CN114505045A - Method for purifying fluorine in acidic wastewater - Google Patents
Method for purifying fluorine in acidic wastewater Download PDFInfo
- Publication number
- CN114505045A CN114505045A CN202011286167.0A CN202011286167A CN114505045A CN 114505045 A CN114505045 A CN 114505045A CN 202011286167 A CN202011286167 A CN 202011286167A CN 114505045 A CN114505045 A CN 114505045A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- composite adsorbent
- wastewater
- calcium
- container
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011737 fluorine Substances 0.000 title claims abstract description 89
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000002351 wastewater Substances 0.000 title claims abstract description 50
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 37
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003463 adsorbent Substances 0.000 claims abstract description 58
- 239000002131 composite material Substances 0.000 claims abstract description 57
- -1 fluorine ions Chemical class 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 239000008394 flocculating agent Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000010842 industrial wastewater Substances 0.000 claims description 30
- 229920001661 Chitosan Polymers 0.000 claims description 18
- 239000010457 zeolite Substances 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000000920 calcium hydroxide Substances 0.000 claims description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000013043 chemical agent Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000005750 Copper hydroxide Substances 0.000 claims description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 3
- 159000000011 group IA salts Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 19
- 230000000694 effects Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 206010016818 Fluorosis Diseases 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 208000004042 dental fluorosis Diseases 0.000 description 2
- 238000009297 electrocoagulation Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 208000008558 Osteophyte Diseases 0.000 description 1
- 208000006735 Periostitis Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 201000010934 exostosis Diseases 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000004798 organs belonging to the digestive system Anatomy 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 210000003460 periosteum Anatomy 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J20/04—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
- B01J20/048—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 containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- 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
- B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/52—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
- C02F1/52—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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for purifying fluorine in acidic wastewater, which comprises the steps of adding a chemical reagent into the acidic wastewater containing the fluorine, adjusting the pH value of the solution, stirring, filtering, and further treating the filtered solution by using a composite adsorbent and a flocculating agent to achieve the purpose of removing fluorine ions in the acidic wastewater. The raw materials of the composite adsorbent used by the invention are wide in source and low in price; the prepared composite adsorbent can well meet the separation requirement, and has the advantages of long service life and quick adsorption.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a method for removing fluorine ions in acidic industrial wastewater by using a combined method.
Background
Fluorine is one of elements widely distributed in nature, is one of trace elements essential for organisms, and is closely related to life activities of human bodies and metabolism of tooth tissues and bone tissues. Fluorine is an indispensable component of teeth and bones, but excessive ingestion causes symptoms such as fluoroossoma and fluorosis teeth.
The discharge of large amounts of industrial waste water with high fluorine content is one of the main factors, except for the fact that individual areas are due to natural factors. Industrial waste water containing fluoride is produced in the production processes of industries such as hydrometallurgy, thermal power generation, petrochemical industry, cement, ceramics and the like, even the processes of manufacturing micro-electrolysis filler fluorine-containing products, coke production, electronic component production, electroplating, glass and silicate production, steel and aluminum manufacturing, metal processing, wood corrosion prevention, pesticide and fertilizer production and the like are included, if fluorine in the acid waste water is not treated, the acid waste water is directly discharged into the environment, and serious hazards are possibly caused to the environment quality and human health.
Research shows that fluorine and fluoride can inhibit the catalytic function of human enzymes, reduce serum calcium and inhibit blood coagulation mechanism. If absorbed by the digestive organs, it can cause poisoning and even death. When the mass concentration of the fluorine ions in the water is higher than 4.0mg/L, periosteum hyperplasia and bone spur are easily caused, fluorosis is formed, and damage to the liver and cardiovascular systems can be caused to different degrees.
