CN115594358A - Treatment method of acylated aluminum-containing wastewater - Google Patents
Treatment method of acylated aluminum-containing wastewater Download PDFInfo
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- CN115594358A CN115594358A CN202211389777.2A CN202211389777A CN115594358A CN 115594358 A CN115594358 A CN 115594358A CN 202211389777 A CN202211389777 A CN 202211389777A CN 115594358 A CN115594358 A CN 115594358A
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- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000002351 wastewater Substances 0.000 title claims abstract description 70
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 151
- 230000003647 oxidation Effects 0.000 claims abstract description 146
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 68
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000706 filtrate Substances 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000011780 sodium chloride Substances 0.000 claims abstract description 34
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 27
- 239000012065 filter cake Substances 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000000108 ultra-filtration Methods 0.000 claims description 34
- 239000012528 membrane Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
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- 239000002131 composite material Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims 1
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 16
- 238000005917 acylation reaction Methods 0.000 abstract description 16
- 230000010933 acylation Effects 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 13
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- 238000004064 recycling Methods 0.000 abstract description 8
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- 230000001590 oxidative effect Effects 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 17
- 239000012028 Fenton's reagent Substances 0.000 description 15
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 14
- 239000005416 organic matter Substances 0.000 description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000001877 deodorizing effect Effects 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 229910001448 ferrous ion Inorganic materials 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 238000001728 nano-filtration Methods 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WEBCKNDFLRJODL-UHFFFAOYSA-N 1-(6-methylnaphthalen-2-yl)propan-1-one Chemical compound C1=C(C)C=CC2=CC(C(=O)CC)=CC=C21 WEBCKNDFLRJODL-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
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- 229920001002 functional polymer Polymers 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 1
- ZACYQVZHFIYKMW-UHFFFAOYSA-N iridium titanium Chemical compound [Ti].[Ir] ZACYQVZHFIYKMW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Images
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
- C01F7/57—Basic aluminium chlorides, e.g. polyaluminium chlorides
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention provides a treatment method of acylated aluminum-containing wastewater, which comprises the steps of adding NaOH into the acylated aluminum-containing wastewater, adjusting the pH value to 8-9, filtering, and collecting a filter cake and filtrate; adding deionized water into the filter cake for dissolving to obtain slurry with the concentration of 30%, dripping concentrated hydrochloric acid into the slurry, heating and stirring, standing for a period of time to obtain liquid PAC, and recovering; and (3) performing advanced oxidation treatment on the filtrate to remove organic pollutants, then entering an ultrafiltration-reverse osmosis system, and separating clear water and NaCl concentrated water for recovery. And (4) recycling clear water, and further preparing NaCl from the NaCl concentrated water through evaporative crystallization. The invention adopts a Fenton oxidation and electrocatalytic oxidation coupled advanced oxidation method, and combines an ultrafiltration-reverse osmosis method to realize zero discharge of the acylation wastewater, and has the characteristics of high efficiency, low energy consumption and easy operation. The method can effectively recycle the byproducts polyaluminum chloride and sodium chloride generated after wastewater treatment, change waste into valuable, and realize zero discharge and resource utilization of wastewater.
Description
Technical Field
The invention relates to the technical field of coal chemical wastewater treatment, in particular to a treatment method of acylated aluminum-containing wastewater.
Background
The coal reserves in China are abundant, and at present, the method has important significance for developing a high added value route of naphthalene as a measure for increasing the comprehensive utilization of heavy components in energy such as coal, petroleum and the like under the condition of increasingly tense energy. Dimethyl 2, 6-Naphthalate (NDC) is a key intermediate of high-end special polyester PEN, is mainly used for producing polyethylene 2, 6-naphthalate (PEN) films, and a PEN material is a novel functional polymer resin material with excellent performance, is short for polyethylene naphthalate and is mainly prepared by esterifying 2,6-NDA and then carrying out high-temperature high-vacuum polycondensation. Therefore, the PEN polyester material is widely applied to the fields of fiber textile materials, film materials, packaging materials, engineering plastics and the like.
The acylation reaction liquid obtained in the PEN acylation reaction section mainly contains nitrobenzene and anhydrous AlCl 3 Catalyst, propionyl chloride, acylation product and 2-methylnaphthalene as raw material, and the reaction is terminated by hydrolysisAnd separating the catalyst and the product. The acylation waste water generated after hydrolysis has extremely strong acidity (pH)<3.0 ) containing a large amount of Al 3+ And Cl - And organic waste, producing about 18 tons of acylation waste water per 1 unit of 2-methyl-6-propionylnaphthalene produced. At present, the Chemical Oxygen Demand (COD) of the acylation waste water is high>10000mg/L, which can not reach the discharge standard, and has strong acidity, and the organic matter is not easy to be removed, which can not be used to produce aluminum-containing by-products. Therefore, aluminum in the acylation wastewater needs to be recycled firstly, and then organic pollutants are removed, so that zero discharge of the acylation wastewater is realized.
