CN113461026A - Preparation method and application of zeolite type phosphorus removal agent for high-salt waste liquid - Google Patents
Preparation method and application of zeolite type phosphorus removal agent for high-salt waste liquid Download PDFInfo
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- CN113461026A CN113461026A CN202110779504.8A CN202110779504A CN113461026A CN 113461026 A CN113461026 A CN 113461026A CN 202110779504 A CN202110779504 A CN 202110779504A CN 113461026 A CN113461026 A CN 113461026A
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- nickel slag
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- 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 135
- 239000010457 zeolite Substances 0.000 title claims abstract description 112
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 74
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000011574 phosphorus Substances 0.000 title claims abstract description 71
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000007788 liquid Substances 0.000 title claims abstract description 20
- 239000002699 waste material Substances 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 99
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 49
- 239000002893 slag Substances 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000003607 modifier Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 26
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 24
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000011268 mixed slurry Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 43
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 37
- 239000012153 distilled water Substances 0.000 claims description 22
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 12
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 11
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 11
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 55
- 230000000694 effects Effects 0.000 description 37
- 238000005259 measurement Methods 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 239000007787 solid Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000005562 Glyphosate Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 6
- 229940097068 glyphosate Drugs 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- -1 zirconium ions Chemical class 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- BFRXZIMAUMUZJH-UHFFFAOYSA-M [OH-].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] Chemical compound [OH-].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] BFRXZIMAUMUZJH-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012798 spherical particle Substances 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
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- 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
- C01B39/026—After-treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a preparation method and application of a zeolite phosphorus removal agent for high-salt waste liquid, wherein the preparation method comprises the following steps: (1) carrying out ball milling treatment on the nickel slag, and adding kaolin and sodium hydroxide into the ball-milled nickel slag to obtain a mixed material; adding water into the mixed material and uniformly stirring to obtain mixed slurry; (2) carrying out hydrothermal reaction on the mixed slurry in the step (1), and filtering, washing and drying the mixed slurry after the reaction is finished to obtain P1 type zeolite; (3) and (2) dipping the zeolite in a modifier to obtain a modified zeolite material, and washing, drying and grinding the modified zeolite material to obtain the zeolite-type phosphorus removal agent. The invention adopts the nickel slag as the raw material, improves the comprehensive utilization rate of the nickel slag, has low price of the nickel slag, and reduces the preparation cost of the zeolite salt-tolerant phosphorous removal agent for high-salinity wastewater; in the saline wastewater, the phosphorus removal rate of the zeolite phosphorus removal agent can reach more than 98%.
Description
Technical Field
The invention relates to a preparation method of a zeolite type phosphorus removing agent, in particular to a preparation method and application of a zeolite type phosphorus removing agent for high-salt waste liquid.
Background
The glyphosate is an efficient, broad-spectrum and low-toxicity organophosphorus herbicide, the dosage of the herbicide is large in agricultural production, the glycine synthesis method is mainly adopted in the current glyphosate production, the method can produce a large amount of byproduct salt, the byproduct salt contains organophosphorus components such as glyphosate and the like, the waste salt can remove nitrogenous organic matter impurities in the waste salt after high-temperature oxygen-critical cracking, and organophosphorus is converted into inorganic phosphorus. The byproduct salt has high phosphorus content, and thus cannot be produced and used. The existing methods for dephosphorizing wastewater are mainly divided into physical methods, chemical methods and biological methods. Wherein the physical method mainly comprises adsorption and extraction, the chemical method comprises a precipitation method, an electrolysis method and the like, and the biological method comprises an activated sludge method and a biofilm method.
