CN118145837A - Coking wastewater advanced treatment process - Google Patents
Coking wastewater advanced treatment process Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 44
- 238000011282 treatment Methods 0.000 title claims abstract description 42
- 238000004939 coking Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 47
- 238000005345 coagulation Methods 0.000 claims abstract description 18
- 230000015271 coagulation Effects 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000008213 purified water Substances 0.000 claims abstract description 17
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000005189 flocculation Methods 0.000 claims abstract description 9
- 230000016615 flocculation Effects 0.000 claims abstract description 9
- 238000004062 sedimentation Methods 0.000 claims abstract description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 8
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000002608 ionic liquid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012629 purifying agent Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- 239000012991 xanthate Substances 0.000 claims description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006845 Michael addition reaction Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims description 2
- BQKHKRLJOPTILQ-UHFFFAOYSA-M 1-(3-methylimidazol-3-ium-1-yl)ethanamine;bromide Chemical compound [Br-].CC(N)[N+]=1C=CN(C)C=1 BQKHKRLJOPTILQ-UHFFFAOYSA-M 0.000 claims 1
- BZERSVXGTADTME-UHFFFAOYSA-N 1-(3-methylimidazol-3-ium-1-yl)propan-1-amine nitrate Chemical compound [O-][N+]([O-])=O.CCC(N)n1cc[n+](C)c1 BZERSVXGTADTME-UHFFFAOYSA-N 0.000 claims 1
- RTOHRHYCOSVZQZ-UHFFFAOYSA-M 1-(3-methylimidazol-3-ium-1-yl)propan-1-amine;bromide Chemical compound [Br-].CCC(N)[N+]=1C=CN(C)C=1 RTOHRHYCOSVZQZ-UHFFFAOYSA-M 0.000 claims 1
- QDFQHLHWUUOVJI-UHFFFAOYSA-N [O-][N+]([O-])=O.CN1C=C[N+](CCN)=C1 Chemical compound [O-][N+]([O-])=O.CN1C=C[N+](CCN)=C1 QDFQHLHWUUOVJI-UHFFFAOYSA-N 0.000 claims 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JPTXDWQZDBNNCG-UHFFFAOYSA-N [N+](=O)(O)[O-].NC(CC)C1=NC=CN1C Chemical compound [N+](=O)(O)[O-].NC(CC)C1=NC=CN1C JPTXDWQZDBNNCG-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- IPKOOFMMRKTNNW-UHFFFAOYSA-N Br.NC(CC)C1=NC=CN1C Chemical compound Br.NC(CC)C1=NC=CN1C IPKOOFMMRKTNNW-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RUISNDKLNVFPBQ-UHFFFAOYSA-N CC(C1=NC=CN1C)N.Br Chemical compound CC(C1=NC=CN1C)N.Br RUISNDKLNVFPBQ-UHFFFAOYSA-N 0.000 description 1
- MIIHAUGMDJIMOF-UHFFFAOYSA-N [N+](=O)(O)[O-].NC(C)C1=NC=CN1C Chemical compound [N+](=O)(O)[O-].NC(C)C1=NC=CN1C MIIHAUGMDJIMOF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/18—Cyanides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The scheme relates to a coking wastewater advanced treatment process, which comprises the steps of introducing coking wastewater into an oil separation tank, adjusting the pH value to 7-8, and adding a magnetic demulsifier; the magnetic demulsifier is recovered, and the effluent is sequentially sent into an air floatation tank, a coagulation tank, a sedimentation tank and a flocculation tank to obtain purified water; the magnetic demulsifier is prepared by taking a carbon nano tube as a carrier, depositing ferric trichloride hexahydrate and copper sulfate pentahydrate on the surface of the carbon nano tube to prepare the magnetic carbon nano tube, secondly, preparing a hyperbranched polymer with terminal double bonds, mixing the two to react to obtain the hyperbranched grafted magnetic carbon nano tube, and finally, continuing to polymerize allyl polyoxyethylene ether in situ. The invention simplifies the treatment process of the coking wastewater, has few treatment steps and greatly improves the treatment efficiency; the water quality treated by the process can reach the national discharge standard in terms of COD, ammonia nitrogen, cyanide and the like, and the demulsifier is also recoverable, so that the energy conservation and consumption reduction can be realized, and the economic benefit is remarkable.
