CN113713770A - Composite adsorption material, preparation method and application thereof, and recycling method of composite adsorption material - Google Patents
Composite adsorption material, preparation method and application thereof, and recycling method of composite adsorption material Download PDFInfo
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- CN113713770A CN113713770A CN202111049558.5A CN202111049558A CN113713770A CN 113713770 A CN113713770 A CN 113713770A CN 202111049558 A CN202111049558 A CN 202111049558A CN 113713770 A CN113713770 A CN 113713770A
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- metal
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- 239000000463 material Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 41
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 39
- 239000006249 magnetic particle Substances 0.000 claims abstract description 38
- 239000010865 sewage Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 26
- 239000012266 salt solution Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000003463 adsorbent Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000440 bentonite Substances 0.000 claims description 10
- 229910000278 bentonite Inorganic materials 0.000 claims description 10
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 10
- -1 aluminum ions Chemical class 0.000 claims description 9
- 239000002028 Biomass Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 16
- 238000007885 magnetic separation Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- 238000003756 stirring Methods 0.000 description 23
- 238000001035 drying Methods 0.000 description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
- B01J20/20—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—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
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the technical field of sewage purification, and particularly relates to a composite adsorption material, a preparation method and application thereof, and a recycling method of the composite adsorption material. The invention provides a composite adsorption material, which comprises a carrier, metal ions and magnetic particles; the metal ions and the magnetic particles are supported on the surface or in the pore structure of the carrier. After the composite adsorbing material provided by the invention adsorbs persistent organic pollutants in sewage, magnetic particles loaded on a carrier are separated from the sewage in a magnetic separation mode, so that the persistent organic pollutants in the sewage are removed; the metal ions on the carrier can catalyze the persistent organic pollutants to carry out oxidative degradation, and decompose and remove the persistent organic pollutants on the composite adsorption material; the composite adsorption material after oxidative degradation can be recycled for repeated reuse.
Description
Technical Field
The invention belongs to the technical field of sewage purification, and particularly relates to a composite adsorption material, a preparation method and application thereof, and a recycling method of the composite adsorption material.
Background
Persistent Organic Pollutants (POPs) have the characteristics of difficult degradability, long-distance transmission, biological accumulation, carcinogenic mutagenicity and the like, have strong biological threat and great removal difficulty, so that the effective removal of the POPs is very important and urgent for improving the water body environment quality.
The traditional physical method for removing the persistent organic pollutants mainly comprises an adsorption method, a flocculation precipitation method and a membrane separation method, and the purpose of separating and removing the pollutants is achieved by utilizing the interaction between materials and molecules of the persistent organic pollutants. For the adsorption method, the commonly used adsorbent is mainly bentonite, on one hand, the commonly used adsorbent can adsorb persistent organic pollutants through electrostatic action, and on the other hand, the commonly used adsorbent can form covalent bonds with the organic pollutants through adsorption centers formed by broken bonds of Si-O-Si and Al-O-Al. After long-time use, the adsorbent is saturated and loses adsorption performance. If the adsorbent is directly discarded, resources are wasted, and the adsorbent adsorbing the toxic substances is directly stacked or buried without being treated, so that a new environmental problem is caused. Therefore, the regeneration of the adsorbent has very important economic significance and environmental protection value.
At present, the traditional regeneration method is mainly a thermal regeneration technology, and although the thermal regeneration technology can be used for removing the adsorbed persistent organic pollutants, the structure of the adsorbent can be damaged during thermal regeneration, so that the adsorption performance of the recovered adsorbent is reduced, and the recovery rate is low.
Disclosure of Invention
The invention aims to provide a composite adsorption material, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a composite adsorption material, which comprises a carrier, metal ions and magnetic particles;
the metal ions and the magnetic particles are supported on the surface or in the pore structure of the carrier.
Preferably, the carrier comprises one or more of bentonite, activated carbon, biomass charcoal, kaolin and sepiolite.
Preferably, the metal ions include one or more of zinc ions, copper ions, aluminum ions, cobalt ions, nickel ions and manganese ions;
the adsorption capacity of the metal ions on the carrier is 5-50 mg/g; the mass of the metal ion is calculated by the mass of the metal element.
