CN107413318B - Efficient nano adsorbent for industrial waste liquid treatment and preparation method thereof - Google Patents
Efficient nano adsorbent for industrial waste liquid treatment and preparation method thereof Download PDFInfo
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- CN107413318B CN107413318B CN201710776988.4A CN201710776988A CN107413318B CN 107413318 B CN107413318 B CN 107413318B CN 201710776988 A CN201710776988 A CN 201710776988A CN 107413318 B CN107413318 B CN 107413318B
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- styrene
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- exchange resin
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002440 industrial waste Substances 0.000 title claims abstract description 12
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 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 claims abstract description 45
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 45
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 45
- 229920001690 polydopamine Polymers 0.000 claims abstract description 19
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 10
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 10
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 10
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 10
- 229960004853 betadex Drugs 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010919 dye waste Substances 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 24
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229920001661 Chitosan Polymers 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 239000007853 buffer solution Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229960003638 dopamine Drugs 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000001723 curing Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 11
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 40
- 239000002351 wastewater Substances 0.000 description 13
- 239000000975 dye Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010842 industrial wastewater Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 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 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention provides a preparation method of an efficient nano adsorbent for industrial waste liquid treatment, which specifically comprises the following steps: (1) pretreating styrene-divinylbenzene ion exchange resin; (2) preparing a styrene-divinylbenzene ion exchange resin-polydopamine cross-linked product; (3) modification of beta-cyclodextrin; (4) loading of nano metal oxide; on one hand, the adsorbent has small nano-aperture and high specific surface area through a styrene-divinylbenzene ion exchange resin framework, and provides abundant adsorption sites; on the other hand, polydopamine is crosslinked on the surface of the framework and in the framework of the framework, and beta-cyclodextrin is modified to further improve the adsorption performance; finally, the nano-adsorbent with excellent performance is obtained by loading the nano-oxide, and the nano-adsorbent has excellent performance in dye waste liquid, heavy metal-containing waste liquid, phosphorus, arsenic and antimony waste liquid.
Description
Technical Field
The invention belongs to the technical field of adsorbents, and particularly relates to an efficient nano adsorbent for treating industrial waste liquid and a preparation method thereof.
Background
With the development of economy, chemical plants in various regions are more and more, the treatment of chemical waste liquid becomes a focus of attention of all the world, and the discharge amount of the traditional electroplating, tanning, metal surface treatment, printing and dyeing, petrifaction and waste liquid containing other organic pollutants is increased day by day.
Dyes are a common pollutant in wastewater, and mainly come from the production process in the industrial fields of textile, leather, paper making, rubber, plastics, cosmetics, pharmacy, food and the like. The wide use of dyes promotes economic development, and simultaneously produces a large amount of dye wastewater to be discharged into environmental water, resulting in pollution of natural water. Therefore, the treatment of dye wastewater has become one of the research hotspots in the field of water treatment. In the early days, the commonly used dye wastewater treatment methods mainly include flocculation precipitation, chemical oxidation, membrane separation and biodegradation. Although these methods can reduce the content of the dye in the dye wastewater to some extent, they still have various disadvantages, such as low adsorption rate, excessive treatment cost, and poor adaptability to the change of the components of the dye wastewater, resulting in poor dye removal effect, and may generate toxic and harmful byproducts or a large amount of sludge during the treatment process, thereby causing secondary pollution.
The heavy metal wastewater treatment method mainly comprises three types: chemical reaction removal, adsorption concentration separation removal, and microorganism or plant removal. The first kind is the method for removing heavy metal ions in the wastewater by chemical reaction, which comprises a neutralization precipitation method, a sulfide precipitation method, a ferrite coprecipitation method, a chemical reduction method, an electrochemical reduction method, a high molecular heavy metal collector method and the like; the second is a method for absorbing, concentrating and separating heavy metals in the wastewater under the condition of not changing the chemical forms of the heavy metals, and comprises the methods of absorption, solvent extraction, evaporation and solidification, ion exchange, membrane separation and the like; the third category is a method for removing heavy metals in wastewater by the flocculation, absorption, accumulation, enrichment and the like of microorganisms or plants, wherein the method comprises biological flocculation, biochemical methods, plant ecological restoration and the like. The traditional treatment process of heavy metal wastewater generally has the defects of high cost, slow reaction, easy secondary pollution, difficult low-concentration wastewater treatment and the like.