Description
Technical Field
The invention relates to the technical field of wastewater treatment materials, in particular to a coking wastewater advanced treatment process.
Background
With the rapid development of industrialization, the wastewater discharge is more serious. With the increasing importance of society on environmental protection, the requirements on water treatment are also increasing. Coking wastewater is a typical toxic and difficult-to-treat industrial organic wastewater, and contains a large amount of toxic and harmful substances such as phenol, benzene, cyanide, ammonia nitrogen, oil and the like, and the coking wastewater with complex components and high content and overproof discharge causes great harm to the environment.
At present, the water treatment process mainly adopts a physical adsorption method, a flocculation sedimentation method, an activated sludge method and the like. However, for coking wastewater with complex components, a single treatment method is difficult to enable the coking wastewater to reach the discharge standard, at present, different types of A/O biological denitrification processes are commonly adopted as main processes for treating the coking wastewater, and modes of coagulating sedimentation, filter membrane and the like are assisted, but the treatment process is complex in steps and long in time consumption. Besides a large amount of organic matters, part of oil exists in the coking wastewater, and if the coking wastewater can be thoroughly separated into water and oil in the early treatment stage, and part of organic matters are removed, part of treatment steps can be optimized, and the water treatment efficiency is improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention creatively designs the magnetic demulsifier for coking wastewater, and the treatment of the coking wastewater can be finished only by coagulation, precipitation and flocculation after demulsification, so that the treatment process is simplified, and the treatment efficiency is greatly improved.
In order to achieve the above purpose, the present invention provides the following technical solutions:
A coking wastewater advanced treatment process comprises the following steps:
1. Introducing the coking wastewater into an oil separation tank, firstly adding a pH regulator to regulate the pH value to 7-8, then adding a magnetic demulsifier into the regulating tank, fully mixing, and standing for 1h;
2. introducing clear water at the lower layer of the oil separation tank into magnetic separation equipment, recovering a magnetic demulsifier, and delivering effluent into an air floatation tank;
3. The water outlet of the air floatation tank is communicated with the coagulation tank, a water purifying agent is put into the coagulation tank, the water is treated for 30-60min, then the water is filtered by a sedimentation tank, and the water is flocculated for 5-10min by a flocculation tank, so that purified water is obtained;
4. Testing the quality of purified water, directly discharging after reaching the discharge standard, and introducing the purified water into a coagulation tank again for secondary treatment until reaching the discharge standard if not reaching the discharge standard;
The magnetic demulsifier is prepared by the following steps:
S1: dispersing carbon nano tubes in deionized water by ultrasonic to form dispersion liquid, mixing and stirring the dispersion liquid with ferric trichloride hexahydrate and copper sulfate pentahydrate for 10-60min, then dripping ammonia water with the concentration of 5-20wt%, adjusting the pH value to 7-8, stirring and reacting for 2-10 h at the temperature of 90-100 ℃, cooling and filtering, alternately flushing solid products of ethanol and water, drying, and calcining for 1-4h in nitrogen atmosphere at the temperature of 400-500 ℃ to prepare the magnetic carbon nano tubes;
S2: carrying out RAFT polymerization under nitrogen atmosphere by taking xanthate of terminal double bond as a chain transfer agent, AIBN as an initiator and acrylamide as a reaction monomer to prepare a hyperbranched polymer;
S3: mixing the magnetic carbon nanotube with amino functional ionic liquid for standby, dissolving hyperbranched polymer in DMF, and carrying out Michael addition reaction of amino-double bond under the catalysis of triethylamine to obtain hyperbranched grafted magnetic carbon nanotube;
s4: continuously dispersing the hyperbranched grafted magnetic carbon nano tube in DMF, adding AIBN, introducing nitrogen to remove air in the system, adding allyl polyoxyethylene ether, heating to 70 ℃, stirring for reaction for 12 hours, separating out solid in glacial methanol after the reaction is completed, and drying to obtain the magnetic carbon nano tube.
Further, in the step S1, the usage amount of ferric trichloride hexahydrate and copper sulfate pentahydrate is n (Fe 3+):n(Cu2 +) =2:1, and the mass ratio of the total mass to the carbon nanotubes is 5-10:1.
