CN107413318A - A kind of industrial wastes processing efficient nano adsorbent and preparation method thereof - Google Patents
A kind of industrial wastes processing efficient nano adsorbent and preparation method thereof Download PDFInfo
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- CN107413318A CN107413318A CN201710776988.4A CN201710776988A CN107413318A CN 107413318 A CN107413318 A CN 107413318A CN 201710776988 A CN201710776988 A CN 201710776988A CN 107413318 A CN107413318 A CN 107413318A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003463 adsorbent Substances 0.000 title claims abstract description 23
- 238000012545 processing Methods 0.000 title claims abstract description 16
- 239000002440 industrial waste Substances 0.000 title claims abstract description 10
- 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 33
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 32
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 229920001690 polydopamine Polymers 0.000 claims abstract description 18
- 239000000975 dye Substances 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- 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
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000011574 phosphorus Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 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 description 27
- 238000003756 stirring Methods 0.000 claims description 21
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- 229960003638 dopamine Drugs 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000005406 washing Methods 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
- 239000006227 byproduct Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000012266 salt solution Substances 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
- 150000002500 ions Chemical class 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 5
- -1 styrene-divinylbenzene ion Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 229920000858 Cyclodextrin Polymers 0.000 abstract 2
- 239000001116 FEMA 4028 Substances 0.000 abstract 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 abstract 2
- 229960004853 betadex Drugs 0.000 abstract 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- 239000002351 wastewater Substances 0.000 description 15
- 238000004176 ammonification Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 230000010355 oscillation Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000005253 cladding Methods 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
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing 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
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 244000005700 microbiome Species 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000009941 weaving Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a kind of industrial wastes processing preparation method of efficient nano adsorbent, specifically include：（1）The pretreatment of SDEB styrene diethylenebenzene ion exchange resin；（2）The preparation of the product of SDEB styrene diethylenebenzene ion exchange resin poly-dopamine crosslinking；（3）The modification of beta cyclodextrin；（4）The load of nano-metal-oxide；On the one hand adsorbent of the present invention has small nano aperture, high specific surface area by SDEB styrene diethylenebenzene ion exchange resin skeleton, there is provided extremely abundant adsorption site；On the other hand poly-dopamine is crosslinked in skeleton surface and its skeleton, modification beta cyclodextrin further improves absorption property；The very excellent nano adsorber of performance is obtained finally by load nano-oxide, the adsorbent all has very excellent performance in dyestuff waste liquid, waste liquid containing heavy metal, phosphorus, arsenic, antimony waste liquid.
Description
Technical field
The invention belongs to technical field of absorbent, and in particular to a kind of processing of industrial wastes with efficient nano adsorbent and its
Preparation method.
Background technology
With expanding economy, the chemical plant of various regions is more and more, the focus for being treated as all circles' concern of chemical waste fluid,
Traditional plating, process hides, Treatment of Metal Surface, printing and dyeing, petrochemical industry and waste liquid discharging amount containing other organic pollutions increasingly increases
Add.
Dyestuff is a class of pollutant common in waste water, mostlys come from weaving, leather, papermaking, rubber, plastics, cosmetic
In the production process of the industrial circles such as product, pharmacy and food.While being widely used in promotion economic development of dyestuff, also produces
Substantial amounts of waste water from dyestuff is discharged into environment water, result in the pollution of natural water.Therefore, the improvement to waste water from dyestuff oneself
One of study hotspot as water treatment field.In early days, conventional dye waste water treatment method mainly includes flocculent precipitation, changed
Learn oxidizing process, membrane separation process and biological degradation method.Although these methods can reduce dyestuff in waste water from dyestuff to a certain extent
Content, but still there is it is of all kinds the defects of, for example, because adsorption rate is low, processing cost it is too high with to waste water from dyestuff into
The bad adaptability of point change, result is not good enough to the removal effect of dyestuff, is also possible to produce in addition in processing procedure poisonous
Harmful side product or a large amount of sludge, so as to cause secondary pollution.
