CN113461026B - Preparation method and application of zeolite type dephosphorizing agent for high-salt waste liquid - Google Patents
Preparation method and application of zeolite type dephosphorizing agent for high-salt waste liquid Download PDFInfo
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- CN113461026B CN113461026B CN202110779504.8A CN202110779504A CN113461026B CN 113461026 B CN113461026 B CN 113461026B CN 202110779504 A CN202110779504 A CN 202110779504A CN 113461026 B CN113461026 B CN 113461026B
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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 141
- 239000010457 zeolite Substances 0.000 title claims abstract description 113
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 103
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 20
- 239000002699 waste material Substances 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 93
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- 239000002893 slag Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 239000003607 modifier Substances 0.000 claims abstract description 28
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 22
- 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 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000011268 mixed slurry Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 20
- 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 16
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002516 radical scavenger Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 18
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005259 measurement Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000005562 Glyphosate Substances 0.000 description 7
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 7
- 229940097068 glyphosate Drugs 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 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
- 238000005470 impregnation Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001556 precipitation Methods 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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003636 chemical group Chemical group 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 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
- 229910018072 Al 2 O 3 Inorganic materials 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- -1 zirconium ions Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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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- 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
- C01B39/026—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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- 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
- 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
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- 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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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a preparation method and application of a zeolite type dephosphorizing agent for high-salt waste liquid, wherein the preparation method comprises the following steps: (1) Ball milling is carried out on the nickel slag, and kaolin and sodium hydroxide are added into the nickel slag after ball milling 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 after the reaction is finished to obtain P1 zeolite; (3) The zeolite is immersed in the modifier to obtain a modified zeolite material, and the modified zeolite material is washed, dried and ground to obtain the zeolite type dephosphorization 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 dephosphorizing agent for high-salt wastewater; in the salt-containing wastewater, the phosphorus removal rate of the zeolite type phosphorus remover can reach more than 98 percent.
Description
Technical Field
The invention relates to a preparation method of a zeolite type dephosphorizing agent, in particular to a preparation method and application of a zeolite type dephosphorizing agent for high-salt waste liquid.
Background
Glyphosate is an efficient, broad-spectrum and low-toxicity organophosphorus herbicide, and has a large dosage in agricultural production, and at present, the glyphosate production mainly adopts a glycine synthesis method, so that a large amount of byproduct salt is produced in the glyphosate production, the byproduct salt contains organophosphorus components such as glyphosate, and the like, and the waste salt can remove nitrogen-containing organic impurities therein after high Wen Lin oxygen pyrolysis, so that the organophosphorus is converted into inorganic phosphorus. The byproduct salt has high phosphorus content, and cannot be produced and used. The current dephosphorization method of wastewater is mainly divided into a physical method, a chemical method and biological method. Wherein the physical method mainly comprises adsorption and extraction, the chemical method comprises precipitation method, electrolytic method and the like, and the biological method comprises an activated sludge method and a biological membrane method.
Although the conventional chemical precipitation method can effectively reduce the phosphorus content in the wastewater, the solution introduces new ion impurities, and the biological method has higher treatment cost and is difficult to realize large-scale production. The adsorption has the advantages that the operation is simple and easy, the existing commonly used adsorbents mainly comprise activated carbon, ion exchange resin and the like, the adsorbents are high in price and high in treatment cost, and the adsorbent is difficult to adsorb and remove phosphorus in wastewater with high salt content, so that the low-cost dephosphorization agent with high adsorption performance for the wastewater with salt content is developed, and is a research hot spot for dephosphorization of glyphosate byproduct salt.
The P-type zeolite has an eight-membered ring two-dimensional pore path rhombic calcium skeleton topological structure which is different from the X-type zeolite and the Y-type zeolite due to smaller size, is widely used in the adsorption field and the ion exchange field, and has Mg 2+ The exchange amount of (2) is 9 times that of the 4A zeolite.
