CN113797893B - Dephosphorizing agent, preparation method thereof and treatment method of phosphorus-containing sewage - Google Patents
Dephosphorizing agent, preparation method thereof and treatment method of phosphorus-containing sewage Download PDFInfo
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- CN113797893B CN113797893B CN202111155526.3A CN202111155526A CN113797893B CN 113797893 B CN113797893 B CN 113797893B CN 202111155526 A CN202111155526 A CN 202111155526A CN 113797893 B CN113797893 B CN 113797893B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 137
- 239000011574 phosphorus Substances 0.000 title claims abstract description 124
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 124
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000010865 sewage Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- -1 aluminum ions Chemical class 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001868 water Inorganic materials 0.000 claims abstract description 34
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 32
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 32
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 150000001768 cations Chemical class 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 42
- 239000000706 filtrate Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 30
- 239000010842 industrial wastewater Substances 0.000 claims description 25
- 230000002378 acidificating effect Effects 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 16
- 239000012670 alkaline solution Substances 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 10
- 239000001110 calcium chloride Substances 0.000 description 10
- 229910001628 calcium chloride Inorganic materials 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- 235000019341 magnesium sulphate Nutrition 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 10
- 229960001763 zinc sulfate Drugs 0.000 description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011964 heteropoly acid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to the technical field of environmental engineering, in particular to a dephosphorizing agent, a preparation method thereof and a treatment method of phosphorus-containing sewage. The preparation method of the dephosphorizing agent comprises the following steps: obtaining a mixed solution of carbon particles, a metal compound, an alkaline compound and water, stirring, filtering, and collecting filter residues to prepare a dephosphorization agent; the metal cations in the dephosphorizing agent are selected from at least three of magnesium ions, aluminum ions, calcium ions, iron ions, copper ions, zinc ions and sodium ions. The invention solves the problem that the dephosphorization agent is easy to lose effectiveness in treating the sewage containing phosphorus, has high dephosphorization rate, and has simple preparation process and simple separation.
Description
Technical Field
The invention relates to the technical field of environmental engineering, in particular to a dephosphorizing agent, a preparation method thereof and a treatment method of phosphorus-containing sewage.
Background
At present, with the progress of society and the rapid development of technology, the chemical industry has achieved a lot of achievements, but simultaneously brings about the problem of ecological environment pollution. When sewage discharged into water bodies such as rivers, lakes, oceans, reservoirs and the like contains excessive elements such as phosphorus, nitrogen and the like, eutrophication of the water bodies can be quickened, aquatic organisms such as algae and the like are greatly propagated, ecological balance of the water bodies is destroyed, and the species quantity and normal reproduction of the biological species of the water bodies are influenced, so that the dephosphorization of the sewage is a non-negligible problem.
The common dephosphorization process is biological and chemical. The biological method mainly comprises the steps of taking phosphorus-containing compounds through microbial reproduction, enriching and fixing the phosphorus-containing compounds in microbial cells from a water body, and achieving the effect of removing phosphorus in the water body. Biological methods are often used for the treatment of wastewater containing organic phosphorus compounds and low-concentration wastewater containing phosphorus. The chemical method is to convert the phosphorus compound dissolved in the phosphorus-containing sewage into the insoluble phosphorus compound by a chemical or physicochemical method or to adsorb the phosphorus compound on an adsorbent, and is specifically divided into a chemical coagulating sedimentation method, an adsorption method and a crystallization method; the chemical coagulating sedimentation method mainly comprises the steps of adding calcium salt, magnesium salt, aluminum salt, ferric salt and the like, forming insoluble inorganic phosphate sediment by metal ions such as iron, aluminum, calcium, magnesium and the like and phosphorus compounds, so as to realize the dephosphorization of the water body, and has the advantages of high dephosphorization rate, simple operation, low cost and the like in simpler sewage water bodies.
At present, an inorganic-organic efficient dephosphorizing agent composed of inorganic salts such as calcium salt, magnesium salt, ferric salt and the like and organic matters such as water-soluble polymer materials is adopted for dephosphorizing, and another scheme is adopted for treating phosphorus-containing sewage by adopting a dephosphorizing agent prepared from the rest of aluminum slag in aluminum industry production. However, the dephosphorization effect of the dephosphorization methods of these schemes hardly meets the standard requirements of the specified elemental phosphorus. In addition, in order to improve the dephosphorization effect, the acquisition of the dephosphorization agent also requires a complex deep processing process and a complex separation process.
Disclosure of Invention
Based on the above, the invention provides a dephosphorizing agent, a preparation method thereof and a treatment method of phosphorus-containing sewage. Solves the problem that the dephosphorization agent is easy to lose effectiveness in treating the sewage containing phosphorus, has high dephosphorization rate, and has simple preparation process and simple separation.