The modes for removing organic matters or reducing COD in the acylation wastewater mainly comprise methods such as an air stripping method, an atmospheric distillation method, an activated carbon adsorption method, biochemical treatment, advanced oxidation, membrane separation and the like, and for removing the organic matters in the acidic aluminum-containing wastewater, the atmospheric distillation method has limited effect, the air stripping method is greatly influenced by external environment and organic matter properties, and the membrane separation method and the activated carbon adsorption method have higher cost. The biochemical treatment is suitable for wastewater with low organic matter concentration, and for strongly acidic wastewater with pH less than 3, nitrobenzene has high toxicity (the content is about 1000 mg/L), the microbial tolerance range is limited, and the impact resistance is poor. The advanced oxidation method is a method for oxidizing and decomposing organic pollutants in water by using hydroxyl radicals (. OH) with strong oxidizing property, and the oxidizing property of the OH is inferior to that of F 2 The method can rapidly, non-selectively and thoroughly oxidize various organic and inorganic pollutants, and the advanced oxidation method develops Fenton oxidation, photocatalytic oxidation, electrochemical oxidation, ozone catalytic oxidation and other technologies at present, so that the application prospect is wide.
In the prior art, some documents disclose that the waste water is treated by an evaporation and concentration process to realize the utilization of resources, but the energy consumption of evaporation and concentration is high. Some documents disclose that the fly ash, natural bauxite and kaolinite ore are used as raw materials and combined with calcium aluminate to produce aluminum chloride under the acidic condition, but industrial waste residues and secondary waste are produced in the production process. Some documents disclose that elements such as iron and manganese are added into raw materials to form composite polyaluminum ferric chloride, but the technical process is complex, the control of other metal elements is not easy to be mastered, and the problem that the content of other metals exceeds the standard is easily caused. There are documents disclosing the removal of toluene and acylating agent by steam distillation, but the removal of organic contaminants is not complete; if calcium aluminate is adopted to adjust the basicity, waste residues are generated; if the activated carbon is used for reducing COD, the cost is high and industrialization is difficult to realize. And the aluminum salt and the sodium salt in the wastewater cannot be fully recycled.
Disclosure of Invention
The invention aims to provide a treatment method of acylated aluminum-containing wastewater, which realizes resource utilization of aluminum salt and sodium salt in wastewater and zero discharge of wastewater.
The embodiment of the application provides a treatment method of acylated aluminum-containing wastewater on one hand, which comprises the following steps:
s1, adding NaOH into the acylated aluminum-containing wastewater, adjusting the pH value to 8-9, filtering, and collecting a filter cake and filtrate, wherein the filter cake contains Al (OH) 3 ；
S2, adding deionized water into the filter cake to dissolve the filter cake to obtain slurry with the concentration of 30%, dropwise adding concentrated hydrochloric acid into the slurry, heating and stirring the slurry, standing the mixture for a period of time to obtain liquid PAC, and recovering the liquid PAC;
and S3, performing advanced oxidation treatment on the filtrate to remove organic pollutants, then entering an ultrafiltration-reverse osmosis system, and separating clear water and NaCl concentrated water for recovery. And (4) recycling clear water, and further preparing NaCl from the NaCl concentrated water through evaporative crystallization.
The invention adopts a Fenton oxidation and electrocatalytic oxidation coupled advanced oxidation method, and combines an ultrafiltration-reverse osmosis method to realize zero discharge of the acylation wastewater, and has the characteristics of high efficiency, low energy consumption and easy operation.
The method can effectively recycle the byproducts polyaluminum chloride and sodium chloride generated after wastewater treatment, change waste into valuable, and realize zero discharge and resource utilization of wastewater.
Wherein, the recovery of the byproduct polyaluminium chloride adopts a heating polymerization method, so that the secondary pollution is not generated, the energy consumption is low, and the requirement on equipment is low; the recycling of the byproduct NaCl adopts a nanofiltration method, and is simple and efficient.
In some embodiments, in step S3, the advanced oxidation treatment includes a fenton oxidation treatment and an electrocatalytic oxidation treatment which are sequentially performed, and the organic contaminants are removed from the filtrate in two steps by the fenton oxidation treatment and the electrocatalytic oxidation treatment.
Among them, the fenton oxidation method is a method of oxidizing a reduced pollutant in water with a fenton reagent. The Fenton reagent is a system consisting of ferrous ions and hydrogen peroxide, and the action mechanism of the Fenton reagent is H 2 O 2 In Fe 2+ Generates hydroxyl free radical with strong oxidizing property under the catalytic action of the catalyst, and in aqueous solution, the hydroxyl free radical and organic matter which is difficult to degrade carry out a series of intermediate reactions, and the hydroxyl free radical is finally oxidized into CO 2 And H 2 And (O). The Fenton oxidation method can effectively treat waste water containing nitrobenzene, ABS and other organic matters and is used for decoloring and deodorizing the waste water.
