CN113428930A - Organic wastewater treatment method based on high-performance polyaniline aerogel - Google Patents
Organic wastewater treatment method based on high-performance polyaniline aerogel Download PDFInfo
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- CN113428930A CN113428930A CN202110745385.4A CN202110745385A CN113428930A CN 113428930 A CN113428930 A CN 113428930A CN 202110745385 A CN202110745385 A CN 202110745385A CN 113428930 A CN113428930 A CN 113428930A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 106
- 239000004964 aerogel Substances 0.000 title claims abstract description 98
- 238000004065 wastewater treatment Methods 0.000 title abstract description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000002351 wastewater Substances 0.000 claims abstract description 55
- 238000001179 sorption measurement Methods 0.000 claims abstract description 42
- 238000011069 regeneration method Methods 0.000 claims abstract description 28
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 24
- 230000008929 regeneration Effects 0.000 claims abstract description 21
- 239000002156 adsorbate Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 13
- 230000015556 catabolic process Effects 0.000 claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 239000000017 hydrogel Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 24
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 14
- 238000007710 freezing Methods 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 14
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010257 thawing Methods 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 12
- 229920000742 Cotton Polymers 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims description 8
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
- 241001330002 Bambuseae Species 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- 229940109262 curcumin Drugs 0.000 claims description 4
- 235000012754 curcumin Nutrition 0.000 claims description 4
- 239000004148 curcumin Substances 0.000 claims description 4
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 claims description 4
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 239000012425 OXONE® Substances 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- YMGGAHMANIOXGP-UHFFFAOYSA-L disodium;oxido sulfate Chemical compound [Na+].[Na+].[O-]OS([O-])(=O)=O YMGGAHMANIOXGP-UHFFFAOYSA-L 0.000 claims 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000006835 compression Effects 0.000 abstract description 6
- 238000007906 compression Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 2
- 150000002505 iron Chemical class 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- 230000000593 degrading effect Effects 0.000 description 7
- 230000001172 regenerating effect Effects 0.000 description 7
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- BUFQZEHPOKLSTP-UHFFFAOYSA-M sodium;oxido hydrogen sulfate Chemical compound [Na+].OS(=O)(=O)O[O-] BUFQZEHPOKLSTP-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical group C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Chemical & Material Sciences (AREA)
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an organic wastewater treatment method based on high-performance polyaniline aerogel. The mechanical strength of polyaniline is enhanced by introducing carboxylated cellulose fibers in the polymerization process of aniline, and rich carboxyl of the carboxylated cellulose fibers is used for complexing Fe3+And the polyaniline aerogel adsorbing material with good compression mechanical property and excellent adsorption property is prepared. Putting the obtained aerogel into organic wastewater for adsorption, taking out the aerogel after the adsorption is saturated, putting the aerogel into a regeneration solution containing an oxidant, and utilizing Fe in the aerogel3+Activated oxidant generationThe free radicals realize the degradation of the organic adsorbate and the regeneration of the polyaniline aerogel. The invention effectively solves the problems that the conventional polyaniline adsorbing material is in a powder shape, is difficult to recover, and is easy to generate secondary pollution after adsorbing organic matters, and provides a new idea and a new method for effectively purifying organic wastewater.
Description
Technical Field
The invention belongs to the field of environmental management, and particularly relates to a method for treating organic wastewater based on high-performance polyaniline aerogel.
Background
As a large country for producing fine chemicals in China, the organic wastewater discharge amount is at the top of the world. The organic wastewater has high organic matter content, mostly exists in the form of aromatic groups such as benzene, naphthalene, anthracene, quinone and the like, and has the characteristics of complex and variable components, stable chemical properties, difficult biodegradation and the like. Therefore, how to efficiently remove organic pollutants in organic wastewater becomes a difficult point and a hot point for environmental management. Among the various methods for treating organic wastewater, the adsorption method is considered to be one of the most effective methods for treating organic wastewater due to its advantages of simple operation, high treatment efficiency, low energy consumption, etc. Therefore, the development of the low-cost and high-performance adsorbing material has important significance for environmental management.
