CN112759196A - Treatment process of esterification wastewater - Google Patents
Treatment process of esterification wastewater Download PDFInfo
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- CN112759196A CN112759196A CN202110005719.4A CN202110005719A CN112759196A CN 112759196 A CN112759196 A CN 112759196A CN 202110005719 A CN202110005719 A CN 202110005719A CN 112759196 A CN112759196 A CN 112759196A
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000002351 wastewater Substances 0.000 title claims abstract description 72
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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
- C02F1/40—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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- 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
- C02F3/30—Aerobic and anaerobic processes
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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)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides a treatment process of lipidation wastewater, and relates to the technical field of wastewater treatment. The invention adopts a process in which the multidimensional electrocatalysis and the external circulation Fenton oxidation tank process supplement each other, the process combination enables the degradation effect of organic matters to be doubled, and the dosage of the medicament is greatly reduced; although the Fenton process is adopted, no sulfate radical is introduced in the process, sulfides which have toxic action on microorganisms cannot be generated in the anaerobic stage, the maximum treatment effect of a biological system can be ensured, a fixed bed catalytic oxidation filter tank is adopted in the operation process, the catalytic oxidation process is free of acid regulation, alkali regulation and mud production, a catalyst can promote hydrogen peroxide to be fully decomposed, hydroxyl radicals can be generated, a series of comprehensive oxidation-reduction reactions are formed, the strong oxidative decomposition of organic matters is realized, meanwhile, sewage is filtered, and the effects of reducing COD (chemical oxygen demand), suspended matters, improving the B/C value and the like can be realized.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a treatment process of esterification wastewater.
Background
The synthetic resin paint is a kind of artificially synthesized high molecular polymer, and the produced lipidated waste water has the features of high organic matter content and low biochemical property. With the improvement of economic level, the production capacity of the coating in China also improves year by year, but the production process and the characteristics of various coatings at the present stage determine that a large amount of toxic and harmful industrial wastewater is generated in the production process, and with the rapid development of the coating industry in China, the treatment of the coating wastewater increasingly becomes an environmental problem which needs high attention; most of the various coatings involve resin synthesis in the production process, and use various chemical raw materials such as organic solvents, auxiliaries and the like.
The esterification wastewater is wastewater with the highest pollution concentration in the coating production wastewater, and the wastewater contains alcohols, lipids, acids and organic solvents with high concentration, so that the treatment difficulty is high, and the esterification wastewater is generally determined as hazardous waste (high-concentration organic waste liquid) by the environmental protection department and needs to be incinerated by a third party. Now, due to the development progress of environmental protection technology and the difficulty in meeting the requirements of enterprises in the treatment capacity of hazardous wastes in various places, the environmental protection department begins to allow the enterprises to treat the esterification wastewater by themselves. However, the concentration of the wastewater is hundreds of times higher than that of the conventional wastewater, and the wastewater has certain biological toxicity, so the conventional biological wastewater treatment process cannot be directly used for treating the esterification wastewater.
At present, the methods for treating esterification wastewater mainly comprise physical methods (adsorption, extraction, membrane separation and the like), chemical oxidation methods (photocatalytic oxidation, supercritical water oxidation, chlorine dioxide oxidation, ultrasonic degradation method, electrochemical oxidation and the like), biological methods (conventional anaerobic and aerobic treatment, pressurized biochemical treatment, high-efficiency degradation bacteria screening and separation) and the like.
Chinese patent application 202010118450.6 discloses a treatment system and a treatment method for esterification wastewater. The treatment system comprises a wastewater adjusting tank, a pre-settling tank, a first pH adjusting tank, a micro-electrolysis tower, a first Fenton oxidation tank, a second pH adjusting tank, a first coagulation tank, a first flocculation tank, a first settling tank, a middle water tank, a pre-acidification tank, an internal circulation anaerobic reaction tower, an aerobic tank, a membrane biological reaction tank, a third pH adjusting tank, a second Fenton oxidation tank, a fourth pH adjusting tank, a second coagulation tank, a second flocculation tank, a second sedimentation tank and a clear water discharge tank which are sequentially connected. The treatment system for treating the esterification wastewater has the advantages of high treatment efficiency and good effect, the discharged water has no secondary pollution, the degradation efficiency is up to more than 98 percent, but the CODCr of the treated wastewater is 88.09mg/L and still higher, and the discharge requirement cannot be met.
