CN108516565B - Method for preparing P-type zeolite molecular sieve by using aluminum calcium powder reaction slag - Google Patents
Method for preparing P-type zeolite molecular sieve by using aluminum calcium powder reaction slag Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 82
- 239000000843 powder Substances 0.000 title claims abstract description 72
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 67
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 64
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000010457 zeolite Substances 0.000 title claims abstract description 64
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 144
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 72
- 238000002386 leaching Methods 0.000 claims abstract description 70
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 8
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 23
- 230000008025 crystallization Effects 0.000 abstract description 23
- 238000001914 filtration Methods 0.000 abstract description 12
- 239000013078 crystal Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000011575 calcium Substances 0.000 abstract description 8
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000007725 thermal activation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- -1 aluminum alkoxide compound Chemical class 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000003189 isokinetic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
-
- 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
Abstract
The invention discloses a method for preparing a P-type zeolite molecular sieve by using aluminum calcium powder reaction residues, which is characterized in that the aluminum calcium powder reaction residues generated in the process of producing polyaluminium chloride by using aluminum calcium powder are used as raw materials, hydrochloric acid is leached out, leachate is returned to prepare the polyaluminium chloride, the hydrochloric acid leaching residues are roasted to obtain a roasted product, the roasted product is mixed with a sodium hydroxide solution, the mixture is uniformly stirred and aged, then crystallization is carried out, and after the crystallization is finished, filtration and drying are carried out to obtain the P-type zeolite molecular sieve. The method is characterized in that the aluminum calcium powder reaction slag structure is changed by adopting hydrochloric acid leaching, impurities such as Fe, Ti, Ca and the like which influence the growth of zeolite crystals are effectively removed, the roasting slag can be directly used for preparing the P-type zeolite molecular sieve, the crystallization time is short, and meanwhile, the hydrochloric acid leaching solution is used for preparing the polyaluminium chloride, so that resources are fully utilized, and the method is an environment-friendly production technology. The P-type zeolite molecular sieve crystallized by adopting a 850 ℃ thermal activation mode has smaller grains, and the crystallinity is up to 92.20%.
Description
Technical Field
The invention relates to a method for preparing a P-type zeolite molecular sieve by using calcium aluminum powder reaction slag, belonging to the technical field of recycling of solid wastes.
Background
During the production of polyaluminium chloride by using the calcium aluminate powder, part of the calcium aluminate powder and other minerals cannot be dissolved and are pressed and filtered to form industrial waste residues, and the amount of the calcium aluminate powder reaction residues generated in the production process of the polyaluminium chloride in China is about 15 ten thousand tons every year. At present, the aluminum calcium powder reaction slag can only be used as solid waste and is treated by related environmental protection units after certain treatment cost is paid. The treatment not only greatly increases the burden of enterprises, but also still has the risk of environmental pollution, and in addition, because the calcium aluminum powder reaction slag also contains a large amount of Al, the calcium aluminum powder reaction slag has good Al recycling value, and if the calcium aluminum powder reaction slag is treated as solid waste, great resource waste is caused.
The P-type zeolite molecular sieve is an earlier synthesized zeolite molecular sieve and has an eight-membered ring channel structure. Having a structural dimension of
And
the unique pore structure provides space limitation for selective adsorption of gas, and the effective pore diameter of the P-type zeolite molecular sieve is within the range of
On the left and right, except for H2O、NH3Gas with small isokinetic diameter does not adsorb other components, and P-type zeolite molecular sieve is used for Ca in aqueous solution2+、Mg2+The plasma has better selectivity, and the characteristics ensure that the P-type zeolite molecular sieve has wider application in the fields of washing aids, water treatment, adsorption separation and the like.
Ibraheem O. ali et al nNa the raw materials silica fume, sodium aluminate, sodium hydroxide and water2O：nSiO2：nAl2O3：nH2O ═ 1.4 to 1.6: (1.4-5.7): 1: 125, aging at 25 ℃ for 30min, and crystallizing at 100 ℃ for 4d to obtain the P-type zeolite molecular sieve. The method can effectively prepare the P-type zeolite with high crystallinity, but the crystallization time is too long, and the energy utilization efficiency is low. [ Ibrahem O. Ali, Said M.El-Sheikh, Tarek M.Salama, et al. controllable synthesis of NaP zeolite and its application in calcium adsorption [ J].Science China Materials,2015,58(8):621-633.]