Process for treating heavy-metal waste water mainly has three classes：Chemically react removal method, Adsorption Concentration separation removal method and micro-
Biology or plant removal method.The first kind is that heavy metal ions in wastewater includes neutralization precipitation by the method removed that chemically reacts
Method, sulphide precipitation, ferrite coprecipitation, chemical reduction method, electrochemical reducing and high molecular heavy metals trapping agent method
Deng；Second class is the side for making the heavy metal in waste water be adsorbed, concentrated under conditions of its chemical form is not changed, separated
Method, including absorption, solvent extraction, evaporation and freezing method, ion exchange and UF membrane etc.；3rd class is by microorganism or plant
Flocculation, absorption, accumulation, the effect such as the enrichment method that removes heavy metal in waste water, including bioflocculation, biochemical process
With plant ecological reparation etc..The conventional processes generally existing cost of heavy metal wastewater thereby is high, reaction is slow, easily causes secondary dirt
The shortcomings of dye, difficult low concentration wastewater processing.
Adsorption treatment technology is a kind of technology of simple and effective processing waste water, containing heavy metal ion industrial wastewater, dye
It is widely used in the processing of material waste water, petrochemical wastewater etc..At present, the active charcoal absorption of Industrial Wastewater Treatment common technology, boiling
Stone exchange etc..Activated carbon is because of the features such as its is expensive, regeneration is complicated, it is difficult to large-scale use.Therefore, exploitation it is a kind of cheap,
The emphasis that property is stable, recyclable and excellent effect sorbing material is adsorption technology development at this stage.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of industrial wastes processing efficient nano
Adsorbent and preparation method thereof, adsorbent price is held high as existing for the adsorbent prepared by the inventive method solves prior art
Expensive, stability is poor, and adsorption efficiency is low, and after difficult for regeneration and regeneration the problem of effect difference, prospect is provided for industrial applications.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of industrial wastes processing preparation method of efficient nano adsorbent, comprises the following steps：
（1）The pretreatment of styrene-divinylbenzene ion exchange resin：At a temperature of 20-30 DEG C, by stryrene divinyl
Benzene ion exchange resin first washs 2-8h with ethanol, then uses 1mol/L salt acid elution 2-5h again, is finally washed with deionized water
Wash to neutrality and be dried for standby；
（2）Under continuous stirring, by step（1）Styrene-divinylbenzene ion exchange resin, the dopamine of pretreatment add
Into cushioning liquid, stirring reaction 12-24h, wash afterwards, be dried to obtain using styrene-divinylbenzene ion exchange resin as
Skeleton and the product for being crosslinked poly-dopamine；
（3）In the reactor, it is separately added into DMF 5-10g, beta-schardinger dextrin 1-2g, after stirring and dissolving, rises
For temperature to 50-60 DEG C, constant temperature is stirred at reflux 4-6h, then adds step（2）The stryrene divinyl of the crosslinking poly-dopamine of preparation
Benzene ion exchange resin 2-4g, the constant temperature back flow reaction 8-10h at 70 DEG C, reaction terminate rear product and washed several times with acetone, so
After dry, it is standby；
（4）By step（3）Obtained product is in the absence of oxygen with chitosan, metal salt solution at a temperature of 30-40 DEG C
6-12h is stirred, then filters, wash to obtain product；
（5）By step（4）Products therefrom adds alkali regulation pH to be 9-12, progress solid precipitation reaction, by product after reaction 12-24h
Filtering, washing, heat aging produce the nano adsorber.
Wherein, the step（2）The quality of middle styrene-divinylbenzene ion exchange resin is 5-10g, dopamine
Quality is 0.8-1.6g, and the volume of cushioning liquid is 300-400mL.
The cushioning liquid is Tris-HCl cushioning liquid, be by trishydroxymethylaminomethane (Tris) aqueous solution,
After 0.1 mo1/L mixed in hydrochloric acid, addition deionized water to 300-400mL is formulated.
The step（4）The addition of middle chitosan is 2-4g, and the molar concentration of metal salt solution is 0.5-2mol/L, its
Addition is 0.5-1.5g.
The metal salt solution includes Fe3+, Fe2+And Ni2+In one or more ions soluble sulphate, nitric acid
Salt or aqueous chloride solution.
The oxygen free condition is nitrogen protection or argon gas protective condition.
The step（5）In alkali be NaOH solution or ammonia spirit.