Preferably, the magnetic particles comprise ferroferric oxide;
the mass ratio of the magnetic particles to the carrier is 1: 5-1: 15.
preferably, the support is a hydrophobically modified support.
The invention also provides a preparation method of the composite adsorbing material in the technical scheme, which comprises the following steps:
mixing the carrier and the metal salt solution, and roasting in a protective atmosphere to obtain a carrier loaded with metal ions;
and growing magnetic particles on the surface of the carrier loaded with the metal ions to obtain the composite adsorbing material.
Preferably, the metal salt in the metal salt solution comprises one or more of zinc salt, copper salt, aluminum salt, cobalt salt, nickel salt and manganese salt;
the concentration of the metal salt solution is 0.1-2.0 mol/L;
the dosage ratio of the carrier to the metal salt solution is 1-10 g: 10 mL;
the roasting temperature is 100-900 ℃, and the roasting time is 0.5-10 h.
Preferably, after the magnetic particles are grown, the method further comprises the step of performing hydrophobic treatment on the carrier on which the magnetic particles are grown;
the process of the hydrophobization treatment comprises the following steps:
the carrier on which the magnetic particles are grown, a hydrophobizing agent, and a polar organic solvent are mixed to perform a hydrophobizing treatment.
The invention also provides the application of the composite adsorbing material in the technical scheme or the composite adsorbing material prepared by the preparation method in the technical scheme in removing persistent organic pollutants in sewage.
The invention also provides a recycling method of the composite adsorption material, which comprises the following steps:
after the persistent organic pollutants in the composite adsorbing material adsorbed with the persistent organic pollutants are oxidized and degraded, the composite adsorbing material is recovered for reuse.
The invention provides a composite adsorption material, which comprises a carrier, metal ions and magnetic particles; the metal ions and the magnetic particles are supported on the surface or in the pore structure of the carrier. After the composite adsorbing material provided by the invention adsorbs persistent organic pollutants in sewage, magnetic particles loaded on a carrier are separated from the sewage in a magnetic separation mode, so that the purpose of removing the persistent organic pollutants in the sewage is realized; the metal ions on the carrier can catalyze the persistent organic pollutants to carry out oxidative degradation, and decompose and remove the persistent organic pollutants on the composite adsorption material; the composite adsorption material after oxidative degradation can be recycled and reused, and the recycling rate is high.
Detailed Description
The invention provides a composite adsorption material, which comprises a carrier, metal ions and magnetic particles;
the metal ions and the magnetic particles are supported on the surface or in the pore structure of the carrier.
In the present invention, the carrier preferably includes one or more of bentonite, activated carbon, biomass charcoal, kaolin and sepiolite, and when the carrier is two or more of the above specific choices, the proportion of the specific substances in the present invention is not particularly limited, and the specific substances may be mixed in any proportion.
In the present invention, the support is preferably a hydrophobically modified support.
In the present invention, the metal ions preferably include one or more of zinc ions, copper ions, aluminum ions, cobalt ions, nickel ions, and manganese ions, and when the metal ions are two or more of the above specific choices, the ratio of the specific substances in the present invention is not particularly limited, and the specific substances may be mixed in any ratio. In the present invention, the adsorption amount of the metal ions on the carrier is preferably 5 to 50mg/g, more preferably 10 to 45mg/g, and even more preferably 15 to 40mg/g, based on the mass of the metal element. In the present invention, the metal ions are distributed on the surface or in the pore structure of the carrier.
In the present invention, the magnetic particles preferably include ferroferric oxide. In the present invention, the mass ratio of the magnetic particles to the carrier is preferably 1: 5-1: 15, more preferably 1: 6-1: 14, more preferably 1: 7-1: 13.
the invention also provides a preparation method of the composite adsorbing material in the technical scheme, which comprises the following steps:
mixing the carrier and the metal salt solution, and roasting in a protective atmosphere to obtain a carrier loaded with metal ions;
and growing magnetic particles on the surface of the carrier loaded with the metal ions to obtain the composite adsorbing material.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
The invention mixes the carrier and the metal salt solution, and then carries out roasting in the protective atmosphere, thus obtaining the carrier loaded with metal ions.