The electrocatalytic oxidation technology is an oxidation reaction that takes electricity as a catalyst and takes hydrogen peroxide, oxygen, ozone and the like as oxidants. The catalytic efficiency is stable, and the utilization rate of the oxidant is up to more than 95%. The electrocatalytic oxidation is a form of advanced oxidation, and the reaction rate of hydroxyl radicals generated in an electrocatalytic oxidation system is 10 higher than that of the direct oxidation of ozone 5 The catalyst has no selectivity, can react with almost all organic matters, so the effect of advanced oxidation is stable and cannot be changed along with the change of residual organic matters in water.
In some embodiments, in step S3, the ultrafiltration-reverse osmosis system comprises an ultrafiltration system and a reverse osmosis system connected in sequence, the filtrate after the advanced oxidation treatment filters particles and suspended matters in the ultrafiltration system and removes organic pollutants for the third time, and the filtrate after the ultrafiltration system enters the reverse osmosis system to separate out fresh water and NaCl concentrated water.
In some embodiments, the concentration of the concentrated hydrochloric acid is 20-30%.
In some embodiments, in step S2, the heating temperature is 80 to 90 ℃, the heating and stirring time is 4 to 5 hours, and the standing time is 12 hours.
In some embodiments, in the fenton oxidation treatment, feSO is added to the filtrate 4 ·7H 2 O, after completely dissolved, is droppedAdding H 2 O 2 Dropwise adding while stirring, wherein the addition amount is FeSO 4 ·7H 2 O：H 2 O 2 : filtrate =16g to 36g:60 g-150 g:1L, after full reaction, dropwise adding NaOH solution until the pH value is 8-9, and then filtering.
In some embodiments, in the electrocatalytic oxidation treatment, the anode is a titanium ruthenium-coated iridium electrode, the cathode is a titanium electrode, the current is 10-30A, the voltage is 8-16V, the electrocatalytic oxidation time is 5-15 h, and the COD of the effluent is less than or equal to 1000mg/L.
In some embodiments, the ultrafiltration membrane is made of cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone, polyvinyl alcohol, polyamide or polypiperazine amide at an operating pressure of 0.3 to 0.8MPa in the ultrafiltration system.
The ultrafiltration system is used for getting rid of macromolecule organic matter, granule and suspended solid, solves the easy problem of blockking up of reverse osmosis membrane, and the tertiary COD of getting rid of, then reverse osmosis concentration and retrieve NaCl, realizes waste water resource utilization and zero release.
In some embodiments, in the reverse osmosis system, the reverse osmosis membrane is made of cellulose acetate, polyamide, polyhydrazide, or a composite membrane, and the operating pressure is less than 3MPa.
In some embodiments, in said step S2, the alumina content in the liquid PAC is >9% and the basicity is 50%.
In some embodiments, the anode used in the electrocatalytic oxidation can also be a titanium iridium-coated tantalum or diamond doped boron coated titanium electrode, and the cathode used can also be a stainless steel electrode.
The invention has the beneficial effects that:
(1) The invention adopts a Fenton oxidation and electrocatalytic oxidation coupled advanced oxidation method, and combines an ultrafiltration-reverse osmosis method to realize zero discharge of the acylation wastewater, and has the characteristics of high efficiency, low energy consumption and easy operation.
(2) The method can effectively recycle the byproducts polyaluminum chloride and sodium chloride generated after the wastewater treatment, changes waste into valuable, and realizes zero discharge and resource utilization of the wastewater.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent from and readily appreciated by reference to the following description of the embodiments taken in conjunction with the accompanying drawings,
wherein:
FIG. 1 is a flow chart of a method for treating an acylated aluminum-containing wastewater in an example of the present application;
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The method for treating an acylated aluminum-containing wastewater according to an embodiment of the present invention will be described with reference to the accompanying drawings.
As shown in FIG. 1, the embodiment of the present application provides a method for treating an acylated aluminum-containing wastewater, comprising the following steps:
s1, adding NaOH into the acylated aluminum-containing wastewater, adjusting the pH value to 8-9 to completely precipitate aluminum, filtering, and collecting a filter cake and filtrate, wherein the filter cake contains Al (OH) 3 ；
S2, adding deionized water into the filter cake to dissolve the filter cake to obtain slurry with the concentration of 30%, dripping concentrated hydrochloric acid into the slurry, heating and stirring the slurry, standing the mixture for a period of time to obtain liquid PAC, and recovering the PAC;
and S3, performing advanced oxidation treatment on the filtrate to remove organic pollutants, then entering an ultrafiltration-reverse osmosis system, and separating clear water and NaCl concentrated water for recovery.
