CN115055157A - Preparation and desorption method of zirconium modified zeolite-bentonite active particle dephosphorization filter material - Google Patents
Preparation and desorption method of zirconium modified zeolite-bentonite active particle dephosphorization filter material Download PDFInfo
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- CN115055157A CN115055157A CN202210274814.9A CN202210274814A CN115055157A CN 115055157 A CN115055157 A CN 115055157A CN 202210274814 A CN202210274814 A CN 202210274814A CN 115055157 A CN115055157 A CN 115055157A
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 60
- 239000000440 bentonite Substances 0.000 title claims abstract description 47
- 229910000278 bentonite Inorganic materials 0.000 title claims abstract description 47
- 239000002245 particle Substances 0.000 title claims abstract description 40
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000003795 desorption Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- -1 zirconium modified zeolite Chemical class 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000001913 cellulose Substances 0.000 claims abstract description 23
- 229920002678 cellulose Polymers 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 22
- 230000001070 adhesive effect Effects 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 19
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010865 sewage Substances 0.000 claims abstract description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 239000011343 solid material Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000002639 bone cement Substances 0.000 claims description 3
- 239000005018 casein Substances 0.000 claims description 3
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 3
- 235000021240 caseins Nutrition 0.000 claims description 3
- 239000004833 fish glue Substances 0.000 claims description 3
- 229920000591 gum Polymers 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229920001864 tannin Polymers 0.000 claims description 3
- 235000018553 tannin Nutrition 0.000 claims description 3
- 239000001648 tannin Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 108010017384 Blood Proteins Proteins 0.000 claims description 2
- 102000004506 Blood Proteins Human genes 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 35
- 239000011574 phosphorus Substances 0.000 abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 35
- 239000000126 substance Substances 0.000 abstract description 2
- 229940088594 vitamin Drugs 0.000 abstract 1
- 229930003231 vitamin Natural products 0.000 abstract 1
- 235000013343 vitamin Nutrition 0.000 abstract 1
- 239000011782 vitamin Substances 0.000 abstract 1
- 150000003722 vitamin derivatives Chemical class 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000012851 eutrophication Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 108010080379 Fibrin Tissue Adhesive Proteins 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
-
- 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
Abstract
The invention relates to a preparation and desorption method of a zirconium modified zeolite-bentonite active particle dephosphorization filter material, which is prepared by a chemical method through zirconium modified zeolite, bentonite, cellulose and an adhesive, and ZrOCl is used for preparing the zirconium modified zeolite-bentonite active particle dephosphorization filter material 2 ·8H 2 Preparing zirconium modified zeolite powder from O and natural zeolite, sequentially mixing the zirconium modified zeolite powder with bentonite, cellulose and an adhesive, oscillating in a constant-temperature water bath, and drying to prepare the active particle dephosphorization filter material which is used for sewage dephosphorization, and can be regenerated and recycled after adsorption saturation. The zirconium modified zeolite-bentonite active particle dephosphorization filter material prepared by the invention not only has good phosphorus adsorption performance of the zirconium modified zeolite and the bentonite, but also has fiberThe stability and good separation performance of the vitamin and the adhesive from water are extremely advantageous new phosphorus removal materials, and the novel phosphorus removal material can be regenerated and recycled after desorption.
Description
Technical Field
The invention belongs to the field of environmental pollution treatment materials, particularly relates to preparation of a phosphorus removal filter material, and particularly relates to a preparation and desorption method of a zirconium modified zeolite-bentonite active particle phosphorus removal filter material.