Further, in the step S2, the xanthate of the terminal double bond has the structural formula ofThe mole ratio of RAFT chain transfer agent, initiator and reaction monomer is 1:0.01:50-100.
Further, in the step S3, the amino-functionalized ionic liquid is selected from one of 1-aminopropyl-3-methylimidazole nitrate, 1-aminopropyl-3-methylimidazole bromide, 1-aminoethyl-3-methylimidazole nitrate and 1-aminoethyl-3-methylimidazole bromide.
Further, in the step S3, the mass ratio of the magnetic carbon nanotube to the amino functionalized ionic liquid to the hyperbranched grafted magnetic carbon nanotube is 1:3:3-10.
Further, in the step S4, the molecular weight range of the allyl polyoxyethylene ether is 300-600, and the mass ratio of the allyl polyoxyethylene ether to the hyperbranched grafted magnetic carbon nanotube is 0.5-1:1.
The coking wastewater mainly comes from the primary cooling of coke oven gas and the production water in the coking production process, the concentration of pollutants in the wastewater is high, the components are complex, the treatment of the coking wastewater at present is mainly focused on removing organic pollutants, but a small amount of oil is also present in the coking wastewater, and the treatment efficiency is affected. Therefore, the application expects to demulsify and deoil the coking wastewater before coagulation treatment or biochemical treatment, and the COD content of the wastewater is reduced on the basis of deoiling, so that the subsequent treatment can be greatly facilitated. However, because the coking wastewater has too complex components and relatively low oil content, the common demulsifier can hardly capture oil molecules so as to enable the oil molecules to be rapidly emulsified and layered. Thus, the demulsifier for coking wastewater is prepared.
Firstly, taking multi-wall Carbon Nanotubes (CNTs) as a carrier, and synthesizing a copper-doped magnetic nano material CuFe 2O4 by virtue of the rich pore structure of the CNTs through in-situ deposition on the CNTs, wherein the magnetic nano material has proved to be a substance with higher magnetic stability compared with Fe 3O4; mixing the obtained magnetic carbon nanotube with amino functionalized ionic liquid, wherein pi-pi interaction exists between the ionic liquid and CNTs, and then carrying out Michael addition reaction on amino in the ionic liquid and hyperbranched polymer with double bonds at the tail end so as to coat a layer of organic polymer on the surface of the magnetic carbon nanotube, so that the hydrophilicity of the material is improved, the dispersibility of the carbon nanotube in a water body is effectively improved, and the contact area is increased; finally, by utilizing the characteristic of active free radical polymerization, allyl Polyoxyethylene Ether (APEG) is continuously polymerized outside the hyperbranched polymer to form the magnetic demulsifier with the multi-branched polyether structure taking the magnetic carbon nano tube as the carrier. The polyether with the multi-branched structure can form a net capturing effect in water, so that oil and water can be quickly gathered in an emulsified state and quickly separated, and the oil removal rate can reach more than 95%; meanwhile, the demulsifier has magnetism, can be recycled after being separated and recovered by magnetism, and the oil removal rate can still reach more than 92% after ten demulsification-recovery-demulsification cycles; the addition amount is small, the deoiling effect is good, and the treatment process of the coking wastewater is simplified.
Compared with the prior art, the invention has the beneficial effects that: the invention simplifies the treatment process of the coking wastewater, has few treatment steps and greatly improves the treatment efficiency; the water quality treated by the process can reach the national discharge standard in terms of COD, ammonia nitrogen, cyanide and the like, and the demulsifier is also recoverable, so that the energy conservation and consumption reduction can be realized, and the economic benefit is remarkable.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Examples: coking wastewater advanced treatment process
1. Introducing the coking wastewater into an oil separation tank, firstly adding a pH regulator to regulate the pH value to 7-8, then adding a magnetic demulsifier into the regulating tank, fully mixing, and standing for 1h;
2. introducing clear water at the lower layer of the oil separation tank into magnetic separation equipment, recovering a magnetic demulsifier, and delivering effluent into an air floatation tank;
3. The water outlet of the air floatation tank is communicated with the coagulation tank, a water purifying agent is put into the coagulation tank, the water is treated for 30-60min, then the water is filtered by a sedimentation tank, and the water is flocculated for 5-10min by a flocculation tank, so that purified water is obtained;
4. And testing the quality of purified water, directly discharging after reaching the discharge standard, and introducing the purified water into the coagulation tank again for secondary treatment until reaching the discharge standard if not reaching the discharge standard.
