraction pattern of pyrophyllite prepared in example 1.
Detailed Description
Example 1
The spodumene used in example 1 is spodumene produced in Sichuan, the analysis results of chemical composition of the concentrate lithium extraction waste residue are shown in table 1, and the analysis of the X-ray powder diffraction pattern is shown in figure 1. XRD results show that the peaks are dispersed, no obvious characteristic absorption peaks exist, and the analysis results of chemical components show that the lithium extraction waste residue is amorphous silicon aluminum waste residue.
TABLE 1 chemical composition analysis results (w) of lithium-extracted waste residue B ％)
Bauxite used in this example was from a certain high-alumina bauxite produced in the dence of the seal, and the chemical composition analysis results thereof are shown in table 2.
TABLE 2 analysis of chemical composition of bauxite (w B ％)
500g of spodumene lithium extraction waste residue is weighed, 3700g of water is added, and the mixture is mixed and stirred into slurry. 8g of NaClO powder was added thereto and reacted at room temperature for 1.5 hours.
Heating the slurry to 70 ℃, weighing 20g of sodium sulfoxylate and 20g of oxalic acid, adding the sodium sulfoxylate and the oxalic acid into the hot slurry, reacting for 1.5 hours, and filtering; washing with 3000mL of water for 4-6 times, and drying at 105 ℃ for 12 hours to obtain a filter cake after impurity removal. The chemical composition analysis results of the filter cake after impurity removal are shown in Table 3. By comparing the components of the waste residue with those of the original waste residue, most of ferric oxide components in the waste residue can be effectively removed.
TABLE 3 analysis of chemical composition of cake after impurity removal (w B ％)
And (3) drying the filter cake after impurity removal, uniformly mixing with 60g of bauxite, placing into an automatic temperature control box type electric furnace, and calcining for 1.5 hours at 800 ℃ to prepare a calcined pyrophyllite product. The X-ray powder diffraction analysis results are shown in FIG. 2, and the chemical composition analysis results are shown in Table 4.XRD results show that the obtained powder diffraction peak is well matched with a PDF standard card (JCPDS: 75-0856) of pyrophyllite, and the impurity peak is less. It can be seen that the pyrophyllite product with better crystallization degree is successfully synthesized by high-temperature calcination in the embodiment. And the analysis result of chemical components shows that the obtained pyrophyllite is a medium-high alumina pyrophyllite product, and meets the index requirement of glass fiber enterprises on the pyrophyllite.
TABLE 4 chemical composition analysis results (w) B ％)
Example 2
The lithium extraction waste residue used in this example is the lithium extraction waste residue of some lithium carbonate processing enterprises in Shandong province, and the chemical composition analysis results are shown in Table 5.
TABLE 5 analysis results of chemical composition of lithium-extracted slag (w B ％)
Bauxite used in this example was the same as in example 1.
500g of spodumene lithium extraction waste residue is weighed, 3000g of water is added, and the mixture is mixed and stirred into slurry. To this was added 20g of H having a mass concentration of 30% 2 O 2 The solution was reacted at room temperature for 2 hours.
Heating the slurry to 90 ℃, weighing 15g of sodium sulfoxylate and 18g of oxalic acid, adding the sodium sulfoxylate and the oxalic acid into the hot slurry, reacting for 1h, and filtering; washing with 3000mL of water for 4-6 times, and drying at 105 ℃ for 12 hours to obtain a filter cake after impurity removal. The chemical composition analysis results of the filter cake after impurity removal are shown in Table 6. By comparing the components of the waste residue with those of the original waste residue, the ferric oxide component in the waste residue can be effectively removed.
TABLE 6 chemical composition analysis results (w B ％)
And (3) drying the filter cake after impurity removal, uniformly mixing with 50g of bauxite, placing into an automatic temperature control box type electric furnace, and calcining for 2 hours at 700 ℃ to prepare a baked pyrophyllite product. The chemical composition analysis results are shown in Table 7. The result shows that the obtained pyrophyllite is a medium-high alumina pyrophyllite product, and meets the index requirements of glass fiber enterprises on the pyrophyllite.
TABLE 7 chemical composition analysis results (w) B ％)
Claims (9)
1. The method for preparing the pyrophyllite by utilizing the spodumene lithium extraction waste residues is characterized by comprising the following steps:
I. uniformly mixing the dried spodumene lithium extraction waste residue with water according to the mass ratio of 1:3-8 to prepare slurry;
II, adding H accounting for 3 to 5 percent of the mass of the waste residue into the slurry 2 O 2 Reacting for 1-2 h under normal temperature;
heating the reacted slurry to 55-95 ℃, adding sodium sulfoxylate accounting for 2.5-4.5% of the mass of waste residue and oxalic acid accounting for 2-5% of the mass of the waste residue, keeping the temperature, reacting for 1-2 h, and filtering, washing and drying to obtain a filter cake after impurity removal;
IV, according to the mass ratio of 1: (0.1-0.5) bauxite is added into the filter cake, and calcined for 1-2 hours at 600-950 ℃ to obtain pyrophyllite.
2. The method for producing pyrophyllite by utilizing spodumene lithium extraction waste residues according to claim 1, wherein the spodumene lithium extraction waste residues contain Al 2 O 3 The content is more than 15 percent.
3. According toThe method for producing pyrophyllite by utilizing spodumene lithium extraction waste residues as recited in claim 1, wherein in the step II, H 2 O 2 The mass percentage concentration of the solution is 25-50%, and the reaction time at normal temperature is 1.5-2 hours.
4. The method for producing pyrophyllite by utilizing spodumene lithium extraction waste residues according to claim 1, wherein in the step II, H 2 O 2 Can be replaced by NaOCl 0.5-2% by mass.
5. The method for producing pyrophyllite by utilizing spodumene extracted lithium waste residues according to claim 1, wherein the reaction temperature of the step III is 60-90 ℃ and the reaction time is 1.5-2 hours.
6. The method for producing pyrophyllite by utilizing spodumene extracted lithium waste residues according to claim 1, wherein the filter cake in the step IV is subjected to co-grinding and uniform mixing before being calcined with bauxite, and the granularity is more than 90% of 80 mesh.
7. The method for producing pyrophyllite by utilizing spodumene lithium extraction waste residues as recited in claim 1, wherein the aluminum in the bauxite in the step IV is Al 2 O 3 The content is more than 40 percent.
8. The method for producing pyrophyllite by utilizing spodumene lithium extraction waste residues according to claim 1, wherein the calcining temperature in the step IV is 650-850 ℃ and the calcining time is 1.5-2 hours.
9. The method for producing pyrophyllite using spodumene lithium-extracting waste residues as claimed in any one of claims 1 to 8, wherein the bauxite in step IV is used with Al (OH) having the same alumina content as the bauxite 3 Or Al 2 O 3 Instead of.
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| CN115072749B (en) * | 2022-06-17 | 2023-04-07 | 中国地质大学（北京） | Method for extracting lithium from spodumene without slag |
| CN118808309A (en) * | 2024-06-06 | 2024-10-22 | 中国地质大学（北京） | A method for preparing heavy metal pollution remediation materials using industrial and agricultural solid waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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