Chinese patent application 201711233179.5 discloses a treatment process of lipidation wastewater, which comprises the following steps: s1, sequentially treating the lipidated wastewater by an oil separation tank and a water collecting tank, and adding H2O2(ii) a S2, carrying out an external circulation micro-electrolysis Fenton oxidation reaction to a neutralization pond; s3, treating the mixture in a neutralization tank and a reaction tank A and then feeding the mixture to an adjusting tank; s4, treating the mixture in an adjusting tank, a hydrolysis acidification tank and an anaerobic adjusting tank, and then feeding the mixture to a UASB reaction tank; s5, treating the mixture by a composite UASB and then feeding the mixture to a multistage contact oxidation tank; s6, treating the mixture in a multistage contact oxidation tank and a sedimentation tank B, and then feeding the mixture into a reaction tank B; s7, precipitating in a precipitation tank C and then transferring to a transfer tank; and S8, pumping the wastewater into a neutral catalytic oxidation tank through a transfer tank, and then flowing into a clean water tank for recycling or discharging through a discharge port to finish the treatment process of the lipidated wastewater. The application is not enough to sewage pretreatment technology in the implementation process, does not completely remove harmful components in the sewage, increases the pressure in subsequent treatment, and does not select a precipitator in the reaction process, so the COD treatment effect on the wastewater is not good.
The prior researches find that the wastewater is pretreated and organic matters, pigments and the like in the wastewater can be effectively precipitated by using a proper precipitator, so that the treatment efficiency is improved.
The invention adds the pretreatment step on the basis of the prior art, selects the type of the precipitant, has the advantages of simple and convenient operation, continuous operation, low energy consumption and the like, and can be popularized and used in industrial production.
Disclosure of Invention
Based on the defects and shortcomings in the prior art, the invention aims to provide the efficient treatment process of the esterification wastewater, which has the advantages of low cost, high recovery value and high purification efficiency and conforms to the economic benefit, social benefit and the green and environment-friendly principle.
A treatment process of lipidation wastewater comprises the following steps:
(1) and introducing the lipidated wastewater into an oil separation tank, and removing grease in the wastewater through the oil separation tank to obtain sewage 1.
(2) Adjusting the water quality of the sewage 1, pumping the sewage into a multi-dimensional electro-catalytic reaction tank and carrying out oxidation reaction on the sewage and an external circulation Fenton oxidation tank to obtain sewage 2;
(3) adjusting the pH value of the sewage 2, adding a demulsifier and a coagulant aid to react impurities in the sludge to generate precipitable sludge, and precipitating in a sedimentation tank to allow supernatant to automatically flow into an adjusting tank to obtain sewage 3;
(4) conveying the sewage 3 to a hydrolysis acidification tank after being regulated by a regulating tank, adding a strain into the hydrolysis acidification tank, and treating the sewage by the hydrolysis acidification tank to obtain sewage 4;
(5) automatically flowing the sewage 4 into an anaerobic regulating tank for regulation, and pumping the wastewater treated in the anaerobic regulating tank into a UASB reaction tank for treatment to obtain sewage 5;
(6) transferring the sewage 5 into a multistage contact oxidation tank, carrying out aeration and oxygenation in the multistage contact oxidation tank to decompose organic matters in the sewage into inorganic matters, and oxidizing ammonia nitrogen into nitrite and nitrate to obtain sewage 6, wherein the sewage 6 flows into a reaction tank automatically after being precipitated in a precipitation tank;
(7) adding coagulant and coagulant aid into the reaction tank, precipitating in a sedimentation tank, allowing supernatant to flow into a transfer tank, pumping into a fixed bed catalytic oxidation filter, adding oxidant into the fixed bed catalytic oxidation filter, further degrading residual organic matters in the sewage, destroying residual microorganism metabolic components such as extracellular polymeric substances and other macromolecular structures in an aerobic tank into micromolecular structures, and obtaining sewage 7 with improved biodegradability,
(8) and the sewage 7 automatically flows into the MBR tank to carry out secondary biological oxidation, and is filtered by the MBR and then recycled by the clean water tank or discharged by a discharge port to finish the treatment process of the lipidated wastewater.
Wherein,
the concrete operation of adjusting the water quality of the sewage 2 in the step (2) is as follows:
the lift pump pumps the wastewater into a multidimensional electro-catalytic reaction tank, the esterified wastewater contains organic acid, the pH value of the esterified wastewater is acidic, hydrochloric acid or sulfuric acid is not required to be added for adjusting the pH value, multidimensional electro-catalytic filler and a graphite electrode are arranged in the tank, the current efficiency and the treatment capacity of the electrode are improved by the filler, the wastewater is decomposed at a high speed by oxygen generated by electrolysis and hydroxyl radicals (HO) generated by reduction on a cathode by aeration oxygenation, iron ions generated by the filler enter a Fenton reaction tank along with effluent, and H is added2O2Oxidizing the organic matters which are difficult to degrade in the water into an inorganic state with the residual iron ion mixed solution;
the sewage 1 after the water quality is adjusted enters an electrocatalysis reaction tank, a multidimensional electrocatalysis filler generates catalytic oxidation under the action of an external electric field, the organic matters which are difficult to degrade in the esterification wastewater are partially oxidized, the filler can generate a large amount of iron ions during the oxidation reaction, and the effluent of the electrocatalysis reaction tank automatically flows to an external circulation Fenton oxidation tank; the multidimensional electric catalysis adopts graphite as an electrode material and adopts iron-carbon composite filler as filling filler, and the graphite has the advantages of stable use chemical property and long service life. The iron-carbon micro-electrolysis filler has conductivity, can synchronously perform catalytic oxidation and catalytic reduction reactions, can release a large amount of iron ions, does not need to add sulfuric acid and ferrous sulfate in subsequent Fenton oxidation like the conventional Fenton process, avoids the inhibition and toxic action of the added sulfate ions on anaerobic bacteria, and ensures that the subsequent anaerobic process can exert the maximum effect.