Nickel slag is solid waste slag produced by smelting ferronickel alloy, and a large amount of nickel slag is discharged from nickel smelters and stainless steel smelters along with the continuous increase of stainless steel output in China. If the nickel slag cannot be properly treated, the nickel slag can occupy a large amount of land resources when being piled up 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 Al 2 O 3 And SiO 2 Meanwhile, the zeolite also has rich magnesium content, thus providing possibility for synthesizing zeolite. Mg of 2+ Can be combined with PO in solution 4 3- React to generate Mg (PO) 4 ) 2 Precipitation is carried out to achieve the effect of dephosphorization.
The existing method for preparing zeolite dephosphorizing agent mainly takes fly ash as raw material to synthesize zeolite dephosphorizing agent, adopts fly ash to carry out acid activation and then carries out hydrothermal crystallization with sodium hydroxide, adopts magnesium chloride and calcium chloride to carry out dipping modification to obtain zeolite dephosphorizing agent, and the method is adopted to synthesize the zeolite dephosphorizing agent possibly introducing Ca 2+ And the hydrothermal time is longer, and the removal rate of phosphorus in the saline solution is not high.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method of a zeolite type dephosphorizing agent for high-salt waste liquid, which has the advantages of low raw material cost, simple operation and high dephosphorizing rate; it is another object of the present invention to provide the use of a zeolite-type phosphorus scavenger.
The technical scheme is as follows: the preparation method of the zeolite type dephosphorizing agent for the high-salt waste liquid comprises the following steps:
(1) Ball milling is carried out on the nickel slag, and kaolin and sodium hydroxide are added into the nickel slag after ball milling 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 after the reaction is finished to obtain P1 zeolite;
(3) The zeolite is immersed in the modifier to obtain a modified zeolite material, and the modified zeolite material is washed, dried and ground to obtain the zeolite type dephosphorization agent.
Preferably, the modifier in step (3) is AlCl 3 ·6H 2 O, polymeric ferric sulfate, zrOCl 2 ·8H 2 O or a mixture of two.
Preferably, the modifier is AlCl 3 ·6H 2 O and ZrOCl 2 ·8H 2 Mixtures of O with AlCl 3 ·6H 2 The mass of O is ZrOCl 2 ·8H 2 0.8 to 1 times of O; or, the modifier is AlCl 3 ·6H 2 Mixtures of O with polymeric ferric sulfate, alCl in said mixtures 3 ·6H 2 The mass of O is 0.8-1 times of that of the polymeric ferric sulfate.
Preferably, in the step (1), the nickel slag is ball-milled 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 mixture.
Preferably, in the step (1), the water is distilled water, and the adding amount of the water is 4-8ml per gram of 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 6-7h. Preferably, the modifier is added in an amount of 1 to 1.4 times that of the zeolite, and the amount of water used in the water washing is 20 to 40ml per gram of modified zeolite material.
Preferably, in the step (3), the impregnation method is that the zeolite and the modifier are placed in a magnetic stirrer for stirring and impregnation, and the impregnation time is 20-24 hours.
The zeolite type dephosphorizing agent prepared by the preparation method of the zeolite type dephosphorizing agent is applied to the treatment of high-salt waste liquid.
The principle of the invention: 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 kaolin are converted into zeolite through crystallization reaction with alkali solution in a certain temperature range, wherein the zeolite is a pore channel structural material with excellent ion exchange and adsorption performance and is commonly used as an adsorbent. The zeolite is impregnated with aluminum salt, ferric salt, etc. to carry out ion exchange on the surface, thereby loading ions with affinity with phosphate radical to form chemical precipitation, and achieving the purpose of dephosphorization.