Although the conventional chemical precipitation method can effectively reduce the phosphorus content in the wastewater, new ionic impurities are introduced into the solution, and the biological method has higher treatment cost and is difficult to realize large-scale production. The adsorption is simple and easy to operate, the currently commonly used adsorbents mainly comprise activated carbon, ion exchange resin and the like, the adsorbents are expensive and too high in treatment cost, and phosphorus is not easy to adsorb in the wastewater with high salt content, so that the development of the phosphorus remover with low cost and high adsorption performance for the wastewater with salt content is a research hotspot for dephosphorization of the glyphosate byproduct salt.
P-type zeolite has eight-membered ring two-dimensional channel orthorhombic calcium framework topological structure, which is different from X-type and Y-type zeolites due to small size and is widely used in the adsorption field and ion exchange field, and Mg of the P-type zeolite2+The exchange amount of (a) is 9 times that of the 4A zeolite.
The nickel slag is solid waste slag produced by smelting ferronickel, and as the yield of stainless steel in China continuously increases, a large amount of nickel slag is discharged from nickel smelting plants and stainless steel smelting plants. If the nickel slag can not be properly treated, the nickel slag can occupy a large amount of land resources when being stacked in the open air, and can cause serious pollution to the environment around water, atmosphere and soil. The main chemical component of the nickel slag is Al2O3And SiO2Meanwhile, the zeolite has rich magnesium content, and provides possibility for synthesizing zeolite. Mg (magnesium)2+Capable of reacting with PO in solution4 3-React to form Mg (PO)4)2The precipitation can achieve the effect of dephosphorization.
The existing method for preparing zeolite phosphorus removing agent mainly uses fly ash as raw material to synthesize zeolite phosphorus removing agent, uses fly ash to perform acid activation and then performs hydrothermal crystallization with sodium hydroxide, uses magnesium chloride and calcium chloride to perform impregnation modification to obtain zeolite phosphorus removing agent, and the method is adopted to synthesize the zeolite phosphorus removing agent possibly introducing Ca2+And the hydrothermal time is long, and the removal rate of phosphorus in the salt-containing solution is not high.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a zeolite type phosphorus removal agent for high-salt waste liquid, which has the advantages of low raw material cost, simple operation and high phosphorus removal rate; the invention also aims to provide an application of the zeolite phosphorus removing agent.
The technical scheme is as follows: the preparation method of the zeolite type phosphorus removal agent for the high-salt waste liquid comprises the following steps:
(1) carrying out ball milling treatment on the nickel slag, and adding kaolin and sodium hydroxide into the ball-milled nickel slag to obtain a mixed material; adding water into the mixed material and uniformly stirring to obtain mixed slurry;
(2) carrying out hydrothermal reaction on the mixed slurry in the step (1), and filtering, washing and drying the mixed slurry after the reaction is finished to obtain P1 type zeolite;
(3) and (2) dipping the zeolite in a modifier to obtain a modified zeolite material, and washing, drying and grinding the modified zeolite material to obtain the zeolite-type phosphorus removal agent.
Preferably, the modifier in step (3) is AlCl3·6H2O, polyferric sulfate, ZrOCl2·8H2One or a mixture of two of O.
Preferably, the modifier is AlCl3·6H2O and ZrOCl2·8H2Mixtures of O, AlCl in said mixtures3·6H2The mass of O is ZrOCl2·8H20.8-1 time of O; or, the modifier is AlCl3·6H2Mixtures of O and polymeric ferric sulfate, AlCl in said mixtures3·6H2The mass of the O is 0.8-1 time of that of the polymeric ferric sulfate.
Preferably, the ball milling of the nickel slag in the step (1) is carried out to 200-320 meshes, the adding mass of the nickel slag is 0.43-2.33 times of that of the kaolin, and the adding mass of the sodium hydroxide is 1-1.6 times of that of the nickel slag-kaolin mixed material.
Preferably, in the step (1), the water is distilled water, and the adding amount of the water is 4-8ml per gram of the mixture material; the stirring is performed by a magnetic stirrer, and the stirring temperature is 80-90 ℃.
