CN117447002A - Coking wastewater treatment process - Google Patents
Coking wastewater treatment process Download PDFInfo
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- CN117447002A CN117447002A CN202311341173.5A CN202311341173A CN117447002A CN 117447002 A CN117447002 A CN 117447002A CN 202311341173 A CN202311341173 A CN 202311341173A CN 117447002 A CN117447002 A CN 117447002A
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title claims abstract description 22
- 238000004939 coking Methods 0.000 title claims abstract description 20
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000011282 treatment Methods 0.000 claims abstract description 48
- 229920000881 Modified starch Polymers 0.000 claims abstract description 29
- 235000019426 modified starch Nutrition 0.000 claims abstract description 28
- 239000004368 Modified starch Substances 0.000 claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 230000000813 microbial effect Effects 0.000 claims abstract description 16
- 238000004062 sedimentation Methods 0.000 claims abstract description 14
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000005345 coagulation Methods 0.000 claims abstract description 10
- 230000015271 coagulation Effects 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000010802 sludge Substances 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 150000003248 quinolines Chemical class 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920002261 Corn starch Polymers 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000008120 corn starch Substances 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 claims description 8
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 229960003540 oxyquinoline Drugs 0.000 claims description 7
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000007265 chloromethylation reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 6
- 238000005189 flocculation Methods 0.000 claims description 5
- 230000016615 flocculation Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000000855 fermentation Methods 0.000 claims description 4
- 230000004151 fermentation Effects 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 241000193744 Bacillus amyloliquefaciens Species 0.000 claims description 3
- 238000012258 culturing Methods 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 229920002472 Starch Polymers 0.000 abstract description 8
- 235000019698 starch Nutrition 0.000 abstract description 8
- 239000008107 starch Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 abstract description 2
- 239000000498 cooling water Substances 0.000 abstract description 2
- 230000003311 flocculating effect Effects 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 5
- 239000008394 flocculating agent Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention relates to a coking wastewater treatment process, which comprises the following steps: s1, preprocessing; s2, flocculating settling: adding a compound of a compound microbial flocculant and modified starch into the coagulation tank, rapidly stirring for 20min, standing, and discharging supernatant; s3, performing aerobic treatment; s4, reverse osmosis membrane treatment: pumping into a reverse osmosis membrane device for advanced treatment, adding modified starch into water after membrane treatment, naturally precipitating for 1h in a secondary sedimentation tank, and then filtering and discharging; wherein the modified starch is obtained by grafting polymerization reaction type quinoline derivatives, PEGMA and AA on the surface of starch. The water treatment agent used in the whole treatment process is mainly modified starch, is assisted by the composite microbial flocculant, has the advantages of small use amount and high treatment efficiency, and the treated water quality is stable, so that the discharge of surplus sludge is basically realized, the scaling can be avoided, the reverse osmosis membrane is ensured not to be polluted, and the treated water is directly discharged or recycled as circulating cooling water.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a coking wastewater treatment process.
Background
With the development of industrialization, the industrial water is greatly increased, and with this, more industrial wastewater is generated. The direct discharge of industrial wastewater can pollute water resources and affect the health and safety of animals and plants, so that the industrial wastewater can be discharged after being treated. The water treatment refers to physical or chemical measures adopted for enabling the water quality to reach a certain use standard, and has important significance for developing industrial production, improving the product quality, protecting the human environment and maintaining ecological balance. Agents for water treatment include: the water treatment agent comprises an adsorbent, a corrosion inhibitor, a bactericide, a flocculant, a scale inhibitor and the like, and water treatment agents with different functions are used for water bodies with different components, and different types of water treatment agents are also required to be used for water bodies with complex components in a combined mode.