At present, fluorine-containing industrial wastewater treatment is a hot problem concerned by many enterprises. With the increase of industrial production, the discharge of industrial waste water containing fluorine at high concentration is increasing and is forbidden frequently. The fluorine-containing industrial wastewater has complex and various components, and various treatment methods are provided, and the common methods mainly comprise a chemical precipitation method, an adsorption method, a reverse osmosis method, an ion exchange resin method, an electrocoagulation method, an electrodialysis method and the like.
Specifically, the chemical precipitation method is to add calcium salt and the like into the wastewater to form insoluble calcium fluoride precipitate so as to achieve the aim of removing the concentration of fluoride ions in the water. The adsorption method is to add active bauxite into the waste water, and the method has small treatment capacity and is commonly used for treating drinking water. The reverse osmosis method utilizes a membrane separation technology that fluoride cannot pass through a semi-permeable membrane, has high fluorine removal efficiency, can realize the riddle of wastewater fluorine removal at normal temperature and normal pressure, but hinders wide application due to the expensive price of the membrane. The ion exchange resin method has high accuracy, but the regeneration process is complicated. Difficult defects are managed. The electrocoagulation method utilizes two major coagulants of iron salt and aluminum salt to form a complex or floccule in water, and has simple operation but the defect of electrode passivation. The electrodialysis method applies direct current at two ends of a semi-permeable membrane to enable positive and negative ions to flow to an anode and a cathode respectively through an ion exchange membrane, although the defluorination efficiency is high, the wastewater needs to be pretreated, and the equipment investment is large.
Therefore, optimizing modern traditional processes to improve the efficiency of removing fluorine from acidic wastewater remains a problem worthy of research.
In view of the above, it is highly desirable to develop a method for effectively removing fluorine from acidic wastewater.
Disclosure of Invention
In order to overcome the problems, the inventor of the invention makes a keen study and researches a method for purifying fluorine in acidic wastewater, wherein a chemical reagent is added into the fluorine-containing acidic wastewater, the pH value of the solution is adjusted, the solution is stirred and filtered, and then the filtered solution is further treated by using a composite adsorbent and a flocculating agent, so that the aim of removing fluorine ions in the acidic wastewater is fulfilled. The raw materials of the composite adsorbent used by the invention are wide in source and low in price; the prepared composite adsorbent can well meet the separation requirement, has the advantages of long service life and quick adsorption, and thus the invention is completed.
Specifically, the present invention aims to provide the following:
in a first aspect, the composite adsorbent is prepared by fully mixing raw materials and grinding.
The raw material comprises one or more of calcium hydroxy phosphate, aluminum hydroxy oxide and natural zeolite; preferably, the starting materials are calcium hydroxy phosphate, aluminium hydroxy oxide and natural zeolites.
The mass ratio of the calcium hydroxy phosphate to the aluminum hydroxy oxide to the natural zeolite in the composite adsorbent is 50-60: 20-30: 15 to 25.
In a second aspect, there is provided a method for purifying fluorine in acidic wastewater, preferably, the composite adsorbent of the first aspect is used, the method comprising the following steps:
step 1, pretreating fluorine-containing industrial wastewater to obtain clear liquid;
step 2, transferring the clear liquid obtained in the step 1 into another container, and adding a composite adsorbent into the container;
and 3, adding a flocculating agent into the container in the step 2, settling and filtering.
In step 1, the pretreatment includes the steps of:
step I, introducing the fluorine-containing industrial wastewater into a container, and adding a chemical reagent.
And step II, stirring, standing and filtering.
In step i, the chemical reagent is an alkaline chemical reagent, including alkali, alkaline oxide, alkaline salt, and the like, preferably, the chemical reagent is alkali, including one or more of sodium hydroxide, calcium hydroxide, copper hydroxide, and ferrous hydroxide, and more preferably, calcium hydroxide.
The vessel is preferably a vessel with a stirring device, more preferably a stirred tank.
In step I, a chemical agent is added to adjust the pH to 5.6-8.0, preferably 6.0-7.5.