The technical proposal is as follows:
The preparation method of the dephosphorizing agent comprises the following steps:
obtaining a mixed solution of carbon particles, a metal compound, an alkaline compound and water, stirring, filtering, and collecting filter residues to prepare a dephosphorization agent;
The metal cations in the dephosphorizing agent are selected from at least three of magnesium ions, aluminum ions, calcium ions, iron ions, copper ions, zinc ions and sodium ions.
In one embodiment, the mass of the carbon particles in the dephosphorizing agent is 1.5-17.5% of the total mass of the dephosphorizing agent.
Optionally, in one embodiment, the metal cations in the phosphorous removal agent include magnesium ions, aluminum ions, calcium ions, iron ions, copper ions, zinc ions, and sodium ions.
Preferably, the mass of the magnesium ions accounts for 2.6-13% of the total mass of the dephosphorizing agent;
the mass of the aluminum ions accounts for 0.8-4% of the total mass of the dephosphorizing agent;
the mass of the calcium ions accounts for 2.3-18% of the total mass of the dephosphorizing agent;
The mass of the iron ions accounts for 0.8-20% of the total mass of the dephosphorizing agent;
the mass of the copper ions accounts for 0.05-0.3% of the total mass of the dephosphorizing agent;
the mass of the zinc ions accounts for 0.02-0.1% of the total mass of the dephosphorizing agent;
The mass of the sodium ions accounts for 4-21% of the total mass of the dephosphorizing agent.
In one embodiment, the pH of the mixture is 7.0-11.0.
In one embodiment, the anions in the dephosphorizing agent are hydroxide ions and/or carbonate ions.
In one embodiment, the alkaline compound is selected from one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium oxide, sodium carbonate, calcium carbonate, and potassium carbonate.
Optionally, in one embodiment, the method for obtaining the mixed solution of carbon particles, metal compound, alkaline compound and water is as follows:
mixing carbon particles, a metal compound, an alkaline compound, and water to prepare a mixed solution.
Optionally, in one embodiment, the method for obtaining the mixed solution of carbon particles, metal compound, alkaline compound and water is as follows:
Obtaining industrial wastewater, wherein the industrial wastewater contains carbon particles, metal compounds and water;
And mixing the industrial wastewater with an alkaline compound to prepare a mixed solution.
In one embodiment, the stirring is for a period of 1h to 3h.
The invention also provides a dephosphorizing agent prepared by the preparation method, which has high-efficiency dephosphorizing effect. After the phosphorus-containing sewage is treated, the standard requirement of the element phosphorus specified in the integrated wastewater discharge Standard of the people's republic of China (GB 8978-1996) can be met.
The invention also provides a treatment method of the phosphorus-containing sewage.
The technical proposal is as follows:
A method for treating phosphorus-containing sewage comprises the following steps:
mixing the dephosphorizing agent and the phosphorus-containing sewage to prepare slurry;
mixing the slurry with an acidic solution, and adjusting the pH value to 0.5-4.5 to prepare an acidic feed liquid;
mixing the acidic feed liquid and the alkaline solution, adjusting the pH value to 7.0-12.5, filtering, and discharging filtrate;
The mass of the alkaline compound in the alkaline solution accounts for 20% -55% of the total mass of the alkaline solution.
In one embodiment, the mass of the dephosphorizing agent is 1-715 times the mass of phosphorus in the phosphorus-containing sewage.
Compared with the traditional scheme, the invention has the following beneficial effects:
According to the invention, the mixed solution containing carbon particles, the metal compound, the alkaline compound and water is stirred, the metal compound is colloid, and the metal compound is enabled to grow around the carbon particles based on the principle that the carbon particles promote colloid flocculation, so that the dephosphorization agent of porous spherical particles supported by the carbon particles is prepared, the preparation process is simple, solid-liquid separation is easy, complex equipment is not needed, and industrial mass production is facilitated. Compared with the ion exchange dephosphorization carried out by a layered structure or an amorphous structure of an iron, aluminum and calcium single-metal or multi-metal dephosphorization agent in the prior art, firstly, the porous spherical structure has larger specific surface area and better dephosphorization effect. Secondly, metal ions in the dephosphorizing agent and phosphate radical, hypophosphite radical, phosphite radical and other phosphorus-containing substances in the phosphorus-containing sewage form metal heteropoly acid or heteropoly acid-like, and chemical adsorption is carried out, and meanwhile, the existence of carbon particles can further promote the conversion of colloid into heteropoly acid or heteropoly acid-like, so that the chemical adsorption efficiency is improved. Thirdly, the porous spherical structure is favorable for providing enough physical adsorption space, and after the heteropoly acid or the heteropoly acid-like is formed, the phosphorus-containing substance is further subjected to physical adsorption, so that the phosphorus removal rate is improved. In addition, the dephosphorizing agent prepared by the invention can avoid a large amount of colloid suspension generated during the elimination of phosphorus by the flocculation of carbon particles when treating phosphorus-containing sewage, and is convenient for discharge. Compared with the preparation of the dephosphorizing agent by biological dephosphorizing, the preparation method of the dephosphorizing agent does not need to provide anaerobic environment and a large sewage pool, has simple operation, is not influenced by the microorganism community in the sewage containing phosphorus and the sewage treatment device and is not influenced by seasons. The preparation method of the dephosphorizing agent has the characteristics of wide raw material sources, environmental protection, simple process, safety, no byproducts and high added value.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Terminology
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
The term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other.