In the invention, the concentration of the metal salt solution is preferably 0.1-2.0 mol/L, more preferably 0.5-1.8 mol/L, and even more preferably 1.0-1.5 mol/L.
In the present invention, the metal salt in the metal salt solution preferably includes one or more of zinc salt, copper salt, aluminum salt, cobalt salt, nickel salt and manganese salt, and when the metal salt is two or more of the above specific choices, the ratio of the specific substances in the present invention is not particularly limited, and the specific substances may be mixed in any ratio. In the present invention, the metal salt is preferably a soluble metal salt, and further preferably includes a hydrochloride, a sulfate or a nitrate.
In the present invention, the kind of the carrier is consistent with that of the carrier in the above technical solution, and is not described herein again.
The present invention also preferably includes pre-treating the support prior to said mixing.
In the present invention, the pretreatment process preferably includes: and mixing the carrier and the pretreatment solution to obtain the pretreatment carrier.
In the present invention, the pretreatment solution preferably comprises a soluble alkali metal salt solution or a soluble alkaline earth metal salt solution; the soluble alkali metal salt solution preferably comprises a sodium salt solution, and further preferably comprises a sodium chloride solution, a sodium hydroxide solution, a sodium carbonate solution or a sodium bicarbonate solution; the soluble alkaline earth salt solution preferably comprises a calcium salt solution or a magnesium salt solution, and the calcium salt solution further preferably comprises a calcium nitrate solution or a calcium hydroxide solution; the magnesium salt solution further preferably comprises a magnesium hydroxide solution or a magnesium chloride solution.
In the invention, the concentration of the pretreatment solution is preferably 0.1-2 mol/L, more preferably 0.5-1.5 mol/L, and even more preferably 0.8-1.2 mol/L. In the present invention, the amount ratio of the carrier to the pretreatment solution is preferably 1 g: 1-100 mL, more preferably 1 g: 5-95 mL, more preferably 1 g: 10-90 mL.
In the invention, the temperature of the pretreatment is preferably 25-120 ℃, more preferably 30-115 ℃, and more preferably 35-110 ℃. In the present invention, the pretreatment is preferably carried out in a stirring manner. In the invention, when stirring is adopted, the rotation speed of stirring is preferably 0-400 r/min, more preferably 50-350 r/min, and even more preferably 100-300 r/min. In the invention, the pretreatment time is preferably 0.5-8 h, more preferably 1-7 h, and even more preferably 2-6 h.
After the pretreatment is finished, the method also preferably comprises the step of carrying out post-treatment on the reaction liquid obtained by the pretreatment, wherein the post-treatment preferably comprises the steps of separating, drying and grinding in sequence.
In the present invention, the separation means is preferably filtration or centrifugation. The present invention does not require any particular filtration or centrifugation procedure, as is well known to those skilled in the art. In the invention, the drying temperature is preferably 50-100 ℃, more preferably 55-95 ℃, and more preferably 60-90 ℃; the time is preferably 1 to 24 hours, more preferably 2 to 23 hours, and still more preferably 3 to 22 hours. The present invention has no special requirements on the grinding process and the particle size after grinding, and the method is well known to those skilled in the art. In the invention, the pretreatment can swell the surface of the carrier and activate groups on the surface of the carrier, thereby further increasing the loading sites of metal ions on the surface of the carrier.
In the invention, the dosage ratio of the carrier to the metal salt solution is preferably 1-10 g: 10mL, more preferably 2 to 9 g: 10mL, more preferably 3-7 g: 10 mL.
In the present invention, the mixing is preferably under stirring. In the invention, the rotation speed of the stirring is preferably 100-400 rpm, more preferably 150-350 rpm, and more preferably 200-300 rpm; the time is preferably 0.5-24 h, more preferably 2-22 h, and even more preferably 3-21 h; the temperature is preferably 25 to 90 ℃, more preferably 30 to 85 ℃, and more preferably 35 to 80 ℃. In the present invention, the stirring is preferably performed in a constant temperature shaker.
