CN109569505B - Preparation and regeneration method of silicon-based material secondary adsorbent - Google Patents
Preparation and regeneration method of silicon-based material secondary adsorbent Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 56
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 22
- 238000011069 regeneration method Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 49
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011133 lead Substances 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 4
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 230000001172 regenerating effect Effects 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000010303 mechanochemical reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
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- 238000013019 agitation Methods 0.000 claims 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000010840 domestic wastewater Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 3
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- 238000012986 modification Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 229920002472 Starch Polymers 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 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 4
- 239000010865 sewage Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 3
- 235000012216 bentonite Nutrition 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
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- 229920005615 natural polymer Polymers 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 101001065501 Escherichia phage MS2 Lysis protein Proteins 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- -1 amino polysaccharide Chemical class 0.000 description 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
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- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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- 238000012216 screening Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
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Abstract
The invention provides a preparation and regeneration method of a silicon-based material secondary adsorbent, belonging to the technical field of material application and resource recovery, which utilizes common natural nontoxic mineral resources such as kaolin, zeolite, diatomite and the like to carry out mechanical force activation and hydrothermal treatment, and can be applied to treatment of high-concentration organic wastewater such as protein wastewater, oil washing wastewater, dye wastewater and the like, treatment of mixed wastewater of one or more ions such as chromium, lead, copper, nickel and the like and element recovery. The material is characterized by mild preparation conditions, organic matters in wastewater are adsorbed under ball milling, and the material is used for sequentially adsorbing heavy metal ions by adopting a wet interface modification effect under the mechanochemical action. The operation environment is good, no waste water and waste discharge exists, and the material can be reused and valuable elements can be recycled without additionally adding equipment.
Description
Technical Field
The invention belongs to the technical field of material application and resource recovery, and relates to a silicon-based material, which is characterized in that an organic pollutant is firstly treated, then mechanical-mechanochemical stabilization and hydrothermal synthesis are carried out, metal ions in sewage are adsorbed by the silicon-based material, and the heavy metal ions in the sewage are sequentially adsorbed after mechanochemical regeneration, so that continuous resource treatment is realized, secondary pollution is avoided, and the maximum utilization of resources is realized.
Technical Field
Organic wastewater and heavy metal wastewater are problems faced by China in the process of industrialization, and can not be effectively degraded in the environment, and if the organic wastewater and the heavy metal wastewater are not properly treated in time, the organic wastewater and the heavy metal wastewater are directly discharged, so that the organic wastewater and the heavy metal wastewater can cause serious harm to the environment and human bodies. The materials commonly used to treat such waste water are generally expensive,
silicon-based materials (kaolin, zeolite and the like) are used as common mineral resources, and due to the special structure, the silicon-based materials have enough pores and larger specific surface, are cheap and easily purchased, and have the foundation capable of being used as treatment materials, so that the research selects steel slag as a raw material to carry out the research on the treatment of organic wastewater and heavy metal wastewater. Therefore, the development of a novel method for effectively treating organic pollution and heavy metal wastewater by using the silicon-based material provides a novel method for treating the organic wastewater and the heavy metal wastewater.
China has abundant bentonite minerals, low price and extremely high ion exchange performance due to the unique layered structure. The method is characterized in that quaternary ammonium salts with carbon chains of different lengths are mixed and modified in Zhuli medium to prepare a series of dicationic organic bentonites, and in the adsorption research on phenol, aniline and p-nitrophenol, the composition and proportion of the quaternary ammonium salts with different carbon chains influence the interlayer spacing of the organic bentonites, so that the removal efficiency of organic matters is influenced. The molecular sieve is silicate or aluminosilicate with regular crystal structure, and has unique pore canal structure, size and very strong polarity, so that it has strong sensitivity to the size and polarity of adsorbed pollutant molecules, especially to small molecular aldehydes and ketones, and its adsorption capacity is higher than that of active carbon. Activated alumina has a developed microporous structure and a rich specific surface area, and is commonly used for defluorination and arsenic removal of drinking water in the adsorption field.