In some specific embodiments, in step S3, the advanced oxidation treatment includes a fenton oxidation treatment and an electrocatalytic oxidation treatment which are sequentially performed, and the organic contaminants are removed from the filtrate in two steps by the fenton oxidation treatment and the electrocatalytic oxidation treatment. Namely, the first step of the advanced oxidation treatment is Fenton oxidation treatment, and organic pollutants are removed for the first time; the second step is electrocatalytic oxidation treatment, and organic pollutants are removed for the second time.
Among them, the fenton oxidation method is a method of oxidizing a reduced pollutant in water with a fenton reagent. The Fenton reagent is a system consisting of ferrous ions and hydrogen peroxide, and the Fenton reagent isThe mechanism of action is H 2 O 2 In Fe 2+ Generates hydroxyl free radical with strong oxidizing property under the catalytic action of the catalyst, and in aqueous solution, the hydroxyl free radical and organic matter which is difficult to degrade carry out a series of intermediate reactions, and the hydroxyl free radical is finally oxidized into CO 2 And H 2 And O. The Fenton oxidation method can effectively treat waste water containing nitrobenzene, ABS and other organic matters and is used for decoloring and deodorizing the waste water.
The electrocatalytic oxidation technology is an oxidation reaction that takes electricity as a catalyst and takes hydrogen peroxide, oxygen, ozone and the like as oxidants. The catalytic efficiency is stable, and the utilization rate of the oxidant is up to more than 95%. The electrocatalytic oxidation is a form of advanced oxidation, and the reaction rate of hydroxyl radicals generated in an electrocatalytic oxidation system is 10 higher than that of the direct oxidation of ozone 5 The catalyst has no selectivity, can react with almost all organic matters, so the effect of advanced oxidation is stable and cannot be changed along with the change of residual organic matters in water.
In some specific embodiments, in step S3, the ultrafiltration-reverse osmosis system comprises an ultrafiltration system and a reverse osmosis system connected in sequence, the filtrate after the advanced oxidation treatment filters particles and suspended matters in the ultrafiltration system and removes organic pollutants for the third time, and the filtrate after the ultrafiltration system enters the reverse osmosis system to separate out fresh water and NaCl concentrated water. Namely, the effluent after electrocatalytic oxidation enters an ultrafiltration-reverse osmosis system, particles and suspended matters in water can be intercepted, and COD is further reduced.
In some specific embodiments, the concentration of concentrated hydrochloric acid is 20-30%.
Preferably, the concentration of concentrated hydrochloric acid is 26%.
In some specific embodiments, in step S2, the heating temperature is 80 to 90 ℃, the heating and stirring time is 4 to 5 hours, and the standing time is 12 hours.
In some embodiments, in the fenton oxidation treatment, feSO is added to the filtrate 4 ·7H 2 O, after complete dissolution, H is added dropwise 2 O 2 Dropwise adding while stirring, wherein the addition amount is FeSO 4 ·7H 2 O：H 2 O 2 : filtrate =16g to 36g:60 g-150 g:1L, after full reaction, dropwise adding NaOH solution until the pH value is 8-9, and then filtering.
In some specific embodiments, in the electrocatalytic oxidation treatment, the anode is a titanium ruthenium-coated iridium electrode, the cathode is a titanium electrode, the current is 10-30A, the voltage is 8-16V, the electrocatalytic oxidation time is 5-15 h, and the COD of the effluent is less than or equal to 1000mg/L.
In some embodiments, the ultrafiltration membrane is made of cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone, polyvinyl alcohol, polyamide or polypiperazine amide at an operating pressure of 0.3-0.8MPa.
The ultrafiltration system is used for getting rid of macromolecule organic matter, granule and suspended solid, solves the easy problem of blockking up of reverse osmosis membrane, and tertiary COD of getting rid of, then reverse osmosis concentration and retrieve NaCl, realizes waste water resource utilization and zero release.
In some embodiments, in the reverse osmosis system, the reverse osmosis membrane is made of cellulose acetate, polyamide, polyhydrazide or a composite membrane, and the operating pressure is less than 3MPa.
In some specific examples, in step S2, the content of alumina in the liquid PAC is >9%, and the basicity is 50%, which meets the requirements of GB/T22627-2014 water treatment agent polyaluminum chloride.
In some specific embodiments, the anode used in the electrocatalytic oxidation can also be a titanium coated iridium tantalum or diamond doped boron coated titanium electrode, and the cathode used can also be a stainless steel electrode.
The invention adopts a Fenton oxidation and electrocatalytic oxidation coupled advanced oxidation method, and combines an ultrafiltration-reverse osmosis method to realize zero discharge of the acylation wastewater, and has the characteristics of high efficiency, low energy consumption and easy operation.
The method can effectively recycle the byproducts polyaluminum chloride and sodium chloride generated after the wastewater treatment, changes waste into valuable, and realizes zero discharge and resource utilization of the wastewater.
Wherein, the recovery of the byproduct polyaluminium chloride adopts a heating polymerization method, so that the secondary pollution is not generated, the energy consumption is low, and the requirement on equipment is low; the recycling of the byproduct NaCl adopts a nanofiltration method, and is simple and efficient.