The beneficial effects are 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 dephosphorizing agent is reduced; in the whole preparation process, a large amount of solid waste of nickel metallurgical waste residues can be consumed, the recycling of nickel residues is realized, and the pollution to the environment is reduced;
(2) The preparation process is simple, the activity of nickel slag is improved through ball milling, a small amount of alkali is added to react with silicon dioxide in the materials, and finally the zeolite salt-resistant dephosphorization agent is prepared through a solution impregnation method, so that the whole process is simple and the operation is easy;
(3) In the salt-containing wastewater, the dephosphorization rate can reach more than 98 percent, aluminum, iron or zirconium ions can be uniformly loaded on the surface of zeolite, and 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 dephosphorizing agent prepared in example 2.
Detailed Description
The technical scheme of the invention is further described below.
Example 1
Zeolite type dephosphorizing agent preparation:
(1) Nickel slag is purchased from Jiangsu salt city, liangshui Delong nickel industry Co., ltd, kaolin is purchased from Henan Hengyuan New Material Co., ltd, ball milling is carried out to 200 meshes of nickel slag, and the proportion of the nickel slag to the kaolin is 7.5:17.5, mixing uniformly, mixing with sodium hydroxide according to a mass ratio of 1:1, adding distilled water and a magnetic stirrer according to a liquid-solid ratio of 200mL/25g, and mixing for 2 hours at 80 ℃ to obtain mixed slurry;
(2) Putting the mixed slurry into a reaction kettle at 120 ℃ to carry out hydrothermal treatment for 6 hours, filtering, washing and drying the reacted material to obtain P1 zeolite;
(3) Mixing the P1 zeolite with AlCl 3 6H2O is mixed vigorously in a magnetic stirrer for 24 hours at room temperature 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 dephosphorization agent, wherein the consumption of washing water is 20mL distilled water for every 1g of modified zeolite material.
Dephosphorization effect determination: the treated water sample is prepared by adopting a high Wen Lin oxygen cracking process of glyphosate byproduct salt produced by limited production of Hubei Xingfu chemical group stock, the total phosphorus content of the water sample is 18.79mg/L, the salt content is 10g/L, a modified zeolite dephosphorizing agent is added into the wastewater with the adding amount of 0.3g/25mL, and the mixture is mixed in a magnetic stirrer for 2 hours, wherein the dephosphorizing result is shown in Table 1.
Example 2
Zeolite type dephosphorizing agent preparation: step (1) is the same as in example 1, (2) the mixed slurry is put into a reaction kettle for hydrothermal treatment at 95 ℃ for 7 hours, and the reacted material is filtered, washed and dried to obtain P1 zeolite; (3) The P1 zeolite and polymeric ferric sulfate are mixed vigorously in a magnetic stirrer for 24 hours at room temperature according to the mass ratio of 1:1 and the solid-liquid ratio of 10g/100mL, and then the modified zeolite dephosphorization agent is obtained through filtration, washing and drying, wherein the consumption of washing water is 40mL distilled water for every 1g of modified zeolite material.
Dephosphorization effect determination: the measurement procedure was the same as in example 1, and dephosphorization results are shown in Table 1.
Example 3
Zeolite type dephosphorizing agent preparation: step (1) is the same as in example 1, (2) the mixed slurry is put into a reaction kettle for hydrothermal treatment at 145 ℃ for 6 hours, and the reacted material is filtered, washed and dried to obtain P1 zeolite; in the step (3), the P1 type zeolite is combined with ZrOCl 2 ·8H 2 And (3) mixing the O with the solid-liquid ratio of 10g/100mL according to the mass ratio of 1:1 in a magnetic stirrer for 20 hours at room temperature, filtering, washing and drying to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the measurement procedure was the same as in example 1, and dephosphorization results are shown in Table 1.
Example 4
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 1, and in step (3), the modifier is AlCl 3 ·H 2 O and ZrOCl 2 ·8H 2 O mixture, alCl therein 3 ·H 2 O and ZrOCl 2 ·8H 2 The O ratio is 4:5, mixing the P1 zeolite and the modifier according to the mass ratio of 1:1, the solid-liquid ratio of 10g/100mL, and filtering, washing and drying after being vigorously mixed in a magnetic stirrer for 20 hours at room temperature to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the measurement procedure was the same as in example 1, and dephosphorization results are shown in Table 1.