The magnetic demulsifier is made of self-made materials, the water purifying agent can be selected from commercial products, and the water purifying agent suitable for advanced treatment of wastewater in coal chemical industry and coking industry in the application patent CN106745818B of the applicant is selected in the scheme.
By adopting the treatment process to treat certain coking wastewater, the water quality condition of the coking wastewater is as follows: COD content 7500mg/L, oil content 85mg/L, ammonia nitrogen 530mg/L, phenol 320mg/L, cyanogen 25mg/L.
Example 1:
1. Introducing the coking wastewater into an oil separation tank, firstly adding a pH regulator to regulate the pH value to 7-8, then adding a magnetic demulsifier into the regulating tank, fully mixing, and standing for 1h;
The magnetic demulsifier is prepared by the following steps:
s1: dispersing 10g of carbon nano tube in deionized water to form dispersion liquid, mixing and stirring with 200ml of 0.8mol/L ferric trichloride hexahydrate and 100ml of 0.8mol/L copper sulfate pentahydrate for 10-60min, then dripping 5-20wt% ammonia water, adjusting pH to 7-8, stirring and reacting for 5h at 90-100 ℃, cooling and filtering, alternately flushing solid product ethanol and water and drying, and calcining for 2h in nitrogen atmosphere at 400 ℃ to obtain the magnetic carbon nano tube;
s2: xanthates with terminal double bonds (Reference Polym.chem.,2011,2,2231-2238. Synthesis, hereinafter referred to as RAFT reagent) as chain transfer agent, AIBN as initiator, acrylamide as reaction monomer, molar ratio of 1:0.01:50, adding all substances into a Schlenk bottle, adding tetrahydrofuran as solvent, introducing nitrogen, and heating to 70 ℃ under nitrogen atmosphere for reaction for 3-5 h to obtain hyperbranched polymer;
S3: mixing 5g of magnetic carbon nano tube with 15g of 1-aminopropyl-3-methylimidazole nitrate for standby, dissolving 15g of hyperbranched polymer in DMF, adding 2g of triethylamine, and reacting for 3 hours at room temperature to obtain hyperbranched grafted magnetic carbon nano tube;
S4: continuously dispersing the hyperbranched grafted magnetic carbon nano tube in DMF, adding 0.5 times of APEG300, adding catalytic amount of AIBN, introducing nitrogen to remove air in the system, heating to 70 ℃, stirring and reacting for 12 hours, separating out solid in glacial methanol after the reaction is completed, and drying to obtain the magnetic demulsifier.
2. Introducing clear water at the lower layer of the oil separation tank into magnetic separation equipment, recovering a magnetic demulsifier, and delivering effluent into an air floatation tank;
3. The water outlet of the air floatation tank is communicated with the coagulation tank, a water purifying agent is put into the coagulation tank, the water is treated for 30-60min, then the water is filtered by a sedimentation tank, and the water is flocculated for 5-10min by a flocculation tank, so that purified water is obtained;
4. The water quality of purified water is tested, the COD content is less than 50mg/L, the oil is less than 0.5mg/L, the ammonia nitrogen is less than 5mg/L, the phenol is less than 0.3mg/L, and the cyanogen is less than 0.2mg/L. After one-time complete process treatment, the national emission standard can be achieved.