Adjusting the pH value of the sewage 2 to 7-8 in the step (3);
the demulsifier is an organic demulsifier;
the organic demulsifier is selected from one or more of polymeric polyol demulsifiers;
the polymeric polyol demulsifier is selected from one or more of GP01, GP02, GP03, GP04 and GP 05;
preferably, the polymeric polyol demulsifier is a mixture of GP01, GP02, GP03, GP04 and GP 05;
the mass ratio of GP01, GP02, GP03, GP04 and GP05 is 1:2:2:2: 1.
The coagulant aid is polyacrylamide;
the ratio of the addition amount of the demulsifier to the volume of the sewage is 0.3-1: 1 (g/L);
the ratio of the addition amount of the coagulant aid to the volume of the sewage is 0.008-0.015: 1 (g/L);
the strain in the step (4) is hydrolytic acidification bacteria, is from activated sludge of a sewage treatment plant, and is added in an amount of 5-30 kg/ton sewage.
The hydrolysis acidification adopts a point-to-point water distributor special for anaerobic reaction, the stirring effect is superior to that of the traditional pulse water distributor and a submersible stirrer, and the hydrolysis acidification pool is ensured to be in the best effect.
The water tank part of the hydrolysis acidification tank flows back to the regulating tank, the reflux ratio is 100-400%, the concentration of toxic and harmful components in the sewage entering the hydrolysis acidification tank can be diluted by the backflow sewage, the sewage can enter the hydrolysis acidification tank at a relatively stable concentration, and the toxic action of residual toxic substances in the esterification wastewater on microorganisms is prevented.
In the step (5), a large amount of anaerobic sludge exists in the UASB reaction tank, the sludge concentration reaches 20-60 kg/ton of sewage, and the main component of the anaerobic sludge is methanogen. The UASB adopts a medium-temperature (35-40 ℃) anaerobic environment, methanogen can organically convert the sewage into carbon dioxide and methane gas in the anaerobic environment, the effluent of the UASB mostly flows back to an anaerobic regulating tank, the reflux ratio is 100-1000%, the COD concentration of the influent water of the UASB is controlled below 8000mg/L through reflux, the stability of the COD concentration of the influent water is ensured, and the stability of the operation of the UASB and the removal efficiency of the COD are improved.
The coagulant mentioned in the step (7) above, polyaluminium chloride; the coagulant aid is polyacrylamide;
the ratio of the addition amount of the flocculating agent to the volume of the sewage is 0.1-0.3: 1 (g/L);
the ratio of the addition amount of the coagulant aid to the volume of the sewage is 0.005-0.008: 1 (g/L).
The oxidizing agent in the step (7) is hydrogen peroxide;
the ratio of the addition amount of the oxidant to the volume of the sewage is 0.05-0.2: 1 (g/L); preferably 0.08-0.012:1 (g/L).
Compared with the prior art, the invention has the beneficial effects that:
(1) the multi-dimensional electrocatalysis and the external circulation Fenton oxidation tank process complement each other, organic matters which are difficult to degrade in the esterification wastewater can be reacted in an electrocatalysis system, the effect is stable, the organic matters cannot change along with the change of residual organic matters in water, a filler in the multi-dimensional electrocatalysis contains a large amount of ferrous ions, redundant ferrous ions and added hydrogen peroxide are subjected to oxidation reaction in the Fenton oxidation tank, the process combination enables the organic matter degradation effect to be doubled, and the dosage of a medicament is greatly reduced;
(2) the conventional Fenton process needs to add hydrochloric acid or sulfuric acid to adjust the pH value, ferrous sulfate is added as a catalyst, sulfate ions can generate a large amount of toxic sulfur ions in subsequent anaerobic treatment, and the toxic sulfur ions have biological toxicity on microorganisms, particularly methanogens in UASB (upflow anaerobic sludge blanket), so that the anaerobic effect is poor. Although the Fenton process is adopted, no sulfate radical is introduced in the process, so that the biological system can be ensured to exert the maximum treatment effect.