The adsorption treatment technology is a simple and effective wastewater treatment technology and is widely applied to treatment of industrial wastewater containing heavy metal ions, dye wastewater, petrochemical wastewater and the like. Currently, the common techniques for industrial wastewater treatment include activated carbon adsorption, zeolite exchange, and the like. The activated carbon is difficult to use in large scale due to its high price and complex regeneration. Therefore, the development of an inexpensive, stable, recyclable and effective adsorbent material is the focus of the development of adsorption technology at this stage.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the efficient nano adsorbent for treating the industrial waste liquid and the preparation method thereof.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of an efficient nano adsorbent for industrial waste liquid treatment comprises the following steps:
(1) pretreatment of styrene-divinylbenzene ion exchange resin: washing styrene-divinylbenzene ion exchange resin with ethanol for 2-8h at the temperature of 20-30 ℃, then washing with 1mol/L hydrochloric acid for 2-5h, finally washing with deionized water to neutrality and drying for later use;
(2) under the condition of continuous stirring, adding the styrene-divinylbenzene ion exchange resin pretreated in the step (1) and dopamine into a buffer solution, stirring and reacting for 12-24h, and then washing and drying to obtain a product which takes the styrene-divinylbenzene ion exchange resin as a framework and cross-links polydopamine;
(3) respectively adding 5-10g of N, N-dimethylformamide and 1-2g of beta-cyclodextrin into a reactor, stirring and dissolving, heating to 50-60 ℃, stirring and refluxing at constant temperature for 4-6h, then adding 2-4g of the styrene-divinylbenzene ion exchange resin of the cross-linked polydopamine prepared in the step (2), refluxing at constant temperature at 70 ℃ for 8-10h, washing the product with acetone for several times after the reaction is finished, and drying for later use;
(4) stirring and mixing the product obtained in the step (3) with chitosan and a metal salt solution at the temperature of 30-40 ℃ for 6-12h under an oxygen-free condition, and then filtering and washing to obtain a product;
(5) and (4) adding alkali into the product obtained in the step (4) to adjust the pH value to 9-12, carrying out solid phase deposition reaction, filtering, washing, heating and curing the product after 12-24h reaction to obtain the nano adsorbent.
Wherein, the mass of the styrene-divinylbenzene ion exchange resin in the step (2) is 5 to 10g, the mass of the dopamine is 0.8 to 1.6g, and the volume of the buffer solution is 300-400 mL.
The buffer solution is Tris-HCl buffer solution, and is prepared by mixing aqueous solution of Tris (hydroxymethyl) aminomethane (Tris) with 0.1 mo1/L hydrochloric acid, and adding deionized water to 300-400 mL.
In the step (4), the addition amount of the chitosan is 2-4g, the molar concentration of the metal salt solution is 0.5-2mol/L, and the addition amount is 0.5-1.5 g.
The metal salt solution comprises Fe3+, Fe2+And Ni2+An aqueous solution of one or more soluble sulfate, nitrate or chloride ions.
The anaerobic condition is a nitrogen protection condition or an argon protection condition.
And (3) the alkali in the step (5) is NaOH solution or ammonia water solution.
In addition, the invention also claims the nano adsorbent prepared by the preparation method.
The invention also claims the application of the nano adsorbent in treating industrial waste liquid, and the industrial waste liquid comprises dye waste liquid, heavy metal-containing waste liquid, and phosphorus, arsenic and antimony waste liquid.