After the mixing is finished, the invention also preferably comprises post-treatment of the reaction liquid obtained after the mixing, wherein the post-treatment preferably comprises filtering, washing and drying which are sequentially carried out. The filtration process is not particularly limited in the present invention, and those skilled in the art will be familiar with the filtration process. In the present invention, the detergent used for the washing is preferably distilled water. The present invention does not require a particular washing process, and may be performed as is well known to those skilled in the art. In the invention, the drying temperature is preferably 50-100 ℃, more preferably 55-95 ℃, and more preferably 60-90 ℃; the time is preferably 1 to 24 hours, more preferably 2 to 23 hours, and still more preferably 3 to 22 hours.
In the present invention, the firing includes a first firing and a second firing performed in this order. In the invention, the first roasting temperature is preferably 100-300 ℃, more preferably 120-280 ℃, and more preferably 150-250 ℃; the time is preferably 0.5 to 5 hours, more preferably 1 to 4.5 hours, and still more preferably 1.5 to 4 hours. In the invention, the second roasting temperature is preferably 300-900 ℃, more preferably 350-850 ℃, and more preferably 400-800 ℃; the time is preferably 0.5 to 24 hours, more preferably 1 to 23 hours, and still more preferably 2 to 22 hours. In the invention, the independent temperature rise speed of the first roasting and the second roasting is preferably 5-10 ℃/min, more preferably 6-9 ℃/min, and even more preferably 7-8 ℃/min. In the present invention, the calcination is preferably performed in a protective atmosphere, and more preferably in an inert gas or nitrogen atmosphere. In the present invention, the calcination is preferably carried out in a vacuum tube furnace.
After the roasting is finished, the roasting product is preferably subjected to post-treatment, and the post-treatment preferably comprises washing and drying which are sequentially carried out. In the present invention, the detergent used for the washing is preferably distilled water, and the number of times of the washing is preferably 3. The drying method is not particularly limited in the present invention, and those skilled in the art can use the drying method. In the invention, the metal ions are loaded on the carrier, so that the oxidative degradation of the persistent organic pollutants adsorbed on the composite adsorption material can be further catalyzed and accelerated.
After the carrier loaded with the metal ions is obtained, magnetic particles grow on the surface of the carrier loaded with the metal ions to obtain the composite adsorbing material.
In the present invention, the method for growing magnetic particles preferably comprises the steps of: mixing the carrier loaded with metal ions, the solution containing magnetic metal ions and the alkaline solution, and carrying out coprecipitation reaction to obtain the carrier with the magnetic particles.
In the present invention, the magnetic metal ion-containing solution is preferably an iron ion-containing solution; the iron ion-containing solution is preferably Fe-containing2+And Fe3+And (3) solution. In the invention, the concentration of the iron ion-containing solution is preferably 0.1-2 mol/L, more preferably 0.2-1.8 mol/L, and even more preferably 0.5-1.5 mol/L. In the present invention, Fe in the iron ion-containing solution2+And Fe3+Is preferably 1: 2. in the invention, the using amount ratio of the carrier loaded with metal ions to the iron ion-containing solution is preferably 2-20 g: 100mL, more preferably 4 to 18 g: 100mL, more preferably 6-16 g: 100mL.
In the invention, the alkaline solution is preferably an ammonia water solution or a sodium hydroxide solution, and the mass concentration of the ammonia water solution is preferably 25%; the molar concentration of the sodium hydroxide is preferably 0.1-1 mol/L, more preferably 0.2-0.9 mol/L, and even more preferably 0.3-0.8 mol/L.
In the present invention, the mixing process is preferably: and mixing the carrier loaded with the metal ions and the magnetic metal ion solution, and then dropwise adding an alkaline solution until the pH value of the reaction solution is 9-10.