In addition, the nano adsorber being prepared by the preparation method is also claimed in the present invention.
Application of the claimed nano adsorber of the present invention in industrial wastes is handled, and the industrial wastes
Including dyestuff waste liquid, waste liquid containing heavy metal, phosphorus, arsenic, antimony waste liquid.
The present invention technique effect be：（1）Adsorbent of the present invention is with the stryrene divinyl with abundant nano-pore structure
Benzene ion exchange resin is basic framework, on the one hand, the nano aperture of the framework material is in 10-20nm, and specific surface area is high
In 600m2/ g, there is provided extremely abundant adsorption site, on the other hand, the framework material swellbility is minimum, and stability is preferable,
Iterative regenerable recycles, and cost is cheap；（2）The present invention is fixed on stryrene divinyl by the auto polymerization of dopamine
The surface of benzene ion exchange resin, poly-dopamine macromolecular chain not only wrap on styrene-divinylbenzene ion exchange resin surface
Cover modification, while intercalation plays to the bulk modified of skeleton through in whole skeleton, is obviously improved its adsorption capacity；（3）This
Invention is further modified the poly-dopamine of cladding using beta-schardinger dextrin, further extends its structure so that and styrene-
The surface of divinylbenzene ion exchange resin skeleton is woven into functional network structure, on the one hand improves its stability, another
Aspect increases its absorption property；（4）The present invention according to chitosan contains great amount of hydroxy group and the characteristic of amino, on the one hand can be with
By metal ion crosslinked in the load factor on framework material, improving metal ion, another aspect chitosan is due to containing abundant
Group, it can be removed from the aqueous solution with combination by the way that hydrogen bond, covalent bond or coordinate bond and organic molecule are firm, improve absorption
The absorption property of agent.
Embodiment
Technical scheme is further elaborated with reference to embodiment：
Embodiment 1
A kind of preparation method of efficient nano adsorbent, comprises the following steps：
（1）The pretreatment of styrene-divinylbenzene ion exchange resin：At a temperature of 30 DEG C, by styrene-divinylbenzene from
Sub-exchange resin first washs 4h with ethanol, then uses 1mol/L salt acid elution 4h again, is finally washed with deionized to neutrality
And it is dried for standby；
（2）Under continuous stirring, by step（1）Styrene-divinylbenzene ion exchange resin 8g, the dopamine 1g of pretreatment
It is added in 300mL Tris-HCl cushioning liquid, stirring reaction 24h, washs, is dried to obtain with stryrene divinyl afterwards
Benzene ion exchange resin is skeleton and is crosslinked the product of poly-dopamine；
（3）In the reactor, it is separately added into DMF 8g, beta-schardinger dextrin 1.5g, after stirring and dissolving, is warming up to
55 DEG C, constant temperature is stirred at reflux 5h, then adds step（2）The styrene-divinylbenzene ion of the crosslinking poly-dopamine of preparation is handed over
Resin 3g is changed, the constant temperature back flow reaction 9h at 70 DEG C, reaction terminates rear product and washed several times with acetone, then dries, standby；
（4）By step（3）Ferric chloride solution of the obtained product with 3g chitosans, 1g 1.5mol/L under conditions of nitrogen exists
8h is stirred at a temperature of 30 DEG C, then filters, wash to obtain product；
（5）By step（4）Products therefrom ammonification water regulation pH is 11, progress solid precipitation reaction, by product mistake after reaction 16h
Filter, washing, heat aging produce the nano adsorber.