Background
The eutrophication problem of water bodies such as lakes, reservoirs and the like in China is very serious, and phosphorus is one of main pollution indexes of rivers, lakes and seas in China and is a limiting factor for overgrowth of algae in lakes and reservoirs, so that the treatment is urgently needed. The discharge standard of sewage treatment plants is continuously improved, and when the discharged water is discharged into key watersheds, lakes, reservoirs and other water areas, the first-level A standard is required to be executed, and the TP limit value is 0.5 mg/L. For some sensitive areas, such as a honeycomb lake, a Yunnan pond and the like, the eutrophication of water bodies cannot be effectively controlled even if the TP of peripheral sewage treatment plants reaches the first grade A standard. At present, the highest limit standard of phosphorus is class I water of 'surface water environment quality standard' (GB3838-2002), the standard regulation cannot exceed 0.02mg/L, the implementation standard of a sewage treatment plant at present is the first-class B standard (1.5 mg/L) in the pollutant discharge standard of an urban sewage treatment plant (GB18918-2002), part of sewage treatment plants are upgraded to the first-class A standard (0.5 mg/L), and many eutrophication-sensitive areas are even required to be further upgraded to the class IV standard (0.3mg/L) of surface water. With the implementation of the discharge standards of cities in various regions, the total phosphorus index is gradually improved to a new standard of 0.3mg/L, so that the deep phosphorus removal upgrading and reconstruction work of sewage plants is imperative.
At present, part of the phosphorus removing agents on the market are chemical agents of aluminum salt and iron salt, so that the agent consumption is large, and the water treatment cost is high; the generated precipitated sludge can further increase the water treatment cost; the other part of the phosphorus removing agent is an adsorbent, and selectively enriches and transfers phosphorus in the sewage to the surface of the adsorbent, but at present, most of the adsorbents belong to solid powder, and solid-liquid separation is needed after the adsorbents are added into the sewage, so that time and labor are wasted.
Disclosure of Invention
The invention aims to solve the problems of high medicament consumption, high treatment cost and time and labor consumption in solid-liquid separation in the prior art, and provides a preparation method, application and desorption method of a zirconium modified zeolite-bentonite active particle dephosphorization filter material which is free of medicament, high in adsorption efficiency, free of sludge, strong in adsorption capacity, free of subsequent solid-liquid separation and high in adsorption stability.
In order to achieve the aim, the invention provides a preparation method of a zirconium modified zeolite-bentonite active particle dephosphorization filter material, which comprises the following steps:
(1) preparing zirconium modified zeolite powder, weighing 10-14 parts by weight of ZrOCl 2 ·8H 2 Placing O and 18-22 parts by weight of natural zeolite into a container, adding 180-220 parts by weight of deionized water, sealing, placing the container into a constant-temperature water bath oscillator at 25 ℃, oscillating and rotating to obtain a suspension, then adjusting the pH value of the suspension to 10 by using an alkali solution, continuously oscillating for 12 hours, performing solid-liquid separation by using a centrifugal machine, repeatedly cleaning by using deionized water to obtain a solid material, placing the obtained solid material into a muffle furnace for calcination, cooling to room temperature, crushing and grinding to obtain zirconium modified zeolite powder;
(2) adding bentonite into the zirconium modified zeolite powder obtained in the step (1) according to the mass ratio of (1-4) to (8), placing the mixture into a container, adding 180-220 parts by weight of deionized water, mixing and stirring, performing ultrasonic treatment, oscillating the mixture in a constant-temperature water bath oscillator at 40 ℃, and fully mixing to obtain a mixed solution A;
(3) adding cellulose into the mixed solution A according to the mass ratio of the cellulose to the zirconium modified zeolite powder of (1-3) to 1, slowly adding 3-7 parts by weight of hydrochloric acid solution with the mass fraction of 2%, mixing and stirring, performing ultrasonic treatment, and then placing in a constant-temperature water bath oscillator at 40 ℃ for oscillation to obtain a mixed solution B;
(4) and dripping 10-20 parts by volume of an adhesive solution with the mass fraction of 5% -10% into the mixed solution B, stirring, placing in a constant-temperature water bath oscillator at 30 ℃ for oscillation until a solid granular filter material is formed, then carrying out solid-liquid separation, washing the filtered solid granular filter material with water, and then transferring the washed solid granular filter material into an oven for drying to obtain the zirconium modified zeolite-bentonite active granular dephosphorization filter material.