Preferably, the temperature of the hydrothermal reaction is 95-145 ℃, and the reaction time is 6-7 h. Preferably, the modifier is added in an amount of 1-1.4 times the amount of zeolite, and the amount of water used in the water washing is 20-40ml per gram of modified zeolite material.
Preferably, in the step (3), the zeolite and the modifier are placed in a magnetic stirrer to be stirred and impregnated for 20-24 h.
The zeolite phosphorus removal agent prepared by the preparation method of the zeolite phosphorus removal agent is applied to treatment of high-salt waste liquid.
The invention principle is as follows: the invention provides a silicon source and an aluminum source by utilizing nickel slag and kaolin, and silicon and aluminum in the nickel slag and the kaolin are converted into zeolite through a crystallization reaction with an alkali solution in a certain temperature range, wherein the zeolite is a porous structure material with excellent ion exchange and adsorption performances and is commonly used as an adsorbent. The zeolite is subjected to impregnation treatment with aluminum salt, iron salt and the like, and ion exchange is carried out on the surface of the zeolite, so that ions with affinity with phosphate radicals are loaded, and chemical precipitation is formed, thereby achieving the purpose of removing phosphorus.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the nickel slag is used as a raw material, so that the comprehensive utilization rate of the nickel slag is improved, the nickel slag is low in price, and the preparation cost of the zeolite-removing salt-resistant phosphorus removal agent is reduced; in the whole preparation process, a large amount of solid waste of the nickel metallurgical waste residue can be consumed, the resource utilization of the nickel residue is realized, and the pollution to the environment is reduced;
(2) the preparation process is simple, the activity of the nickel slag is improved by ball milling, a small amount of alkali is added to react with silicon dioxide in the material, and finally the zeolite salt and phosphorus removal agent is prepared by a solution impregnation method, so that the whole process is simple and easy to operate;
(3) in the salt-containing wastewater, the phosphorus removal rate can reach more than 98%, and aluminum, iron or zirconium ions can be uniformly loaded on the surface of zeolite, so that the precipitation efficiency of phosphate ions is improved.
Drawings
FIG. 1 is an XRD pattern of the products prepared in examples 1-3 and comparative example 2;
FIG. 2 is an SEM image of the zeolite-type phosphorous removal agent prepared in example 2.
Detailed Description
The technical solution of the present invention is further explained below.
Example 1
Preparation of zeolite type phosphorus removing agent:
(1) the nickel slag is purchased from Songhuiong nickel industry Co., Ltd, Jiangsu salt city, and the kaolin is purchased from Henan constant-source new material Co., Ltd, the nickel slag is ball-milled to 200 meshes, and the nickel slag and the kaolin are mixed according to the proportion of 7.5:17.5, uniformly mixing, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water according to the liquid-solid ratio of 200mL/25g, and mixing with a magnetic stirrer at 80 ℃ for 2 hours to obtain mixed slurry;
(2) putting the mixed slurry into a reaction kettle at 120 ℃ for hydrothermal for 6 hours, and filtering, washing and drying the reacted materials to obtain P1 zeolite;
(3) mixing the above P1 type zeolite with AlCl36H2O at 1:1 mass ratio and 10g/100mL solid-to-liquid ratio, magnetically stirring at room temperatureAnd (3) after being mixed vigorously in a mixer for 24 hours, filtering, washing and drying to obtain the modified zeolite dephosphorizing agent, wherein the dosage of washing water is 20ml of distilled water for every 1g of modified zeolite material.
And (3) dephosphorization effect determination: the method is characterized in that a water sample to be treated is prepared from phosphorus-containing waste salt obtained by limited production of glyphosate byproduct salt by Hubei Xingcheng chemical group, through high-temperature oxygen cracking, the total phosphorus content of the water sample is 18.79mg/L, the salt content of the water sample is 10g/L, 0.3g/25mL of modified zeolite phosphorus removing agent is added into the waste water, the materials are mixed in a magnetic stirrer for 2 hours, and the phosphorus removing result is shown in Table 1.