The invention has the technical effects that: (1) the adsorbent of the invention takes styrene-divinylbenzene ion exchange resin with rich nano-pore structure as a basic framework, on one hand, the nano-pore diameter of the framework material is 10-20nm, and the specific surface area is higher than 600m2The dopamine-containing skeleton material has the advantages that (1) the dopamine-containing skeleton material is fixed on the surface of styrene-divinylbenzene ion exchange resin through self-polymerization, a polydopamine macromolecular chain is not only coated and modified on the surface of the styrene-divinylbenzene ion exchange resin, but also penetrates through the whole skeleton to perform integral modification on the skeleton and remarkably improve the adsorption capacity of the styrene-divinylbenzene ion exchange resin, and (3) the coated polydopamine is further modified by β -cyclodextrin to further extend the structure of the polydopamine, so that benzene is enabled to be adsorbed on the surface of the styrene-divinylbenzene ion exchange resinThe surface of the ethylene-divinylbenzene ion exchange resin skeleton is interwoven into a functional net structure, so that the stability of the resin is improved on one hand, and the adsorption performance of the resin is improved on the other hand; (4) according to the characteristic that chitosan contains a large number of hydroxyl and amino, on one hand, metal ions can be crosslinked on a framework material to improve the loading rate of the metal ions, and on the other hand, the chitosan contains abundant groups, so that the chitosan can be removed from an aqueous solution through the firm and same combination of hydrogen bonds, covalent bonds or coordination bonds and organic molecules, and the adsorption performance of the adsorbent is improved.
Detailed Description
The technical scheme of the invention is further explained by combining the embodiment as follows:
example 1
A preparation method of a high-efficiency nano adsorbent comprises the following steps:
(1) pretreatment of styrene-divinylbenzene ion exchange resin: washing styrene-divinylbenzene ion exchange resin with ethanol for 4h at the temperature of 30 ℃, then washing with 1mol/L hydrochloric acid for 4h, finally washing with deionized water to be neutral and drying for later use;
(2) under continuous stirring, adding 8g of the styrene-divinylbenzene ion exchange resin pretreated in the step (1) and 1g of dopamine into 300mL of Tris-HCl buffer solution, stirring for reaction for 24h, and then washing and drying to obtain a product which takes the styrene-divinylbenzene ion exchange resin as a framework and is crosslinked with polydopamine;
(3) respectively adding 8g of N, N-dimethylformamide and 1.5g of beta-cyclodextrin into a reactor, stirring and dissolving, heating to 55 ℃, stirring and refluxing at constant temperature for 5h, then adding 3g of the styrene-divinylbenzene ion exchange resin of the cross-linked polydopamine prepared in the step (2), refluxing at constant temperature at 70 ℃ for 9h, washing the product with acetone for several times after the reaction is finished, and drying for later use;
(4) stirring and mixing the product obtained in the step (3) with 3g of chitosan and 1g of 1.5mol/L ferric chloride solution at the temperature of 30 ℃ for 8 hours under the condition of nitrogen, and then filtering and washing to obtain a product;
(5) and (4) adding ammonia water into the product obtained in the step (4) to adjust the pH value to 11, carrying out solid phase deposition reaction, filtering, washing, heating and curing the product after reacting for 16 hours to obtain the nano adsorbent.
Example 2
A preparation method of a high-efficiency nano adsorbent comprises the following steps:
(1) pretreatment of styrene-divinylbenzene ion exchange resin: washing styrene-divinylbenzene ion exchange resin with ethanol for 6h at the temperature of 25 ℃, then washing with 1mol/L hydrochloric acid for 3h, finally washing with deionized water to be neutral and drying for later use;
(2) under continuous stirring, adding 5g of the styrene-divinylbenzene ion exchange resin pretreated in the step (1) and 0.8g of dopamine into 300mL of Tris-HCl buffer solution, stirring for reacting for 18h, and then washing and drying to obtain a product which takes the styrene-divinylbenzene ion exchange resin as a framework and crosslinks polydopamine;
(3) respectively adding 6g of N, N-dimethylformamide and 1g of beta-cyclodextrin into a reactor, stirring and dissolving, heating to 55 ℃, stirring and refluxing at constant temperature for 5h, then adding 2g of the styrene-divinylbenzene ion exchange resin of the cross-linked polydopamine prepared in the step (2), refluxing at constant temperature at 70 ℃ for 10h, washing the product with acetone for several times after the reaction is finished, and drying for later use;
(4) stirring and mixing the product obtained in the step (3) with 2g of chitosan and 0.5g of 1mol/L ferric nitrate solution at the temperature of 35 ℃ for 10 hours under the condition of nitrogen, and then filtering and washing to obtain a product;
(5) and (4) adding ammonia water into the product obtained in the step (4) to adjust the pH value to 10, carrying out solid phase deposition reaction, filtering, washing, heating and curing the product after reacting for 18h to obtain the nano adsorbent.