(3) The fixed bed catalytic oxidation filter tank is adopted in the step (7), the whole process does not adjust acid, adjust alkali and produce mud,
the catalyst can promote the hydrogen peroxide to be fully decomposed to generate hydroxyl radicals and form a series of comprehensive oxidation-reduction reactions, so that the strong oxidative decomposition of organic matters is realized, and the effects of reducing COD, improving B/C value and the like can be realized.
The main components of the catalyst are a mixture of carbon-supported nano-copper oxide, carbon-supported nano-zirconium oxide, manganese oxide and iron carbide, the mass ratio of the mixture is 3:2:1:1, the surface effect, the quantum size effect, the volume effect, the macroscopic quantum tunneling effect and the catalytic activity of the nano-copper oxide and the nano-zirconium oxide and the synergistic effect of the nano-iron are fully utilized, the adsorption and the decomposition of hydrogen peroxide are fully completed in a short time, the hydrogen peroxide is efficiently catalyzed to generate hydroxyl radicals, and the radicals form a series of chain reactions under the action of the catalyst, so that the conversion efficiency and the initiation capacity of the hydrogen peroxide are greatly improved, the generation of the high-concentration and high-strength hydroxyl radicals can be realized, and the concentrated degradation of organic matters in the wastewater is realized; meanwhile, the existence of the catalyst can initiate a series of oxidation-reduction reactions to directly mineralize a plurality of organic matters into carbon dioxide and water.
Wherein, the hydraulic retention time of the sewage in the fixed bed catalytic oxidation filter is 3-4 hours.
(4) After the fixed bed catalytic oxidation filter tank, a part of organic pollutants in the sewage are degraded, a part of molecular structures are destroyed, and the biodegradability is improved.
Under the synergistic effect of a plurality of factors, the method can effectively remove COD in the wastewater and destroy related chromophoric groups in the wastewater to a certain degree, thereby achieving the decolorization effect; for high-concentration nondegradable wastewater, the biodegradability of the wastewater can be greatly improved.
The lipidation wastewater treatment process claimed by the application has no residue and no pollution after decomposition of hydrogen peroxide; the process has no change to the conductivity of the wastewater; the reaction has no requirement on the salinity of the inlet water.
Drawings
FIG. 1 is a flow diagram of a process for treating lipidated wastewater according to the present invention;
reference numerals: a-an oil separation tank; b, a water collecting tank; a C-multidimensional electro-catalytic reaction tank; d-external circulation Fenton oxidation tank; e-a neutralization pond; f-reaction tank 1; g-a sedimentation tank 1; h-adjusting pool; i, a hydrolytic acidification tank; j-anaerobic adjusting tank; a K-UASB reaction tank; an L-multi-stage contact oxidation pond; m-a sedimentation tank 2; n-reaction tank 2; an O-sedimentation tank 3; p-transfer pool; q-fixed bed catalytic oxidation filter; an R-MBR tank; s-a clean water tank; a T-materialized sludge tank; u-biochemical sludge tank; a V-filter press; alpha-esterified water; beta-hydrogen peroxide; gamma-base, demulsifiers and coagulants; delta-coagulants and coagulant aids; transporting the epsilon-sludge outside.
Detailed Description
Example 1 treatment Process of lipidated wastewater
The method comprises the following steps:
(1) and introducing the lipidated wastewater into an oil separation tank, and removing grease in the wastewater through the oil separation tank to obtain sewage 1.
(2) Adjusting the water quality of the sewage 1, pumping the sewage into a multi-dimensional electro-catalytic reaction tank and carrying out oxidation reaction on the sewage and an external circulation Fenton oxidation tank to obtain sewage 2;
(3) adjusting the pH value of the sewage 2 to 7, adding a mixture of GP01, GP02, GP03, GP04 and GP05 and polyacrylamide in a mass ratio of 1:2:2:2:1 to react impurities in the sludge to generate precipitable sludge, and allowing supernatant to flow into an adjusting tank after precipitation in a precipitation tank to obtain sewage 3;
(4) conveying the sewage 3 to a hydrolysis acidification tank after being regulated by a regulating tank, adding strains into the hydrolysis acidification tank, refluxing part of a water pool of the hydrolysis acidification tank to the regulating tank with the reflux ratio of 100%, and treating the sewage by the hydrolysis acidification tank to obtain sewage 4;
(5) automatically flowing the sewage 5 into an anaerobic regulating tank for regulation, pumping the wastewater treated in the anaerobic regulating tank into a UASB reaction tank for treatment, and refluxing part of the sewage in the UASB reaction tank into the anaerobic regulating tank at a reflux ratio of 100% to obtain the sewage 5;
(6) transferring the sewage 5 into a multistage contact oxidation tank, carrying out aeration and oxygenation in the multistage contact oxidation tank to decompose organic matters in the sewage into inorganic matters, and oxidizing ammonia nitrogen into nitrite and nitrate to obtain sewage 6, wherein the sewage 6 flows into a reaction tank automatically after being precipitated in a precipitation tank;
(7) adding polyaluminium chloride and polyacrylamide into a reaction tank, precipitating in a sedimentation tank, allowing supernatant to automatically flow into a transfer tank, pumping into a fixed bed catalytic oxidation filter tank, adding hydrogen peroxide into the fixed bed catalytic oxidation filter tank, wherein a catalyst is a mixture of carbon-supported nano-grade copper oxide, carbon-supported nano-grade zirconium oxide, manganese oxide and iron carbide with the mass ratio of 3:2:1:1, further degrading residual organic matters in the sewage, destroying macromolecular structures such as extracellular polymers and the like of residual microbial metabolic components in an aerobic tank into micromolecular structures, and obtaining sewage 7 with improved biodegradability,
(8) and the sewage 7 automatically flows into the MBR tank to carry out secondary biological oxidation, and is filtered by the MBR and then recycled by the clean water tank or discharged by a discharge port to finish the treatment process of the lipidated wastewater.