The wastewater in coking, nitrogenous fertilizer and steel industry is one of the most difficult-to-degrade high-concentration organic wastewater, has complex components, and has the problems of high COD, high ammonia nitrogen, high salt and the like. At present, most of coking plant treatment wastewater adopts primary treatment and secondary treatment processes, a large amount of chemical agents are needed to be added in the treatment process for water quality conditioning such as sedimentation, filtration, coagulation, flocculation, corrosion inhibition, scale inhibition and the like, but the use of the chemical agents is multiple, and the use of the chemical agents in large amounts clearly aggravates the treatment cost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel water treatment agent for coking wastewater treatment process, which can reduce the use types and the use amount of the water treatment agent and realize high-efficiency and environment-friendly water treatment.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a coking wastewater treatment process, comprising the following steps:
s1, pretreatment
Introducing the coking wastewater into a sedimentation tank for natural sedimentation for 2-4h, filtering and introducing into a coagulation tank;
s2, flocculation sedimentation
Adding a compound of a compound microbial flocculant and modified starch into the coagulation tank, rapidly stirring for 20min, standing, and discharging supernatant;
s3, aerobic treatment
Introducing the supernatant into an aerobic tank, and adding activated sludge into water according to the ratio of water to activated sludge of 1:0.1 for aerobic treatment; the treated water is intercepted by an inorganic membrane filtering device at the water outlet of the aerobic tank, and the passing water is subjected to reverse osmosis membrane treatment;
s4, reverse osmosis membrane treatment
Pumping the membrane filter liquid in the step S3 into a reverse osmosis membrane device for advanced treatment, adding modified starch into the water after membrane treatment, naturally precipitating for 1h in a secondary sedimentation tank, and then filtering and discharging;
the preparation process of the modified starch comprises the following steps:
step one, preparing a reactive quinoline derivative by chloromethylation, sulfonation and chloro-substitution reaction by taking 8-hydroxyquinoline as a starting material;
adding a certain amount of corn starch and deionized water into a reaction bottle, heating, stirring, gelatinizing for half an hour, then keeping the temperature at 60-70 ℃, introducing inert gas, bubbling for 30min, adding an initiator under the protection of the inert gas, and then adding a reactive quinoline derivative, polyethylene glycol monomethyl ether methacrylate (PEGMA) and Acrylic Acid (AA), and reacting for a certain time;
and thirdly, naturally cooling to room temperature after the reaction is finished, pouring reactants into ethanol, standing, filtering and drying to obtain the catalyst.
Further, the mass ratio of the fermentation broth prepared by culturing and fermenting bacillus amyloliquefaciens to the modified starch of the composite microbial flocculant is 1:1.
Further, the adding amount of the compound microbial flocculant and the modified starch in the coagulation tank is 50-100 mg/L.
Further, in the step S4, the feeding amount of the modified starch is 30-50 mg/L.
Further, in the second step, the heating and stirring temperature is 80-90 ℃ and stirring is carried out for 3-5 hours.
Further, the initiator is potassium persulfate and sodium sulfite, and the use amount of the initiator is 0.08-0.1 of the mass of the corn starch.
Further, the molar ratio of the reactive quinoline derivative to the polyethylene glycol monomethyl ether methacrylate to the acrylic acid is 6-8:1-3:1; the mass ratio of the sum of the monomer mass and the corn starch is 3-5:1.
Compared with the prior art, the invention has the beneficial effects that: in the application, the novel water treatment agent is prepared by taking corn starch as a carrier material, grafting reaction type quinoline derivatives, polyethylene glycol monomethyl ether methacrylate (PEGMA) and acrylic acid on the surface of the corn starch, wherein the starch has good adsorption performance, and the starch is organically modified and then is also adsorbed with a microbial flocculant as a carrier, so that pollutants in a water body are adsorbed, net-caught and degraded, and the flocculation effect is good. Meanwhile, the modified corn starch also has the functions of corrosion inhibition and scale inhibition, avoids scaling, ensures that a reverse osmosis membrane is not polluted, and directly discharges treated water or is recycled as circulating cooling water. The water treatment agent used in the whole treatment process is mainly modified starch, is assisted by a composite microbial flocculant, has the advantages of small use amount and high treatment efficiency, and the treated water quality is stable, so that the discharge of residual sludge is basically realized.
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.
A coking wastewater treatment process, comprising the following steps:
s1, pretreatment
Introducing the coking wastewater into a sedimentation tank for natural sedimentation for 2-4h, filtering and introducing into a coagulation tank;
s2, flocculation sedimentation
Adding a compound of a compound microbial flocculant and modified starch into a coagulation tank, wherein the adding amount is 50-100 mg/L, rapidly stirring for 20min, standing, and discharging supernatant;
s3, aerobic treatment
Introducing the supernatant into an aerobic tank, and adding activated sludge into water according to the ratio of water to activated sludge of 1:0.1 for aerobic treatment; the treated water is intercepted by an inorganic membrane filtering device at the water outlet of the aerobic tank, and the passing water is subjected to reverse osmosis membrane treatment;
s4, reverse osmosis membrane treatment
Pumping the membrane filter liquid obtained in the step S3 into a reverse osmosis membrane device for advanced treatment, adding 30-50 mg/L modified starch into the water after membrane treatment, naturally precipitating for 1h in a secondary sedimentation tank, and then filtering and discharging;
the preparation process of the modified starch comprises the following steps:
step one, preparing a reactive quinoline derivative by chloromethylation, sulfonation and chloro-substitution reaction by taking 8-hydroxyquinoline as a starting material;
adding a certain amount of corn starch and deionized water into a reaction bottle, heating, stirring, gelatinizing for half an hour, then keeping the temperature at 60-70 ℃, introducing inert gas, bubbling for 30min, adding an initiator under the protection of the inert gas, and then adding a reactive quinoline derivative, PEGMA (Mn=500 g/mol) and acrylic acid, and reacting for a certain time;
and thirdly, naturally cooling to room temperature after the reaction is finished, pouring reactants into ethanol, standing, filtering and drying to obtain the catalyst.