Herein, "one or several" means any one, any two or more of the listed items. Wherein "several" means any two or more.
In this context, "preferred" is merely to describe embodiments or examples that are more effective, and it should be understood that they are not intended to limit the scope of the invention.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical range is referred to, and both ends of the numerical range are included unless otherwise specified.
The percentage content referred to in the present invention refers to mass percentage for both solid-liquid mixing and solid-solid mixing and volume percentage for liquid-liquid mixing unless otherwise specified.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
The invention provides a dephosphorizing agent, a preparation method thereof and a treatment method of phosphorus-containing sewage. Solves the problem that the dephosphorization agent is easy to lose effectiveness in treating the sewage containing phosphorus, has high dephosphorization rate, and has simple preparation process and simple separation.
The technical proposal is as follows:
The preparation method of the dephosphorizing agent comprises the following steps:
obtaining a mixed solution of carbon particles, a metal compound, an alkaline compound and water, stirring, filtering, and collecting filter residues to prepare a dephosphorization agent;
The metal cations in the dephosphorizing agent are selected from at least three of magnesium ions, aluminum ions, calcium ions, iron ions, copper ions, zinc ions and sodium ions.
According to the invention, the mixed solution containing carbon particles, the metal compound, the alkaline compound and water is stirred, the metal compound is colloid, and the metal compound is enabled to grow around the carbon particles based on the principle that the carbon particles promote colloid flocculation, so that the dephosphorization agent of porous spherical particles supported by the carbon particles is prepared, the preparation process is simple, solid-liquid separation is easy, complex equipment is not needed, and industrial mass production is facilitated. Compared with the ion exchange dephosphorization carried out by a layered structure or an amorphous structure of an iron, aluminum and calcium single-metal or multi-metal dephosphorization agent in the prior art, firstly, the porous spherical structure has larger specific surface area and better dephosphorization effect. Secondly, metal ions in the dephosphorizing agent and phosphate radical, hypophosphite radical, phosphite radical and other phosphorus-containing substances in the phosphorus-containing sewage form metal heteropoly acid or heteropoly acid-like, and chemical adsorption is carried out, and meanwhile, the existence of carbon particles can further promote the conversion of colloid into heteropoly acid or heteropoly acid-like, so that the chemical adsorption efficiency is improved. Thirdly, the porous spherical structure is favorable for providing enough physical adsorption space, and after the heteropoly acid or the heteropoly acid-like is formed, the phosphorus-containing substance is further subjected to physical adsorption, so that the phosphorus removal rate is improved. In addition, the dephosphorizing agent prepared by the invention can avoid a large amount of colloid suspension generated during the elimination of phosphorus by the flocculation of carbon particles when treating phosphorus-containing sewage, and is convenient for discharge. Compared with the preparation of the dephosphorizing agent by biological dephosphorizing, the preparation method of the dephosphorizing agent does not need to provide anaerobic environment and a large sewage pool, has simple operation, is not influenced by the microorganism community in the sewage containing phosphorus and the sewage treatment device and is not influenced by seasons. The preparation method of the dephosphorizing agent has the characteristics of wide raw material sources, environmental protection, simple process, safety, no byproducts and high added value.
Optionally, the carbon particles are selected from graphite or activated carbon.
The carbon particles may be amorphous or spherical in shape.
In one embodiment, the mass of the carbon particles in the dephosphorizing agent is 1.5-17.5% of the total mass of the dephosphorizing agent.
Optionally, in one embodiment, the metal cations in the phosphorous removal agent include magnesium ions, aluminum ions, calcium ions, iron ions, copper ions, zinc ions, and sodium ions.
The method utilizes the complexing and adsorption of iron, aluminum, magnesium, calcium, copper, zinc and sodium to phosphate radical and other physical and chemical actions, compared with the common adsorption method for dephosphorization and chemical coagulation precipitation method for dephosphorization, the method avoids the problems that the conventional process is easily influenced by organic matters and other components possibly existing in industrial sewage to cause the decrease of the dephosphorization rate and the failure possibly occurs when the phosphorus content in the phosphorus-containing sewage exceeds 500mg/L, and has the advantages of strong applicability and wide applicability.
Preferably, the mass of the magnesium ions accounts for 2.6-13% of the total mass of the dephosphorizing agent;
the mass of the aluminum ions accounts for 0.8-4% of the total mass of the dephosphorizing agent;
the mass of the calcium ions accounts for 2.3-18% of the total mass of the dephosphorizing agent;
The mass of the iron ions accounts for 0.8-20% of the total mass of the dephosphorizing agent;
the mass of the copper ions accounts for 0.05-0.3% of the total mass of the dephosphorizing agent;
the mass of the zinc ions accounts for 0.02-0.1% of the total mass of the dephosphorizing agent;
The mass of the sodium ions accounts for 4-21% of the total mass of the dephosphorizing agent.