Embodiment 2
A kind of preparation method of efficient nano adsorbent, comprises the following steps：
（1）The pretreatment of styrene-divinylbenzene ion exchange resin：At a temperature of 25 DEG C, by styrene-divinylbenzene from
Sub-exchange resin first washs 6h with ethanol, then uses 1mol/L salt acid elution 3h again, is finally washed with deionized to neutrality
And it is dried for standby；
（2）Under continuous stirring, by step（1）Styrene-divinylbenzene ion exchange resin 5g, the dopamine of pretreatment
0.8g is added in 300mL Tris-HCl cushioning liquid, stirring reaction 18h, is washed, is dried to obtain with styrene-two afterwards
Ethenylbenzene ion exchange resin is skeleton and is crosslinked the product of poly-dopamine；
（3）In the reactor, it is separately added into DMF 6g, beta-schardinger dextrin 1g, after stirring and dissolving, is warming up to 55
DEG C, constant temperature is stirred at reflux 5h, then adds step（2）The styrene-divinylbenzene ion exchange of the crosslinking poly-dopamine of preparation
Resin 2g, the constant temperature back flow reaction 10h at 70 DEG C, reaction terminates rear product and washed several times with acetone, then dried, standby；
（4）By step（3）Iron nitrate solution of the obtained product with 2g chitosans, 0.5g 1mol/L under conditions of nitrogen exists
10h is stirred at a temperature of 35 DEG C, then filters, wash to obtain product；
（5）By step（4）Products therefrom ammonification water regulation pH is 10, progress solid precipitation reaction, by product mistake after reaction 18h
Filter, washing, heat aging produce the nano adsorber.
Embodiment 3
A kind of preparation method of efficient nano adsorbent, comprises the following steps：
（1）The pretreatment of styrene-divinylbenzene ion exchange resin：At a temperature of 20 DEG C, by styrene-divinylbenzene from
Sub-exchange resin first washs 8h with ethanol, then uses 1mol/L salt acid elution 3h again, is finally washed with deionized to neutrality
And it is dried for standby；
（2）Under continuous stirring, by step（1）Styrene-divinylbenzene ion exchange resin 10g, the dopamine of pretreatment
1.6g is added in 350mL Tris-HCl cushioning liquid, stirring reaction 24h, is washed, is dried to obtain with styrene-two afterwards
Ethenylbenzene ion exchange resin is skeleton and is crosslinked the product of poly-dopamine；
（3）In the reactor, it is separately added into DMF 10g, beta-schardinger dextrin 2g, after stirring and dissolving, is warming up to 55
DEG C, constant temperature is stirred at reflux 5h, then adds step（2）The styrene-divinylbenzene ion exchange of the crosslinking poly-dopamine of preparation
Resin 4g, the constant temperature back flow reaction 10h at 70 DEG C, reaction terminates rear product and washed several times with acetone, then dried, standby；
（4）By step（3）Obtained product under conditions of argon gas with 3g chitosans, 1g 1mol/L nickel chloride solution 30
12h is stirred at a temperature of DEG C, then filters, wash to obtain product；
（5）By step（3）Products therefrom ammonification water regulation pH is 9, carries out solid precipitation reaction, filter product after reaction 24h,
Washing, heat aging produce the nano adsorber.
Embodiment 4
A kind of preparation method of efficient nano adsorbent, comprises the following steps：
（1）The pretreatment of styrene-divinylbenzene ion exchange resin：At a temperature of 25 DEG C, by styrene-divinylbenzene from
Sub-exchange resin first washs 7h with ethanol, then uses 1mol/L salt acid elution 4h again, is finally washed with deionized to neutrality
And it is dried for standby；
（2）Under continuous stirring, by step（1）Styrene-divinylbenzene ion exchange resin 7g, the dopamine 1g of pretreatment
It is added in 300mL Tris-HCl cushioning liquid, stirring reaction 16h, washs, is dried to obtain with stryrene divinyl afterwards
Benzene ion exchange resin is skeleton and is crosslinked the product of poly-dopamine；
（3）In the reactor, it is separately added into DMF 7g, beta-schardinger dextrin 1.2g, after stirring and dissolving, is warming up to
60 DEG C, constant temperature is stirred at reflux 4h, then adds step（2）The styrene-divinylbenzene ion of the crosslinking poly-dopamine of preparation is handed over
Resin 3g is changed, the constant temperature back flow reaction 9h at 70 DEG C, reaction terminates rear product and washed several times with acetone, then dries, standby；
（4）By step（3）Obtained product under conditions of nitrogen with 2.5g chitosans, 0.7g 1mol/L metal salt solution
8h is stirred at a temperature of 30 DEG C, then filters, wash to obtain product；
（5）By step（4）Products therefrom ammonification water regulation pH is 12, progress solid precipitation reaction, by product mistake after reaction 15h
Filter, washing, heat aging produce the nano adsorber.