The organic polymer adsorption material is classified according to the source, and comprises ion exchange resin and various natural polymer materials. The ion exchange resin is a synthetic high molecular material with specific functional groups and a spatial network structure, comprises cation exchange resin and anion exchange resin, can be used for selectively removing organic matters in water, recovering heavy metals and softening hard water, and has the advantages of stable chemical property, high mechanical strength, strong adsorption capacity, simple regeneration and the like. Zhang Jianbo et al chose macroporous strong acid type ion exchange resin for adsorbing copper ions in concentrated organic wastewater, and the result shows that the Cu content after treatment is lower than 0.1pg/mL, and meanwhile, the resin has stable ion exchange performance and good regeneration performance.
The natural polymer adsorption material mainly comprises cellulose, starch and chitosan, and has the characteristics of rich sources, low price, reproducibility, no toxicity, biocompatibility and the like. When the materials are directly used, the adsorption capacity is not strong, so researchers carry out various physicochemical modifications on the materials so as to adapt to different sewage treatment systems. The modification of cellulose mainly comprises esterification, etherification and graft copolymerization of hydroxyl, and heavy metals and organic matters in water are removed by introducing functional groups such as carboxymethyl, ortho-thiol, amidogen and the like. Starch molecules also contain a large number of hydroxyl groups, and can be subjected to crosslinking and etherificationEsterification, oxidation and graft copolymerization. The double-deformation starch is prepared by using epichlorohydrin to crosslink starch, using ammonium ceric nitrate as an initiator to graft acrylonitrile on the starch, and is successfully used for Cu in water2+And adsorption of Cr (VI). The chitosan is a natural amino polysaccharide, contains a large amount of amino groups in molecules besides hydroxyl groups, is easy to generate coordination with metal ions, and can form cage-shaped molecules similar to a net structure by means of hydrogen bonds and ionic bonds, so that the chitosan can effectively adsorb various pollutants, and has wide application prospects in the field of water treatment.
The method is mainly characterized in that silicon-based materials such as kaolin, zeolite, diatomite and the like are utilized to carry out simple pretreatment, then the silicon-based materials are combined with organic pollutants through mechanochemistry, the combination of the materials and the organic pollutants is stable through low-temperature hydrothermal reaction, then the materials are used for adsorbing heavy metals, the regeneration of the adsorbent is completed through a secondary mechanochemistry method, the purpose of sequential adsorption is realized, the cyclic treatment is realized, and the sequential adsorption and recycling of organic matters and heavy metal ions can be completed so as to realize the preparation of the continuous adsorbent for resource treatment.
Disclosure of Invention
The invention provides a method for preparing a sequential adsorbent by utilizing a silicon-based material, which can achieve the aim of sequentially adsorbing two kinds of wastewater after treating low-cost raw materials, and the overall preparation process flow is shown in figure 1.
The technical scheme of the invention is as follows:
a method for preparing and regenerating a silicon-based material secondary adsorbent comprises the following steps:
(1) firstly, silicon-based materials are pretreated by acid with the concentration of 0.5-3mol/L for 1-3 hours, after washing, the silicon-based materials are activated by 0.5-3mol/L NaOH solution for 1-3 hours, washed to be neutral by deionized water, dried at the temperature of 75-120 ℃, and the obtained activated materials are ground by a crusher to obtain powdery adsorbent A;
(2) carrying out mechanochemical reaction on the adsorbent A according to the mass g of the adsorbent and the volume ml of the organic wastewater as 1:500-1500, wherein the reaction time is 0.5-4 h; directly feeding the adsorbent A for adsorbing organic matters into a hydrothermal reaction kettle, treating for 2-4 hours at 80-500 ℃, cooling, washing with deionized water, drying at 75-120 ℃ to obtain a new adsorbent B, and sealing and storing;
(3) adding the adsorbent B into the heavy metal wastewater according to the mass g of the adsorbent and the volume ml ratio of the heavy metal wastewater of 1:500-1000, and stirring for 0.5-24 hours; removing part of heavy metals; after adsorption, the adsorbent B is placed into a ball milling kettle and added with water for ball milling regeneration, and the adsorbed heavy metal is influenced by mechanochemistry and falls into water from the adsorbent B, so that the cyclic recycling of the adsorbent B is realized.