The present application is further illustrated by the following specific examples.
Example 1
A treatment method of acylated aluminum-containing wastewater comprises the following steps:
s1, adding NaOH into the acylated aluminum-containing wastewater, adjusting the pH value to 8-9 to completely precipitate aluminum, then filtering, and collecting a filter cake and filtrate, wherein the filter cake contains Al (OH) 3 ；
And S2, adding deionized water into the filter cake to dissolve the filter cake to obtain 30% slurry, dropwise adding concentrated hydrochloric acid with the concentration of 26% into the slurry, heating to 80 ℃, rapidly stirring for 4 hours, standing for 12 hours to cure to obtain liquid PAC meeting the requirements, and recovering. The content of alumina in the liquid PAC is 10 percent, and the basicity is 50 percent, thereby meeting the requirements of GB/T22627-2014 water treatment agent polyaluminium chloride.
And S3, performing advanced oxidation treatment on the filtrate to remove organic pollutants, then entering an ultrafiltration-reverse osmosis system, and separating clear water and NaCl concentrated water for recovery.
Wherein, advanced oxidation treatment comprises Fenton oxidation treatment and electrocatalytic oxidation treatment which are carried out in sequence, and organic pollutants are removed from the filtrate twice through the Fenton oxidation treatment and the electrocatalytic oxidation treatment. Namely, the first step of the advanced oxidation treatment is Fenton oxidation treatment, and organic pollutants are removed for the first time; the second step is electrocatalytic oxidation treatment, and organic pollutants are removed for the second time.
Among them, the fenton oxidation method is a method for oxidizing a reduced pollutant in water by using a fenton reagent. The Fenton reagent is a system consisting of ferrous ions and hydrogen peroxide, and the action mechanism of the Fenton reagent is H 2 O 2 In the presence of Fe 2+ Generates hydroxyl free radical with strong oxidizing property under the catalytic action of the catalyst, and in aqueous solution, the hydroxyl free radical and organic matter which is difficult to degrade carry out a series of intermediate reactions, and the hydroxyl free radical is finally oxidized into CO 2 And H 2 And O. The Fenton oxidation method can effectively treat waste water containing nitrobenzene, ABS and other organic matters and is used for decoloring and deodorizing the waste water.
The electrocatalytic oxidation technology is an oxidation reaction that takes electricity as a catalyst and takes hydrogen peroxide, oxygen, ozone and the like as oxidants. The catalytic efficiency is stable, and the utilization rate of the oxidant is up to more than 95%. The electrocatalytic oxidation is a form of advanced oxidation, and the reaction rate of hydroxyl radicals generated in an electrocatalytic oxidation system is 10 times higher than that of the direct oxidation of ozone 5 The catalyst has no selectivity, can react with almost all organic matters, so that the effect of advanced oxidation is stable and cannot be changed along with the change of residual organic matters in water.
The ultrafiltration-reverse osmosis system comprises an ultrafiltration system and a reverse osmosis system which are sequentially connected, the filtrate after advanced oxidation treatment filters particles and suspended matters in the ultrafiltration system and removes organic pollutants for the third time, and the filtrate after the ultrafiltration system enters the reverse osmosis system to separate out clear water and NaCl concentrated water. Namely, the effluent after electrocatalytic oxidation enters an ultrafiltration-reverse osmosis system, particles and suspended matters in water can be intercepted, and COD is further reduced.
In this example, feSO was added to the filtrate in the Fenton oxidation treatment 4 ·7H 2 O, after complete dissolution, H is added dropwise 2 O 2 Dropwise adding while stirring, wherein the addition amount is FeSO 4 ·7H 2 O：H 2 O 2 : filtrate =16g:65g:1L, after full reaction, adding NaOH solution dropwise until the pH value is 8, and then filtering.
In the embodiment, in the electrocatalytic oxidation treatment, the anode is a titanium ruthenium-coated iridium electrode, the cathode is a titanium electrode, the current is 10A, the voltage is 9V, the electrocatalytic oxidation time is 15h, and the effluent COD is less than or equal to 1000mg/L.
In this example, the ultrafiltration membrane of the ultrafiltration system was made of cellulose acetate, and the operating pressure was 0.3MPa.
The ultrafiltration system is used for getting rid of macromolecule organic matter, granule and suspended solid, solves the easy problem of blockking up of reverse osmosis membrane, and the tertiary COD of getting rid of, then reverse osmosis concentration and retrieve NaCl, realizes waste water resource utilization and zero release.
In this example, the reverse osmosis membrane is made of polyamide and the operating pressure is less than 3MPa in the reverse osmosis system.
The invention adopts a Fenton oxidation and electrocatalytic oxidation coupled advanced oxidation method, and combines an ultrafiltration-reverse osmosis method to realize zero discharge of the acylation wastewater, and has the characteristics of high efficiency, low energy consumption and easy operation.