Example 3
A preparation method of a high-efficiency nano adsorbent comprises the following steps:
(1) pretreatment of styrene-divinylbenzene ion exchange resin: washing styrene-divinylbenzene ion exchange resin with ethanol for 8 hours at the temperature of 20 ℃, then washing with 1mol/L hydrochloric acid for 3 hours, finally washing with deionized water to be neutral and drying for later use;
(2) under continuous stirring, adding 10g of the styrene-divinylbenzene ion exchange resin pretreated in the step (1) and 1.6g of dopamine into 350mL of Tris-HCl buffer solution, stirring for reaction for 24h, and then washing and drying to obtain a product which takes the styrene-divinylbenzene ion exchange resin as a framework and crosslinks polydopamine;
(3) respectively adding 10g of N, N-dimethylformamide and 2g of beta-cyclodextrin into a reactor, stirring and dissolving, heating to 55 ℃, stirring and refluxing at constant temperature for 5h, then adding 4g of the styrene-divinylbenzene ion exchange resin of the cross-linked polydopamine prepared in the step (2), refluxing at constant temperature at 70 ℃ for 10h, washing the product with acetone for several times after the reaction is finished, and drying for later use;
(4) stirring and mixing the product obtained in the step (3) with 3g of chitosan and 1g of 1mol/L nickel chloride solution at the temperature of 30 ℃ for 12 hours under the condition of argon, and then filtering and washing to obtain a product;
(5) and (4) adding ammonia water into the product obtained in the step (3) to adjust the pH value to 9, carrying out solid phase deposition reaction, filtering, washing, heating and curing the product after 24 hours of reaction to obtain the nano adsorbent.
Example 4
A preparation method of a high-efficiency nano adsorbent comprises the following steps:
(1) pretreatment of styrene-divinylbenzene ion exchange resin: washing styrene-divinylbenzene ion exchange resin with ethanol for 7 hours at the temperature of 25 ℃, then washing with 1mol/L hydrochloric acid for 4 hours, finally washing with deionized water to be neutral and drying for later use;
(2) under continuous stirring, adding 7g of the styrene-divinylbenzene ion exchange resin pretreated in the step (1) and 1g of dopamine into 300mL of Tris-HCl buffer solution, stirring for reacting for 16h, and then washing and drying to obtain a product which takes the styrene-divinylbenzene ion exchange resin as a framework and is crosslinked with polydopamine;
(3) respectively adding 7g of N, N-dimethylformamide and 1.2g of beta-cyclodextrin into a reactor, stirring and dissolving, heating to 60 ℃, stirring and refluxing at constant temperature for 4h, then adding 3g of the styrene-divinylbenzene ion exchange resin of the cross-linked polydopamine prepared in the step (2), refluxing at constant temperature at 70 ℃ for 9h, washing the product with acetone for several times after the reaction is finished, and drying for later use;
(4) stirring and mixing the product obtained in the step (3) with 2.5g of chitosan and 0.7g of 1mol/L metal salt solution at the temperature of 30 ℃ for 8 hours under the condition of nitrogen, and then filtering and washing to obtain a product;
(5) and (4) adding ammonia water into the product obtained in the step (4) to adjust the pH value to 12, carrying out solid phase deposition reaction, filtering, washing, heating and curing the product after reacting for 15 hours to obtain the nano adsorbent.