Example 5
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 1, and in step (3), the modifier is AlCl 3 ·H 2 O and ZrOCl 2 ·8H 2 O mixture, alCl therein 3 ·H 2 O and ZrOCl 2 ·8H 2 The O ratio is 1: mixing the 1, P1 type zeolite with a modifier according to a mass ratio of 1:1, a solid-liquid ratio of 10g/100mL, and carrying out vigorous mixing in a magnetic stirrer for 24 hours at room temperature, and then filtering, washing and drying to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the measurement procedure was the same as in example 1, and dephosphorization results are shown in Table 1.
Example 6
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 1, and in step (3), the modifier is AlCl 3 ·H 2 Mixtures of O with polymeric ferric sulfate, alCl 3 ·H 2 The ratio of O to polymeric ferric sulfate is 4:5, mixing the P1 zeolite and the modifier according to the mass ratio of 1:1, the solid-liquid ratio of 10g/100mL, and filtering, washing and drying after being vigorously mixed for 24 hours in a magnetic stirrer at room temperature to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the measurement procedure was the same as in example 1, and dephosphorization results are shown in Table 1.
Example 7
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 1, and in step (3), the modifier is AlCl 3 ·H 2 Mixtures of O with polymeric ferric sulfate, alCl 3 ·H 2 The ratio of O to polymeric ferric sulfate is 1: mixing the 1, P1 type zeolite and the modifier according to the mass ratio of 1:1, the solid-liquid ratio of 10g/100mL, and filtering, washing and drying after being vigorously mixed for 24 hours in a magnetic stirrer at room temperature to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the measurement procedure was the same as in example 1, and dephosphorization results are shown in Table 1.
Table 1 dephosphorization effect tables of examples 1 to 7
As is clear from the above table, examples 1 to 7 were excellent in dephosphorization effect, and the total phosphorus removal rate was about 98% except for example 6, and the adsorption capacity was about 1.54 mg/g.
Example 8
Zeolite type dephosphorizing agent preparation:
(1) Nickel slag is purchased from Jiangsu salt city, liangshui Delong nickel industry Co., ltd, kaolin is purchased from Henan Hengyuan New Material Co., ltd, ball milling is carried out to 320 meshes of nickel slag, and the nickel slag and the kaolin are mixed according to the proportion of 7.5:17.5, mixing uniformly, mixing with sodium hydroxide according to a mass ratio of 1:1, adding distilled water and a magnetic stirrer according to a liquid-solid ratio of 200mL/25g, and mixing for 2 hours at 80 ℃ to obtain mixed slurry;
(2) Putting the mixed slurry into a reaction kettle at 120 ℃ to carry out hydrothermal treatment for 6 hours, filtering, washing and drying the reacted material to obtain P1 zeolite;
(3) Mixing the P1 zeolite with AlCl 3 ·6H 2 And (3) mixing the O with distilled water in an amount of 1g/20ml in a magnetic stirrer for 24 hours at room temperature, filtering, washing and drying to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the treated water sample is prepared by adopting a high Wen Lin oxygen cracking process of glyphosate byproduct salt produced by limited production of Hubei Xingfu chemical group stock, the total phosphorus content of the water sample is 18.79mg/L, the salt content is 10g/L, a modified zeolite dephosphorizing agent is added into the wastewater with the adding amount of 0.3g/25mL, and the mixture is mixed in a magnetic stirrer for 2 hours, wherein the dephosphorizing result is shown in Table 2.
Example 9
Zeolite type dephosphorizing agent preparation: in the step (3), the P1 zeolite and the polymeric ferric sulfate are mixed vigorously in a magnetic stirrer for 24 hours at room temperature according to the mass ratio of 1:1, the distilled water addition amount is 1g/20ml, and then the modified zeolite dephosphorization agent is obtained through filtration, washing and drying.