In the patent of a preparation method (CN103274427A) of a P-type molecular sieve, one or more of alumina, soluble aluminum salt, aluminate and organic aluminum alkoxide compound are used as an aluminum source, and one or more of silica sol, water glass and organic silicate are used as a silicon source. nNa parts of silicon source, aluminum source, sodium hydroxide and water2O：nSiO2：nAl2O3：nH2O ═ 3 to 7: (2-5): 1: (50-250) mixing to form a precursor, adding a silicon-aluminum molecular sieve with a GIS structure as a seed crystal, wherein the addition amount of the seed crystal is Al contained in the seed crystal2O3The amount of the substance(s) is Al in the precursor2O3The amount of the substance is from 2 to 50% and is from 70 to 19%Crystallizing for 4-168 h at 0 ℃ to obtain the P-type zeolite molecular sieve. The method prepares the P-type zeolite with the relative crystallinity of 99.7 percent, but has high requirements on the quality of a silicon source and an aluminum source, and has higher production cost because seed crystals need to be added in the preparation process.
In the patent of a microwave preparation method (CN106745058A) of a P-type molecular sieve, one or more of alumina, soluble aluminum salt, aluminate and organic aluminum alkoxide compound are used as an aluminum source, and one or more of silica sol, water glass and organic silicate are used as a silicon source. nNa parts of silicon source, aluminum source, sodium hydroxide and water2O：nSiO2：nAl2O3：nH2O ═ 5 to 20: (2-8): 1: (1000-2500), and stirring for 10-120 min at 20-60 ℃ to obtain a P-type molecular sieve mother liquor; transferring the P-type molecular sieve mother liquor into a microwave reaction kettle, firstly crystallizing for 0.1-12 h at 80-140 ℃, and then crystallizing for 0.5-24 h at 150-200 ℃ to obtain the P-type molecular sieve. The method prepares the P-type zeolite with uniform crystal size distribution and relatively high crystallization in a microwave heating mode. But the secondary synthesis is needed, the secondary crystallization temperature is higher, the energy consumption is higher, the requirements on the quality of the silicon source and the aluminum source are high, and the production cost is higher.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a high-crystallinity P-type zeolite molecular sieve by using calcium-aluminum powder reaction slag, which has the advantages of simple process, low cost and no secondary pollution.
In order to achieve the above purpose, the invention provides the following technical scheme:
adding the reaction slag of the aluminum calcium powder into hydrochloric acid with the concentration of 6-10 mol/L for leaching, performing solid-liquid separation to obtain leaching slag and leaching liquid, roasting the leaching slag to obtain a roasted product, adding the roasted product into a sodium hydroxide solution to obtain slurry, aging the slurry, performing hydrothermal reaction, washing and drying the obtained hydrothermal product to obtain the P-type zeolite molecular sieve.
According to the technical scheme, the aluminum calcium powder reaction slag with an island-shaped silicate structure is converted into a silicate mineral with a layered structure by adopting a hydrochloric acid leaching mode, and then the zeolite molecular sieve is prepared by taking layered silicate as a raw material and adopting a hydrothermal synthesis method.
In the technical scheme of the invention, SiO in leaching slag obtained by leaching reaction slag of aluminum calcium powder with hydrochloric acid2With Al2O3In a molar ratio of 6: 1-9: 1. SiO in leaching slag2With Al2O3The molar ratio of (A) is within the range of the ratio, and an ideal P-type zeolite molecular sieve can be obtained after crystallization.
The inventor finds that the concentration of hydrochloric acid has great influence on the preparation of the P-type zeolite molecular sieve, the concentration of the hydrochloric acid is too low, the leaching rate of aluminum is low, and a roasted product SiO2With Al2O3The ratio of the amount of the substances cannot reach 6: 1-9: 1, aluminum resources cannot be effectively recycled, and an ideal P-type zeolite molecular sieve cannot be obtained after crystallization. Too high concentration of hydrochloric acid also causes SiO in the leached residue2With Al2O3The ratio of the amount of the substances cannot be within 6: 1-9: 1, and in addition, the concentration of hydrochloric acid is too high, so that the volatilization of the hydrochloric acid is serious, the loss of the hydrochloric acid is high, and the corrosion of equipment is severe.