The invention has no special requirement on the mixing mode of the carrier loaded with the metal ions and the magnetic metal ion solution, and the method is well known by the technical personnel in the field. In the invention, the dripping speed is preferably 50-300 mL/h, more preferably 60-290 mL/h, and even more preferably 70-280 mL/h. In the invention, the dripping is preferably carried out under the condition of stirring, and the rotating speed of the stirring is preferably 100-400 rpm, more preferably 150-350 rpm, and more preferably 200-300 rpm; the time is preferably 0.5 to 3 hours, more preferably 1 to 2.5 hours, and still more preferably 1.5 to 2 hours.
In the invention, the temperature of the coprecipitation reaction is preferably 25-80 ℃, more preferably 30-75 ℃, and more preferably 35-70 ℃.
After the coprecipitation reaction is completed, the reaction solution obtained by the reaction is preferably subjected to post-treatment, and the post-treatment preferably comprises centrifugal separation, washing and drying which are sequentially performed. The present invention does not require any particular process for such centrifugation, and may be practiced using techniques well known to those skilled in the art. In the present invention, the detergent used for the washing is preferably deionized water. The invention has no special requirements on the washing process, and can obtain a neutral product. The present invention has no particular requirement for the drying process, as long as a dried product is obtained. In the invention, the composite carrier adsorbing persistent organic pollutants can be separated from the sewage in a magnetic separation mode by growing the magnetic particles on the surface of the carrier, so that the storage amount of the pollutants in the sewage is reduced, and the aim of purifying the sewage is fulfilled.
After the magnetic particles are grown, the present invention preferably further comprises subjecting the support on which the magnetic particles are grown to a hydrophobic treatment. In the present invention, the process of the hydrophobization treatment preferably includes: mixing the carrier with the magnetic particles, a hydrophobic agent and a polar organic solvent, and carrying out hydrophobic treatment.
In the present invention, the hydrophobic agent preferably includes one or more of a positive soap, a halogenated alkane, an organosilicate and an organosiloxane; the positive soap preferably comprises cetyltrimethylammonium bromide; the organosilicate preferably comprises ethyl orthosilicate; the organosiloxane preferably comprises octadecyltrichlorosilane or trimethylchlorosilane; when the hydrophobizing agent is two or more of the above specific choices, the ratio of the specific substances in the present invention is not particularly limited, and those known to those skilled in the art may be used.
In the present invention, the polar organic solvent preferably includes ethanol or N, N-dimethylformamide.
In the present invention, the amount ratio of the carrier to the polar organic solvent is preferably 1 g: 1-10 mL, more preferably 1 g: 2-9 mL, more preferably 1 g: 3-8 mL. In the present invention, the volume ratio of the water repellent agent and the polar organic solvent is preferably 1: 1-5, and more preferably 1: 2-4, more preferably 1: 3.
in the present invention, the time for the hydrophobization treatment is preferably 1 to 24 hours, more preferably 5 to 20 hours, and still more preferably 8 to 18 hours. In the present invention, the pretreatment is preferably carried out by soaking.
After the hydrophobization treatment is completed, the present invention preferably further includes drying the hydrophobized product. In the invention, the drying time is preferably 100-130 ℃, more preferably 105-125 ℃, and more preferably 110-120 ℃; the time is preferably 1 to 3 hours, and more preferably 2 hours. In the present invention, the drying is preferably performed in an oven. In the invention, the hydrophobization treatment can further increase the adsorption amount of the composite adsorption material on persistent organic pollutants.
The invention also provides the application of the composite adsorbing material in the technical scheme or the composite adsorbing material prepared by the preparation method in the technical scheme in removing persistent organic pollutants in sewage.
In the present invention, the application preferably comprises the steps of:
and (3) soaking the composite adsorbing material in sewage containing persistent organic pollutants, and separating to obtain the composite adsorbing material adsorbing the persistent organic pollutants.
The composite adsorbing material is soaked in sewage containing persistent organic pollutants and then separated to obtain the composite adsorbing material adsorbing the persistent organic pollutants.
In the present invention, the persistent organic contaminant in the wastewater containing persistent organic contaminant preferably includes perfluorooctane sulfonyl compound (PFOS) or methylene blue. In the invention, the concentration of the sewage containing the persistent organic pollutants is preferably 0.01-500 mg/L, more preferably 0.05-490 mg/L, and even more preferably 0.1-485 mg/L.