In step 3, the flocculating agent is preferably one or more selected from polyacrylamide, polyaluminium chloride, polyaluminium ferric silicate, ferric trichloride and chitosan; preferably, the flocculant is chitosan, more preferably, the flocculant is chitosan with a molecular weight of 60-80 ten thousand.
In a third aspect, there is provided the use of the composite adsorbent of the first aspect or the method of the second aspect for the treatment of industrial waste water, preferably for the treatment of fluorine-containing acidic industrial waste water.
The invention has the advantages that:
(1) the method takes the fluorine-containing acidic wastewater as a raw material, and removes the fluorine ions in the acidic wastewater by adjusting the pH and adding the composite adsorbent and the flocculant, has low cost, simple operation and easy realization, can better achieve the purpose of removing the fluorine ions in the wastewater, and has the fluorine removal rate of more than 90 percent.
(2) The composite adsorbent used in the invention has the adsorption effect greater than that of adsorbing raw material monomers, the synergistic effect of the mixed use of the raw materials further improves the fluorine removal rate and the adsorption rate of the acidic wastewater, and meanwhile, the composite adsorbent has the advantages of longer service life and realization of quick adsorption.
(3) The method for removing fluorine from acid wastewater provided by the invention is suitable for industrial wastewater with the fluorine ion mass concentration of 20-500mg/L in a wide range, and has a wide application range.
Detailed Description
The present invention will be described in further detail below with reference to examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In a first aspect of the invention, a composite adsorbent is provided, which is obtained by fully mixing and grinding raw materials.
Wherein the raw material comprises one or more of calcium hydroxy phosphate, aluminum hydroxy oxide and natural zeolite.
In a further preferred embodiment, the starting materials are calcium hydroxy phosphate, aluminium hydroxy oxide and natural zeolites.
In the present invention, the hydroxyl group of the calcium hydroxyphosphate is not ionized as a whole, but is more easily substituted by losing a hydrogen atom, and hydrogen in the hydroxyl group is substituted by fluorine, and simultaneously, a polymerization reaction occurs to produce the polymeric calcium hydroxyphosphate.
In the present invention, the aluminum oxyhydroxide refers to a generic term for hydroxides, oxyhydroxides, and dehydration products of each stage thereof of aluminum. The aluminum oxyhydroxide has larger specific surface area, various pore structures and pore size distribution, is an ideal adsorbent, and has a great effect on eliminating the color and the smell of industrial wastewater.
In the present invention, the natural zeolite has a unique structure, and the internal surface area of the zeolite is large, and thus the adsorption amount of ions is large.
Natural zeolites are hydrous aluminosilicates of alkali and alkaline earth metals with alumina as the major component, where alumina is the ion exchanger in acidic solution with great selectivity for fluoride ions. In addition, the natural zeolite also contains mineral elements such as sodium, potassium, calcium, magnesium, vanadium, iron, copper, manganese, zinc and the like, and the toxic elements such as lead and arsenic contained in the natural zeolite are in a safe range. The natural zeolite features higher molecular porosity, better adsorptivity, ion exchange and catalytic performance.
In the invention, calcium hydroxy phosphate, aluminum hydroxy oxide and natural zeolite are preferably mixed to prepare the composite adsorbent, and the composite adsorbent can perform substitution reaction and polymerization reaction with fluorine ions in the acidic wastewater, and has the functions of ion exchange, adsorption and catalysis, so that the composite adsorbent has a very good effect on removing the fluorine ions in the acidic wastewater under the synergistic effect of the composite adsorbent. In the prior art, the raw materials with adsorption or reaction are prepared into the composite adsorbent which is applied to the aspect of removing fluorine from acidic wastewater, and reports are not found yet.
In the invention, the mass ratio of the composite adsorbent, namely the calcium hydroxy phosphate, the hydroxy alumina and the natural zeolite is 50-60: 20-30: 15 to 25
In the invention, the inventor researches and discovers that the content is 50-60: 20-30: and when the time is 15-25 hours, the fluorine removal effect on the acidic wastewater is the best.