In a preferable scheme, the concentration of the hydrochloric acid is 7-10 mol/L.
More preferably, the concentration of the hydrochloric acid is 8-9 mol/L.
In a preferable scheme, the liquid-solid ratio of the hydrochloric acid to the aluminum calcium powder reaction slag is 3: 1-6: 1(mL: g).
In a preferable scheme, the hydrochloric acid leaching solution is returned to be used as a raw material in the process of producing the polyaluminium chloride by using the aluminum calcium powder.
The inventor finds that the liquid-solid ratio has larger influence on the leaching of impurity metal ions, the liquid-solid ratio is too low, and Ca2+、Ti4+、Fe3+The leaching rate is low, the purity of the zeolite molecular sieve is reduced, the liquid-solid ratio is too high, the mass percentage of aluminum in the hydrochloric acid leaching solution is reduced, and the hydrochloric acid leaching solution is not favorable to be returned to be used as a raw material in the process of producing the polyaluminium chloride by using the aluminum calcium powder; then preparing the polyaluminium chloride by using a reaction kettle,
more preferably, the liquid-solid ratio of the hydrochloric acid to the aluminum calcium powder reaction slag is 4:1:6:1(mL: g).
More preferably, the liquid-solid ratio of the hydrochloric acid to the aluminum calcium powder reaction slag is 5:1(mL: g).
The inventor finds that the leaching rate of impurity metal ions is higher when the liquid-solid ratio of the hydrochloric acid to the reaction slag of the aluminum calcium powder is 5:1, and the leaching solution is most suitable for preparing the polyaluminium chloride.
The invention adopts a hydrochloric acid leaching process, which can convert the island-shaped silicate structure of the reaction slag of the aluminum calcium powder into a layered structure and convert part of metal ions (mainly Ca) into calcium ions2+、Ti4+、Fe3+Etc.) are leached to generate a large number of active points, which is beneficial to the crystallization in the subsequent hydrothermal reaction process and improves the purity of zeolite, and thirdly, SiO in the obtained leaching slag is extracted by the leaching process of the invention2With Al2O3The molar ratio of (a) is 6.0-9.0, and the silicon-aluminum ratio in the range can ensure that the P-type zeolite molecular sieve with high crystallinity is finally obtained and can also ensure that only the P-type molecular sieve is formed. Fourthly, the invention takes hydrochloric acid as the leaching solution, so the leaching solution can be directly used as a raw material in the process of producing the polyaluminium chloride by using the aluminum calcium powder, the closed cycle recovery of resources is realized, and zero emission is realized!
In the preferable scheme, the leaching temperature is 60-95 ℃, and the leaching time is 2-4 h.
In the preferable scheme, the roasting temperature is 600-900 ℃, and the roasting time is 2-4 h.
More preferably, the roasting temperature is 800-850 ℃. The inventors have found that the calcination temperature has an effect on the crystallinity of the P-type molecular sieve, and in this preferred range, the crystallinity of the resulting P-type molecular sieve is highest.
In a preferable scheme, the concentration of the sodium hydroxide solution is 2-6 mol/L.
Further preferably, the concentration of the sodium hydroxide solution is 3-4 mol/L.
In a preferable scheme, the solid-to-solid ratio of the sodium hydroxide solution to the roasting slag is 2: 1-6: 1(L: kg).
More preferably, the solid-to-solid ratio of the sodium hydroxide solution to the roasting slag is 3:1 to 5:1(L: kg).
In the preferred scheme, the aging temperature is 20-80 ℃, and the aging time is 2-24 h.
Preferably, the aging temperature is 40-60 ℃, and the aging time is 2-6 h.
In a preferable scheme, the temperature of the hydrothermal reaction is 90-130 ℃, and the time of the hydrothermal reaction is 12-20 h.
More preferably, the temperature of the hydrothermal reaction is 100-120 ℃, and the time of the hydrothermal reaction is 14-18 h.
In the invention, the crystallinity of the obtained P-type zeolite molecular sieve is more than or equal to 80 percent.