Example 2
Preparation of zeolite type phosphorus removing agent: step (1) is the same as the embodiment 1, (2) the mixed slurry is put into a reaction kettle at 95 ℃ to be hydrothermal for 7 hours, and the reacted materials are filtered, washed and dried to obtain P1 zeolite; (3) the P1 type zeolite and polyferric sulfate are mixed vigorously in a magnetic stirrer at room temperature for 24 hours according to the mass ratio of 1:1 and the solid-liquid ratio of 10g/100mL, and then the mixture is filtered, washed and dried to obtain the modified zeolite dephosphorizing agent, wherein the dosage of washing water is 40mL of distilled water for each 1g of modified zeolite material.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 1.
Example 3
Preparation of zeolite type phosphorus removing agent: step (1) is the same as the embodiment 1, (2) the mixed slurry is put into a reaction kettle at 145 ℃ for hydrothermal for 6 hours, and the reacted materials are filtered, washed and dried to obtain P1 zeolite; in step (3), zeolite P1, and ZrOCl2·8H2And (3) according to the mass ratio of 1:1 and the solid-liquid ratio of 10g/100mL, violently mixing the materials in a magnetic stirrer at room temperature for 20 hours, and filtering, washing and drying to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 1.
Example 4
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 1, and in step (3), AlCl was used as the modifier3·H2O and ZrOCl2·8H2O mixture of wherein AlCl3·H2O and ZrOCl2·8H2The O ratio is 4: 5, mixing the P1 type zeolite and the modifier according to the mass ratio of 1:1, wherein the solid-liquid ratio is 10g/100mL, violently mixing the mixture in a magnetic stirrer at room temperature for 20h, and filtering, washing and drying the mixture to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 1.
Example 5
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 1, and in step (3), AlCl was used as the modifier3·H2O and ZrOCl2·8H2O mixture of wherein AlCl3·H2O and ZrOCl2·8H2The O ratio is 1:1, P1 type zeolite is mixed with a modifier according to the mass ratio of 1:1, the solid-liquid ratio is 10g/100mL, the mixture is violently mixed in a magnetic stirrer at room temperature for 24 hours, and then the mixture is filtered, washed and dried to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 1.
Example 6
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 1, and in step (3), AlCl was used as the modifier3·H2Mixtures of O with polymeric ferric sulfates, in which AlCl3·H2The ratio of O to polymeric ferric sulfate is 4: 5, mixing the P1 type zeolite and a modifier according to the mass ratio of 1:1, wherein the solid-liquid ratio is 10g/100mL, violently mixing the mixture in a magnetic stirrer at room temperature for 24 hours, and filtering, washing and drying the mixture to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 1.
Example 7
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 1, and in step (3), AlCl was used as the modifier3·H2Mixtures of O with polymeric ferric sulfates, in which AlCl3·H2The ratio of O to polyferric sulfate is 1:1, mixing P1 type zeolite and a modifier according to the mass ratio of 1:1, wherein the solid-liquid ratio is 10g/100mL, violently mixing the mixture in a magnetic stirrer at room temperature for 24 hours, and filtering, washing and drying the mixture to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 1.
TABLE 1 dephosphorization Effect tables of examples 1 to 7
As can be seen from the above table, the dephosphorization effect of examples 1-7 is excellent, and the total phosphorus removal rate is about 98% and the adsorption capacity is about 1.54mg/g except for example 6.