Preferably, the step of preparing the zirconium-modified zeolite powder in step (1) comprises:
first, 12g ZrOCl was weighed 2 ·8H 2 Placing O and 20g of natural zeolite in a 500mL conical flask, adding 200mL of deionized water, sealing, placing the conical flask in a constant-temperature water bath oscillator at 25 ℃, and oscillating and rotating at the rotating speed of 150r/min for 1h to obtain a suspension;
then, adjusting the pH value of the suspension in the conical flask to 10 by using a NaOH solution with the concentration of 1mol/L, continuously oscillating the conical flask at the rotating speed of 150r/min for 12h, performing solid-liquid separation by using a centrifugal machine, and then repeatedly cleaning the solid by using deionized water;
and finally, placing the obtained solid material in a muffle furnace at 500 ℃ for calcining for 8h, cooling to room temperature, and crushing and grinding to obtain the zirconium modified zeolite powder.
Preferably, the solid material is repeatedly washed with deionized water until no Cl is present in the supernatant - 。
Preferably, in the step (2), the time of ultrasonic treatment is 10-20 min; in the step (2), the oscillation parameters in the constant-temperature water bath oscillator are as follows: oscillating at a rotating speed of 150r/min for 1-3 h.
Preferably, in the step (2), the time of ultrasonic treatment is 8-15 min; in the step (3), the oscillation parameters in the constant temperature water bath oscillator are as follows: oscillating for 4-6 h at a rotating speed of 150 r/min.
Preferably, in the step (4), the oscillation parameters in the constant temperature water bath oscillator are as follows: oscillating for 8-12 h at a rotating speed of 150 r/min.
Preferably, in the step (4), the drying temperature of the oven is 100-110 ℃.
Preferably, the adhesive is a natural polymer, such as animal adhesive including fish glue, bone glue, shellac, casein, fibrin glue, etc., or plant adhesive including tannin, starch, gum, sodium alginate, etc.
The invention also aims to provide an application of the preparation method of the zirconium modified zeolite-bentonite active particle dephosphorization filter material in sewage dephosphorization, which comprises the step of filling the prepared zirconium modified zeolite-bentonite active particle dephosphorization filter material into a fixed bed filter column for dephosphorization.
The invention also aims to provide a desorption method of the zirconium modified zeolite-bentonite active particle dephosphorization filter material, which comprises the following steps:
cleaning the zirconium modified zeolite-bentonite active particle dephosphorization filter material with saturated adsorption with deionized water, adding 3mol/L alkali liquor, placing the mixture in a constant-temperature water bath oscillator at 25 ℃ for desorption, carrying out solid-liquid separation after desorption for 6-8 h at the rotation speed of 150r/min, and cleaning the solid with water to obtain the desorbed zirconium modified zeolite-bentonite active particle dephosphorization filter material.
Based on the technical scheme, the invention has the advantages that:
the zirconium modified zeolite-bentonite active particle dephosphorization filter material prepared by the invention has good phosphorus adsorption performance of the zirconium modified zeolite and the bentonite, and simultaneously has the stability of cellulose and adhesive and good separation performance with water, so that the filter material is a novel dephosphorization material with great advantages, and compared with the traditional dephosphorization filter material, the filter material has the following advantages:
(1) no medicament is needed, and no medicament is needed to be added except the phosphorus removal filter material during treatment;
(2) no sludge and no counter anion are generated, phosphorus in the sewage is adsorbed on the surface of the filter material, no sludge is generated, and no counter anion is generated;
(3) no additional solid-liquid separation treatment step after adsorption;
(4) can be desorbed and regenerated for recycling.
Detailed Description
The technical solution of the present invention is further described in detail by the following examples.