In one embodiment, the pH of the mixture is 7.0-11.0. Within this range, there is little adverse effect on the dephosphorization effect of the prepared dephosphorization agent.
In one embodiment, the anions in the dephosphorizing agent are hydroxide ions and/or carbonate ions.
In one embodiment, the alkaline compound is selected from one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium oxide, sodium carbonate, calcium carbonate, and potassium carbonate. Cations in the basic compound may also be transferred to the metal cations of the dephosphorizing agent.
Optionally, in one embodiment, the method for obtaining the mixed solution of carbon particles, metal compound, alkaline compound and water is as follows:
mixing carbon particles, a metal compound, an alkaline compound, and water to prepare a mixed solution.
In this embodiment, the mixing method may be a mixing method conventional in the industry.
In one embodiment, the metal compound is a metal salt, which may be a sulfate, chloride, or nitrate of a metal.
It will be appreciated that the type and quality of the metal compound may be adjusted according to the quality of the desired metal cation type in the dephosphorizing agent, and the mixture may be finally prepared.
In some embodiments, a phosphorus scavenger containing 2.6-13% magnesium ion, 0.8-4% aluminum ion, 2.3-18% calcium ion, 0.8-20% iron ion, 0.05-0.3% copper ion, 0.02-0.1% zinc ion, 4-21% sodium ion, and 1.5-17.5% carbon particles (the above proportions being based on the total mass of the phosphorus scavenger), may be added with a mixture containing 1-10% magnesium ion, 0.3-15% aluminum ion, 0.1-18% calcium ion, 0.2-17.5% iron ion, 0.001-0.3% copper ion, 0.002-0.1% zinc ion, 0.05-23% sodium ion, 0.1-13% carbon particles (the above proportions being based on the mass of the mixture). The solubility products of different metals at different pH values are different, the pH value in the preparation process is changed, the metal content of the dephosphorizing agent is correspondingly changed, and compared with the addition amount of original metal ions, the content of metal ions in the dephosphorizing agent is increased, and the content of metal ions is reduced.
Optionally, in one embodiment, the method for obtaining the mixed solution of carbon particles, metal compound, alkaline compound and water is as follows:
Obtaining industrial wastewater, wherein the industrial wastewater contains carbon particles, metal compounds and water;
And mixing the industrial wastewater with an alkaline compound to prepare a mixed solution.
The industrial wastewater is used as the raw material, the common components such as iron, aluminum, magnesium, calcium, copper, zinc, sodium, carbon particles and the like in the industrial wastewater are fully utilized, no additional auxiliary agent is needed, and the maximum utilization of the resources such as iron, aluminum, magnesium, calcium, copper, zinc, sodium, carbon particles and the like is realized while the industrial wastewater is treated.
In one embodiment, the industrial wastewater is industrial wastewater in daily production of lithium ion battery recycling related enterprises, and the industrial wastewater contains a large amount of hydroxides of metals with low added values, such as iron, aluminum, calcium and the like.
It is understood that the industrial wastewater contains 0.01% or less of phosphorus.
In some embodiments, a phosphorus scavenger containing 2.6-13% magnesium ion, 0.8-4% aluminum ion, 2.3-18% calcium ion, 0.8-20% iron ion, 0.05-0.3% copper ion, 0.02-0.1% zinc ion, 4-21% sodium ion, 1.5-17.5% carbon particles (above proportions are based on the total mass of the phosphorus scavenger), and an industrial wastewater containing 1-10% magnesium ion, 0.3-15% aluminum ion, 0.1-18% calcium ion, 0.2-17.5% iron ion, 0.001-0.3% copper ion, 0.002-0.1% zinc ion, 0.05-23% sodium ion, 0.1-13% carbon particles (above proportions are based on the mass of the industrial wastewater) may be added. The solubility products of different metals at different pH values are different, the pH value of the preparation process is changed, the metal content of the dephosphorizing agent is correspondingly changed, and compared with the metal ion content in the original industrial wastewater, the content of some metal ions in the dephosphorizing agent is increased, and the content of some metal ions is reduced.
It can be understood that after the industrial wastewater containing carbon particles, metal compounds and water is obtained, the carbon particles, the metal compounds and the alkaline compounds are further added to prepare a mixed solution, and the content of the carbon particles and the metal cations in the dephosphorizing agent can be regulated.
In one embodiment, the stirring is for a period of 1h to 3h.
The invention also provides a dephosphorizing agent prepared by the preparation method, which has high-efficiency dephosphorizing effect. After the phosphorus-containing sewage is treated, the standard requirement of the element phosphorus specified in the integrated wastewater discharge Standard of the people's republic of China (GB 8978-1996) can be met, and even the first-level standard can be met.
The invention also provides a treatment method of the phosphorus-containing sewage.