Example 8
Preparation of zeolite type phosphorus removing agent:
(1) the nickel slag is purchased from Songhuiong nickel industry Co., Ltd, Jiangsu salt city, and the kaolin is purchased from Henan constant source new material Co., Ltd, the nickel slag is ball-milled to 320 meshes, and the nickel slag and the kaolin are mixed according to the proportion of 7.5:17.5, uniformly mixing, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water according to the liquid-solid ratio of 200mL/25g, and mixing with a magnetic stirrer at 80 ℃ for 2 hours to obtain mixed slurry;
(2) putting the mixed slurry into a reaction kettle at 120 ℃ for hydrothermal for 6 hours, and filtering, washing and drying the reacted materials to obtain P1 zeolite;
(3) mixing the above P1 type zeolite with AlCl3·6H2And O is added according to the mass ratio of 1:1, the adding amount of distilled water is 1g/20ml, the mixture is violently mixed in a magnetic stirrer at room temperature for 24 hours, and then the mixture is filtered, washed and dried to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the method is characterized in that a water sample to be treated is prepared from phosphorus-containing waste salt obtained by limited production of glyphosate byproduct salt by Hubei Xingcheng chemical group, through high-temperature oxygen cracking, the total phosphorus content of the water sample is 18.79mg/L, the salt content of the water sample is 10g/L, 0.3g/25mL of modified zeolite phosphorus removing agent is added into the waste water, the materials are mixed in a magnetic stirrer for 2 hours, and the phosphorus removing result is shown in Table 2.
Example 9
Preparation of zeolite type phosphorus removing agent: the steps (1) and (2) are the same as the embodiment 8, in the step (3), the P1 type zeolite and the polymeric ferric sulfate are mixed according to the mass ratio of 1:1, the adding amount of distilled water is 1g/20ml, the mixture is mixed vigorously in a magnetic stirrer at room temperature for 24 hours, and then the mixture is filtered, washed and dried to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 10
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 8, and in step (3), P1 type zeolite and ZrOCl were used2·8H2The O ratio is 1:1, the adding amount of distilled water is 1g/20ml, the modified zeolite phosphate removing agent is obtained by filtering, washing and drying after the distilled water is mixed vigorously in a magnetic stirrer for 24 hours at room temperature.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 11
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 8, and in step (3), AlCl was used as the modifier3·H2O and ZrOCl2·8H2O mixture of wherein AlCl3·H2O and ZrOCl2·8H2The O ratio is 4: 5, mixing the P1 type zeolite and the modifier according to the mass ratio of 1:1, wherein the solid-liquid ratio is 10g/100mL, violently mixing the mixture in a magnetic stirrer at room temperature for 24 hours, and filtering, washing and drying the mixture to obtain the modified zeolite dephosphorizing agent.
Example 12
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 8, and in step (3), AlCl was used as the modifier3·H2O and ZrOCl2·8H2O mixture of wherein AlCl3·H2O and ZrOCl2·8H2The O ratio is 4: 5, mixing the P1 type zeolite and the modifier according to the mass ratio of 1:1, wherein the solid-liquid ratio is 10g/100mL, violently mixing the mixture in a magnetic stirrer at room temperature for 24 hours, and filtering, washing and drying the mixture to obtain the modified zeolite dephosphorizing agent.