The invention provides a preparation method of a zirconium modified zeolite-bentonite active particle dephosphorization filter material, which is prepared from zirconium modified zeolite, bentonite, cellulose and an adhesive by a chemical method, and comprises the following steps:
(1) preparing zirconium modified zeolite powder, weighing 10-14 parts by weight of ZrOCl 2 ·8H 2 Placing O and 18-22 parts by weight of natural zeolite into a container, adding 180-220 parts by weight of deionized water, sealing, placing the container into a constant-temperature water bath oscillator at 25 ℃, oscillating and rotating to obtain a suspension, then adjusting the pH value of the suspension to 10 with an alkali solution, continuously oscillating for 12 hours, performing solid-liquid separation with a centrifuge, repeatedly cleaning with deionized water to obtain a solid material, placing the obtained solid material into a muffle furnace for calcination, cooling to room temperature, crushing and grinding to obtain zirconium modified zeolite powder.
The zeolite has wide source and low cost, the zeolite has a tetrahedral structure and has good ion exchange and adsorption capacity, and the zeolite is modified by zirconium to ensure that the Zr is contained 2+ Loading to natural zeolite to make Ca existing in zeolite 2+ And Na + Plasma and Zr 2+ The ion exchange is carried out, the adsorption capacity is greatly improved, and the wastewater treatment capacity is effectively improved.
Preferably, the step of preparing the zirconium-modified zeolite powder in step (1) comprises:
first, 12g ZrOCl was weighed 2 ·8H 2 Placing O and 20g of natural zeolite in a 500mL conical flask, adding 200mL of deionized water, sealing, placing the conical flask in a constant-temperature water bath oscillator at 25 ℃, and oscillating and rotating at the rotating speed of 150r/min for 1h to obtain a suspension; then, adjusting the pH value of the suspension in the conical flask to 10 by using NaOH solution with the concentration of 1mol/L, continuously oscillating the conical flask at the rotating speed of 150r/min for 12h, performing solid-liquid separation by using a centrifugal machine, and then repeatedly washing the solid by using deionized water until no Cl exists in the supernatant - (ii) a And finally, placing the obtained solid material in a muffle furnace at 500 ℃ for calcining for 8h, cooling to room temperature, and crushing and grinding to obtain the zirconium modified zeolite powder.
(2) Adding bentonite into the zirconium modified zeolite powder obtained in the step (1-4) by mass ratio of 8, placing the mixture into a container, adding 180-220 parts by weight of deionized water, mixing and stirring, performing ultrasonic treatment, oscillating in a constant-temperature water bath oscillator at 40 ℃, and fully mixing to obtain a mixed solution A. The bentonite has larger specific surface area, huge surface energy, and better adsorption capacity and ion exchange capacity.
Preferably, in the step (2), the time of ultrasonic treatment is 10-20 min; in the step (2), the oscillation parameters in the constant-temperature water bath oscillator are as follows: oscillating at a rotating speed of 150r/min for 1-3 h. More preferably, in the step (2), the time of ultrasonic treatment is 8-15 min; in the step (3), the oscillation parameters in the constant temperature water bath oscillator are as follows: oscillating for 4-6 h at a rotating speed of 150 r/min.
(3) And adding cellulose into the mixed solution A according to the mass ratio of the cellulose to the zirconium modified zeolite powder of (1-3) to 1, slowly adding 3-7 parts by weight of hydrochloric acid solution with the mass fraction of 2%, mixing and stirring, performing ultrasonic treatment, and then placing in a constant-temperature water bath oscillator at 40 ℃ for oscillation to obtain a mixed solution B.
Cellulose has polarity as polysaccharide molecules, the interaction force between molecular chains is strong, hydrogen bonds can be formed in cellulose molecules and between cellulose molecules, particularly the hydrogen bonds in the cellulose molecules and between the cellulose molecules, so that the glycosidic bonds can not rotate, the rigidity of the cellulose is greatly increased, and the function of agglomerating zirconium modified zeolite and bentonite particles into large particles can be achieved.
(4) And dripping 10-20 parts by volume of an adhesive solution with the mass fraction of 5% -10% into the mixed solution B, stirring, placing in a constant-temperature water bath oscillator at 30 ℃ for oscillation until a solid granular filter material is formed, then carrying out solid-liquid separation, washing the filtered solid granular filter material with water, and then transferring the washed solid granular filter material into an oven for drying to obtain the zirconium modified zeolite-bentonite active granular dephosphorization filter material.