The technical proposal is as follows:
A method for treating phosphorus-containing sewage comprises the following steps:
mixing the dephosphorizing agent and the phosphorus-containing sewage to prepare slurry;
mixing the slurry with an acidic solution, and adjusting the pH value to 0.5-4.5 to prepare an acidic feed liquid;
mixing the acidic feed liquid and the alkaline solution, adjusting the pH value to 7.0-12.5, filtering, and discharging filtrate;
The mass of the alkaline compound in the alkaline solution accounts for 20% -55% of the total mass of the alkaline solution.
The applicant found through research that when the content of the alkaline compound in the alkaline solution is lower than 20%, the phosphorus removal effect is affected, and when the content of the alkaline compound in the alkaline solution is higher than 55%, the alkaline compound competes with metal sites in heteropolyacid generated by the phosphorus removal agent in the phosphorus removal process, occupies metal ion sites, and weakens the removal of phosphorus-containing substances by the phosphorus removal agent.
In one embodiment, the mass of the dephosphorizing agent is 1-715 times the mass of phosphorus in the phosphorus-containing sewage.
It will be appreciated that the purpose of filtration is to separate the filter residue from the filtrate after a sufficient reaction.
Preferably, the acidic solution is selected from an aqueous sulfuric acid solution and/or an aqueous hydrochloric acid solution.
In one embodiment, the aqueous sulfuric acid solution has a mass concentration greater than 10%. Preferably, the mass concentration of the sulfuric acid aqueous solution is 10% -98%.
In one embodiment, the aqueous hydrochloric acid solution has a mass concentration greater than 10%.
Preferably, the alkaline solution is selected from one or more of aqueous sodium hydroxide solution, aqueous calcium hydroxide solution and aqueous potassium hydroxide solution.
In one embodiment, the alkaline substance in the alkaline solution has a mass concentration of 20-55%.
The following examples are further offered by way of illustration, and the materials used in the following examples are commercially available unless otherwise indicated, and the apparatus used is commercially available unless otherwise indicated, and the processes involved, unless otherwise indicated, are routine selections by those skilled in the art.
Example 1
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing amorphous graphite particles, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare a pH=7 mixed solution, stirring the mixed solution for 1.5 hours, filtering, and collecting filter residues to prepare the dephosphorizing agent containing 2.6% of magnesium ions, 0.8% of aluminum ions, 2.3% of calcium ions, 0.8% of iron ions, 0.05% of copper ions, 0.02% of zinc ions, 4% of sodium ions and 1.5% of graphite particles by weight percent based on the total mass of the dephosphorizing agent.
2) Adding 0.1kg of the dephosphorizing agent prepared in the above steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 98% sulfuric acid solution to adjust pH to 0.5, uniformly mixing to obtain acidic feed liquid, adding 55% sodium hydroxide solution to adjust pH to 7.0, fully reacting, separating filter residues from filtrate, and discharging filtrate.
Example 2
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing amorphous graphite particles, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare a pH=7 mixed solution, stirring the mixed solution for 1.5 hours, filtering, and collecting filter residues to prepare a dephosphorizing agent containing 13% of magnesium ions, 4% of aluminum ions, 18% of calcium ions, 20% of iron ions, 0.3% of copper ions, 0.1% of zinc ions, 21% of sodium ions and 17.5% of graphite particles by weight percent of the total mass of the dephosphorizing agent.
2) Adding 0.1kg of the dephosphorizing agent prepared in the above steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 98% sulfuric acid solution to adjust pH to 0.5, uniformly mixing to obtain acidic feed liquid, adding 55% sodium hydroxide solution to adjust pH to 7.0, fully reacting, separating filter residues from filtrate, and discharging filtrate.
Example 3
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing amorphous graphite particles, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare a pH=7 mixed solution, stirring the mixed solution for 1.5 hours, filtering, and collecting filter residues to prepare the dephosphorizing agent containing 2.6% of magnesium ions, 0.8% of aluminum ions, 2.3% of calcium ions, 0.8% of iron ions, 0.05% of copper ions, 0.02% of zinc ions, 4% of sodium ions and 1.5% of graphite particles by weight percent based on the total mass of the dephosphorizing agent.
2) Adding 0.1kg of the dephosphorizing agent prepared in the above steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 98% sulfuric acid solution to adjust pH to 1.5, uniformly mixing to obtain acidic feed liquid, adding 55% sodium hydroxide solution to adjust pH to 8.0, fully reacting, separating filter residues from filtrate, and discharging filtrate.
Example 4
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing amorphous graphite particles, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare a pH=7 mixed solution, stirring the mixed solution for 1.5 hours, filtering, and collecting filter residues to prepare the dephosphorizing agent containing 2.6% of magnesium ions, 0.8% of aluminum ions, 2.3% of calcium ions, 0.8% of iron ions, 0.05% of copper ions, 0.02% of zinc ions, 4% of sodium ions and 1.5% of graphite particles by weight percent based on the total mass of the dephosphorizing agent.