Example 13
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 8, and in step (3), AlCl was used as the modifier3·H2O and polymeric ferric sulfate mixture, wherein AlCl3·H2The ratio of O to polymeric ferric sulfate is 4: 5And mixing the P1 type zeolite and the modifier according to the mass ratio of 1:1, wherein the solid-liquid ratio is 10g/100mL, violently mixing the mixture in a magnetic stirrer at room temperature for 24 hours, and filtering, washing and drying the mixture to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 14
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 8, and in step (3), AlCl was used as the modifier3·H2O and polymeric ferric sulfate mixture, wherein AlCl3·H2The ratio of O to polyferric sulfate is 1: mixing 1, P1 type zeolite and the modifier according to the mass ratio of 1:1, wherein the solid-liquid ratio is 10g/100mL, violently mixing the mixture in a magnetic stirrer at room temperature for 24 hours, and filtering, washing and drying the mixture to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 15
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 8, and step (3) was carried out with zeolite P1 and AlCl3·6H2And O is added into the mixture according to the mass ratio of 1:1.4, the distilled water is added into the mixture in an amount of 1g/20ml, the mixture is vigorously mixed in a magnetic stirrer at room temperature for 24 hours, and then the mixture is filtered, washed and dried to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 16
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 8, and step (3) was performed with AlCl3·6H2And O is added into the mixture according to the mass ratio of 1:1, the amount of the distilled water is 1g/40ml, the mixture is vigorously mixed in a magnetic stirrer at room temperature for 24 hours, and then the mixture is filtered, washed and dried to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 17
Preparation of zeolite type phosphorus removing agent: steps (1) and (2) were the same as in example 8, and step (3) was carried out with zeolite P1 and AlCl3·6H2And O is mixed vigorously in a magnetic stirrer with the mass ratio of 1:1.4 for 20 hours at room temperature in distilled water, and the mixture is filtered, washed and dried to obtain the modified zeolite dephosphorizing agent.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
TABLE 2 dephosphorization Effect tables of examples 8 to 17
As can be seen from the above table, examples 8 to 17 all showed excellent dephosphorization, and except example 13, the total phosphorus removal rate was about 98%, and the adsorption capacity was about 1.54 mg/g.
Comparative example 1:
mixing nickel slag and kaolin according to the proportion of 7.5:17.5, uniformly mixing, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water according to the liquid-solid ratio of 200mL/25g, mixing with a magnetic stirrer at 80 ℃ for 2h, then putting into a reaction kettle at 120 ℃ for hydrothermal for 6h, and filtering, washing and drying the reacted materials to obtain the P1 zeolite.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
Comparative example 2:
uniformly mixing nickel slag and kaolin according to a ratio of 10:15, mixing the nickel slag and the kaolin with sodium hydroxide according to a mass ratio of 1:1, adding distilled water according to a liquid-solid ratio of 200mL/25g, mixing the distilled water and a magnetic stirrer at 80 ℃ for 2 hours, putting the mixture into a reaction kettle at 120 ℃ for hydrothermal for 6 hours, and filtering, washing and drying the reacted materials to obtain the P1 zeolite.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
Comparative example 3:
uniformly mixing nickel slag and kaolin according to a ratio of 12.5:12.5, mixing with sodium hydroxide according to a mass ratio of 1:1, adding distilled water according to a liquid-solid ratio of 200mL/25g, mixing for 2 hours at 80 ℃ in a magnetic stirrer, heating for 6 hours at 120 ℃ in a reaction kettle, filtering, washing and drying the reacted materials to obtain the P1 zeolite.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
Comparative example 4:
uniformly mixing the nickel slag and kaolin according to a ratio of 17.5:7.5, mixing the nickel slag and the kaolin with sodium hydroxide according to a mass ratio of 1:1, adding distilled water according to a liquid-solid ratio of 200mL/25g, mixing the mixture in a magnetic stirrer at 80 ℃ for 2h, then carrying out hydrothermal reaction in a reaction kettle at 120 ℃ for 6h, and filtering, washing and drying the reacted materials to obtain the P1 zeolite.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
Comparative example 5