The polyaniline has the characteristics of low cost, good environmental stability, high specific surface area, rich adsorption active sites and the like, and has wide application prospect in adsorbing and removing organic pollutants in wastewater. Yan and the like synthesize a three-dimensional coralliform polyaniline layered micro-nano structure by adjusting a traditional chemical oxidation method, and realize effective adsorption on acid red G under the conditions that the pH is 2.0 and 298K, wherein the maximum adsorption capacity is as high as 310mg/G [ Polymer,2019,162:130-1 ]. Akti et al synthesized polyaniline/zeolite composite materials by chemical oxidative polymerization technique, which exhibited excellent adsorption properties to acid violet 90 dye [ Journal of Polymers and the Environment,2018,26(11):4233-4242 ]. Although polyaniline and the composite material thereof exhibit excellent adsorption performance on organic matters in wastewater, the practical application of polyaniline and the composite material thereof still has the following limitations: firstly, polyaniline is usually in powder particle shape and is difficult to separate, recover and reuse; secondly, the regeneration process of the polyaniline and the composite material thereof mainly desorbs adsorbates through acid washing or alkali washing, and a large amount of secondary wastewater is easy to generate. Therefore, the development of a high-performance polyaniline adsorption material which is easy to recover and does not produce secondary pollution is still very challenging.
The invention provides a high-performance polymerAniline aerogel preparation and adsorption-regeneration integrated organic wastewater treatment method. The carboxylated cellulose fiber is introduced in the polymerization process of the polyaniline to enhance the mechanical strength of the polyaniline, so that the polyaniline aerogel with good compression mechanical property and excellent adsorption property is obtained. In addition, Fe is added in the preparation process3+Complexing it with the rich carboxyl groups of carboxylated cellulose fibers by using Fe3+The advanced oxidation technology of activating the oxidant to generate free radicals can realize the degradation of organic adsorbates and the regeneration of polyaniline aerogel.
The preparation of the polyaniline aerogel and the method for treating organic wastewater by integrating adsorption and regeneration are environment-friendly, simple and efficient, and provide a new idea and a new method for effectively purifying organic wastewater.
Disclosure of Invention
The invention provides an organic wastewater treatment method based on high-performance polyaniline aerogel. According to the invention, the carboxylated cellulose fiber is introduced into an aniline polymerization system, and the mechanical strength of polyaniline is enhanced by utilizing the hydrogen bond effect of the carboxylated cellulose fiber and aniline, so that the polyaniline aerogel adsorption material with good compression mechanical property and excellent adsorption property is obtained to degrade the organic adsorbate in the organic wastewater.
Technical scheme
A method for treating organic wastewater based on high-performance polyaniline aerogel is characterized by comprising the following steps:
(1) mixing 20mL of 0.1-0.5 mmol/L ferric salt solution and 0.5-2 mL aniline monomer, slowly adding 0.5-2 g of carboxylated cellulose fiber under stirring, taking out after 10min, placing in a mold, freezing for 5-12 h, thawing to obtain hydrogel, soaking the hydrogel in an acidic solution containing an oxidant for 7-24 h to oxidize and polymerize aniline, washing with ethanol and deionized water, and freeze-drying to obtain the polyaniline aerogel.
(2) And (3) putting a proper amount of polyaniline aerogel into the organic wastewater, taking out the polyaniline aerogel after the polyaniline aerogel is saturated by adsorption, putting the polyaniline aerogel into a 0.5-5 mmol/L regeneration solution for 30min, so as to realize the degradation of organic adsorbates and the regeneration of the polyaniline aerogel, wherein the regenerated polyaniline aerogel can be repeatedly used.
Preferably, the iron salt is one or more of ferric nitrate nonahydrate, ferric chloride hexahydrate and ferric sulfate hydrate.
Preferably, the cellulose fiber is one or more of cotton fiber, bamboo fiber, wood pulp fiber and curcumin fiber.