In the invention, the dosage ratio of the composite adsorbing material to the sewage containing persistent organic pollutants is preferably 0.5-10 g: 1L, more preferably 1 to 9 g: 1L, more preferably 2-8 g: 1L of the compound.
In the present invention, the soaking is preferably performed under stirring. In the invention, the rotation speed of the stirring is preferably 100-400 rpm, more preferably 150-350 rpm, and more preferably 200-300 rpm; the time is preferably 0.5 to 10 hours, more preferably 1 to 9 hours, and even more preferably 2 to 8 hours. In the present invention, the stirring is preferably performed in a constant temperature water bath or a constant temperature shaker.
In the present invention, the separation is preferably magnetic separation.
In the invention, the adsorption rate of the composite adsorption material to the persistent organic pollutants is preferably more than or equal to 85%.
The invention also provides a recycling method of the composite adsorption material, which comprises the following steps:
after the persistent organic pollutants in the composite adsorbing material adsorbed with the persistent organic pollutants are oxidized and degraded, the composite adsorbing material is recovered for reuse.
The composite adsorbing material is prepared by oxidizing and degrading the persistent organic pollutants in the composite adsorbing material adsorbed with the persistent organic pollutants, and then recovering and reusing the composite adsorbing material.
In the present invention, the oxidative degradation preferably includes: and mixing the composite adsorbing material adsorbed with the persistent organic pollutants with an electrolyte solution containing an oxidant to perform oxidative degradation reaction.
In the present invention, the electrolyte solution is preferably a sodium chloride solution or a sodium sulfate solution. In the present invention, the molar concentration of the electrolyte solution is preferably 0.01 to 0.5mol/L, more preferably 0.1 to 0.45mol/L, and still more preferably 0.15 to 0.4 mol/L.
In the invention, the oxidant comprises ozone and/or hydrogen peroxide. In the invention, when the oxidant is hydrogen peroxide, the volume ratio of the hydrogen peroxide to the electrolyte solution is preferably 50-300 mL: 1L, more preferably 100 to 250 mL: 1L, more preferably 150-200 mL: 1L of the compound. In the present invention, when the oxidant is ozone, the ratio of the amount of ozone to the electrolyte solution is preferably 50 to 150 mg: 1L, more preferably 60-140 mg: 1L, more preferably 70-130 mg: 1L of the compound. In the invention, when the oxidant is hydrogen peroxide and ozone, the dosage ratio of the hydrogen peroxide to the ozone to the electrolyte solution is preferably 50-200 mL: 50-100 mg: 1L, more preferably 60-180 mL: 60-90 mg: 1L, more preferably 70-170 mL: 70-80 mg: 1L of the compound.
In the present invention, the solid-to-liquid ratio of the composite adsorbent material adsorbing persistent organic pollutants to the electrolyte solution containing an oxidizing agent is preferably 1 g: 1-500 mL, more preferably 1 g: 10-490 mL, more preferably 1 g: 20-480 mL. In the present invention, the oxidative degradation reaction is preferably carried out under stirring. In the invention, the rotation speed of the stirring is preferably 100-300 r/min, more preferably 150-250 r/min, and even more preferably 160-240 r/min; the time is preferably 0.5 to 3 hours, more preferably 1 to 2.5 hours, and still more preferably 1.5 to 2 hours. In the present invention, the temperature of the oxidative degradation reaction is preferably room temperature.
After the oxidative degradation is finished, the composite adsorbing material is preferably separated by adopting a filtering or centrifuging mode, and the composite adsorbing material is recovered for reuse.
In the present invention, after the separation of the composite adsorbent, it is preferable to further include subjecting the obtained composite adsorbent to a hydrophobization treatment. In the present invention, the step of the hydrophobization treatment is consistent with the above technical scheme, and is not described herein again.