2) 71.5Kg of the dephosphorizing agent prepared in the above steps is added into 200L of phosphorus-containing sewage with phosphorus content of 100g, 98% sulfuric acid solution is added to adjust pH to 3.0 after slurry preparation, and the mixture is uniformly mixed to obtain acid feed liquid, 55% sodium hydroxide solution is added into the acid feed liquid to adjust pH to 10.0, filter residues and filtrate are separated after full reaction, and filtrate is discharged.
Example 5
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing amorphous graphite particles, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare a pH=7 mixed solution, stirring the mixed solution for 1.5 hours, filtering, and collecting filter residues to prepare the dephosphorizing agent containing 2.6% of magnesium ions, 0.8% of aluminum ions, 2.3% of calcium ions, 0.8% of iron ions, 0.05% of copper ions, 0.02% of zinc ions, 4% of sodium ions and 1.5% of graphite particles by weight percent based on the total mass of the dephosphorizing agent.
2) Adding 35kg of the dephosphorizing agent prepared in the steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 37% hydrochloric acid solution to adjust pH to 4.5, uniformly mixing to obtain acidic feed liquid, adding 55% sodium hydroxide solution to adjust pH to 12.5, fully reacting, separating filter residues from filtrate, and discharging the filtrate.
Example 6
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing amorphous graphite particles, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare a pH=7 mixed solution, stirring the mixed solution for 1.5 hours, filtering, and collecting filter residues to prepare a dephosphorizing agent containing 13% of magnesium ions, 4% of aluminum ions, 18% of calcium ions, 20% of iron ions, 0.3% of copper ions, 0.1% of zinc ions, 21% of sodium ions and 17.5% of graphite particles by weight percent of the total mass of the dephosphorizing agent.
2) Adding 35kg of the dephosphorizing agent prepared in the steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 37% hydrochloric acid solution to adjust pH to 4.5, uniformly mixing to obtain acidic feed liquid, adding 20% potassium hydroxide solution to the acidic feed liquid to adjust pH to 7.0, fully reacting, separating filter residues from filtrate, and discharging the filtrate.
Example 7
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing amorphous graphite particles, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare a pH=7 mixed solution, stirring the mixed solution for 1.5 hours, filtering, and collecting filter residues to prepare the dephosphorizing agent containing 8.0% of magnesium ions, 2.3% of aluminum ions, 10.0% of calcium ions, 11.0% of iron ions, 0.16% of copper ions, 0.06% of zinc ions, 9.0% of sodium ions and 10.5% of graphite particles by weight percent of the total mass of the dephosphorizing agent.
2) Adding 35kg of the dephosphorizing agent prepared in the steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 37% hydrochloric acid solution to adjust pH to 4.5, uniformly mixing to obtain acidic feed liquid, adding 20% calcium hydroxide solution to the acidic feed liquid to adjust pH to 7.0, fully reacting, separating filter residues from filtrate, and discharging the filtrate.
Example 8
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing amorphous graphite particles, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare a pH=11 mixed solution, stirring the mixed solution for 1.5 hours, filtering, and collecting filter residues to prepare the dephosphorizing agent containing 8.0% of magnesium ions, 2.3% of aluminum ions, 10.0% of calcium ions, 11.0% of iron ions, 0.16% of copper ions, 0.06% of zinc ions, 9.0% of sodium ions and 10.5% of graphite particles by weight percent of the total mass of the dephosphorizing agent.
2) Adding 35kg of the dephosphorizing agent prepared in the steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 98% sulfuric acid solution to adjust pH to 0.5, uniformly mixing to obtain acidic feed liquid, adding 55% sodium hydroxide solution to adjust pH to 12.5, fully reacting, separating filter residues from filtrate, and discharging the filtrate.
Example 9
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Taking industrial wastewater 2000L containing 5.2% of magnesium ions, 2.0% of aluminum ions, 6.8% of calcium ions, 7.3% of iron ions, 0.02% of copper ions, 0.03% of zinc ions, 8.3% of sodium ions, 12.6% of amorphous activated carbon particles and less than 0.005% of phosphorus content, adding calcium hydroxide, preparing a mixed solution with pH of 10, stirring the mixed solution for 0.5 hour, filtering by using a plate-and-frame filter, and collecting filter residues to obtain a dephosphorizing agent containing 11.3% of magnesium ions, 3.2% of aluminum ions, 16.5% of calcium ions, 17.0% of iron ions, 0.05% of copper ions, 0.05% of zinc ions, 5.2% of sodium ions and 17.3% of activated carbon particles.
2) Adding 10kg of the dephosphorizing agent prepared in the steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 98% sulfuric acid solution to adjust pH to 0.5, stirring for 0.5h, uniformly mixing to obtain acidic feed liquid, adding 55% sodium hydroxide solution to adjust pH to 12.5, stirring for full reaction for 1h, separating filter residues and filtrate by using a plate-frame filter, and discharging the filtrate.