In a preferred embodiment of the invention, the crystallinity of the obtained P-type zeolite molecular sieve is 89.42-92.20%.
In the present invention, the molecular sieve crystallinity is calculated according to the following formula:
in the formula:
Xcdegree of crystallinity
Ic-sum of intensities of diffraction peaks of zeolite crystals of the sample
Ia-sum of diffraction intensities of characteristic peaks of zeolite crystals
Selecting the zeolite molecular sieve crystals with the 2 theta of 12.5 degrees, 17.7 degrees, 21.6 degrees, 28.2 degrees and 33.4 degrees as characteristic diffraction peaks, wherein the relative crystallinity is the sum of the intensities of five characteristic peaks of the sample compared with the intensity of five characteristic peaks of the standard peaks of the zeolite crystals.
The invention has the following beneficial effects:
aiming at the defects of long synthesis time, complex synthesis method and high synthesis cost of the existing P-type zeolite molecular sieve, the invention takes the reaction slag of the aluminum calcium powder generated in the process of producing the polyaluminium chloride by the aluminum calcium powder as the raw material and adopts hydrochloric acid leaching, roasting and hydrothermal crystallization methods to prepare the P-type zeolite molecular sieve. The method converts the original aluminum calcium powder reaction slag which can only be treated as waste slag into a high-value product P-type zeolite molecular sieve, thereby changing waste into valuable, realizing zero emission in the whole process, and having important chemical value and environmental protection value.
The invention firstly adopts the hydrochloric acid leaching process to convert the island-shaped silicate structure of the reaction slag of the aluminum calcium powder into a layered structure, and simultaneously, impurity metal ions (mainly Ca) in the reaction slag of the aluminum calcium powder2+、Ti4+、Fe3+Etc.) are leached out, a large number of active points are generated, and the roasting slag can be directly used for preparing the P-type zeolite molecular sieve with short crystallization time. In addition, by the leaching process, SiO in the obtained leaching slag2With Al2O3The molar ratio of (a) is 6: 1-9: 1, and the silicon-aluminum ratio in the range can ensure that the P-type zeolite molecular sieve with high crystallinity is finally obtained and can also ensure that only the P-type molecular sieve is formed.
The layered silicate obtained by the acid leaching process is combined to obtain SiO in the reaction slag of the aluminum calcium powder2And Al2O3Often still in the crystal structure, and are difficult to react with acids or bases and, after calcination, convert to highly reactive silicon-aluminum species.
In the crystallization process, a hydrothermal method is still used, the method is simple in process, and the P-type zeolite molecular sieve with high crystallinity can be rapidly prepared.
The leachate produced in the invention can be directly used as a raw material in the process of producing polyaluminium chloride from calcium aluminum powder, so that resources are fully utilized, zero emission is realized in the whole process, and no secondary pollution is caused.
In conclusion, the method has the advantages of simple and controllable process, low cost, short flow, no secondary pollution, realization of recycling of the aluminum calcium powder reaction slag, and great economic and environmental significance.
The attached drawings of the specification:
figure 1 is the XRD pattern of the zeolite P molecular sieve obtained in example 1.
Figure 2 is the XRD pattern of the zeolite P molecular sieve obtained in example 2.
Figure 3 is an XRD pattern of the zeolite P molecular sieve obtained in example 3.
Figure 4 is an XRD pattern of the zeolite P molecular sieve obtained in example 4.
Fig. 5 is an XRD pattern of the product obtained in comparative example 1.
FIG. 6 is an XRD pattern of the product obtained in comparative example 2.
The specific implementation mode is as follows:
the preparation method of the aluminum calcium powder reaction slag used in the following embodiments of the invention is as follows: injecting 900L hydrochloric acid with the mass concentration of 31% into a reaction tank, adding 265kg of aluminum hydroxide powder, starting stirring, reacting for 4 hours at 100 ℃, adding 1300L of water, adding 350kg of aluminum calcium powder, reacting for 2 hours at 85 ℃, filtering to obtain 135kg of aluminum calcium powder reaction slag with the water content of 26.6%, and drying the aluminum calcium powder reaction slag, wherein the chemical components are shown in Table 1.