The method can effectively recycle the byproducts polyaluminum chloride and sodium chloride generated after the wastewater treatment, changes waste into valuable, and realizes zero discharge and resource utilization of the wastewater.
Wherein, the recovery of the byproduct polyaluminium chloride adopts a heating polymerization method, so that the secondary pollution is avoided, the energy consumption is low, and the requirement on equipment is low; the recycling of the byproduct NaCl adopts a nanofiltration method, and is simple and efficient.
Example 2
A treatment method of acylated aluminum-containing wastewater comprises the following steps:
s1, adding NaOH into the acylated aluminum-containing wastewater, adjusting the pH value to 8-9 to completely precipitate aluminum, then filtering, and collecting a filter cake and a filtrate, wherein the filter cake contains Al (OH) 3 ；
S2, adding deionized water into the filter cake to dissolve the filter cake to obtain slurry with the concentration of 30%, dripping concentrated hydrochloric acid with the concentration of 26% into the slurry, heating the slurry to 90 ℃, quickly stirring the slurry for 5 hours, standing the slurry for 12 hours to cure the slurry to obtain liquid PAC meeting the requirements, and recycling the liquid PAC. The content of alumina in the liquid PAC is 12 percent, the basicity is 50 percent, and the requirements of GB/T22627-2014 water treatment agent polyaluminum chloride are met.
And S3, performing advanced oxidation treatment on the filtrate to remove organic pollutants, then entering an ultrafiltration-reverse osmosis system, and separating clear water and NaCl concentrated water for recovery.
Wherein, advanced oxidation treatment comprises Fenton oxidation treatment and electrocatalytic oxidation treatment which are carried out in sequence, and organic pollutants are removed from the filtrate twice through the Fenton oxidation treatment and the electrocatalytic oxidation treatment. Namely, the first step of the advanced oxidation treatment is Fenton oxidation treatment, and organic pollutants are removed for the first time; the second step is electrocatalytic oxidation treatment, and organic pollutants are removed for the second time.
Wherein the Fenton oxidation method is to utilize Fenton reagent to treat waterA method for oxidizing a reducing pollutant. The Fenton reagent is a system consisting of ferrous ions and hydrogen peroxide, and the action mechanism of the Fenton reagent is H 2 O 2 In Fe 2+ Generates hydroxyl free radical with strong oxidizing property under the catalytic action of the catalyst, and in aqueous solution, the hydroxyl free radical and organic matter which is difficult to degrade carry out a series of intermediate reactions, and the hydroxyl free radical is finally oxidized into CO 2 And H 2 And O. The Fenton oxidation method can effectively treat waste water containing nitrobenzene, ABS and other organic matters and is used for decoloring and deodorizing the waste water.
The electrocatalytic oxidation technology is an oxidation reaction that takes electricity as a catalyst and takes hydrogen peroxide, oxygen, ozone and the like as oxidants. The catalytic efficiency is stable, and the utilization rate of the oxidant is up to more than 95%. The electrocatalytic oxidation is a form of advanced oxidation, and the reaction rate of hydroxyl radicals generated in an electrocatalytic oxidation system is 10 higher than that of the direct oxidation of ozone 5 The catalyst has no selectivity, can react with almost all organic matters, so the effect of advanced oxidation is stable and cannot be changed along with the change of residual organic matters in water.
The ultrafiltration-reverse osmosis system comprises an ultrafiltration system and a reverse osmosis system which are sequentially connected, the filtrate after advanced oxidation treatment filters particles and suspended matters in the ultrafiltration system and removes organic pollutants for the third time, and the filtrate after the ultrafiltration system enters the reverse osmosis system to separate out clear water and NaCl concentrated water. Namely, the effluent after electrocatalytic oxidation enters an ultrafiltration-reverse osmosis system, particles and suspended matters in water can be intercepted, and COD is further reduced.
In this example, feSO was added to the filtrate in the Fenton oxidation treatment 4 ·7H 2 O, after complete dissolution, H is added dropwise 2 O 2 Dropwise adding while stirring, wherein the addition amount is FeSO 4 ·7H 2 O：H 2 O 2 : filtrate =33g:130g:1L, after full reaction, adding NaOH solution dropwise until the pH value is 9, and then filtering.
In the embodiment, in the electrocatalytic oxidation treatment, the anode is a titanium ruthenium-coated iridium electrode, the cathode is a titanium electrode, the current is 20A, the voltage is 10V, the electrocatalytic oxidation time is 10h, and the effluent COD is less than or equal to 1000mg/L.
In this embodiment, in the ultrafiltration system, the material of the ultrafiltration membrane is sulfonated polysulfone, and the operating pressure is 0.8MPa.
The ultrafiltration system is used for getting rid of macromolecule organic matter, granule and suspended solid, solves the easy problem of blockking up of reverse osmosis membrane, and the tertiary COD of getting rid of, then reverse osmosis concentration and retrieve NaCl, realizes waste water resource utilization and zero release.