Embodiment 5
A kind of preparation method of efficient nano adsorbent, comprises the following steps：
（1）The pretreatment of styrene-divinylbenzene ion exchange resin：At a temperature of 25 DEG C, by styrene-divinylbenzene from
Sub-exchange resin first washs 3h with ethanol, then uses 1mol/L salt acid elution 5h again, is finally washed with deionized to neutrality
And it is dried for standby；
（2）Under continuous stirring, by step（1）Styrene-divinylbenzene ion exchange resin 9g, the dopamine of pretreatment
0.9g is added in 320mL Tris-HCl cushioning liquid, stirring reaction 15h, is washed, is dried to obtain with styrene-two afterwards
Ethenylbenzene ion exchange resin is skeleton and is crosslinked the product of poly-dopamine；
（3）In the reactor, it is separately added into DMF 9g, beta-schardinger dextrin 1.6g, after stirring and dissolving, is warming up to
50 DEG C, constant temperature is stirred at reflux 5h, then adds step（2）The styrene-divinylbenzene ion of the crosslinking poly-dopamine of preparation is handed over
Resin 2.4g is changed, the constant temperature back flow reaction 8h at 70 DEG C, reaction terminates rear product and washed several times with acetone, then dries, standby；
（4）By step（3）Obtained product is molten with the metal salt of 2.5g chitosans, 0.8g 1.2mol/L under conditions of nitrogen
Liquid is stirred 8h at a temperature of 35 DEG C, then filters, washs to obtain product；
（5）By step（4）Products therefrom ammonification water regulation pH is 9, carries out solid precipitation reaction, filter product after reaction 16h,
Washing, heat aging produce the nano adsorber.
Comparative example 1
A kind of preparation method of nano adsorber, comprises the following steps：
（1）The pretreatment of styrene-divinylbenzene ion exchange resin：At a temperature of 30 DEG C, by styrene-divinylbenzene from
Sub-exchange resin first washs 4h with ethanol, then uses 1mol/L salt acid elution 4h again, is finally washed with deionized to neutrality
And it is dried for standby；
（2）By step（1）Ferric chloride solution of the obtained product with 3g chitosans, 1g 1.5mol/L under conditions of nitrogen exists
8h is stirred at a temperature of 30 DEG C, then filters, wash to obtain product；
（3）By step（2）Products therefrom ammonification water regulation pH is 11, progress solid precipitation reaction, by product mistake after reaction 16h
Filter, washing, heat aging produce the nano adsorber.
Adsorption experiment I:Embodiment 1-5 and comparative example 1 are to the adsorption experiment of the waste liquid containing phenol, its result such as table 1 below：
Adsorption experiment II:Embodiment 1-5 and comparative example 1 are to the absorption containing heavy metal ion industrial wastewater.
Take containing each ion concentration be respectively 8.Omg/L Cu2+, Sb3+, Zn2+, Hg2+Industrial wastewater 40mL, respectively
Adsorbent 0.05g is added, 100r/min constant temperature oscillations 2h, ICP (inductive coupling plasma emission spectrograph) are detected at 25 DEG C
Metal ion changes before and after reaction, and its result is as shown in table 2.
| Cu2+（Before processing concentration 8.0mg/L） | Sb3+（Before processing concentration 8.Omg/L） | Zn2+（Before processing concentration 8.0mg/L） | Hg2+（Before processing concentration 8.0mg/L） | |
| Implement Example 1 | 0.16 mg/L | 0.15 mg/L | 0.17 mg/L | 0.19 mg/L |
| Implement Example 2 | 0.19 mg/L | 0.18 mg/L | 0.20 mg/L | 0.20 mg/L |
| Implement Example 3 | 0.20 mg/L | 0.21 mg/L | 0.16 mg/L | 0.21 mg/L |
| Implement Example 4 | 0.17 mg/L | 0.20 mg/L | 0.19 mg/L | 0.18mg/L |
| Implement Example 5 | 0.21 mg/L | 0.18mg/L | 0.22 mg/L | 0.19 mg/L |
| Compare Example 1 | 4.24 mg/L | 4.05 mg/L | 4.12 mg/L | 4.13 mg/L |
It can be drawn by Tables 1 and 2, embodiment 1-5 adsorbent shows good absorption property, and is better than comparative example
1 adsorbent.