The ratio of the addition amount of the demulsifier to the volume of the sewage in the step (3) is 0.3: 1 (g/L); the ratio of the addition amount of the coagulant to the volume of the sewage is 0.008: 1 (g/L);
the ratio of the addition amount of the flocculant in the step (7) to the volume of the sewage is 0.1: 1 (g/L); the ratio of the addition amount of the coagulant aid to the volume of the sewage is 0.005: 1 (g/L); the ratio of the addition amount of the oxidant to the volume of the sewage is 0.05: 1 (g/L).
Example 2 treatment process of lipidated wastewater
The method comprises the following steps:
(1) and introducing the lipidated wastewater into an oil separation tank, and removing grease in the wastewater through the oil separation tank to obtain sewage 1.
(2) Adjusting the water quality of the sewage 1, pumping the sewage into a multi-dimensional electro-catalytic reaction tank and carrying out oxidation reaction on the sewage and an external circulation Fenton oxidation tank to obtain sewage 2;
(3) adjusting the pH value of the sewage 2 to be 8, then adding a mixture of GP01, GP02, GP03, GP04 and GP05 and polyacrylamide in a mass ratio of 1:2:2:2:1 to react impurities in the sludge to generate precipitable sludge, and after precipitation in a precipitation tank, enabling supernatant to automatically flow into an adjusting tank to obtain sewage 3;
(4) conveying the sewage 3 to a hydrolysis acidification tank after being regulated by a regulating tank, adding strains into the hydrolysis acidification tank, refluxing part of a water pool of the hydrolysis acidification tank to the regulating tank, wherein the reflux ratio is 400%, and treating the sewage by the hydrolysis acidification tank to obtain sewage 4;
(5) automatically flowing the sewage 4 into an anaerobic regulating tank for regulation, pumping the wastewater treated in the anaerobic regulating tank into a UASB reaction tank for treatment, and refluxing part of the sewage in the UASB reaction tank into the anaerobic regulating tank at a reflux ratio of 1000% to obtain sewage 5;
(6) transferring the sewage 5 into a multistage contact oxidation tank, carrying out aeration and oxygenation in the multistage contact oxidation tank to decompose organic matters in the sewage into inorganic matters, and oxidizing ammonia nitrogen into nitrite and nitrate to obtain sewage 6, wherein the sewage 6 flows into a reaction tank automatically after being precipitated in a precipitation tank;
(7) adding polyaluminium chloride and polyacrylamide into a reaction tank, precipitating in a sedimentation tank, allowing supernatant to automatically flow into a transfer tank, pumping into a fixed bed catalytic oxidation filter tank, adding hydrogen peroxide into the fixed bed catalytic oxidation filter tank, wherein a catalyst is a mixture of carbon-supported nano-grade copper oxide, carbon-supported nano-grade zirconium oxide, manganese oxide and iron carbide with the mass ratio of 3:2:1:1, further degrading residual organic matters in the sewage, destroying macromolecular structures such as extracellular polymers and the like of residual microbial metabolic components in an aerobic tank into micromolecular structures, and obtaining sewage 7 with improved biodegradability,
(8) and the sewage 7 automatically flows into the MBR tank to carry out secondary biological oxidation, and is filtered by the MBR and then recycled by the clean water tank or discharged by a discharge port to finish the treatment process of the lipidated wastewater.
The ratio of the addition amount of the demulsifier to the volume of the sewage in the step (3) is 1:1 (g/L); the ratio of the addition amount of the coagulant to the volume of the sewage is 0.015: 1 (g/L);
the ratio of the addition amount of the flocculant in the step (7) to the volume of the sewage is 0.3: 1 (g/L); the ratio of the addition amount of the coagulant aid to the volume of the sewage is 0.008: 1 (g/L); the ratio of the addition amount of the oxidant to the volume of the sewage is 0.2: 1 (g/L).