The silica-based material is silicon-containing natural minerals and industrial waste of the natural minerals, and comprises, but is not limited to, kaolin, zeolite, diatomite, silica fume and ZSM5 molecular sieve.
The organic wastewater includes but is not limited to oily wastewater, protein wastewater, dye wastewater, biomass wastewater and domestic sewage with high COD.
And (3) carrying out hydrothermal synthesis reaction after the first adsorption is finished, wherein the used solvent is water, acid and acid mixture, and alkali mixture.
The heavy metal wastewater comprises but is not limited to one or the mixture of more than two of lead, copper, nickel, chromium, vanadium, manganese and titanium, and the concentration range of heavy metal ions is 0.5-1000 mg/L.
The reactor used in the mechanochemical reaction is a device for providing stirring and extrusion, including but not limited to a ball mill, a pulverizer and a stirrer, and the stirring and extrusion force and energy provided by the reactor are equivalent to the rotation speed of the ball mill of 100 revolutions per minute and 1000 revolutions per minute.
The adsorbent prepared by the invention can be used for enterprises producing high-concentration organic wastewater and heavy metal wastewater simultaneously, can realize the recycling of heavy metal while treating wastewater by using the low-cost adsorbent, and has wide market prospect.
The method has the beneficial effects that organic matter molecules are adsorbed firstly, special groups of organic matters in the wastewater are used as characteristic sites of the material, the organic matters are fixed on the surface of a silicon-based material through a hydrothermal method, so that the removal capacity of the silicon-based adsorbent material to heavy metals is enhanced, then the adsorbent is eluted and recycled in a mechanochemical mode, heavy metals are enriched, the adsorbent is recycled, secondary pollution is avoided, and the maximum utilization of resources is realized. The preparation process is simple, environment friendly, low in cost and other advantages, and may be used in preparing continuous adsorbent for selective heavy metal enriching and treating heavy metal waste water.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is an electron micrograph of the silicon-based adsorbent treated (a) on a 20 μm scale and (b) on a 3 μm scale.
Fig. 3 is a graph of the contaminant removal efficiency of the adsorbent B recycling.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
After zeolite is subjected to acid-base activation pretreatment and screening, the obtained adsorbent A is subjected to mechanochemical reaction with 500mg/L protein wastewater in a ball milling tank at the rotation speed of 500rpm according to the adding proportion of 0.5-1.2g/L at different temperatures, the ball milling tank is made of aluminum oxide and made of zirconium oxide, the ball milling time is about 120min, the removal rate of protein wastewater organic matters is 75% in terms of COD (chemical oxygen demand), the adsorbent is filtered and directly enters a hydrothermal reaction kettle, water is supplemented until the kettle is full of 80%, the hydrothermal temperature is 240 ℃ and the hydrothermal time is 2h, then the adsorbent A is taken out, filtered, washed and dried to obtain an adsorbent B, and an electron microscope picture is shown in figure 2.
Example 2
Adding the adsorbent B into heavy metal solutions of Pb (II), Ni (II) and Cu (II) according to the adding proportion of 0.1-1.5g/L, controlling the concentration of the heavy metal solution to be 5-50 mg/L, oscillating a shaking table for 2h, and enabling the adsorbent B to show selective adsorption effect on Pb (II) to achieve adsorption balance within 60 min. Under the same experimental condition, when the concentration of heavy metal is 30mg/L, the adsorption amounts of the adsorbent B to Pb (II), Ni (II) and Cu (II) at room temperature are respectively 17.92mg/g, 0.54mg/g and 0.02 mg/g; the adsorbent B after heavy metal adsorption is filtered and collected, mechanical force activation regeneration is carried out in a ball milling tank, the recovery rate of Pb (II) is 60-70%, the capacity of the adsorbent B is reduced, after the adsorbent B is repeatedly used for 5 times, the recovery rate of Pb (II) is 20-30%, the adsorbent B can be recycled, and the adsorption result is shown in figure 3.