Dephosphorization effect determination: the procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 10
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 8, and in step (3), zeolite P1 and ZrOCl 2 ·8H 2 The O ratio is 1:1, the adding amount of distilled water is 1g/20ml, and the modified zeolite dephosphorization agent is obtained by filtering, washing and drying after being vigorously mixed in a magnetic stirrer for 24 hours at room temperature.
Dephosphorization effect determination: the procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 11
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 8, and in step (3), the modifier is AlCl 3 ·H 2 O and ZrOCl 2 ·8H 2 O mixture, alCl therein 3 ·H 2 O and ZrOCl 2 ·8H 2 The O ratio is 4: mixing 5, P1 zeolite and the modifier in the mass ratio of 1 to 1, with the solid-liquid ratio of 10g/100mL, and filtering, washing and drying after being mixed vigorously in a magnetic stirrer for 24 hours at room temperature to obtain the modified zeoliteAn acidic zeolite dephosphorizing agent.
Example 12
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 8, and in step (3), the modifier is AlCl 3 ·H 2 O and ZrOCl 2 ·8H 2 O mixture, alCl therein 3 ·H 2 O and ZrOCl 2 ·8H 2 The O ratio is 4:5, mixing the P1 zeolite and the modifier according to the mass ratio of 1:1, the solid-liquid ratio of 10g/100mL, and filtering, washing and drying after being vigorously mixed in a magnetic stirrer for 24 hours at room temperature to obtain the modified zeolite dephosphorization agent.
Example 13
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 8, and in step (3), the modifier is AlCl 3 ·H 2 Mixtures of O with polymeric ferric sulfate, alCl 3 ·H 2 The ratio of O to polymeric ferric sulfate is 4:5, mixing the P1 zeolite and the modifier according to the mass ratio of 1:1, the solid-liquid ratio of 10g/100mL, and filtering, washing and drying after being vigorously mixed in a magnetic stirrer for 24 hours at room temperature to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 14
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 8, and in step (3), the modifier is AlCl 3 ·H 2 Mixtures of O with polymeric ferric sulfate, alCl 3 ·H 2 The ratio of O to polymeric ferric sulfate is 1: mixing the 1, P1 type zeolite with the modifier according to the mass ratio of 1:1, the solid-liquid ratio of 10g/100mL, and filtering, washing and drying after being vigorously mixed in a magnetic stirrer for 24 hours at room temperature to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 15
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 8, in step (3), zeolite P1, and AlCl 3 ·6H 2 O is mixed vigorously in a magnetic stirrer at room temperature according to the mass ratio of 1:1.4, the distilled water addition amount is 1g/20mlAnd filtering, washing and drying after 24 hours to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 16
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 8, step (3), with AlCl 3 ·6H 2 O is mixed vigorously in a magnetic stirrer for 24 hours at room temperature according to the mass ratio of 1:1, distilled water is added in an amount of 1g/40ml, and then the modified zeolite dephosphorization agent is obtained through filtration, washing and drying.
Dephosphorization effect determination: the procedure was the same as in example 1, and the dephosphorization results are shown in Table 2.
Example 17
Zeolite type dephosphorizing agent preparation: steps (1) and (2) are the same as in example 8, in step (3), zeolite P1, and AlCl 3 ·6H 2 The O is mixed with distilled water in the mass ratio of 1:1.4 in a magnetic stirrer of 1g/20ml for 20h at room temperature, and then filtered, washed and dried to obtain the modified zeolite dephosphorization agent.
Dephosphorization effect determination: the 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 is clear from the above table, examples 8 to 17 were excellent in dephosphorization effect, and the total phosphorus removal rate was about 98% except for example 13, and the adsorption capacity was about 1.54 mg/g.
Comparative example 1:
nickel slag and kaolin are mixed according to the proportion of 7.5:17.5, mixing uniformly, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water and a magnetic stirrer according to the liquid-solid ratio of 200mL/25g, mixing for 2 hours at 80 ℃, putting into a reaction kettle, carrying out hydrothermal reaction for 6 hours at 120 ℃, filtering, washing and drying the reacted material to obtain the P1 zeolite.