Example 3 treatment Process of lipidated wastewater
The method comprises the following steps:
(1) and introducing the lipidated wastewater into an oil separation tank, and removing grease in the wastewater through the oil separation tank to obtain sewage 1.
(2) Adjusting the water quality of the sewage 1, pumping the sewage into a multi-dimensional electro-catalytic reaction tank and carrying out oxidation reaction on the sewage and an external circulation Fenton oxidation tank to obtain sewage 2;
(3) adjusting the pH value of the sewage 2 to 7.5, then adding a mixture of GP01, GP02, GP03, GP04 and GP05 and polyacrylamide in a mass ratio of 1:2:2:2:1 to react impurities in the sludge to generate precipitable sludge, precipitating in a precipitation tank, and enabling supernatant to automatically flow into an adjusting tank to obtain sewage 3;
(4) conveying the sewage 3 to a hydrolysis acidification tank after being regulated by a regulating tank, adding strains into the hydrolysis acidification tank, refluxing part of a water pool of the hydrolysis acidification tank to the regulating tank with the reflux ratio of 300%, and treating the sewage by the hydrolysis acidification tank to obtain sewage 4;
(5) automatically flowing the sewage 4 into an anaerobic regulating tank for regulation, pumping the wastewater treated in the anaerobic regulating tank into a UASB reaction tank for treatment, and refluxing part of the sewage in the UASB reaction tank into the anaerobic regulating tank at a reflux ratio of 800% to obtain sewage 5;
(6) transferring the sewage 5 into a multistage contact oxidation tank, carrying out aeration and oxygenation in the multistage contact oxidation tank to decompose organic matters in the sewage into inorganic matters, and oxidizing ammonia nitrogen into nitrite and nitrate to obtain sewage 6, wherein the sewage 6 flows into a reaction tank automatically after being precipitated in a precipitation tank;
(7) adding polyaluminium chloride and polyacrylamide into a reaction tank, precipitating in a sedimentation tank, allowing supernatant to automatically flow into a transfer tank, pumping into a fixed bed catalytic oxidation filter tank, adding hydrogen peroxide into the fixed bed catalytic oxidation filter tank, wherein a catalyst is a mixture of carbon-supported nano-grade copper oxide, carbon-supported nano-grade zirconium oxide, manganese oxide and iron carbide with the mass ratio of 3:2:1:1, further degrading residual organic matters in the sewage, destroying macromolecular structures such as extracellular polymers and the like of residual microbial metabolic components in an aerobic tank into micromolecular structures, and obtaining sewage 7 with improved biodegradability,
(8) and the sewage 7 automatically flows into the MBR tank to carry out secondary biological oxidation, and is filtered by the MBR and then recycled by the clean water tank or discharged by a discharge port to finish the treatment process of the lipidated wastewater.
The ratio of the addition amount of the demulsifier to the volume of the sewage in the step (3) is 0.5: 1 (g/L); the ratio of the addition amount of the coagulant to the volume of the sewage is 0.01: 1 (g/L);
the ratio of the addition amount of the flocculant in the step (7) to the volume of the sewage is 0.2: 1 (g/L); the ratio of the addition amount of the coagulant aid to the volume of the sewage is 0.006: 1 (g/L); the ratio of the addition amount of the oxidant to the volume of the sewage is 0.015: 1 (g/L).
Comparative example 1
The difference from example 3 is that: the catalyst in step (7) is a mixture of carbon-supported nano-scale copper oxide, manganese oxide and iron carbide in a mass ratio of 3:1:1, and other operations and steps are the same as those in example 3.
Comparative example 2
The difference from example 3 is that: the catalyst in step (7) was a mixture of carbon-supported nano-copper oxide, carbon-supported nano-zirconium oxide and iron carbide in a mass ratio of 3:2:1, and the other operations and steps were the same as in example 3.
Comparative example 3
The difference from example 3 is that: the catalyst in step (7) was a mixture of carbon-supported nano-copper oxide, carbon-supported nano-zirconium oxide, manganese oxide and iron carbide in a mass ratio of 1:1:2:3, and the other operations and steps were the same as in example 3.
Comparative example 4
The difference from example 3 is that: the polyphosphate demulsifier described in step (3) was the same as in example 3 with respect to the other operations and steps.
Comparative example 5
The difference from example 3 is that: adjusting the water quality of the sewage 1 in the step (2), pumping the sewage into an external circulation Fenton oxidation tank (ferrous sulfate is required to be added as a catalyst) for oxidation reaction to obtain the sewage 2, namely, a multidimensional electro-catalytic reaction tank is not arranged, and other operations and steps are the same as those in the embodiment 3.
Effect test
The esterification wastewater is treated by the methods provided in examples 1 to 3, and the indexes of the treated water are finally detected, and the detection results are shown in table 1 below.