Adsorption experiment III：The absorption of embodiment 1-5 and comparative example 1 to the printing and dyeing industrial waste water containing methylene blue.
0.05g adsorbents accurately are weighed in 250mL conical flasks, add 50.OmL, concentration containing methylene blue is 100mg/L
Dyeing waste water solution, 100r/min at 25 DEG C, constant temperature oscillation takes from bottle at regular intervals to balancing in adsorption process
Clear liquid, it is as shown in table 3 with spectrophotometric determination solution concentration, its result.
It can be drawn by table 3, embodiment 1-5 adsorbent containing Congo red dyeing waste water solution to showing good suction
Attached performance and recycling performance, and better than the adsorbent of comparative example 1.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (9)
1. a kind of preparation method of industrial wastes processing efficient nano adsorbent, it is characterised in that comprise the following steps：
（1）The pretreatment of styrene-divinylbenzene ion exchange resin：At a temperature of 20-30 DEG C, by stryrene divinyl
Benzene ion exchange resin first washs 2-8h with ethanol, then uses 1mol/L salt acid elution 2-5h again, is finally washed with deionized water
Wash to neutrality and be dried for standby；
（2）Under continuous stirring, by step（1）Styrene-divinylbenzene ion exchange resin, the dopamine of pretreatment add
Into cushioning liquid, stirring reaction 12-24h, wash afterwards, be dried to obtain using styrene-divinylbenzene ion exchange resin as
Skeleton and the product for being crosslinked poly-dopamine；
（3）In the reactor, it is separately added into DMF 5-10g, beta-schardinger dextrin 1-2g, after stirring and dissolving, rises
For temperature to 50-60 DEG C, constant temperature is stirred at reflux 4-6h, then adds step（2）The stryrene divinyl of the crosslinking poly-dopamine of preparation
Benzene ion exchange resin 2-4g, the constant temperature back flow reaction 8-10h at 70 DEG C, reaction terminate rear product and washed several times with acetone, so
After dry, it is standby；
（4）By step（3）Obtained product is in the absence of oxygen with chitosan, metal salt solution at a temperature of 30-40 DEG C
6-12h is stirred, then filters, wash to obtain product；
（5）By step（4）Products therefrom adds alkali regulation pH to be 9-12, progress solid precipitation reaction, by product after reaction 12-24h
Filtering, washing, heat aging produce the nano adsorber.
2. preparation method according to claim 1, it is characterised in that the step（2）Middle styrene-divinylbenzene ion
The quality of exchanger resin is 5-10g, and the quality of dopamine is 0.8-1.6g, and the volume of cushioning liquid is 300-400mL.
3. preparation method according to claim 2, it is characterised in that the cushioning liquid is Tris-HCl cushioning liquid,
It is by trishydroxymethylaminomethane (Tris) aqueous solution, after 0.1 mo1/L mixed in hydrochloric acid, adds deionized water extremely
300-400mL is formulated.
4. preparation method according to claim 3, it is characterised in that the step（4）The addition of middle chitosan is 2-
4g, the molar concentration of metal salt solution is 0.5-2mol/L, and its addition is 0.5-1.5g.
5. according to the preparation method described in claim any one of 1-4, it is characterised in that the metal salt solution includes Fe3+,
Fe2+And Ni2+In one or more ions soluble sulphate, nitrate or aqueous chloride solution.
6. according to the preparation method described in claim any one of 1-5, it is characterised in that the oxygen free condition be nitrogen protect or
Argon gas protective condition.
7. according to the preparation method described in claim any one of 1-5, it is characterised in that the step（5）In alkali be NaOH
Solution or ammonia spirit.
8. the nano adsorber being prepared according to any one of the claim 1-7 preparation methods.
A kind of 9. application of the nano adsorber described in claim 8 in industrial wastes is handled, it is characterised in that the Industry Waste
Liquid includes dyestuff waste liquid, waste liquid containing heavy metal, phosphorus, arsenic, antimony waste liquid.
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