Example 10
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Taking industrial wastewater 2000L containing 2.2% of magnesium ions, 0.37% of aluminum ions, 2.1% of calcium ions, 0.87% of iron ions, 0.1% of copper ions, 0.02% of zinc ions, 22.3% of sodium ions, 1.35% of amorphous graphite particles and less than 0.01% of phosphorus content, adding calcium hydroxide, preparing a mixed solution with pH of 7, stirring the mixed solution for 0.5 hour, filtering by using a plate-and-frame filter, and collecting filter residues to obtain a dephosphorizing agent containing 3.8% of magnesium ions, 0.9% of aluminum ions, 2.5% of calcium ions, 1.1% of iron ions, 0.26% of copper ions, 0.1% of zinc ions, 20.4% of sodium ions and 2.0% of graphite particles.
2) Adding 10kg of the dephosphorizing agent prepared in the steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 37% hydrochloric acid to adjust the pH of the slurry to 4.5, stirring for 0.5h, uniformly mixing to obtain acidic feed liquid, adding 20% potassium hydroxide solution into the acidic feed liquid to adjust the pH to 7.0, stirring for fully reacting for 1h, separating filter residues and filtrate in a plate-frame filter, and discharging the filtrate.
Example 11
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Taking industrial wastewater 2000L containing 7.85% of magnesium ions, 2.2% of aluminum ions, 9.5% of calcium ions, 8.95% of iron ions, 0.2% of copper ions, 0.025% of zinc ions, 7.3% of sodium ions, 9.55% of amorphous activated carbon particles and less than 0.01% of phosphorus content, adding potassium hydroxide, preparing a mixed solution with pH of 9.0, stirring the mixed solution for 0.5 hours, filtering by using a plate-frame filter, and collecting filter residues to obtain a dephosphorizing agent containing 8.6% of magnesium ions, 2.5% of aluminum ions, 10.1% of calcium ions, 11.1% of iron ions, 0.13% of copper ions, 0.03% of zinc ions, 9.0% of sodium ions and 12.4% of activated carbon particles.
2) Adding 10kg of the dephosphorizing agent prepared in the steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 50% sulfuric acid solution to adjust pH to 0.5, stirring for 0.5h, uniformly mixing to obtain acidic feed liquid, adding 30% calcium hydroxide solution to the acidic feed liquid to adjust pH to 9.0, stirring for full reaction for 1h, separating filter residues and filtrate in a plate-frame filter, and discharging the filtrate.
Example 12
The embodiment provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Taking industrial wastewater 2000L containing 5.8% of magnesium ions, 2.2% of aluminum ions, 8.22% of calcium ions, 13.2% of iron ions, 0.05% of copper ions, 0.03% of zinc ions, 14.2% of sodium ions, 6.52% of amorphous graphite particles and phosphorus content of less than 0.01%, adding sodium hydroxide into the industrial wastewater 2000L to prepare a mixed solution with pH of 11.0, stirring the mixed solution for 0.5 hours, filtering the mixed solution by using a plate-frame filter, and collecting filter residues to obtain a dephosphorizing agent containing 6.6% of magnesium ions, 3.7% of aluminum ions, 13.9% of calcium ions, 15.1% of iron ions, 0.20% of copper ions, 0.08% of zinc ions, 16.8% of sodium ions and 7.6% of graphite particles.
2) Adding 10kg of the dephosphorizing agent prepared in the steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 10% hydrochloric acid solution to adjust pH to 3.5, stirring for 0.5h, uniformly mixing to obtain acidic feed liquid, adding 40% potassium hydroxide solution to the acidic feed liquid to adjust pH to 10.0, stirring for full reaction for 1h, separating filter residues and filtrate in a plate-frame filter, and discharging the filtrate.
The phosphorus removal rate of each example was tested. The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the phosphorus removal rates of examples 1-8 are high, and the first-class standard requirements of elemental phosphorus specified in the Integrated wastewater discharge Standard of the people's republic of China (GB 8978-1996) can be met. The dephosphorizing agents prepared by using industrial sewage with different metal ion concentrations in the examples 9-12 have good dephosphorizing effect and can meet the requirements of the secondary/tertiary standard of the element phosphorus specified in the integrated wastewater discharge Standard of the people's republic of China (GB 8978-1996).
In the above embodiment, the carbon particles mainly act as a support of the spherical structure, similar to the template agent, and can promote the dephosphorization agent to form a porous spherical structure in the form of a carrier, if the proportion of the carbon particles in the dephosphorization agent is low, the spherical structure cannot be formed, so that the dephosphorization effect is reduced, and if the proportion is high, the adsorption of the metal compound component to the phosphorus-containing substance is affected, so that the dephosphorization effect is poor.