The detection method comprises the following steps: detecting with ultraviolet-visible intelligent multi-parameter water quality tester (LH-3BA) and intelligent multi-parameter digestion instrument.
Table 1 various indexes of water obtained after each stage of the treatment process of lipidated wastewater provided in examples 1-3
According to the detection data in the table 1, the lipidation wastewater treatment process provided by the invention can be seen, by adopting a method of combining multidimensional electrocatalysis and an external circulation Fenton oxidation tank, the two processes supplement each other, organic matters which are difficult to degrade in the esterification wastewater in an electrocatalysis system can react, the effect is stable, and the organic matters can not change along with the change of residual organic matters in water, a filler in the multidimensional electrocatalysis contains a large amount of ferrous ions, the redundant ferrous ions and added hydrogen peroxide have oxidation reaction in the Fenton oxidation tank, the process combination enables the degradation effect of the organic matters to be doubled, the dosage of a medicament is greatly reduced, and no sulfate radical is introduced in the process, so that a biological system can be ensured to exert the maximum treatment effect;
in the fixed bed catalytic oxidation step, a mixture of carbon-supported nano-grade copper oxide, carbon-supported nano-grade zirconium oxide, manganese oxide and iron carbide with the mass ratio of 3:2:1:1 is used as a catalyst, the surface effect, the quantum size effect, the volume effect, the macroscopic quantum tunneling effect and the catalytic activity of the nano-grade copper oxide and the nano-grade zirconium oxide and the synergistic effect of nano-grade iron are fully utilized, the adsorption and decomposition of hydrogen peroxide are fully completed in a short time, the hydrogen peroxide is efficiently catalyzed to generate hydroxyl radicals, and the radicals form a series of chain reactions under the action of the catalyst, so that the conversion efficiency and the initiation capability of the hydrogen peroxide are greatly improved, the output of the hydroxyl radicals with high concentration and high strength can be realized, and the concentrated degradation of organic matters in wastewater is realized; meanwhile, the existence of the catalyst can initiate a series of oxidation-reduction reactions to directly mineralize a plurality of organic matters into carbon dioxide and water;
and GP01, GP02, GP03, GP04 and GP05 with the mass ratio of 1:2:2: 1 are selected as the demulsifier, so that the demulsification effect is obviously improved, a foundation is provided for the implementation of the following working procedures, all the steps in the whole process are supplemented and matched with each other, the COD removal rate in the sewage treatment process is improved to 99.94-99.97%, the COD removal rate is obviously higher than the existing level, and the method is suitable for industrial production.
The indexes of the water obtained after the treatment of each stage of the lipidation wastewater treatment process provided by the comparative examples 1-5 are shown in the following tables 2-4.
The sewage 6 obtained by the reaction precipitation 2 in the step (6) of example 3 was divided into 3 parts and subjected to sewage treatment using the processes disclosed in comparative examples 1 to 3, respectively, and the treatment results are shown in table 2 below.
TABLE 2 indexes of water obtained after each stage of the treatment process for lipidated wastewater provided in comparative examples 1-3
According to the detection data in the table 2, it can be seen that when the type of the catalyst in the fixed bed catalytic oxidation step is changed or the mass ratio of the components of the catalyst is changed, the COD removal rate of the sewage in the fixed bed catalytic oxidation filter step is obviously reduced compared with the embodiment when the type of the catalyst is not within the preferable range of the invention, so that the removal of the COD in the sewage in the whole process is influenced, and the total removal rate of the COD in the sewage is reduced.
The effluent 2 obtained in example 3 was taken out for effluent treatment using the process disclosed in comparative example 4, and the treatment results are shown in table 3 below.
TABLE 3 indexes of water obtained after each stage of the lipidated wastewater treatment process provided in comparative example 4
According to the detection data in the table 3, it can be seen that the change of the type of the demulsifier in the comparative example 4 can obviously affect the removal rate of the COD in the sewage in the step 1 of the reaction precipitation, thereby affecting the sewage treatment effect of the whole process and reducing the total removal rate of the COD in the sewage.
The effluent 1 from the oil interceptor of example 3 was taken out for wastewater treatment using the process disclosed in comparative example 5, and the treatment results are shown in table 4 below.
TABLE 4 indexes of water obtained after each stage of the lipidated wastewater treatment process provided in comparative example 5
According to the detection data in the above table 3, it can be seen that in the comparative example 5, the multidimensional electro-catalytic process is omitted, the fenton treatment process is directly used, although the overall removal rate is not reduced too much, ferrous sulfate needs to be additionally added as a catalyst, the removal rates of subsequent hydrolysis acidification, UASB and contact oxidation are greatly reduced, the cost of the reagents needed to be added for the subsequent reaction precipitation 2 and the fixed bed catalytic oxidation filter tank cable is ten times higher than that of the embodiment, the biochemical treatment equipment is also affected, the service life of the biochemical treatment equipment is obviously shortened, and the sewage treatment efficiency of the whole process is reduced.