And thirdly, naturally cooling to room temperature after the reaction is finished, pouring reactants into ethanol, standing, filtering and drying to obtain the catalyst.
The composite microbial flocculant is a fermentation bacterial liquid prepared by culturing and fermenting bacillus amyloliquefaciens, and the mass ratio of the fermentation bacterial liquid to modified starch is 1:1.
The applicant deeply ploughs the technical field of water treatment, and has a certain research on water treatment agents and water treatment processes, and partial results have obtained the invention patent. In patent CN114735795B, a compound magnetic flocculant of sodium alginate-diatomaceous earth is prepared, in which a reactive quinoline derivative prepared by using 8-hydroxyquinoline as a starting material plays an important role in the process of modifying diatomaceous earth, and although the effect is remarkable, the cost is increased a lot. After continuous and intensive research, researchers of the subject group find that the graft polymerization of the reactive quinoline derivative on the natural scale inhibitor can improve the corrosion and scale inhibition of the material, can be used as a water quality stabilizer to be added into the industrial circulating water treatment process, and greatly widens the application range.
The starch is a natural adsorbent and also has certain scale inhibition performance, and has the characteristics of low cost, wide sources, environmental protection and no pollution. However, when the starch is used as a scale inhibitor, the stability is poor, and the dosage is large. Therefore, organic chemical modification of starch is required. In the scheme, corn starch is used as a modified carrier, and a polymerization reaction type quinoline derivative, polyethylene glycol monomethyl ether methacrylate (PEGMA) and acrylic acid are grafted on the surface of the modified carrier, so that the formed polymer grafted modified starch can be adsorbed on the metal surface to form a compact protective layer due to the fact that abundant hetero atoms (N, S, O), heterocyclic structures and quaternary ammonium salts are introduced, and the modified starch has high corrosion inhibition performance. In the application, the prepared reactive type derivative has large steric hindrance effect in molecules, low polymerization activity and difficult self-polymerization on the surface of starch, so that proper polymerization monomers are needed to be selected to be copolymerized with the reactive type derivative to exert the function to the greatest extent. After multiple test screening, it is found that the long-chain PEGMA monomer is assisted with a small amount of acrylic acid as a comonomer, and the reactive type starch grafted with the copolymer chain of the derivative of the reactive type can be successfully prepared, and has corrosion inhibition and scale inhibition.
Compared with other types of flocculating agents, the microbial flocculating agent has the advantages of safety, no toxicity and environmental protection. Microbial flocculants are generally used as coagulant aids in combination with other flocculants to more effectively perform their functions.
Based on the preparation process, the composite microbial flocculant used in the application refers to the preparation of MBF (MBF) in section 1 in the section 5 of 'removal of xanthate and lead ions in microbial flocculant degree wastewater' of the university of Chinese mining university, 9 month of 2022, volume 51, and meanwhile, the application also provides the following specific modified starches as samples.
Modified starch sample 1:
step one, preparing a reactive quinoline derivative by chloromethylation, sulfonation and chloro-substitution reaction by taking 8-hydroxyquinoline as a starting material;
step two, adding 5g of corn starch and 200ml of deionized water into a reaction bottle, heating to 85 ℃ for gelatinization for half an hour, then keeping the temperature at 70 ℃, introducing inert gas for bubbling for 30min, adding 0.4g of potassium persulfate under the protection of the inert gas, and then adding 3g of monomer (the mol ratio of the reactive quinoline derivative to PEGMA to acrylic acid is 5:4:1), and reacting for a certain time;
and thirdly, naturally cooling to room temperature after the reaction is finished, pouring reactants into ethanol, standing, filtering and drying to obtain the catalyst.