Comparative example 1
The comparative example provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing bentonite, magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water, preparing a pH=7 mixed solution, stirring the mixed solution for 1.5 hours, filtering, collecting filter residues, and preparing the dephosphorizing agent containing 13% of magnesium ions, 4% of aluminum ions, 18% of calcium ions, 20% of iron ions, 0.3% of copper ions, 0.1% of zinc ions, 21% of sodium ions and 17.5% of bentonite by weight percent of the total mass of the dephosphorizing agent.
2) Adding 0.1kg of the dephosphorizing agent prepared in the above steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 98% sulfuric acid solution to adjust pH to 0.5, uniformly mixing to obtain acidic feed liquid, adding 55% sodium hydroxide solution to adjust pH to 7.0, fully reacting, separating filter residues from filtrate, and discharging filtrate.
Comparative example 2
The comparative example provides a treatment method of phosphorus-containing sewage, which comprises the following steps:
1) Mixing magnesium sulfate, aluminum sulfate, calcium chloride, ferric chloride, copper nitrate, zinc sulfate, sodium chloride, potassium hydroxide and water to prepare the dephosphorizing agent containing 13% magnesium ions, 4% aluminum ions, 18% calcium ions, 20% iron ions, 0.3% copper ions, 0.1% zinc ions and 21% sodium ions by weight percent of the total mass of the dephosphorizing agent.
2) Adding 0.1kg of the dephosphorizing agent prepared in the above steps into 200L of phosphorus-containing sewage with phosphorus content of 100g, preparing slurry, adding 98% sulfuric acid solution to adjust pH to 0.5, uniformly mixing to obtain acidic feed liquid, adding 55% sodium hydroxide solution to adjust pH to 7.0, fully reacting, separating filter residues from filtrate, and discharging filtrate.
The phosphorus removal rate of each comparative example was tested. The results are shown in Table 2.
TABLE 2
Therefore, the dephosphorizing agent has high dephosphorizing rate and good dephosphorizing effect, and is obviously better than the dephosphorizing effect of the existing metal dephosphorizing agent.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the dephosphorizing agent is characterized by comprising the following steps:
Obtaining industrial wastewater produced by recycling lithium ion batteries, wherein the industrial wastewater contains carbon particles, metal compounds and water;
Mixing the industrial wastewater with an alkaline compound to prepare a mixed solution, stirring the mixed solution, filtering, and collecting filter residues to prepare a dephosphorization agent;
The metal cations in the dephosphorizing agent are at least three of magnesium ions, aluminum ions, calcium ions, iron ions, copper ions, zinc ions and sodium ions;
the carbon particles are selected from graphite or activated carbon.
2. The method for producing a phosphorus removal agent according to claim 1, wherein the mass of carbon particles in the phosphorus removal agent is 1.5 to 17.5% of the total mass of the phosphorus removal agent.
3. The method for preparing a dephosphorizing agent according to claim 1, wherein the metal cations in the dephosphorizing agent comprise magnesium ions, aluminum ions, calcium ions, iron ions, copper ions, zinc ions and sodium ions.
4. The method for preparing a dephosphorizing agent according to claim 3, wherein the mass of the magnesium ions is 2.6-13% of the total mass of the dephosphorizing agent;
the mass of the aluminum ions accounts for 0.8-4% of the total mass of the dephosphorizing agent;
the mass of the calcium ions accounts for 2.3-18% of the total mass of the dephosphorizing agent;
The mass of the iron ions accounts for 0.8-20% of the total mass of the dephosphorizing agent;
the mass of the copper ions accounts for 0.05-0.3% of the total mass of the dephosphorizing agent;
the mass of the zinc ions accounts for 0.02-0.1% of the total mass of the dephosphorizing agent;
The mass of the sodium ions accounts for 4-21% of the total mass of the dephosphorizing agent.
5. The method for producing a phosphorus removal agent according to any one of claims 1 to 4, wherein the pH of the mixed solution is 7.0 to 11.0.
6. The method for producing a phosphorus scavenger according to claim 5, wherein the anion in the phosphorus scavenger is hydroxide ion and/or carbonate ion.
7. The method for producing a phosphorus scavenger according to claim 5, wherein the alkaline compound is one or more selected from the group consisting of sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium oxide, sodium carbonate, calcium carbonate and potassium carbonate.
8. A dephosphorizing agent prepared by the preparation method of any one of claims 1 to 7.
9. The method for treating the phosphorus-containing sewage is characterized by comprising the following steps of:
Mixing the phosphorous removal agent of claim 8 with a phosphorous contaminated water to produce a slurry;
mixing the slurry with an acidic solution, and adjusting the pH value to 0.5-4.5 to prepare an acidic feed liquid;
mixing the acidic feed liquid and the alkaline solution, adjusting the pH value to 7.0-12.5, filtering, and discharging filtrate;
The mass of the alkaline compound in the alkaline solution accounts for 20% -55% of the total mass of the alkaline solution.
10. The method for treating phosphorus-containing wastewater according to claim 9, wherein the mass of the phosphorus removing agent is 1 to 715 times the mass of phosphorus in the phosphorus-containing wastewater.
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