Example 5
A preparation method of a high-efficiency nano adsorbent comprises the following steps:
(1) pretreatment of styrene-divinylbenzene ion exchange resin: washing the styrene-divinylbenzene ion exchange resin with ethanol for 3h at the temperature of 25 ℃, then washing with 1mol/L hydrochloric acid for 5h, finally washing with deionized water to neutrality and drying for later use;
(2) adding 9g of the styrene-divinylbenzene ion exchange resin pretreated in the step (1) and 0.9g of dopamine into 320mL of Tris-HCl buffer solution under continuous stirring, stirring for reacting for 15h, and then washing and drying to obtain a product which takes the styrene-divinylbenzene ion exchange resin as a framework and crosslinks polydopamine;
(3) respectively adding 9g of N, N-dimethylformamide and 1.6g of beta-cyclodextrin into a reactor, stirring and dissolving, heating to 50 ℃, stirring and refluxing at constant temperature for 5h, then adding 2.4g of the styrene-divinylbenzene ion exchange resin of the cross-linked polydopamine prepared in the step (2), refluxing at constant temperature at 70 ℃ for 8h, washing a product with acetone for several times after the reaction is finished, and drying for later use;
(4) stirring and mixing the product obtained in the step (3) with 2.5g of chitosan and 0.8g of 1.2mol/L metal salt solution at the temperature of 35 ℃ for 8 hours under the condition of nitrogen, and then filtering and washing to obtain a product;
(5) and (4) adding ammonia water into the product obtained in the step (4) to adjust the pH value to 9, carrying out solid phase deposition reaction, filtering, washing, heating and curing the product after reacting for 16 hours to obtain the nano adsorbent.
Comparative example 1
A preparation method of a nano adsorbent comprises the following steps:
(1) pretreatment of styrene-divinylbenzene ion exchange resin: washing styrene-divinylbenzene ion exchange resin with ethanol for 4h at the temperature of 30 ℃, then washing with 1mol/L hydrochloric acid for 4h, finally washing with deionized water to be neutral and drying for later use;
(2) stirring and mixing the product obtained in the step (1) with 3g of chitosan and 1g of 1.5mol/L ferric chloride solution at the temperature of 30 ℃ for 8 hours under the condition of nitrogen, and then filtering and washing to obtain a product;
(3) and (3) adding ammonia water into the product obtained in the step (2) to adjust the pH value to 11, carrying out solid phase deposition reaction, filtering, washing, heating and curing the product after reacting for 16h to obtain the nano adsorbent.
Adsorption experiment I examples 1 to 5 and comparative example 1 the results of the adsorption experiment on phenol-containing waste liquid are shown in Table 1 below:
adsorption experiment II adsorption of heavy metal ion-containing industrial wastewater according to examples 1 to 5 and comparative example 1.
Taking Cu with each ion concentration of 8, Omg/L2+, Sb3+, Zn2+, Hg2+40mL of the industrial wastewater solutions were added with 0.05g of each adsorbent, and the solutions were shaken at a constant temperature of 100r/min at 25 ℃ for 2 hours, and the changes of the metal ions before and after the reaction were detected by ICP (inductively coupled plasma emission spectrometer), and the results are shown in Table 2.
| Cu2+(concentration 8.0mg/L before treatment) | Sb3+(concentration before treatment 8. Omg/L) | Zn2+(concentration 8.0mg/L before treatment) | Hg2+(concentration 8.0mg/L before treatment) | |
| Example 1 | 0.16 mg/L | 0.15 mg/L | 0.17 mg/L | 0.19 mg/L |
| Example 2 | 0.19 mg/L | 0.18 mg/L | 0.20 mg/L | 0.20 mg/L |
| Example 3 | 0.20 mg/L | 0.21 mg/L | 0.16 mg/L | 0.21 mg/L |
| Example 4 | 0.17 mg/L | 0.20 mg/L | 0.19 mg/L | 0.18mg/L |
| Example 5 | 0.21 mg/L | 0.18mg/L | 0.22 mg/L | 0.19 mg/L |
| Comparative example 1 | 4.24 mg/L | 4.05 mg/L | 4.12 mg/L | 4.13 mg/L |
As can be seen from tables 1 and 2, the adsorbents of examples 1 to 5 all showed good adsorption performance and were superior to the adsorbent of comparative example 1.