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:
mixing nickel slag and kaolin uniformly according to the mass ratio of 10:15, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water and a magnetic stirrer according to the liquid-solid ratio of 200mL/25g, mixing for 2 hours at 80 ℃, placing the mixture into a reaction kettle for hydrothermal treatment at 120 ℃ for 6 hours, and filtering, washing and drying the reacted material to obtain the P1 zeolite.
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:
mixing nickel slag and kaolin uniformly according to the mass ratio of 12.5:12.5, 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 for 2 hours at 80 ℃ by a magnetic stirrer, carrying out hydrothermal reaction for 6 hours at 120 ℃ in a reaction kettle, filtering, washing and drying the reacted material to obtain the P1 zeolite.
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:
mixing nickel slag and kaolin uniformly according to the mass ratio of 17.5:7.5, 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 for 2 hours at 80 ℃ by a magnetic stirrer, carrying out hydrothermal reaction for 6 hours at 120 ℃ in a reaction kettle, filtering, washing and drying the reacted material to obtain the P1 zeolite.
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
Nickel slag and kaolin are mixed according to the proportion of 7.5:17.5, mixing evenly, adding distilled water into sodium hydroxide according to the mass ratio of 1:1.2 and the liquid-solid ratio of 200mL/25g, mixing for 2 hours at 80 ℃ by a magnetic stirrer, carrying out hydrothermal reaction for 6 hours at 120 ℃ in a reaction kettle, filtering, washing and drying the reacted material to obtain the P1 zeolite.
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:
nickel slag and kaolin are mixed according to the proportion of 7.5:17.5, mixing uniformly, 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 a magnetic stirrer, carrying out hydrothermal reaction for 6 hours in a reaction kettle, filtering, washing and drying the reacted material to obtain the P1 zeolite.
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:
nickel slag and kaolin are mixed 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 with a magnetic stirrer according to the liquid-solid ratio of 200mL/25g at 80 ℃ for 2 hours, carrying out hydrothermal reaction at 120 ℃ in a reaction kettle for 6 hours, filtering, washing and drying the reacted material to obtain the P1 zeolite. 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:
nickel slag and kaolin are mixed according to the proportion of 7.5:17.5, mixing uniformly, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water and a magnetic stirrer according to the liquid-solid ratio of 200mL/25g, mixing for 2 hours at 80 ℃, carrying out hydrothermal reaction in a reaction kettle at 95 ℃ for 6 hours, filtering, washing and drying the reacted material to obtain the P1 zeolite. 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:
nickel slag and kaolin are mixed according to the proportion of 7.5:17.5, mixing uniformly, mixing with sodium hydroxide according to the mass ratio of 1:1, adding distilled water and a magnetic stirrer according to the liquid-solid ratio of 200mL/25g, mixing for 2 hours at 80 ℃, then carrying out hydrothermal reaction in a reaction kettle at 145 ℃ for 6 hours, filtering, washing and drying the reacted material to obtain the P1 zeolite.
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 Table of comparative examples 1 to 9
From the dephosphorization effect of comparative examples 1 to 4, it can be seen that the dephosphorization effect is better when the mass ratio of nickel slag to kaolin in the preparation of the P1 zeolite is selected to be 7.5:17.5-17.5:7.5, and the ratio of nickel slag to kaolin is 7.5:17.5, because the mass ratio condition has a more suitable silicon-aluminum ratio for synthesizing the P1 zeolite, which is favorable for the formation of the P1 zeolite.
From the dephosphorization effect of comparative examples 5 to 7, it can be seen that the mass ratio of the mixture to sodium hydroxide is preferably 1:1 to 1:1.6, the proportion of alkali has larger influence on the synthetic zeolite dephosphorizing agent, and the larger alkali concentration is not beneficial to the conversion of the P1 zeolite type zeolite, and has better adsorption effect when the proportion of sodium hydroxide to the mixed material is 1:1.