Mixing nickel slag and kaolin according to the proportion of 7.5:17.5, uniformly mixing the mixture with sodium hydroxide according to the mass ratio of 1:1.2 and the liquid-solid ratio of 200mL/25g, adding distilled water into a magnetic stirrer, mixing the mixture for 2 hours at 80 ℃, heating the mixture for 6 hours in a reaction kettle at 120 ℃, and filtering, washing and drying the reacted materials to obtain the P1 zeolite.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
Comparative example 6:
mixing nickel slag and kaolin according to the proportion of 7.5:17.5, uniformly mixing, mixing with sodium hydroxide according to the mass ratio of 1:1.4, adding distilled water according to the liquid-solid ratio of 200mL/25g, mixing for 2 hours at 80 ℃ by using a magnetic stirrer, heating for 6 hours in a reaction kettle, filtering, washing and drying the reacted materials to obtain the P1 zeolite.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
Comparative example 7:
mixing nickel slag and kaolin according to the proportion of 7.5:17.5, mixing uniformly, mixing with sodium hydroxide according to the mass ratio of 1:1.6, mixing in a magnetic stirrer according to the liquid-solid ratio of 200mL/25g at 80 ℃ for 2h, heating in a reaction kettle at 120 ℃ for 6h, filtering, washing and drying the reacted materials to obtain the P1 zeolite. And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
Comparative example 8:
mixing nickel slag and kaolin according to the proportion of 7.5:17.5, uniformly mixing, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water according to the liquid-solid ratio of 200mL/25g, mixing with a magnetic stirrer at 80 ℃ for 2h, heating in a reaction kettle at 95 ℃ for 6h, filtering, washing and drying the reacted materials to obtain the P1 zeolite. And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
Comparative example 9:
mixing nickel slag and kaolin according to the proportion of 7.5:17.5, uniformly mixing, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water according to the liquid-solid ratio of 200mL/25g, mixing with a magnetic stirrer at 80 ℃ for 2h, heating in a reaction kettle at 145 ℃ for 6h, filtering, washing and drying the reacted materials to obtain the P1 zeolite.
And (3) dephosphorization effect determination: the measurement procedure was the same as in example 1, and the dephosphorization results are shown in Table 3.
TABLE 3 dephosphorization Effect tables of comparative examples 1 to 9
From the dephosphorization effects of the comparative examples 1 to 4, it can be seen that the mass ratio of the nickel slag to the kaolin in the preparation of the P1 zeolite is selected to be 7.5:17.5 to 17.5:7.5, and the dephosphorization effect is better when the mass ratio of the nickel slag to the kaolin is 7.5:17.5, because the mass ratio condition has a more suitable silica-alumina ratio for synthesizing the P1 zeolite, which is favorable for the formation of the P1 zeolite.
From the dephosphorization effects of comparative examples 5 to 7, it can be seen that the mass ratio of the mixed material to sodium hydroxide is preferably 1:1 to 1:1.6, the ratio of the alkali has great influence on the synthetic zeolite dephosphorizing agent, the concentration of the alkali is not favorable for converting the zeolite into P1 zeolite, and the ratio of the sodium hydroxide to the mixed material is 1:1, so that the adsorption effect is better.
From the dephosphorization effects of comparative examples 8 to 9, it can be seen that the hydrothermal temperature in the hydrothermal reaction is preferably in the range of 95 to 145 ℃, wherein the dephosphorization effect is the best when the hydrothermal temperature is selected to be 120 ℃. The reason is that P1 zeolite can be synthesized at 120 ℃, P1 zeolite is primarily formed at 95 ℃, and hydroxysodalite is synthesized at 145 ℃, which is not beneficial to phosphorus removal.
Compared with the phosphorus removal effect of the comparative example, the total phosphorus removal rate is obviously increased, and the removal rate is improved by more than one time; the adsorption capacity is obviously increased by nearly 3 times.
XRD analysis is respectively carried out on the Al modified zeolite dephosphorizing agent prepared in the example 1, the polymeric ferric sulfate modified zeolite dephosphorizing agent prepared in the example 2, the Zr modified zeolite dephosphorizing agent prepared in the example 3 and the P1 zeolite prepared in the comparative example 2 to obtain a graph 1, and the graph shows that the P1 zeolite has an obvious P1 zeolite crystal phase, an aluminum silicate crystal phase appears through the Al modified zeolite, the polymeric ferric sulfate modified zeolite has an iron-silicon-aluminum salt crystal phase to show that aluminum and iron are loaded on the surface of the zeolite, and the P1 zeolite crystal phase disappears when the Zr modified zeolite is found.