Adsorption experiment III: examples 1 to 5 and comparative example 1 adsorption of printing and dyeing industrial wastewater containing methylene blue.
0.05g of the adsorbent was accurately weighed into a 250mL conical flask, 50, OmL of a printing and dyeing wastewater solution containing methylene blue at a concentration of 100mg/L was added, the mixture was shaken at a constant temperature at 25 ℃ for 100r/min until equilibrium was reached, the supernatant liquid was taken from the flask at regular intervals during the adsorption, the solution concentration was measured by a spectrophotometer, and the results are shown in Table 3.
As can be seen from Table 3, the adsorbents of examples 1 to 5 all showed good adsorption performance and recycling performance for printing and dyeing wastewater solutions containing Congo red, and were superior to the adsorbent of comparative example 1.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of an efficient nano adsorbent for industrial waste liquid treatment is characterized by comprising the following steps:
(1) pretreatment of styrene-divinylbenzene ion exchange resin: washing styrene-divinylbenzene ion exchange resin with ethanol for 2-8h at the temperature of 20-30 ℃, then washing with 1mol/L hydrochloric acid for 2-5h, finally washing with deionized water to neutrality and drying for later use;
(2) under the condition of continuous stirring, adding the styrene-divinylbenzene ion exchange resin pretreated in the step (1) and dopamine into a buffer solution, stirring and reacting for 12-24h, and then washing and drying to obtain a product which takes the styrene-divinylbenzene ion exchange resin as a framework and cross-links polydopamine;
(3) respectively adding 5-10g of N, N-dimethylformamide and 1-2g of beta-cyclodextrin into a reactor, stirring and dissolving, heating to 50-60 ℃, stirring and refluxing at constant temperature for 4-6h, then adding 2-4g of the styrene-divinylbenzene ion exchange resin of the cross-linked polydopamine prepared in the step (2), refluxing at constant temperature at 70 ℃ for 8-10h, washing the product with acetone for several times after the reaction is finished, and drying for later use;
(4) stirring and mixing the product obtained in the step (3) with chitosan and a metal salt solution at the temperature of 30-40 ℃ for 6-12h under an oxygen-free condition, and then filtering and washing to obtain a product;
the metal salt solution comprises Fe3+, Fe2+And Ni2+An aqueous solution of one or more soluble sulfate, nitrate or chloride ions of (a);
(5) and (4) adding alkali into the product obtained in the step (4) to adjust the pH value to 9-12, carrying out solid phase deposition reaction, filtering, washing, heating and curing the product after 12-24h reaction to obtain the nano adsorbent.
The mass of the styrene-divinylbenzene ion exchange resin in the step (2) is 5-10g, the mass of the dopamine is 0.8-1.6g, and the volume of the buffer solution is 300-400 mL;
the industrial waste liquid comprises dye waste liquid and phosphorus, arsenic and antimony waste liquid.
2. The method as claimed in claim 1, wherein the buffer solution is Tris-HCl buffer solution, which is prepared by mixing Tris (hydroxymethyl) aminomethane aqueous solution with 0.1 mo1/L hydrochloric acid, and adding deionized water to 300-400 mL.
3. The method according to claim 2, wherein the chitosan is added in an amount of 2 to 4g, the metal salt solution has a molar concentration of 0.5 to 2mol/L, and the chitosan is added in an amount of 0.5 to 1.5g in the step (4).
4. The method of claim 3, wherein the oxygen-free condition is a nitrogen protection condition or an argon protection condition.
5. The production method according to any one of claims 1 to 4, wherein the base in the step (5) is NaOH solution or aqueous ammonia solution.
6. The nano adsorbent prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the nano-adsorbent of claim 6 in the treatment of industrial waste streams, wherein the industrial waste streams include dye waste streams, phosphorus, arsenic and antimony waste streams.
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