In order to further illustrate the present invention, the following will describe in detail the composite adsorbent material provided by the present invention, its preparation method and application, and the method for recycling the composite adsorbent material, with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 15g of bentonite and 150mL of 0.1mol/L sodium chloride solution, stirring at 25 ℃ for 3h at the rotating speed of 300r/min, and then sequentially filtering, drying and grinding to obtain pretreated bentonite;
10g of pretreated bentonite and 100mL of Cu-containing solution with the concentration of 0.5mol/L2+、Mn2+And Co2+Mixing salt solutions, stirring for 2h at the rotation speed of 150rpm at 80 ℃, drying for 24h at the temperature of 60 ℃ after centrifugation, roasting the dried material in a vacuum tube furnace at 200 ℃ for 1h, and roasting at 500 ℃ for 1.5h to obtain bentonite loaded with copper ions, manganese ions and cobalt ions;
8g of bentonite loaded with copper ions, manganese ions and cobalt ions and 50mL of bentonite containing Fe with the concentration of 0.5mol/L2+And Fe3+Solution (in which Fe2+And Fe3+Is preferably 1: 2) after mixing, dropwise adding ammonia water with the mass concentration of 25% at the speed of 50mL/h at the rotating speed of 200rpm until the pH value of the reaction liquid is 9, then continuing stirring for 0.5h, carrying out centrifugal separation on the reaction liquid, washing the separated material to be neutral by using deionized water, and drying to obtain a carrier with magnetic particles;
5g of the carrier with the magnetic particles growing thereon, 5mL of cetyltrimethylammonium bromide and 20mL of ethanol are mixed, kept stand for 7 hours, and then dried for 1 hour at 100 ℃ to obtain the composite adsorbing material.
Example 2
Mixing 20g of biomass carbon with 400mL of 0.1mol/L calcium nitrate solution, stirring at 25 ℃ for 5 hours at a rotating speed of 200r/min, and then sequentially filtering, drying and grinding to obtain pretreated activated carbon;
10g of the pretreated biomass charcoal and 50mL of Zn-containing solution with the concentration of 0.5mol/L2+Mixing the salt solutions, stirring for 3h at the rotating speed of 200rpm at 80 ℃, centrifuging, drying for 18h at the temperature of 80 ℃, roasting the dried material in a vacuum tube furnace at 200 ℃ for 0.5h, and roasting at 550 ℃ for 2h to obtain the active carbon loaded with zinc ions;
5g of biomass charcoal loaded with zinc ions and 50mL of Fe-containing carbon with the concentration of 1mol/L2+And Fe3+Solution (in which Fe2+And Fe3+In a molar ratio ofPreferably 1: 2) after mixing, dropwise adding a sodium hydroxide solution with the concentration of 0.1mol/L at the speed of 80mL/h at the rotating speed of 250rpm until the pH value of the reaction solution is above 9, then continuously stirring for 0.5h, carrying out centrifugal separation on the reaction solution, washing the separated material to be neutral by using deionized water, and drying to obtain a carrier with magnetic particles;
mixing 4g of carrier with magnetic particles, 5mL of tetraethoxysilane, 5mL of octadecyl trichlorosilane and 20mLN, N-dimethylformamide, standing for 5h, and drying at 100 ℃ for 1h to obtain the composite adsorbing material.
Application example 1
Mixing 0.5g of the composite adsorbing material obtained in the example 1 with 200mL of methylene blue solution with the concentration of 400mg/L, adsorbing for 5 hours in a water bath oscillator, and separating the composite adsorbing material adsorbed with the methylene blue in a magnetic separation mode; the adsorption rate of the composite adsorption material to methylene blue is 92.5%;
mixing 0.5g of composite adsorbing material adsorbed with methylene blue with 30mL of sodium chloride solution containing hydrogen peroxide (wherein the volume ratio of hydrogen peroxide to sodium chloride solution is 1: 10), stirring at room temperature at a stirring speed of 100r/min for 30min, and separating the composite adsorbing material in a centrifugal mode after oxidative degradation is finished; the oxidative degradation rate of the methylene blue is 97.5 percent;
and (3) mixing 0.5g of the separated composite adsorbing material, 5mL of hexadecyltrimethylammonium bromide and 20mL of ethanol, standing for 5 hours, drying at 100 ℃ for 5 hours to obtain a recovered composite adsorbing material, reusing the recovered composite adsorbing material for methylene blue adsorption, and circulating for 5 times, wherein the adsorption rate of the composite adsorbing material on the methylene blue is 91.1%, and the oxidative degradation rate of the methylene blue is 96.7%.