Claims (10)
1. A method for preparing and regenerating a silicon-based material secondary adsorbent is characterized by comprising the following steps:
(1) firstly, silicon-based materials are pretreated by acid with the concentration of 0.5-3mol/L for 1-3 hours, after washing, the silicon-based materials are activated by 0.5-3mol/L NaOH solution for 1-3 hours, washed to be neutral by deionized water, dried at the temperature of 75-120 ℃, and the obtained activated materials are ground by a crusher to obtain powdery adsorbent A;
(2) carrying out mechanochemical reaction on the adsorbent A according to the mass g of the adsorbent and the volume ml of the organic wastewater as 1:500-1500, wherein the reaction time is 0.5-4 h; directly feeding the adsorbent A for adsorbing organic matters into a hydrothermal reaction kettle, treating for 2-4 hours at 240 ℃, cooling, cleaning with deionized water, drying at 75-120 ℃ to obtain a new adsorbent B, and sealing and storing;
(3) adding the adsorbent B into the heavy metal wastewater according to the mass g of the adsorbent and the volume ml ratio of the heavy metal wastewater of 1:500-1000, and stirring for 0.5-24 hours; removing part of heavy metals; after adsorption, the adsorbent B is placed into a ball milling kettle and added with water for ball milling regeneration, and the adsorbed heavy metal is influenced by mechanochemistry and falls into water from the adsorbent B, so that the cyclic recycling of the adsorbent B is realized.
2. The method for preparing and regenerating the secondary silica-based material adsorbent of claim 1, wherein the silica-based material is silicon-containing natural minerals and industrial waste materials of natural minerals, including kaolin, zeolite, diatomaceous earth, silica fume, ZSM5 molecular sieve.
3. The method for preparing and regenerating the secondary adsorbent of silica-based materials according to claim 1 or 2, wherein the organic wastewater comprises oily wastewater, protein wastewater, dye wastewater, biomass wastewater and high COD domestic wastewater.
4. The method for preparing and regenerating the secondary silica-based material adsorbent according to claim 1 or 2, wherein the hydrothermal synthesis reaction is performed after the first adsorption is completed, and the solvent used is water, acid or alkali.
5. The method for preparing and regenerating the secondary silica-based material adsorbent of claim 3, wherein the solvent used in the hydrothermal synthesis reaction after the first adsorption is completed is water, acid or alkali.
6. The method for preparing and regenerating the secondary silicon-based material adsorbent according to claim 1, 2 or 5, wherein the heavy metal wastewater comprises one or more of lead, copper, nickel, chromium, vanadium, manganese and titanium, and the concentration of heavy metal ions is 0.5-1000 mg/L.
7. The method for preparing and regenerating the secondary silicon-based material adsorbent according to claim 3, wherein the heavy metal wastewater comprises one or a mixture of more than two of lead, copper, nickel, chromium, vanadium, manganese and titanium, and the concentration of the heavy metal ions is 0.5-1000 mg/L.
8. The method for preparing and regenerating the secondary silicon-based material adsorbent according to claim 4, wherein the heavy metal wastewater comprises one or a mixture of more than two of lead, copper, nickel, chromium, vanadium, manganese and titanium, and the concentration of heavy metal ions is 0.5-1000 mg/L.
9. The method for preparing and regenerating a silicon-based material secondary adsorbent as set forth in claim 1, 2, 5, 7 or 8, wherein the mechanochemical reaction uses a reactor for providing agitation and extrusion with a device including a ball mill, a pulverizer, and a stirrer, and the stirring and extrusion force and energy are equivalent to 100-1000 rpm of the ball mill.
10. The method for preparing and regenerating a secondary silica-based adsorbent as set forth in claim 6, wherein the mechanochemical reaction uses a reactor for providing agitation and extrusion, including a ball mill, a pulverizer, and a stirrer, and the stirring and extrusion force and energy are equivalent to 100-1000 rpm of the rotation of the ball mill.
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CN103212367A (en) * | 2013-04-01 | 2013-07-24 | 北京工业大学 | Method for preparing binary oxide modified diatomite powder through recycled waste WC-TiC (wolfram carbide-titanium carbide) alloy |
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