Preferably, in the step (4), the oscillation parameters in the constant temperature water bath oscillator are as follows: oscillating for 8-12 h at a rotating speed of 150 r/min. More preferably, in the step (4), the drying temperature of the oven is 100-110 ℃. Further, the adhesive is natural polymer, such as animal adhesive including fish glue, bone glue, lac, casein, blood protein glue, etc., or plant adhesive including tannin, starch, gum, sodium alginate, etc.
The adhesive can connect two or more parts or materials together through the actions of adhesion, cohesion and the like of an interface, can reinforce large particles, greatly improves the stability of the large particles, enables single cellulose molecules to be mutually connected through the adhesive, and enables zirconium modified zeolite particles and bentonite particles to be uniformly dispersed among the cellulose molecules.
The zirconium modified zeolite-bentonite active particle dephosphorization filter material prepared by the invention not only has good phosphorus adsorption performance of the zirconium modified zeolite and the bentonite, but also has the stability of cellulose and adhesive and good separation performance with water, and is a new material with great advantages for dephosphorization
The invention also provides an application of the preparation method of the zirconium modified zeolite-bentonite active particle dephosphorization filter material in sewage dephosphorization, which comprises the step of filling the prepared zirconium modified zeolite-bentonite active particle dephosphorization filter material into a fixed bed filter column for dephosphorization.
The zirconium modified zeolite-bentonite active particle dephosphorization filter material prepared by the preparation method has large particle size and can be filled into a fixed bed filter column. Because the inside of the particles is of a porous structure and the gaps among the particles are large, sewage can easily pass through the filter column, the problem of separation between the adsorbent and water after adsorption is completely solved, and phosphorus in the water is removed while filtration is carried out. After the sewage passes through the adsorption column, phosphorus is intercepted by the filter material, so that additional solid-liquid separation treatment is not needed, and the operation is very simple and convenient.
The zirconium modified zeolite-bentonite active particle dephosphorization filter material prepared by the invention can be regenerated and recycled after desorption after adsorption saturation. The invention also provides a desorption method of the zirconium modified zeolite-bentonite active particle dephosphorization filter material, which comprises the following steps:
cleaning the zirconium modified zeolite-bentonite active particle dephosphorization filter material with saturated adsorption with deionized water, adding 3mol/L NaOH, placing the filter material in a constant-temperature water bath oscillator at 25 ℃ for desorption, carrying out solid-liquid separation after desorption for 6-8 h at the rotation speed of 150r/min, and cleaning the solid with water to obtain the desorbed zirconium modified zeolite-bentonite active particle dephosphorization filter material.
Example 1
First, 12g ZrOCl was weighed 2 ·8H 2 Placing O and 20g of natural zeolite in a 500mL conical flask, adding 200mL of deionized water, sealing, placing the conical flask in a constant-temperature water bath oscillator at 25 ℃, and rotating for 1h at the rotating speed of 150r/min in an oscillating manner. Then adjusting the pH value of the suspension in the conical flask to 10 by using NaOH solution with the concentration of 1mol/L, continuously oscillating the conical flask at the rotating speed of 150r/min for 12h, and then carrying out solid-liquid separation by using a centrifugal machine. The solid was then washed repeatedly with deionized water until no Cl was present in the supernatant - . And finally, placing the obtained solid material in a muffle furnace at 500 ℃ for calcining for 8h, cooling to room temperature, crushing and grinding to obtain zirconium modified zeolite powder, and collecting for later use.
3g of the prepared zirconium-modified zeolite powder and 24g of bentonite were added to a 500mL conical flask, 200mL of water was added to the flask, and after mixing and stirring, the flask was subjected to ultrasonic treatment for 15 minutes, and then the conical flask was placed in a 40 ℃ constant temperature water bath oscillator and oscillated at a rotation speed of 150r/min for 2 hours to sufficiently mix the zirconium-modified zeolite powder and the bentonite, thereby obtaining a mixed solution A.