TABLE 1 chemical composition of dried aluminum calcium powder reaction slag (%)
Example 1
Weighing 20kg of aluminum calcium powder reaction slag, placing the aluminum calcium powder reaction slag into a reactor, adding 58.72L of hydrochloric acid with the concentration of 10mol/L according to the solid-to-solid ratio (L: kg) of the hydrochloric acid to the aluminum calcium powder reaction slag liquid (L: 1), starting stirring, leaching for 3h at 85 ℃, filtering, washing and drying to obtain 10kg of hydrochloric acid leaching slag and 77.6L of hydrochloric acid leaching liquid, and drying the chemical components of the hydrochloric acid leaching slag as shown in Table 2. The main chemical components of the hydrochloric acid leaching solution are shown in table 3. SiO in hydrochloric acid leaching residue2With Al2O3The ratio of the amounts of substances (a) to (b) was 8.9.
TABLE 2 chemical composition of oven-dried hydrochloric acid leaching residue (%)
TABLE 3 main chemical composition (g/L) of hydrochloric acid leach liquor
Weighing 2.2kg of hydrochloric acid leaching residue, placing the hydrochloric acid leaching residue into a muffle furnace, controlling the roasting temperature to be 630 ℃, roasting for 2h to obtain roasting residue, placing 2kg of roasting residue into a reactor, adding 8L of sodium hydroxide solution with the concentration of 2mol/L according to the solid-to-solid ratio (L: kg) of the sodium hydroxide solution to the roasting residue (L: 1), uniformly stirring, aging for 4h at 50 ℃, transferring to a reaction kettle, crystallizing, and crystallizing for 16h at 100 ℃. Filtering and drying after crystallization to obtain the 1.1kgP type zeolite molecular sieve. The XRD pattern of the zeolite molecular sieve is shown in figure 1 by X-ray diffraction, and the relative crystallinity of the zeolite molecular sieve is determined to be 80.46 percent.
Placing 77.6L of hydrochloric acid leachate obtained in the example into a reactor, adding 15.5kg of aluminum powder according to the solid-to-solid ratio (L: kg) of the hydrochloric acid leachate to the aluminum powder (L: 1), reacting at 100 ℃ for 4h, adding 15.5kg of calcium powder according to the solid-to-solid ratio (L: kg) of the hydrochloric acid leachate to the calcium powder (L: 1), reacting at 85 ℃ for 2h, and filtering to obtain 83.6L of polyaluminum chloride containing Al2O3The content is 12.58%, and the basicity is 57.08%. It is demonstrated that the hydrochloric acid leaching solution obtained in the example can be directly reacted for preparing the polyaluminium chloride.
Example 2
Weighing 15kg of aluminum calcium powder reaction slag, placing the aluminum calcium powder reaction slag in a reactor, adding 55.1L of hydrochloric acid with the concentration of 8mol/L according to the solid-to-solid ratio (L: kg) of the hydrochloric acid to the aluminum calcium powder reaction slag liquid (L: 1), starting stirring, leaching for 3h at 85 ℃, and filtering, washing and drying to obtain 7.4kg of hydrochloric acid leaching slag and 77.6L of hydrochloric acid leaching liquid. SiO in hydrochloric acid leaching residue2With Al2O3The ratio of the amounts of the substances of (a) to (b) was 8.0.
Putting 3kg of hydrochloric acid leaching residue into a muffle furnace, controlling the roasting temperature to be 800 ℃, roasting for 2h to obtain roasting residue, putting 2.5kg of roasting residue into a reactor, adding 10L of sodium hydroxide solution with the concentration of 3mol/L according to the solid-to-solid ratio (L: kg) of the sodium hydroxide solution to the roasting residue (L: 1), uniformly stirring, aging for 4h at 50 ℃, transferring to a reaction kettle, crystallizing, and crystallizing for 16h at 100 ℃. After crystallization, filtering and drying are carried out to obtain the 1.4kgP type zeolite molecular sieve, the XRD pattern of the molecular sieve is shown in figure 2 by X-ray diffraction, and the relative crystallinity of the P type zeolite molecular sieve is determined to be 89.42%.