In the invention, the raw materials of the composite adsorbent are wide in source and low in price. Besides, the prepared composite adsorbent has the advantages of high selectivity, high adsorption capacity, high chemical stability, high chemical inertness, high pollution resistance and high mechanical strength, can meet the separation requirement in the use process, has long service life, avoids undesirable chemical reaction and realizes quick adsorption.
In the present invention, it is preferable to conduct the milling using a small-sized disk crusher. The small disc crusher has the advantages of high strength, direct and effective operation effect, movable crushing, more uniform crushing on the particle size of the composite adsorbent and capability of meeting the test requirement.
In a second aspect of the present invention, there is provided a method for purifying fluorine in acidic wastewater, preferably using the composite adsorbent of the first aspect, the method comprising the steps of:
step 1, pretreating fluorine-containing industrial wastewater to obtain clear liquid.
Wherein the pretreatment comprises the following steps:
step I, introducing the fluorine-containing industrial wastewater into a container, and adding a chemical reagent.
In the invention, the fluorine ion concentration in the fluorine-containing industrial wastewater is 20-500mg/L, and the pH value of the fluorine-containing industrial wastewater is 1.0-5.0.
In step I, the vessel is not limited to any vessel in which the reaction can be carried out, and preferably, the vessel is a vessel with a stirring device, more preferably, a stirring tank.
In the invention, the container is opened, and a chemical reagent is added into the container to adjust the pH value of the acidic wastewater, wherein the chemical reagent is an alkaline chemical reagent and comprises alkali, alkaline oxide, alkaline salt and the like, preferably, the chemical reagent is alkali and comprises one or more of sodium hydroxide, calcium hydroxide, copper hydroxide and ferrous hydroxide, and more preferably, the calcium hydroxide is used.
In the invention, calcium hydroxide is preferably used as a chemical reagent, and not only plays a role in adjusting pH, but also plays a role in helping coagulation of colloidal particles in wastewater, so that the sedimentation of insoluble substances is accelerated; besides, the calcium hydroxide has lower market price and is the preferred alkaline neutralizer.
In the present invention, the pH is adjusted to 5.6 to 8.0, preferably 6.0 to 7.5.
In the present invention, the inventor has found that the acid wastewater pH increases and the fluoride ion concentration decreases as the calcium hydroxide dosage increases, and when the pH reaches about 7.5, the fluoride ion concentration is the lowest and the fluoride removal effect is the best, and as the calcium hydroxide dosage continues to increase, the pH increases and the fluoride ion concentration begins to increase, and presumably the reason for this is that the calcium ion concentration decreases and the fluoride removal effect deteriorates because a large amount of hydroxide ions and calcium ions in the wastewater form calcium hydroxide which is slightly soluble in water.
And step II, stirring, standing and filtering.
In the present invention, the stirring is mechanical stirring. The stirring time is 0.5-3 hours.
In the present invention, the fluorine ion concentration is decreased as the stirring time is prolonged, and the fluorine ion concentration is conversely increased when the stirring time is too long, and the reason for this is presumably that the insoluble calcium fluoride precipitated at the bottom of the vessel is broken up during the stirring, and the fluorine ions are re-dissolved in the solution, thereby increasing the fluorine ion concentration.
In the present invention, the standing time is 4 hours, preferably 8 hours, and more preferably 15 hours. When the standing time reaches 24h, the precipitation is complete.
After standing, solid-liquid separation was carried out.
And 2, transferring the clear liquid obtained in the step 1 into another container, and adding a composite adsorbent into the container.
Introducing the filtered clear liquid in the step 1 into another container. The container is not limited to any container capable of carrying out a reaction, and preferably, the container is a container with a stirring device, and more preferably, a stirring tank.
The composite adsorbent is preferably the composite adsorbent according to the first aspect.