Application example 2
Mixing 0.5g of the composite adsorbing material obtained in the example 2 with 100mL of 100mg/LPFOs solution, adsorbing the mixture in a water bath oscillator for 24 hours, and separating the composite adsorbing material adsorbed with PFOS in a magnetic separation mode; the adsorption rate of the compound adsorbing material to PFOS is 90.5%;
mixing 0.5g of PFOS-adsorbed composite adsorbing material with 50mL of sodium chloride solution containing hydrogen peroxide (wherein the volume ratio of hydrogen peroxide to sodium chloride solution is 1: 5), stirring at room temperature at a stirring speed of 100r/min for 30min, and separating the composite adsorbing material in a filtering and collecting mode after oxidative degradation is finished; the oxidative degradation rate of the PFOS is 92.5 percent;
and (3) mixing 0.5g of the separated composite adsorbing material, 5mL of hexadecyltrimethylammonium bromide and 20mL of ethanol, standing for 5 hours, drying at 100 ℃ for 5 hours to obtain a recovered composite adsorbing material, reusing the PFOS adsorption of the separated composite adsorbing material, and circulating for 3 times, wherein the PFOS adsorption rate of the composite adsorbing material is 87.5%, and the PFOS oxidative degradation rate is 90.8%.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The composite adsorption material is characterized by comprising a carrier, metal ions and magnetic particles;
the metal ions and the magnetic particles are supported on the surface or in the pore structure of the carrier.
2. A composite adsorbent material according to claim 1, wherein the carrier comprises one or more of bentonite, activated carbon, biomass charcoal, kaolin and sepiolite.
3. A composite adsorption material according to claim 1, wherein the metal ions comprise one or more of zinc ions, copper ions, aluminum ions, cobalt ions, nickel ions and manganese ions;
the adsorption capacity of the metal ions on the carrier is 5-50 mg/g; the mass of the metal ion is calculated by the mass of the metal element.
4. A composite adsorbent material as set forth in claim 1, wherein the magnetic particles comprise ferroferric oxide;
the mass ratio of the magnetic particles to the carrier is 1: 5-1: 15.
5. a composite adsorbent material according to claim 1 or 2, characterized in that the support is a hydrophobically modified support.
6. A preparation method of the composite adsorbing material as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
mixing the carrier and the metal salt solution, and roasting in a protective atmosphere to obtain a carrier loaded with metal ions;
and growing magnetic particles on the surface of the carrier loaded with the metal ions to obtain the composite adsorbing material.
7. The preparation method of claim 6, wherein the metal salt in the metal salt solution comprises one or more of zinc salt, copper salt, aluminum salt, cobalt salt, nickel salt and manganese salt;
the concentration of the metal salt solution is 0.1-2.0 mol/L;
the dosage ratio of the carrier to the metal salt solution is 1-10 g: 10 mL;
the roasting temperature is 100-900 ℃, and the roasting time is 0.5-10 h.
8. The method according to claim 6, wherein after the magnetic particles are grown, the method further comprises subjecting the support on which the magnetic particles are grown to a hydrophobization treatment;
the process of the hydrophobization treatment comprises the following steps:
the carrier on which the magnetic particles are grown, a hydrophobizing agent, and a polar organic solvent are mixed to perform a hydrophobizing treatment.
9. The composite adsorbing material as set forth in any one of claims 1 to 5 or the composite adsorbing material prepared by the preparation method as set forth in any one of claims 6 to 8 is applied to removal of persistent organic pollutants in sewage.
10. A method for recycling composite adsorption materials is characterized by comprising the following steps:
after the persistent organic pollutants in the composite adsorbing material adsorbed with the persistent organic pollutants are oxidized and degraded, the composite adsorbing material is recovered for reuse.
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