Example 3
Weighing 20kg of calcium aluminum powder reaction slag, placing the calcium aluminum powder reaction slag into a reactor, and adding hydrochloric acid and the calcium aluminum powder reaction slag according to the liquid-solid ratio (L: kg)) Adding 73.4L of hydrochloric acid with the concentration of 9mol/L into the mixture at a ratio of 5:1, starting stirring, leaching for 3 hours at 85 ℃, and then filtering, washing and drying to obtain 10.0kg of hydrochloric acid leaching residue and 38.8L of hydrochloric acid leaching solution. SiO in hydrochloric acid leaching residue2With Al2O3The ratio of the amounts of the substances of (a) to (b) was 8.0.
Putting 2.5kg of hydrochloric acid leaching residue into a muffle furnace, controlling the roasting temperature to be 850 ℃, roasting for 2h to obtain roasting residue, putting 1.6kg of roasting residue into a reactor, adding 6.4L of sodium hydroxide solution with the concentration of 4mol/L according to the solid-to-solid ratio (L: kg) of the sodium hydroxide solution to the roasting residue liquid being 4:1, stirring uniformly, aging for 4h at 50 ℃, transferring to a reaction kettle, crystallizing, and crystallizing for 16h at 100 ℃. After crystallization, filtering and drying are carried out to obtain 0.9kgP type zeolite molecular sieve, XRD pattern of the zeolite molecular sieve is shown in figure 3 by X-ray diffraction, and the relative crystallinity of the P type zeolite molecular sieve is determined to be 92.20%.
Example 4
10kg of aluminum calcium powder reaction slag is weighed and placed in a reactor, 44.0L of hydrochloric acid with the concentration of 7mol/L is added according to the solid-to-solid ratio (L: kg) of the hydrochloric acid to the aluminum calcium powder reaction slag liquid (L: 1), stirring is started, leaching is carried out for 3h at 85 ℃, and then filtering, washing and drying are carried out to obtain 5.0kg of hydrochloric acid leaching slag and 38.8L of hydrochloric acid leaching liquid. SiO in hydrochloric acid leaching residue2With Al2O3The ratio of the amounts of substances (a) to (b) was 7.4.
Putting 2.5kg of hydrochloric acid leaching residue into a muffle furnace, controlling the roasting temperature to be 850 ℃, roasting for 2h to obtain roasting residue, putting 1.6kg of roasting residue into a reactor, adding 6.4L of 6mol/L sodium hydroxide solution according to the solid-to-solid ratio (L: kg) of the sodium hydroxide solution to the roasting residue (L: 1), uniformly stirring, aging for 4h at 50 ℃, transferring to a reaction kettle, crystallizing, and crystallizing for 16h at 130 ℃. After crystallization, filtering and drying are carried out to obtain the 0.9kgP type zeolite molecular sieve, the XRD pattern of the molecular sieve is shown in figure 4 by X-ray diffraction, and the relative crystallinity of the P type zeolite molecular sieve is determined to be 82.35%.
Comparative example 1
This comparative example illustrates the experimental procedure and results of the crystallization after calcination of the reaction slag with calcium and aluminum powders.
The difference from example 3 is that in this comparative example, the reaction slag of aluminum calcium powder is directly roasted and crystallized.
2.5kg of calcium aluminum powder reaction slag is taken and put into a muffle furnace, the roasting temperature is controlled to be 850 ℃, roasting is carried out for 2h to obtain roasting slag, 1.5kg of roasting slag is put into a reactor, 6L of sodium hydroxide solution with the concentration of 4mol/L is added according to the solid-to-solid ratio (L: kg) of the sodium hydroxide solution to the roasting slag liquid of 4:1, the mixture is uniformly stirred, the mixture is aged for 4h at the temperature of 50 ℃ and then transferred into a reaction kettle for crystallization, and the crystallization is carried out for 16h at the temperature of 100 ℃. After crystallization, the product is filtered and dried to obtain 1.2kg, the XRD pattern of the product is shown in figure 5 by X-ray diffraction, and the relative crystallinity of the P-type zeolite molecular sieve is determined to be 32.68 percent.
Comparative example 2
This comparative example illustrates the experimental process and results of roasting, crystallization after leaching with 3mol/L hydrochloric acid in the hydrochloric acid leaching process.
The difference from example 3 is that this comparative example was leached with 3mol/L hydrochloric acid during the hydrochloric acid leaching.