In step 2, the composite adsorbent is ground by disc crushing, and the particle size is not less than 60 meshes, preferably not less than 80 meshes, and more preferably not less than 100 meshes.
In the invention, when the particle size of the composite adsorbent is not less than 100 meshes, the fluorine removal effect is best. This is because the larger the mesh number of the composite adsorbent is, the smaller the particle size thereof is, the larger the diffusion coefficient is, the larger the adsorption rate is, and the better the adsorption effect is.
Wherein, in the step 2, the mass concentration of the added composite adsorbent is 0.05-5.0 g/L.
In the invention, the concentration of the fluorine ions in the clear liquid is reduced along with the increase of the mass of the composite adsorbent, and when the mass concentration of the composite adsorbent is 0.05-5.0 g/L, the concentration of the fluorine ions is the lowest, so that the aim of removing fluorine can be achieved, and unnecessary waste caused by excessive addition of the composite adsorbent can be avoided.
In the step 2, the composite adsorbent is added into another container for stirring, wherein the stirring is mechanical stirring, and the stirring time is 4-16 hours.
In the invention, when the stirring time reaches 4-16 hours, the fluorine ion concentration is lowest, and the fluorine removal effect is best.
And 3, adding a flocculating agent into the container in the step 2, and filtering.
In step 3, agitation is stopped and the flocculant is added to the vessel of step 2. Wherein, the flocculating agent is preferably selected from one or more of polyacrylamide, polyaluminium chloride, polyaluminum ferric silicate, ferric trichloride and chitosan; preferably, the flocculant is chitosan, more preferably, the flocculant is chitosan with a molecular weight of 60-80 ten thousand.
In the invention, the flocculant can effectively reduce or even eliminate the precipitation stability and polymerization stability of the dispersed particles in water, and the dispersed particles are coagulated and flocculated into aggregates to be removed. In the invention, the flocculating agent is used for deeply treating fluoride ions in the wastewater and colloidal particles formed in the step 2 process, so that the turbidity of the water is further reduced.
In the present invention, the flocculant is preferably chitosan, which is a typical cationic flocculant, colloidal particles and fluorine ions in wastewater in a container are negatively charged, and when chitosan having a positive charge is close to the colloidal particles, the negative charges of the fluorine ions and the colloidal particles in the wastewater are neutralized, and collide with each other to be precipitated. The chitosan is used as a flocculating agent, is more easily degraded by microorganisms in the environment, and cannot generate secondary pollution. The chitosan contains a large amount of hydroxyl and amino groups, and can be firmly combined with hydrogen bonds, covalent bonds or coordination bonds contained in the wastewater.
The molecular weight of chitosan generally varies from several thousands to millions, and in the present invention, chitosan having a molecular weight of 60 to 80 ten thousand is preferred. In the present invention, 60-80 ten thousand of chitosan forms a suspension in the solution of step 2, and the suspension is dispersed in the aqueous solution, and the flocculation effect is remarkable.
In the invention, a flocculating agent is added, and the final concentration of the flocculating agent is 0.004-0.012 g/L.
In the invention, the flocculating effect is best when the concentration of the added flocculating agent is 0.004-0.012 g/L.
In the present invention, after flocculation is added, the sedimentation is carried out for less than 180min, preferably less than 150min, more preferably 20-120 min. When the settling time is more than 180min, the flocculation effect basically can not be changed any more.
After sedimentation and filtration, the concentration of the fluorine ions in the obtained clear liquid is lower than 5mg/L and lower than the sewage discharge standard specified in China.
In a third aspect of the invention, there is provided the use of the composite adsorbent of the first aspect or the method of the second aspect for the treatment of industrial waste water, preferably for the treatment of fluorine-containing acidic industrial waste water.
Wherein, the fluorine ion concentration in the fluorine-containing industrial wastewater is 20-500mg/L, and the pH value of the fluorine-containing industrial wastewater is 1.0-5.0.