Example 2:
1. Introducing the coking wastewater into an oil separation tank, firstly adding a pH regulator to regulate the pH value to 7-8, then adding a magnetic demulsifier into the regulating tank, fully mixing, and standing for 1h;
The magnetic demulsifier is prepared by the following steps:
s1: dispersing 10g of carbon nano tube in deionized water to form dispersion liquid, mixing and stirring with 200ml of 0.8mol/L ferric trichloride hexahydrate and 100ml of 0.8mol/L copper sulfate pentahydrate for 10-60min, then dripping 5-20wt% ammonia water, adjusting pH to 7-8, stirring and reacting for 5h at 90-100 ℃, cooling and filtering, alternately flushing solid product ethanol and water and drying, and calcining for 2h in nitrogen atmosphere at 400 ℃ to obtain the magnetic carbon nano tube;
S2: n (RAFT reagent: AIBN: acrylamide) =1:0.01:60, adding all substances into a Schlenk bottle, adding tetrahydrofuran as a solvent, introducing nitrogen, and heating to 70 ℃ under nitrogen atmosphere for reaction for 3-5 hours to prepare a hyperbranched polymer;
S3: mixing 5g of magnetic carbon nano tube with 15g of 1-aminopropyl-3-methylimidazole nitrate for standby, dissolving 17g of hyperbranched polymer in DMF, adding 2g of triethylamine, and reacting for 3 hours at room temperature to obtain hyperbranched grafted magnetic carbon nano tube;
S4: continuously dispersing the hyperbranched grafted magnetic carbon nano tube in DMF, adding 0.5 times of APEG300, adding catalytic amount of AIBN, introducing nitrogen to remove air in the system, heating to 70 ℃, stirring and reacting for 12 hours, separating out solid in glacial methanol after the reaction is completed, and drying to obtain the magnetic demulsifier.
2. Introducing clear water at the lower layer of the oil separation tank into magnetic separation equipment, recovering a magnetic demulsifier, and delivering effluent into an air floatation tank;
3. The water outlet of the air floatation tank is communicated with the coagulation tank, a water purifying agent is put into the coagulation tank, the water is treated for 30-60min, then the water is filtered by a sedimentation tank, and the water is flocculated for 5-10min by a flocculation tank, so that purified water is obtained;
4. The water quality of purified water is tested, the COD content is less than 40mg/L, the oil is less than 0.5mg/L, the ammonia nitrogen is less than 5mg/L, the phenol is less than 0.3mg/L, and the cyanogen is less than 0.2mg/L. After one-time complete process treatment, the national emission standard can be achieved.
Example 3:
1. Introducing the coking wastewater into an oil separation tank, firstly adding a pH regulator to regulate the pH value to 7-8, then adding a magnetic demulsifier into the regulating tank, fully mixing, and standing for 1h;
The magnetic demulsifier is prepared by the following steps:
s1: dispersing 10g of carbon nano tube in deionized water to form dispersion liquid, mixing and stirring with 200ml of 0.8mol/L ferric trichloride hexahydrate and 100ml of 0.8mol/L copper sulfate pentahydrate for 10-60min, then dripping 5-20wt% ammonia water, adjusting pH to 7-8, stirring and reacting for 5h at 90-100 ℃, cooling and filtering, alternately flushing solid product ethanol and water and drying, and calcining for 2h in nitrogen atmosphere at 400 ℃ to obtain the magnetic carbon nano tube;
s2: n (RAFT reagent: AIBN: acrylamide) =1:0.01:70, adding all substances into a Schlenk bottle, adding tetrahydrofuran as a solvent, introducing nitrogen, and heating to 70 ℃ under nitrogen atmosphere for reaction for 3-5 hours to prepare a hyperbranched polymer;
s3: mixing 5g of magnetic carbon nano tube with 15g of 1-aminopropyl-3-methylimidazole bromide for later use, dissolving 20g of hyperbranched polymer in DMF, adding 2g of triethylamine, and reacting for 3 hours at room temperature to obtain hyperbranched grafted magnetic carbon nano tube;
S4: continuously dispersing the hyperbranched grafted magnetic carbon nano tube in DMF, adding 0.8 times of APEG400, adding catalytic amount of AIBN, introducing nitrogen to remove air in the system, heating to 70 ℃, stirring and reacting for 12 hours, separating out solid in glacial methanol after the reaction is completed, and drying to obtain the magnetic demulsifier.
2. Introducing clear water at the lower layer of the oil separation tank into magnetic separation equipment, recovering a magnetic demulsifier, and delivering effluent into an air floatation tank;
3. The water outlet of the air floatation tank is communicated with the coagulation tank, a water purifying agent is put into the coagulation tank, the water is treated for 30-60min, then the water is filtered by a sedimentation tank, and the water is flocculated for 5-10min by a flocculation tank, so that purified water is obtained;
4. The water quality of purified water is tested, the COD content is less than 40mg/L, the oil is less than 0.3mg/L, the ammonia nitrogen is less than 4mg/L, the phenol is less than 0.2mg/L, and the cyanogen is less than 0.2mg/L. After one-time complete process treatment, the national emission standard can be achieved.