Adding 2g of cellulose into the obtained mixed solution A, slowly adding 5mL of hydrochloric acid solution with the mass fraction of 2%, mixing and stirring, sealing the conical flask, putting the sealed conical flask into an ultrasonic cleaning instrument for ultrasonic treatment for 10 minutes, then putting the conical flask into a constant-temperature water bath oscillator at 40 ℃, and oscillating for 5 hours at the rotating speed of 150r/min to obtain a mixed solution B.
And (3) dripping an adhesive solution with the mass fraction of 5% into the mixed solution B, stirring, placing in a constant-temperature water bath oscillator with the temperature of 30 ℃, and oscillating at the rotating speed of 150r/min for 10 hours to form the granular filter material. And (3) carrying out solid-liquid separation on the obtained turbid liquid, washing the filtered solid for 5 times, then drying in a drying oven at 105 ℃, and cooling to room temperature to obtain the active particle dephosphorization filter material of the embodiment 1.
Example 2
The process for preparing a phosphorus removing filter material of example 2 was performed in the same manner as in example 1, except that the amount of the zirconium modified zeolite added was 6 g.
Example 3
The process for preparing a phosphorus removing filter material of example 3 was the same as that of example 1 except that the amount of the zirconium-modified zeolite added was 12 g.
Example 4
The process for preparing the phosphorus removing filter material of example 4 was the same as that of example 1 except that the amount of the added cellulose was 1 g.
Example 5
The process for preparing the phosphorus removing filter material of example 5 was the same as that of example 1 except that the amount of the added cellulose was 3 g.
Example 6
In the preparation process of the phosphorus removal filter material in example 6, the process is the same as that in example 1 except that the mass fraction of the added adhesive is 7%.
Example 7
In the preparation process of the phosphorus removal filter material in example 7, the process is the same as that in example 1 except that the mass fraction of the added adhesive is 10%.
Preparing a potassium dihydrogen phosphate solution with the phosphorus content of 10mgP/L by using a potassium dihydrogen phosphate reagent, taking 7 500mL conical bottles, respectively adding 200mL 10mgP/L potassium dihydrogen phosphate solution into the conical bottles, respectively adding 0.1g of each phosphorus removal filter material prepared in the embodiments 1-7 into the conical bottles, and performing adsorption treatment for 5 hours. The end point phosphorus concentration for each example was measured and the corresponding phosphorus removal and phosphorus adsorption capacity were calculated, and the results are shown in the following table.
As can be seen from the above table, the phosphorus removal performance of the active particle phosphorus removal filter material prepared in examples 1 to 7 is relatively good, and the removal rate of phosphorus is mostly over 70%, wherein the lowest removal rate is example 7, the removal rate of phosphorus is only 52.7%, and the highest removal rate of phosphorus is 97.3% in example 2; the phosphorus adsorption capacity was mostly 15mg/g or more, the lowest was example 7, which was only 10.54mg/g, and the highest was example 2, which was 19.46 mg/g. In summary, the best embodiment is the embodiment 2, and the addition amounts of the components are respectively as follows: 6g of zirconium modified zeolite, 24g of bentonite, 2g of cellulose and 5% of adhesive by mass.
Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit the same; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a zirconium modified zeolite-bentonite active particle dephosphorization filter material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) preparing zirconium modified zeolite powder, weighing 10-14 parts by weight of ZrOCl 2 ·8H 2 Placing O and 18-22 parts by weight of natural zeolite into a container, adding 180-220 parts by weight of deionized water, sealing, placing the container into a constant-temperature water bath oscillator at 25 ℃, oscillating and rotating to obtain a suspension, then adjusting the pH value of the suspension to 10 by using an alkali solution, continuously oscillating for 12 hours, performing solid-liquid separation by using a centrifugal machine, repeatedly cleaning by using deionized water to obtain a solid material, placing the obtained solid material into a muffle furnace for calcination, cooling to room temperature, crushing and grinding to obtain zirconium modified zeolite powder;
(2) adding bentonite into the zirconium modified zeolite powder obtained in the step (1) according to the mass ratio of (1-4) to (8), placing the mixture into a container, adding 180-220 parts by weight of deionized water, mixing and stirring, performing ultrasonic treatment, oscillating the mixture in a constant-temperature water bath oscillator at 40 ℃, and fully mixing to obtain a mixed solution A;
(3) adding cellulose into the mixed solution A according to the mass ratio of the cellulose to the zirconium modified zeolite powder (1-3): 1, slowly adding 3-7 parts by weight of hydrochloric acid solution with the mass fraction of 2%, mixing, stirring, performing ultrasonic treatment, and then placing in a constant-temperature water bath oscillator at 40 ℃ for oscillation to obtain a mixed solution B;
(4) and dripping 10-20 parts by volume of an adhesive solution with the mass fraction of 5% -10% into the mixed solution B, stirring, placing in a constant-temperature water bath oscillator at 30 ℃ for oscillation until a solid granular filter material is formed, then carrying out solid-liquid separation, washing the filtered solid granular filter material with water, and then transferring the washed solid granular filter material into an oven for drying to obtain the zirconium modified zeolite-bentonite active granular dephosphorization filter material.
2. The method of claim 1, wherein: the step of preparing the zirconium-modified zeolite powder in step (1) includes:
first, 12 are weighedgZrOCl 2 ·8H 2 Placing O and 20g of natural zeolite in a 500mL conical flask, adding 200mL of deionized water, sealing, placing the conical flask in a constant-temperature water bath oscillator at 25 ℃, and oscillating and rotating at the rotating speed of 150r/min for 1h to obtain a suspension;
then, adjusting the pH value of the suspension in the conical flask to 10 by using a NaOH solution with the concentration of 1mol/L, continuously oscillating the conical flask at the rotating speed of 150r/min for 12h, performing solid-liquid separation by using a centrifugal machine, and then repeatedly cleaning the solid material by using deionized water;
and finally, placing the obtained solid material in a muffle furnace at 500 ℃ for calcining for 8h, cooling to room temperature, and crushing and grinding to obtain the zirconium modified zeolite powder.
3. The production method according to claim 2, characterized in that: repeated washing of the solid material with deionized water until no Cl is present in the supernatant - 。
4. The method of claim 1, wherein: in the step (2), the ultrasonic treatment time is 10-20 min; in the step (2), the oscillation parameters in the constant-temperature water bath oscillator are as follows: oscillating at a rotating speed of 150r/min for 1-3 h.
5. The method of claim 1, wherein: in the step (2), the ultrasonic treatment time is 8-15 min; in the step (3), the oscillation parameters in the constant temperature water bath oscillator are as follows: oscillating for 4-6 h at a rotating speed of 150 r/min.
6. The method of claim 1, wherein: in the step (4), the oscillation parameters in the constant temperature water bath oscillator are as follows: oscillating for 8-12 h at a rotating speed of 150 r/min.
7. The method of claim 1, wherein: in the step (4), the drying temperature of the oven is 100-110 ℃.
8. The method of claim 1, wherein: the adhesive comprises fish glue, bone glue, lac, casein, blood protein glue, tannin, starch, gum or sodium alginate.
9. An application of the zirconium modified zeolite-bentonite active particle dephosphorization filter material as in any one of claims 1 to 8 in sewage dephosphorization is characterized in that the prepared zirconium modified zeolite-bentonite active particle dephosphorization filter material is filled into a fixed bed filter column for dephosphorization.
10. A desorption method of the zirconium modified zeolite-bentonite active particle dephosphorization filter material as claimed in any one of claims 1 to 8, which is characterized in that: the desorption method comprises the following steps:
cleaning the zirconium modified zeolite-bentonite active particle dephosphorization filter material with saturated adsorption with deionized water, adding 3mol/L NaOH, placing the filter material in a constant-temperature water bath oscillator at 25 ℃ for desorption, carrying out solid-liquid separation after desorption for 6-8 h at the rotation speed of 150r/min, and cleaning the solid with water to obtain the desorbed zirconium modified zeolite-bentonite active particle dephosphorization filter material.
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