In the invention, when the mass concentration of the fluorine ions in the fluorine-containing industrial wastewater is lower than 20mg/L, the sedimentation efficiency is reduced due to the excessively low concentration of the fluorine ions, and the fluorine removal effect is deteriorated; when the mass concentration of the fluorine ions in the fluorine-containing industrial wastewater is higher than 500mg/L, the treatment range of the composite adsorbent is exceeded, and the fluorine ion removal effect is poor.
Experiments show that the composite adsorbent of the first aspect of the invention or the method of the second aspect of the invention can be used for treating the fluorine-containing acidic industrial wastewater, the composite adsorbent can adapt to industrial wastewater with the mass concentration of fluorine ions in a wide range of 20-500mg/L, the fluorine removal effect is good, the removal rate reaches more than 90%, and the concentration of the fluorine ions in the treated water can meet the provisions of the comprehensive wastewater discharge standard of GB8978-1996 in China.
Examples
The present invention is further described below by way of specific examples, which are merely exemplary and do not limit the scope of the present invention in any way.
Example 1
Preparation of composite adsorbent
Fully mixing calcium hydroxy phosphate, aluminum hydroxy oxide and natural zeolite, wherein the mass is 1100g, 500g and 400g respectively, and the mass ratio is 55: 25: 20, mixing and grinding to obtain the composite adsorbent with the granularity of 120 meshes.
Example 2
Preparation of composite adsorbent
Fully mixing calcium hydroxy phosphate, aluminum hydroxy oxide and natural zeolite, wherein the mass is 1100g, 500g and 400g respectively, and the mass ratio is 55: 25: 20, mixing and grinding to obtain the composite adsorbent with the granularity of 200 meshes.
Example 3
And (3) treating the fluorine-containing acidic wastewater:
(1) the source of the fluorine-containing acidic wastewater is self-prepared and is prepared by hydrofluoric acid and hydrochloric acid according to a proportion, wherein the concentration of fluorine ions is 280mg/L, and the pH value is 1.80;
(2) introducing the fluorine-containing industrial wastewater in the step (1) into a stirring tank A, adding calcium hydroxide to adjust the pH value of the wastewater to 7.0, filtering, and then introducing a clear liquid into a stirring tank B;
(3) adding the composite adsorbent prepared by the method in example 1 into a stirring tank B, adding the composite adsorbent with the mass concentration of 3.2g/L, and stirring for reaction for 12 hours;
(4) adding chitosan with the average molecular weight of 60 ten thousand into the stirring tank B as a flocculating agent, wherein the concentration is 0.008g/L, and settling for 120 min;
(5) and (4) performing centrifugal solid-liquid separation to obtain a treated solution and waste residues.
Example 4
And (3) treating the fluorine-containing acidic wastewater:
(1) the source of the fluorine-containing acidic wastewater is self-prepared and is prepared by hydrofluoric acid and hydrochloric acid according to a proportion, wherein the concentration of fluorine ions is 38mg/L, and the pH value is 2.62;
(2) introducing the fluorine-containing industrial wastewater in the step (1) into a stirring tank A, adding calcium hydroxide to adjust the pH value of the wastewater to 7.0, and filtering to obtain clear liquid which enters a stirring tank B;
(3) adding the composite adsorbent prepared by the method in the embodiment 2 into a stirring tank B, adding the composite adsorbent with the mass concentration of 1.08g/L, and stirring for reacting for 8 hours;
(4) adding chitosan with average molecular weight of 75 ten thousand as flocculant into the stirring tank B, wherein the concentration is 0.005g/L, and settling for 40 min;
(5) and (4) performing centrifugal solid-liquid separation to obtain a treated solution and waste residues.
Example 5
The method for treating the fluorine-containing acidic wastewater in this example is the same as that of example 3, except that the concentration of the fluorine ions in step (1) is 100 mg/L.