Preferably, the molar ratio of the oxidant to the aniline monomer is (1-3): 1, the oxidant is one or more of ferric nitrate nonahydrate, ferric trichloride hexahydrate, ammonium persulfate and potassium dichromate.
Preferably, the regeneration solution is one or more of hydrogen peroxide, sodium persulfate, potassium persulfate, sodium hydrogen peroxymonosulfate, potassium peroxymonosulfate.
The invention has the following beneficial effects:
(1) the polyaniline aerogel prepared by the method has compression resilience, is not easy to damage in a macroscopic block structure, and is easy to separate, recover and recycle.
(2) The polyaniline aerogel prepared by the invention can effectively adsorb organic pollutants in wastewater, is separated from water and then is immersed in a regeneration solution, so that the adsorbed organic pollutants can be rapidly degraded, and meanwhile, the regeneration of the polyaniline aerogel is realized.
(3) Adding Fe in the preparation process of polyaniline aerogel3+Complexing it with the rich carboxyl groups of carboxylated cellulose fibers by using Fe3+The advanced oxidation technology of activating the oxidant to generate free radicals can realize the degradation of organic adsorbates and the regeneration of polyaniline aerogel. The method is environment-friendly, simple and efficient, and provides a new idea and a new method for effectively purifying organic wastewater.
Drawings
Fig. 1 is a photograph of a polyaniline aerogel prepared in example 1 as a physical object and a photograph of its compression recovery;
fig. 2(a) shows the removal rate of organic wastewater COD adsorbed by polyaniline aerogel prepared in example 1;
fig. 2(b) is a graph showing the effect of the polyaniline aerogel prepared in example 1 on adsorbing organic wastewater for repeated use;
FIG. 2(c) is a photograph of wastewater before and after the polyaniline aerogel prepared in example 1 adsorbs organic wastewater;
fig. 3(a) shows the COD removal rate of the organic wastewater treated by cumulative adsorption-regeneration of the polyaniline aerogel prepared in example 1 for 3 times;
FIG. 3(b) is the COD removal rate of the organic wastewater of different batches processed 3 times in the cumulative adsorption-regeneration treatment organic wastewater cumulative cycle of the polyaniline aerogel prepared in example 1
Fig. 3(c) is a photograph showing the color change of the organic wastewater after the organic wastewater is subjected to the cumulative adsorption-regeneration treatment for 3 times in the case of the polyaniline aerogel prepared in example 1.
Detailed Description
The invention is further illustrated below with reference to specific examples and the accompanying drawings. These embodiments are merely illustrative of the present invention and are not intended to limit the scope of the present invention. In addition, after reading the teaching of the present invention, those skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
The invention provides an organic wastewater treatment method based on high-performance polyaniline aerogel, which comprises the following steps:
(1) mixing 20mL of 0.1-0.5 mmol/L ferric salt solution and 0.5-2 mL aniline monomer, slowly adding 0.5-2 g of carboxylated cellulose fiber under stirring, taking out after 10min, placing in a mold, freezing for 5-12 h, thawing to obtain hydrogel, soaking the hydrogel in an acidic solution containing an oxidant for 7-24 h to oxidize and polymerize aniline, washing with ethanol and deionized water, and freeze-drying to obtain the polyaniline aerogel.
(2) And (3) putting a proper amount of polyaniline aerogel into the organic wastewater, taking out the polyaniline aerogel after the polyaniline aerogel is saturated by adsorption, putting the polyaniline aerogel into a 0.5-5 mmol/L regeneration solution for 30min, so as to realize the degradation of organic adsorbates and the regeneration of the polyaniline aerogel, wherein the regenerated polyaniline aerogel can be repeatedly used.
Preferably, the iron salt is one or more of ferric nitrate nonahydrate, ferric chloride hexahydrate and ferric sulfate hydrate.
Preferably, the cellulose fiber is one or more of cotton fiber, bamboo fiber, wood pulp fiber and curcumin fiber.