In this embodiment, in the reverse osmosis system, the reverse osmosis membrane is made of polyhydrazide and the operating pressure is less than 3MPa.
The invention adopts a Fenton oxidation and electrocatalytic oxidation coupled advanced oxidation method, and combines an ultrafiltration-reverse osmosis method to realize zero discharge of the acylation wastewater, and has the characteristics of high efficiency, low energy consumption and easy operation.
The method can effectively recycle the byproducts polyaluminum chloride and sodium chloride generated after the wastewater treatment, changes waste into valuable, and realizes zero discharge and resource utilization of the wastewater.
Wherein, the recovery of the byproduct polyaluminium chloride adopts a heating polymerization method, so that the secondary pollution is not generated, the energy consumption is low, and the requirement on equipment is low; the recycling of the byproduct NaCl adopts a nanofiltration method, and is simple and efficient.
Example 3
A treatment method of acylated aluminum-containing wastewater comprises the following steps:
s1, adding NaOH into the acylated aluminum-containing wastewater, adjusting the pH value to 8-9 to completely precipitate aluminum, then filtering, and collecting a filter cake and a filtrate, wherein the filter cake contains Al (OH) 3 ；
S2, adding deionized water into the filter cake to dissolve the filter cake to obtain slurry with the concentration of 30%, dropwise adding concentrated hydrochloric acid with the concentration of 26% into the slurry, heating to 85 ℃, rapidly stirring for 5 hours, standing for 12 hours to cure to obtain liquid PAC meeting the requirements, and recovering. The content of alumina in the liquid PAC is 13 percent, and the basicity is 50 percent, thereby meeting the requirements of GB/T22627-2014 water treatment agent polyaluminium chloride.
And S3, performing advanced oxidation treatment on the filtrate to remove organic pollutants, then entering an ultrafiltration-reverse osmosis system, and separating clear water and NaCl concentrated water for recovery.
Wherein, advanced oxidation treatment comprises Fenton oxidation treatment and electrocatalytic oxidation treatment which are carried out in sequence, and organic pollutants are removed from the filtrate twice through the Fenton oxidation treatment and the electrocatalytic oxidation treatment. Namely, the first step of the advanced oxidation treatment is Fenton oxidation treatment, and organic pollutants are removed for the first time; the second step is electrocatalytic oxidation treatment, and organic pollutants are removed for the second time.
Among them, the fenton oxidation method is a method of oxidizing a reduced pollutant in water with a fenton reagent. The Fenton reagent is a system consisting of ferrous ions and hydrogen peroxide, and the action mechanism of the Fenton reagent is H 2 O 2 In the presence of Fe 2+ Generates hydroxyl free radical with strong oxidizing property under the catalytic action of the catalyst, and in aqueous solution, the hydroxyl free radical and organic matter which is difficult to degrade carry out a series of intermediate reactions, and the hydroxyl free radical is finally oxidized into CO 2 And H 2 And O. The Fenton oxidation method can effectively treat waste water containing nitrobenzene, ABS and other organic matters and is used for decoloring and deodorizing the waste water.
The electrocatalytic oxidation technique is an oxidation reaction that uses electricity as a catalyst and hydrogen peroxide, oxygen, ozone, or the like as an oxidant. The catalytic efficiency is stable, and the utilization rate of the oxidant is up to more than 95%. The electrocatalytic oxidation is a form of advanced oxidation, and the reaction rate of hydroxyl radicals generated in an electrocatalytic oxidation system is 10 times higher than that of the direct oxidation of ozone 5 The catalyst has no selectivity, can react with almost all organic matters, so the effect of advanced oxidation is stable and cannot be changed along with the change of residual organic matters in water.
The ultrafiltration-reverse osmosis system comprises an ultrafiltration system and a reverse osmosis system which are sequentially connected, the filtrate after advanced oxidation treatment filters particles and suspended matters in the ultrafiltration system and removes organic pollutants for the third time, and the filtrate after the ultrafiltration system enters the reverse osmosis system to separate out clear water and NaCl concentrated water. Namely, the effluent after electrocatalytic oxidation enters an ultrafiltration-reverse osmosis system, so that particles and suspended matters in water can be intercepted, and COD is further reduced.
In the present embodimentIn the Fenton oxidation treatment, feSO is added to the filtrate 4 ·7H 2 O, after complete dissolution, H is added dropwise 2 O 2 Dropwise adding while stirring, wherein the addition amount is FeSO 4 ·7H 2 O：H 2 O 2 : filtrate =20g:70g:1L, after full reaction, adding NaOH solution dropwise until the pH value is 9, and then filtering.
In the embodiment, in the electrocatalytic oxidation treatment, the anode is a titanium ruthenium-coated iridium electrode, the cathode is a titanium electrode, the current is 30A, the voltage is 12V, the electrocatalytic oxidation time is 6h, and the COD of the effluent is less than or equal to 1000mg/L.