Modified starch sample 2:
step one, preparing a reactive quinoline derivative by chloromethylation, sulfonation and chloro-substitution reaction by taking 8-hydroxyquinoline as a starting material;
step two, adding 5g of corn starch and 200ml of deionized water into a reaction bottle, heating to 85 ℃ for gelatinization for half an hour, then keeping the temperature at 70 ℃, introducing inert gas for bubbling for 30min, adding 0.4g of potassium persulfate under the protection of the inert gas, and then adding 3g of monomer (the mol ratio of the reactive quinoline derivative to PEGMA to acrylic acid is 6:3:1), and reacting for a certain time;
and thirdly, naturally cooling to room temperature after the reaction is finished, pouring reactants into ethanol, standing, filtering and drying to obtain the catalyst.
Modified starch sample 3:
step one, preparing a reactive quinoline derivative by chloromethylation, sulfonation and chloro-substitution reaction by taking 8-hydroxyquinoline as a starting material;
step two, adding 5g of corn starch and 200ml of deionized water into a reaction bottle, heating to 85 ℃ for gelatinization for half an hour, then keeping the temperature at 70 ℃, introducing inert gas for bubbling for 30min, adding 0.4g of potassium persulfate under the protection of the inert gas, and then adding 3g of monomer (the mol ratio of the reactive quinoline derivative to PEGMA to acrylic acid is 7:2:1), and reacting for a certain time;
and thirdly, naturally cooling to room temperature after the reaction is finished, pouring reactants into ethanol, standing, filtering and drying to obtain the catalyst.
Taking the wastewater discharged from a local coking plant as an example, COD 2300mg/L, ammonia nitrogen 220mg/L and salt content 8500mg/L are respectively treated by using the modified starch samples 1-3 in combination with the treatment process, after the treatment, COD is less than or equal to 15mg/L, ammonia nitrogen is less than or equal to 5mg/L, and the desalination rate is more than or equal to 95%.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (7)
1. The coking wastewater treatment process is characterized by comprising the following steps of:
s1, pretreatment
Introducing the coking wastewater into a sedimentation tank for natural sedimentation for 2-4h, filtering and introducing into a coagulation tank;
s2, flocculation sedimentation
Adding a compound of a compound microbial flocculant and modified starch into the coagulation tank, rapidly stirring for 20min, standing, and discharging supernatant;
s3, aerobic treatment
Introducing the supernatant into an aerobic tank, and adding activated sludge into water according to the ratio of water to activated sludge of 1:0.1 for aerobic treatment; the treated water is intercepted by an inorganic membrane filtering device at the water outlet of the aerobic tank, and the passing water is subjected to reverse osmosis membrane treatment;
s4, reverse osmosis membrane treatment
Pumping the membrane filter liquid in the step S3 into a reverse osmosis membrane device for advanced treatment, adding modified starch into the water after membrane treatment, naturally precipitating for 1h in a secondary sedimentation tank, and then filtering and discharging;
the preparation process of the modified starch comprises the following steps:
step one, preparing a reactive quinoline derivative by chloromethylation, sulfonation and chloro-substitution reaction by taking 8-hydroxyquinoline as a starting material;
adding a certain amount of corn starch and deionized water into a reaction bottle, heating, stirring and gelatinizing for half an hour, then keeping the temperature at 60-70 ℃, introducing inert gas to bubble for 30min, adding an initiator under the protection of the inert gas, and then adding a reactive quinoline derivative, polyethylene glycol monomethyl ether methacrylate and acrylic acid for reacting for a certain time;
and thirdly, naturally cooling to room temperature after the reaction is finished, pouring reactants into ethanol, standing, filtering and drying to obtain the catalyst.
2. The coking wastewater treatment process according to claim 1, wherein the mass ratio of the composite microbial flocculant to the modified starch is 1:1, wherein the fermentation broth is prepared by culturing and fermenting bacillus amyloliquefaciens.
3. The coking wastewater treatment process according to claim 1, wherein the dosage of the compound microbial flocculant and the modified starch in the coagulation tank is 50-100 mg/L.
4. The coking wastewater treatment process according to claim 1, wherein in the step S4, the feeding amount of the modified starch is 30 to 50mg/L.
5. The coking wastewater treatment process according to claim 1, wherein in the second step, the heating and stirring temperature is 80-90 ℃ and stirring is carried out for 3-5 hours.
6. The coking wastewater treatment process according to claim 1, wherein the initiator is potassium persulfate and sodium sulfite, and the initiator is used in an amount of 0.08-0.1 of the mass of the corn starch.
7. The coking wastewater treatment process according to claim 1, wherein the molar ratio of the reactive quinoline derivative, the polyethylene glycol monomethyl ether methacrylate and the acrylic acid is 6-8:1-3:1; the mass ratio of the sum of the monomer mass and the corn starch is 3-5:1.
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