The present invention has been further described with reference to specific embodiments, which are only exemplary and do not limit the scope of the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A lipidation wastewater treatment process is characterized in that: the method comprises the following steps:
(1) and introducing the lipidated wastewater into an oil separation tank, and removing grease in the wastewater through the oil separation tank to obtain sewage 1.
(2) Adjusting the water quality of the sewage 1, pumping the sewage into a multi-dimensional electro-catalytic reaction tank and carrying out oxidation reaction on the sewage and an external circulation Fenton oxidation tank to obtain sewage 2;
(3) adjusting the pH value of the sewage 2, adding a demulsifier and a coagulant aid to react impurities in the sludge to generate precipitable sludge, and precipitating in a sedimentation tank to allow supernatant to automatically flow into an adjusting tank to obtain sewage 3;
(4) conveying the sewage 3 to a hydrolysis acidification tank after being regulated by a regulating tank, adding a strain into the hydrolysis acidification tank, and treating the sewage by the hydrolysis acidification tank to obtain sewage 4;
(5) automatically flowing the sewage 4 into an anaerobic regulating tank for regulation, and pumping the wastewater treated in the anaerobic regulating tank into a UASB reaction tank for treatment to obtain sewage 5;
(6) transferring the sewage 5 into a multistage contact oxidation tank, carrying out aeration and oxygenation in the multistage contact oxidation tank to decompose organic matters in the sewage into inorganic matters, and oxidizing ammonia nitrogen into nitrite and nitrate to obtain sewage 6, wherein the sewage 6 flows into a reaction tank automatically after being precipitated in a precipitation tank;
(7) adding a coagulant and a coagulant aid into the reaction tank, precipitating in the sedimentation tank, allowing supernatant to automatically flow into a transfer tank, pumping into a fixed bed catalytic oxidation filter, adding an oxidant into the fixed bed catalytic oxidation filter, further degrading residual organic matters in the sewage, and destroying the residual microbial metabolic components such as extracellular polymers and other macromolecular structures in the aerobic tank into micromolecular structures to obtain the biochemical-improved sewage 7;
(8) and the sewage 7 automatically flows into the MBR tank to carry out secondary biological oxidation, and is filtered by the MBR and then recycled by the clean water tank or discharged by a discharge port to finish the treatment process of the lipidated wastewater.
2. The lipidated wastewater treatment process of claim 1, wherein: the demulsifier in the step (3) is an organic demulsifier; the organic demulsifier is selected from one or more of polymeric polyol demulsifiers.
3. The lipidated wastewater treatment process of claim 2, wherein: the polymeric polyol demulsifier is selected from one or more of GP01, GP02, GP03, GP04 and GP 05.
4. The lipidated wastewater treatment process of claim 3, wherein: the demulsifier is a mixture of GP01, GP02, GP03, GP04 and GP05 in a mass ratio of 1:2:2: 1.
5. The lipidated wastewater treatment process of claim 1, wherein: the ratio of the addition amount of the demulsifier to the volume of the sewage in the step (3) is 0.3-1: 1 (g/L); the ratio of the addition amount of the coagulant aid to the volume of the sewage is 0.008-0.015: 1 (g/L).
6. The lipidated wastewater treatment process of claim 1, wherein: the ratio of the addition amount of the flocculating agent to the volume of the sewage in the step (7) is 0.1-0.3: 1 (g/L); the ratio of the addition amount of the coagulant aid to the volume of the sewage is 0.005-0.008: 1 (g/L).
7. The lipidated wastewater treatment process of claim 1, wherein: the catalyst adopted by the fixed bed catalytic oxidation filter tank adopted in the step (7) is a carbon-based catalyst.
8. The lipidated wastewater treatment process of claim 7, wherein: the carbon-based catalyst is selected from a mixture of carbon-supported nano-copper oxide, carbon-supported nano-zirconium oxide, manganese oxide and iron carbide.
9. The lipidated wastewater treatment process of claim 7, wherein: the carbon-based catalyst is a mixture of carbon-supported nano-grade copper oxide, carbon-supported nano-grade zirconium oxide, manganese oxide and iron carbide in a mass ratio of 3:2:1: 1.
10. The lipidated wastewater treatment process of claim 1, wherein: and (3) adopting MBR for the second biological oxidation in the step (8).
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| CN111153565A (en) * | 2020-02-26 | 2020-05-15 | 广东广深环保科技有限公司 | Treatment system and treatment method for esterification wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101955280A (en) * | 2010-08-13 | 2011-01-26 | 南京赛佳环保实业有限公司 | Technology for processing high-concentration organic wastewater in composite electrochemical method |
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