SEM detection of the zeolite type phosphorus removing agent prepared in example 2 shows that FIG. 2 shows that the polyferric sulfate modified zeolite is in the form of small spherical particles and has a rough surface.
Claims (9)
1. A preparation method of a zeolite type phosphorus removal agent for high-salt waste liquid is characterized by comprising the following steps: the method comprises the following steps:
(1) carrying out ball milling treatment on the nickel slag, and adding kaolin and sodium hydroxide into the ball-milled nickel slag to obtain a mixed material; adding water into the mixed material and uniformly stirring to obtain mixed slurry;
(2) carrying out hydrothermal reaction on the mixed slurry in the step (1), and filtering, washing and drying the mixed slurry after the reaction is finished to obtain P1 type zeolite;
(3) and (2) dipping the zeolite in a modifier to obtain a modified zeolite material, and washing, drying and grinding the modified zeolite material to obtain the zeolite-type phosphorus removal agent.
2. The method for preparing zeolite-type phosphorus removal agent of claim 1, wherein the modifier in step (3) is AlCl3·6H2O, polymeric ferric sulfate, ZrOCl2·8H2One or a mixture of two of O.
3. The method for preparing zeolite-type phosphorus removal agent of claim 2, wherein the modifier is AlCl3·6H2O and ZrOCl2·8H2Mixtures of O, AlCl in said mixtures3·6H2The mass of O is ZrOCl2·8H20.8-1 time of O; or, the modifier is AlCl3·6H2Mixtures of O and polymeric ferric sulfate, AlCl in said mixtures3·6H2The mass of the O is 0.8-1 time of that of the polymeric ferric sulfate.
4. The preparation method of the zeolite type phosphorus removing agent as claimed in claim 1, wherein the nickel slag is ball-milled to 200-320 mesh in step (1), the adding mass of the nickel slag is 0.43-2.33 times of that of kaolin, and the adding mass of the sodium hydroxide is 1-1.6 times of that of the nickel slag-kaolin mixture.
5. The method for preparing a zeolite-type phosphorus removing agent according to claim 1, wherein in the step (1), the water is distilled water, and the addition amount of the water is 4-8ml per gram of the mixture material; the stirring is performed by a magnetic stirrer, and the stirring temperature is 80-90 ℃.
6. The method for preparing a zeolite-type phosphorus removal agent as claimed in claim 1, wherein in step (2), the hydrothermal reaction temperature is 95-145 ℃ and the reaction time is 6-7 h.
7. The method for preparing a zeolite type phosphorus removing agent according to claim 1, wherein in the step (3), the addition amount of the modifying agent is 1-1.4 times of that of the zeolite, and the amount of water used in water washing is 20-40ml per gram of the modified zeolite material.
8. The method for preparing a zeolite-type phosphorus removing agent as claimed in claim 1, wherein in the step (3), the zeolite and the modifier are immersed in a magnetic stirrer for 20-24h under stirring.
9. The application of the zeolite phosphorus removal agent prepared by the preparation method of the zeolite phosphorus removal agent according to any one of claims 1 to 8 in the treatment of high-salt waste liquid.
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| CN114163084A (en) * | 2021-12-15 | 2022-03-11 | 兰州交通大学 | Electrocatalytic oxidation coupling multi-medium biological slow filter and water treatment system |
| CN114163084B (en) * | 2021-12-15 | 2023-02-03 | 兰州交通大学 | Electrocatalytic oxidation coupling multi-medium biological slow filter and water treatment system |
| CN115055158A (en) * | 2022-06-17 | 2022-09-16 | 安徽理工大学 | Synthesis method of metal ion modified zeolite capable of realizing efficient magnetic separation |
| CN115055158B (en) * | 2022-06-17 | 2023-11-21 | 安徽理工大学 | Synthesis method of metal ion modified zeolite capable of being efficiently and magnetically separated |
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| CN113461026B (en) | 2023-11-10 |
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