Example 6
The method for treating the fluorine-containing acidic wastewater in this example is the same as that of example 3, except that the concentration of the fluorine ions in step (1) is 200 mg/L.
Example 7
The method for treating the fluorine-containing acidic wastewater in this example is the same as that of example 3, except that the concentration of the fluorine ions in step (1) is 400 mg/L.
Example 8
The method for treating the fluorine-containing acidic wastewater in this example is the same as that of example 3, except that the concentration of the fluorine ions in step (1) is 500 mg/L.
Example 9
The method for treating the fluorine-containing acidic wastewater in this example is the same as that of example 3, except that the composite adsorbent is added in a mass concentration of 0.05g/L in step (3).
Example 10
The method for treating the fluorine-containing acidic wastewater in this example is the same as that of example 3, except that the composite adsorbent is added in a mass concentration of 4.0g/L in step (3).
Example 11
The method for treating the fluorine-containing acidic wastewater in this example is the same as that of example 3, except that the composite adsorbent is added in a mass concentration of 5.0g/L in step (3).
Examples of the experiments
The results of measuring the fluoride ion concentration in the solutions treated in examples 3 to 11 are shown in Table 1.
TABLE 1 fluorine ion concentration and fluorine ion removal rate before and after treatment with fluorine-containing acidic solution
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalents, and changes may be made to the technical disclosure and embodiments thereof without departing from the spirit and scope of the present invention, which is within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The composite adsorbent is characterized by being prepared by fully mixing raw materials and grinding.
2. The composite adsorbent of claim 1, wherein the raw material comprises one or more of calcium hydroxy phosphate, aluminum hydroxy oxide, natural zeolite; preferably, the raw materials are calcium hydroxy phosphate, aluminum hydroxy oxide and natural zeolite.
3. The composite adsorbent according to claim 2, wherein the mass ratio of the calcium hydroxy phosphate, the aluminum hydroxy oxide and the natural zeolite in the raw materials is 50-60: 20-30: 15 to 25.
4. A method for purifying fluorine in acidic wastewater, preferably by using the composite adsorbent of any one of claims 1 to 3, wherein the method comprises the following steps:
step 1, pretreating fluorine-containing industrial wastewater to obtain clear liquid;
step 2, transferring the clear liquid obtained in the step 1 into another container, and adding a composite adsorbent into the container;
and 3, adding a flocculating agent into the container in the step 2, settling and filtering.
5. The method according to claim 4, wherein in step 1, the pre-processing comprises the steps of:
step I, introducing fluorine-containing industrial wastewater into a container, and adding a chemical reagent;
and step II, stirring, standing and filtering.
6. The method according to claim 5, wherein in step I, the chemical agent is an alkaline chemical agent, including alkali, alkaline oxide, alkaline salt and the like, preferably, the chemical agent is alkali, including one or more of sodium hydroxide, calcium hydroxide, copper hydroxide and ferrous hydroxide, and more preferably, calcium hydroxide.
7. A method according to claim 4 or 5, wherein the vessel is preferably a vessel with stirring means, more preferably a stirred tank.
8. The process according to claim 5, characterized in that in step I, a chemical agent is added to adjust the pH to 5.6-8.0, preferably 6.0-7.5.
9. The method according to claim 4, wherein in step 3, the flocculant is preferably one or more selected from polyacrylamide, polyaluminium chloride, polyaluminium ferric silicate, ferric chloride and chitosan; preferably, the flocculant is chitosan, more preferably, the flocculant is chitosan with a molecular weight of 60-80 ten thousand.
10. Use of the composite adsorbent according to any one of claims 1 to 3 or the method according to any one of claims 4 to 9 for the treatment of industrial waste water, preferably for the treatment of fluorine-containing acidic industrial waste water.
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| CN101507911A (en) * | 2008-11-11 | 2009-08-19 | 中国科学院生态环境研究中心 | Defluorination absorbing material based on aluminum base composite oxides and its preparation method and use and special device of the preparation method |
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