Preferably, the molar ratio of the oxidant to the aniline monomer is (1-3): 1, the oxidant is one or more of ferric nitrate nonahydrate, ferric trichloride hexahydrate, ammonium persulfate and potassium dichromate.
Preferably, the regeneration solution is one or more of hydrogen peroxide, sodium persulfate, potassium persulfate, sodium hydrogen peroxymonosulfate, potassium peroxymonosulfate.
The following is illustrated in detail by way of examples:
example 1
Mixing 20mL of 0.1mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 1.2g of carboxylated cotton fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: 26.6g of ferric nitrate nonahydrate was weighed in an amount of 1, dissolved in a 2.0mol/L nitric acid solution, and the resulting hydrogel was immersed in the solution for 24 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. As shown in fig. 1, the obtained polyaniline aerogel is a three-dimensional block material with certain compression mechanical properties, and can still completely recover deformation after being compressed for multiple times.
80mg of polyaniline aerogel is put into 20mL of organic wastewater for adsorption, and COD removal rates of the wastewater with different adsorption times are shown in figure 2 (a). After 50min of adsorption, the removal rate of COD in the wastewater reaches 78.1 percent. Taking out the polyaniline aerogel with saturated adsorption, and placing the polyaniline aerogel in 3mmol/L H2O2And (5) degrading the organic adsorbate and regenerating the polyaniline aerogel in the solution for 30 min. After the polyaniline aerogel is repeatedly used for 7 times through adsorption-regeneration, the removal rate of COD in the wastewater can still reach 69.7% (fig. 2b), and the color of the wastewater is obviously lightened after the polyaniline aerogel is adsorbed (fig. 2c), which indicates that the polyaniline aerogel has good adsorption performance on organic wastewater. In addition, after the organic wastewater is subjected to three times of adsorption-regeneration cycles, the COD removal rate of the wastewater is as high as 96.3 percent (figure 3a), most of organic pollutants are removed, and the color of the wastewater is changed from original reddish brown to almost colorless and transparent (figure 3c), so that the wastewater is beneficial to treatmentAfter 5 batches of organic wastewater are sequentially treated by accumulative three times of adsorption-regeneration cycles, the removal rate of COD can still reach 84.2 percent (figure 3 b).
Examples 2 to 3
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 1, and the other conditions were the same as in example 1.
Example 4
Mixing 20mL of 0.1mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 1g of carboxylated bamboo fiber under stirring, taking out after 10min, placing in a mold, freezing for 10h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: 26.6g of ferric nitrate nonahydrate was weighed in an amount of 1, dissolved in a 2.0mol/L nitric acid solution, and the resulting hydrogel was immersed in the solution for 24 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. 80mg of polyaniline aerogel is put into 20mL of organic wastewater for adsorption, taken out after the adsorption is saturated and placed in 3mmol/L H2O2And (5) degrading the organic adsorbate and regenerating the polyaniline aerogel in the solution for 30 min.
Examples 5 to 6
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 4, and the other conditions were the same as in example 4.
Example 7
Mixing 20mL of 0.2mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 0.5g of carboxylated wood pulp fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: 26.6g of ferric nitrate nonahydrate was weighed in an amount of 1, dissolved in a 2.0mol/L nitric acid solution, and the resulting hydrogel was immersed in the solution for 12 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. Putting 60mg of polyaniline aerogel into 20mL of organic wastewater for adsorption, taking out after adsorption saturation, and placing in 3mmol/L H2O2And (5) degrading the organic adsorbate and regenerating the polyaniline aerogel in the solution for 30 min.
Examples 8 to 9
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 7, and the other conditions were the same as in example 7.
Example 10
Mixing 20mL of 0.2mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 1.2g of carboxylated curcumin fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 1: 1 weigh 8.9g of ferric nitrate nonahydrate, and the resulting solution was dissolved in 2.0mol/L nitric acid solution, and the resulting hydrogel was immersed in the solution for 10 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. 100mg of polyaniline aerogel is put into 20mL of organic wastewater for adsorption, taken out after adsorption saturation and placed in 3mmol/L H2O2And (5) degrading the organic adsorbate and regenerating the polyaniline aerogel in the solution for 30 min.