Comparative example 1:
in comparison with example 1, the demulsifier was not used.
The water quality of purified water is tested, the COD content is less than 1000mg/L, the oil is less than 80mg/L, the ammonia nitrogen is less than 70mg/L, the phenol is less than 40mg/L, and the cyanogen is less than 5mg/L. The primary treatment fails to meet the national emission standard.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (6)
1. The coking wastewater advanced treatment process is characterized by comprising the following steps of:
1. Introducing the coking wastewater into an oil separation tank, firstly adding a pH regulator to regulate the pH value to 7-8, then adding a magnetic demulsifier into the regulating tank, fully mixing, and standing for 1h;
2. introducing clear water at the lower layer of the oil separation tank into magnetic separation equipment, recovering a magnetic demulsifier, and delivering effluent into an air floatation tank;
3. The water outlet of the air floatation tank is communicated with the coagulation tank, a water purifying agent is put into the coagulation tank, the water is treated for 30-60min, then the water is filtered by a sedimentation tank, and the water is flocculated for 5-10min by a flocculation tank, so that purified water is obtained;
4. Testing the quality of purified water, directly discharging after reaching the discharge standard, and introducing the purified water into a coagulation tank again for secondary treatment until reaching the discharge standard if not reaching the discharge standard;
The magnetic demulsifier is prepared by the following steps:
S1: dispersing carbon nano tubes in deionized water by ultrasonic to form dispersion liquid, mixing and stirring the dispersion liquid with ferric trichloride hexahydrate and copper sulfate pentahydrate for 10-60min, then dripping ammonia water with the concentration of 5-20wt%, adjusting the pH value to 7-8, stirring and reacting for 2-10 h at the temperature of 90-100 ℃, cooling and filtering, alternately flushing solid products of ethanol and water, drying, and calcining for 1-4h in nitrogen atmosphere at the temperature of 400-500 ℃ to prepare the magnetic carbon nano tubes;
S2: carrying out RAFT polymerization under nitrogen atmosphere by taking xanthate of terminal double bond as a chain transfer agent, AIBN as an initiator and acrylamide as a reaction monomer to prepare a hyperbranched polymer;
S3: mixing the magnetic carbon nanotube with amino functional ionic liquid for standby, dissolving hyperbranched polymer in DMF, and carrying out Michael addition reaction of amino-double bond under the catalysis of triethylamine to obtain hyperbranched grafted magnetic carbon nanotube;
s4: continuously dispersing the hyperbranched grafted magnetic carbon nano tube in DMF, adding AIBN, introducing nitrogen to remove air in the system, adding allyl polyoxyethylene ether, heating to 70 ℃, stirring for reaction for 12 hours, separating out solid in glacial methanol after the reaction is completed, and drying to obtain the magnetic carbon nano tube.
2. The coking wastewater advanced treatment process according to claim 1, wherein in the step S1, the amount of ferric trichloride hexahydrate and copper sulfate pentahydrate is n (Fe 3+):n(Cu2+) =2:1, and the mass ratio of the total mass to the carbon nanotubes is 5-10:1.
3. The coking wastewater advanced treatment process according to claim 1, wherein in the step S2, the xanthate of the terminal double bond has a structural formula ofThe mole ratio of RAFT chain transfer agent, initiator and reaction monomer is 1:0.01:50-100.
4. The coking wastewater advanced treatment process according to claim 1, wherein in the step S3, the amino-functionalized ionic liquid is selected from one of 1-aminopropyl-3-methylimidazolium nitrate, 1-aminopropyl-3-methylimidazolium bromide, 1-aminoethyl-3-methylimidazolium nitrate, and 1-aminoethyl-3-methylimidazolium bromide.
5. The coking wastewater advanced treatment process according to claim 1, wherein in the step S3, the mass ratio of the magnetic carbon nanotubes to the amino-functional ionic liquid to the hyperbranched grafted magnetic carbon nanotubes is 1:3:3-10.
6. The coking wastewater advanced treatment process according to claim 1, wherein in the step S4, the molecular weight of the allyl polyoxyethylene ether ranges from 300 to 600, and the mass ratio of the allyl polyoxyethylene ether to the hyperbranched grafted magnetic carbon nanotubes ranges from 0.5 to 1:1.
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