Weighing 10kg of aluminum calcium powder reaction slag, placing the aluminum calcium powder reaction slag in a reactor, adding 36.7L of hydrochloric acid with the concentration of 3mol/L according to the solid-to-solid ratio (L: kg) of the hydrochloric acid to the aluminum calcium powder reaction slag liquid (L: 1), starting stirring, leaching for 3h at 85 ℃, and filtering, washing and drying to obtain 5.3kg of hydrochloric acid leaching slag and 37.5L of hydrochloric acid leaching liquid.
2.5kg of calcium aluminum powder reaction slag is taken and put into a muffle furnace, the roasting temperature is controlled to be 850 ℃, roasting is carried out for 2h to obtain roasting slag, 1.5kg of roasting slag is put into a reactor, 6L of sodium hydroxide solution with the concentration of 4mol/L is added according to the solid-to-solid ratio (L: kg) of the sodium hydroxide solution to the roasting slag liquid of 4:1, the mixture is uniformly stirred, the mixture is aged for 4h at the temperature of 50 ℃ and then transferred into a reaction kettle for crystallization, and the crystallization is carried out for 16h at the temperature of 100 ℃. After crystallization, the product is filtered and dried to obtain 1.0kg, the XRD pattern of the product is shown in figure 6 by X-ray diffraction, and the relative crystallinity of the P-type zeolite molecular sieve is determined to be 36.42%.
Claims (7)
1. A method for preparing a P-type zeolite molecular sieve by using aluminum calcium powder reaction slag is characterized by comprising the following steps: adding the reaction slag of the aluminum calcium powder into hydrochloric acid with the concentration of 6-10 mol/L for leaching, performing solid-liquid separation to obtain leaching slag and leaching liquid, roasting the leaching slag to obtain a roasted product, adding the roasted product into a sodium hydroxide solution to obtain slurry, aging the slurry, performing hydrothermal reaction, washing and drying the obtained hydrothermal product to obtain the P-type zeolite molecular sieve;
the liquid-solid ratio of the hydrochloric acid to the aluminum calcium powder reaction slag is 3: 1-6: 1(L: kg);
the concentration of the hydrochloric acid is 7-10 mol/L,
SiO in the leaching slag2With Al2O3The molar ratio of (a) to (b) is 6: 1-9: 1;
the leaching temperature is 60-95 ℃, and the leaching time is 2-4 h;
the aluminum calcium powder reaction slag is dissolved in the polyaluminium chloride produced by aluminum calcium powder, and part of calcium aluminate powder and other minerals can not be dissolved in the polymerization process and are pressed and filtered out to form industrial waste slag.
2. The method for preparing the P-type zeolite molecular sieve by using the reaction slag of the aluminum calcium powder according to claim 1, which is characterized by comprising the following steps: the hydrochloric acid leaching solution is returned to be used as a raw material in the process of producing the polyaluminium chloride by using the aluminum calcium powder.
3. The method for preparing the P-type zeolite molecular sieve by using the reaction slag of the aluminum calcium powder according to claim 1, which is characterized by comprising the following steps: the roasting temperature is 600-900 ℃, and the roasting time is 2-4 h.
4. The method for preparing the P-type zeolite molecular sieve by using the reaction slag of the aluminum calcium powder according to claim 1, which is characterized by comprising the following steps: the concentration of the sodium hydroxide solution is 2-6 mol/L.
5. The method for preparing the P-type zeolite molecular sieve by using the reaction slag of the aluminum calcium powder according to claim 1, which is characterized by comprising the following steps: the solid-to-solid ratio of the sodium hydroxide solution to the roasting slag is 2: 1-6: 1(L: kg).
6. The method for preparing the P-type zeolite molecular sieve by using the reaction slag of the aluminum calcium powder according to claim 1, which is characterized by comprising the following steps: the aging temperature is 20-80 ℃, and the aging time is 2-24 h.
7. The method for preparing the P-type zeolite molecular sieve by using the reaction slag of the aluminum calcium powder according to claim 1, which is characterized by comprising the following steps: the temperature of the hydrothermal reaction is 90-130 ℃, and the time of the hydrothermal reaction is 12-20 h.
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