Examples 11 to 12
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 10, and the other conditions were the same as in example 10.
Example 13
Mixing 20mL of 0.1mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 1.2g of carboxylated cotton fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 2:1 weigh 11.9g of ferric chloride hexahydrate, dissolve in 2.0mol/L nitric acid solution, and soak the resulting hydrogel in the above solution for 10 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. Putting 60mg of polyaniline aerogel into 20mL of organic wastewater for adsorption, taking out after adsorption saturation, and placing in 3mmol/L H2O2And (5) degrading the organic adsorbate and regenerating the polyaniline aerogel in the solution for 30 min.
Examples 14 to 15
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 13, and the other conditions were the same as in example 13.
Example 16
Mixing 20mL of 0.3mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 1.2g of carboxylated cotton fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: ammonium persulfate (15.0 g) was weighed into 1 and dissolved in a nitric acid solution (2.0 mol/L), and the resulting hydrogel was immersed in the solution for 20 hours to effect oxidative polymerization of aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. 100mg of polyaniline aerogel is put into 20mL of organic wastewater for adsorption, taken out after adsorption saturation and placed in 3mmol/L H2O2And (5) degrading the organic adsorbate and regenerating the polyaniline aerogel in the solution for 30 min.
Examples 17 to 18
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 16, and the other conditions were the same as in example 16.
Example 19
Mixing 20mL of 0.1mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 1.2g of carboxylated cotton fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: 1 weigh 19.4g of potassium dichromate, dissolve in 2.0mol/L nitric acid solution, and soak the resulting hydrogel in the above solution for 10 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. Putting 60mg of polyaniline aerogel into 20mL of organic wastewater for adsorption, taking out after adsorption saturation, and placing in 3mmol/L H2O2And (5) degrading the organic adsorbate and regenerating the polyaniline aerogel in the solution for 30 min.
Examples 20 to 21
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 19, and the other conditions were the same as in example 19.
Example 22
Mixing 20mL of 0.1mmol/L ferric salt solution and 1mL of aniline monomer, slowly adding 1.2g of carboxylated cotton fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: 26.6g of ferric nitrate nonahydrate was weighed in an amount of 1, dissolved in a 2.0mol/L nitric acid solution, and the resulting hydrogel was immersed in the solution for 12 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. 80mg of polyaniline aerogel is put into 20mL of organic wastewater to be treated for adsorption, taken out after adsorption saturation and placed in 2mmol/L sodium persulfate solution for 30min, so that degradation of organic adsorbate and regeneration of polyaniline aerogel are realized.
Examples 23 to 24
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 22, and the other conditions were the same as in example 22.
Example 25
Mixing 20mL of 0.1mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 1.2g of carboxylated cotton fiber under stirring, taking out after 10min, placing in a mold, freezing for 7h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: 26.6g of ferric nitrate nonahydrate was weighed in an amount of 1, dissolved in a 2.0mol/L nitric acid solution, and the resulting hydrogel was immersed in the solution for 12 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. 80mg of polyaniline aerogel is put into 20mL of organic wastewater for adsorption, and the polyaniline aerogel is taken out after the adsorption is saturated and placed in 4mmol/L potassium persulfate solution for 30min, so that the degradation of organic adsorbates and the regeneration of the polyaniline aerogel are realized.
Examples 26 to 27
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 25, and the other conditions were the same as in example 25.
Example 28
Mixing 20mL of 0.1mmol/L ferric salt solution and 2mL of aniline monomer, slowly adding 1g of carboxylated cotton fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: 26.6g of ferric nitrate nonahydrate was weighed in an amount of 1, dissolved in a 2.0mol/L nitric acid solution, and the resulting hydrogel was immersed in the solution for 24 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. And putting 100mg of polyaniline aerogel into 20mL of organic wastewater for adsorption, taking out after adsorption saturation, and putting the polyaniline aerogel into a 4mmol/L sodium hydrogen peroxymonosulfate solution for 30min to realize degradation of organic adsorbates and regeneration of the polyaniline aerogel.