From the dephosphorization effect 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℃and that the dephosphorization effect is the best when the hydrothermal temperature is selected to be 120 ℃. This is because P1 zeolite can be synthesized at 120 c, P1 zeolite is initially formed at 95 c, and hydroxysodalite is synthesized at 145 c, which is disadvantageous for phosphorus removal.
Compared with the dephosphorization effect of the comparative example, the total phosphorus removal rate is obviously increased, and the removal rate is doubled; the adsorption capacity is obviously increased, and the adsorption capacity is increased by nearly 3 times.
XRD analysis was performed on the Al-modified zeolite dephosphorizing agent prepared in example 1, the polymeric ferric sulfate-modified zeolite dephosphorizing agent prepared in example 2, the Zr-modified zeolite dephosphorizing agent prepared in example 3, and the P1 zeolite prepared in comparative example 2, respectively, to obtain FIG. 1, and it is clear from the graph 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 Fe-Si-Al salt crystal phase to indicate that aluminum and iron have been loaded on the surface of the zeolite, and the Zr-modified zeolite finds that the P1 zeolite crystal phase disappears.
SEM examination of the zeolite-type dephosphorizing agent obtained in example 2 gave FIG. 2, which shows that the polymeric ferric sulfate-modified zeolite was in the form of small spherical particles and had a rough surface.
Claims (6)
1. A preparation method of a zeolite type dephosphorizing agent for high-salt waste liquid is characterized by comprising the following steps: the method comprises the following steps:
(1) Ball milling is carried out on the nickel slag, and kaolin and sodium hydroxide are added into the nickel slag after ball milling to obtain a mixed material; adding water into the mixed material and stirring uniformly to obtain mixed slurry, wherein nickel slag and kaolin are mixed according to the proportion of 7.5:17.5, mixing the nickel slag-kaolin mixture and sodium hydroxide according to the mass ratio of 1:1; the addition amount of water is 4-8ml per gram of mixture material;
(2) Carrying out hydrothermal reaction on the mixed slurry in the step (1), and filtering, washing and drying after the reaction is finished to obtain P1 zeolite, wherein the temperature of the hydrothermal reaction is 95-145 ℃ and the reaction time is 6-7 h;
(3) Impregnating zeolite in a modifier to obtain a modified zeolite material, wherein the modifier is AlCl 3 •6H 2 O, polymeric ferric sulfate, zrOCl 2 • 8 H 2 One or two of O; the modified zeolite material is washed, dried and ground to obtain the zeolite dephosphorization agent, wherein the adding amount of the modification agent is 1 to 1.4 times of that of zeolite.
2. The method for preparing zeolite type dephosphorizing agent according to claim 1, wherein the modifier is AlCl 3 •6H 2 O and ZrOCl 2 •8H 2 Mixtures of O with AlCl 3 •6H 2 The mass of O is ZrOCl 2 •8H 2 0.8-1 times of O; or, the modifier is AlCl 3 •6H 2 Mixtures of O with polymeric ferric sulfate, alCl in said mixtures 3 •6H 2 The mass of O is 0.8-1 times of that of the polymeric ferric sulfate.
3. The method for producing a zeolite phosphorus scavenger according to claim 1, wherein in step (1), the water is distilled water; the stirring is performed by a magnetic stirrer, and the stirring temperature is 80-90 ℃.
4. The method for producing a zeolite phosphorus scavenger according to claim 1, wherein in the step (3), the amount of water used in the water washing is 20 to 40. 40ml per gram of the modified zeolite material.
5. The method for preparing zeolite dephosphorizing agent according to claim 1, wherein in the step (3), the zeolite and the modifier are placed in a magnetic stirrer for stirring and dipping, and the dipping time is 20-24h.
6. The use of a zeolite-type phosphorus scavenger prepared by the method for preparing a zeolite-type phosphorus scavenger according to any one of claims 1 to 5 in the treatment of high-salt waste liquid.
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