In this example, the ultrafiltration membrane of the ultrafiltration system was polypiperazine amide, and the operating pressure was 0.5MPa.
The ultrafiltration system is used for getting rid of macromolecule organic matter, granule and suspended solid, solves the easy problem of blockking up of reverse osmosis membrane, and tertiary COD of getting rid of, then reverse osmosis concentration and retrieve NaCl, realizes waste water resource utilization and zero release.
In this embodiment, in the reverse osmosis system, the reverse osmosis membrane is a composite membrane of cellulose acetate and polyamide, and the operating pressure is less than 3MPa.
The invention adopts a Fenton oxidation and electrocatalytic oxidation coupled advanced oxidation method, and combines an ultrafiltration-reverse osmosis method to realize zero discharge of the acylation wastewater, and has the characteristics of high efficiency, low energy consumption and easy operation.
The method can effectively recycle the byproducts polyaluminum chloride and sodium chloride generated after the wastewater treatment, changes waste into valuable, and realizes zero discharge and resource utilization of the wastewater.
Wherein, the recovery of the byproduct polyaluminium chloride adopts a heating polymerization method, so that the secondary pollution is not generated, the energy consumption is low, and the requirement on equipment is low; the recycling of the byproduct NaCl adopts a nanofiltration method, and is simple and efficient.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The treatment method for acylating aluminum-containing wastewater is characterized by comprising the following steps of:
s1, adding NaOH into the acylated aluminum-containing wastewater, adjusting the pH value to 8-9, filtering, and collecting a filter cake and filtrate, wherein the filter cake contains Al (OH) 3 ；
S2, adding deionized water into the filter cake to dissolve the filter cake to obtain slurry with the concentration of 30%, dripping concentrated hydrochloric acid into the slurry, heating and stirring the slurry, standing the mixture for a period of time to obtain liquid PAC, and recovering the PAC;
and S3, performing advanced oxidation treatment on the filtrate to remove organic pollutants, then entering an ultrafiltration-reverse osmosis system, and separating clear water and NaCl concentrated water for recovery.
2. The method for treating acylated aluminum-containing wastewater according to claim 1, wherein in step S3, the advanced oxidation treatment comprises a Fenton oxidation treatment and an electrocatalytic oxidation treatment which are sequentially performed, and the filtrate is subjected to the Fenton oxidation treatment and the electrocatalytic oxidation treatment to remove organic pollutants in two times.
3. The method for treating the acylated aluminum-containing wastewater as claimed in claim 1, wherein in the step S3, the ultrafiltration-reverse osmosis system comprises an ultrafiltration system and a reverse osmosis system which are connected in sequence, the filtrate after the advanced oxidation treatment is filtered to remove particles and suspended matters in the ultrafiltration system and organic pollutants are removed for the third time, and the filtrate after the ultrafiltration system enters the reverse osmosis system to separate clear water and NaCl concentrated water.
4. The method for treating acylated aluminum-containing wastewater according to claim 1, wherein the concentration of the concentrated hydrochloric acid is 20-30%.
5. The method of treating an acylated aluminum-containing wastewater according to any one of claims 1 to 4, wherein in the step S2, the heating temperature is 80 to 90 ℃, the heating and stirring time is 4 to 5 hours, and the standing time is 12 hours.
6. The method according to claim 2, wherein FeSO is added to the filtrate in the Fenton oxidation treatment 4 ·7H 2 O, after complete dissolution, H is added dropwise 2 O 2 Dropwise adding while stirring, wherein the addition amount is FeSO 4 ·7H 2 O：H 2 O 2 : filtrate =16g to 36g:60 g-150 g:1L, after full reaction, dropwise adding NaOH solution until the pH value is 8-9, and then filtering.
7. The method for treating acylated aluminum-containing wastewater according to claim 6, wherein in the electrocatalytic oxidation treatment, the anode is a titanium-coated ruthenium iridium, the cathode is a titanium electrode, the current is 10-30A, the voltage is 8-16V, the electrocatalytic oxidation time is 5-15 h, and the COD of the effluent is less than or equal to 1000mg/L.
8. The method for treating acylated aluminum-containing wastewater according to claim 3, wherein in the ultrafiltration system, the ultrafiltration membrane is made of cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone, polyvinyl alcohol, polyamide or polypiperazine amide, and the operating pressure is 0.3-0.8MPa.
9. The method for treating the acylated aluminum-containing wastewater according to claim 3, wherein in the reverse osmosis system, the reverse osmosis membrane is made of cellulose acetate, polyamide, polyhydrazide or a composite membrane, and the operating pressure is less than 3MPa.
10. The method for treating wastewater containing aluminum acylate according to claim 1, wherein in the step S2, the content of aluminum oxide in the liquid PAC is >9%, and the basicity is 50%.
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