Examples 29 to 30
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 28, and the other conditions were identical to those of example 28.
Example 31
Mixing 20mL of 0.1mmol/L ferric salt solution and 1mL of aniline monomer, slowly adding 2g of carboxylated cotton fiber under stirring, taking out after 10min, placing in a mold, freezing for 5h, and thawing to obtain the hydrogel. According to the molar ratio of the oxidant to the aniline of 3: 26.6g of ferric nitrate nonahydrate was weighed in an amount of 1, dissolved in a 2.0mol/L nitric acid solution, and the resulting hydrogel was immersed in the solution for 24 hours to oxidatively polymerize aniline. And washing the polymerized hydrogel with ethanol and deionized water to remove impurities such as oligomers, and finally, freeze-drying to obtain the polyaniline aerogel. 80mg of polyaniline aerogel is put into 20mL of organic wastewater for adsorption, and the polyaniline aerogel is taken out after the adsorption is saturated and placed in 3mmol/L potassium hydrogen peroxymonosulfate solution for 30min, so that the degradation of organic adsorbate and the regeneration of polyaniline aerogel are realized.
Examples 32 to 33
Hydrogels were prepared using ferric chloride hexahydrate, ferric sulfate hydrate as the iron salt instead of ferric nitrate nonahydrate in example 31, and the other conditions were the same as in example 31.
The above description is only a part of the embodiments of the present invention, and does not represent all technical solutions under the inventive concept, and the protective scope of the present invention is not limited to the above-mentioned embodiments. It should be noted that any additions and modifications to the adsorbent material without departing from the principles of the present invention are considered to be within the scope of the present invention.
Claims (5)
1. A method for treating organic wastewater based on high-performance polyaniline aerogel is characterized by comprising the following steps:
(1) mixing 20mL of 0.1-0.5 mmol/L ferric salt solution and 0.5-2 mL aniline monomer, slowly adding 0.5-2 g of carboxylated cellulose fiber under stirring, taking out after 10min, placing in a mold, freezing for 5-12 h, thawing to obtain hydrogel, soaking the hydrogel in an acidic solution containing an oxidant for 7-24 h to oxidize and polymerize aniline, washing with ethanol and deionized water, and freeze-drying to obtain the polyaniline aerogel.
(2) And (3) putting a proper amount of polyaniline aerogel into the organic wastewater, taking out the polyaniline aerogel after the polyaniline aerogel is saturated by adsorption, and putting the polyaniline aerogel into 0.5-5 mmol/L regeneration solution for 30min to realize the degradation of organic adsorbates and the regeneration of the polyaniline aerogel, wherein the regenerated polyaniline aerogel can be repeatedly used.
2. The method for treating organic wastewater based on high-performance polyaniline aerogel as claimed in claim 1, wherein the ferric salt is one or more of ferric nitrate nonahydrate, ferric chloride hexahydrate and ferric sulfate hydrate.
3. The method for treating organic wastewater based on high-performance polyaniline aerogel as claimed in claim 1, wherein the cellulose fiber is one or more of cotton fiber, bamboo fiber, wood pulp fiber and curcumin fiber.
4. The method for treating organic wastewater based on high-performance polyaniline aerogel as claimed in claim 1, wherein the molar ratio of the oxidant to the aniline monomer is (1-3): 1, the oxidant is one or more of iron nitrate nonahydrate, ferric chloride hexahydrate, ammonium persulfate and potassium dichromate.
5. The method for treating organic wastewater based on high-performance polyaniline aerogel as claimed in claim 1, wherein the regeneration solution is one or more of hydrogen peroxide, sodium persulfate, potassium persulfate, sodium peroxymonosulfate and potassium peroxymonosulfate.
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