CN106430801B - Method for treating coking wastewater - Google Patents
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Abstract
The invention provides a method for treating coking wastewater, which comprises the following steps: the coking wastewater enters an anoxic tank for denitrification reaction, the coking wastewater is stirred uniformly to mix water quality and prevent activated sludge from depositing, the pH value of the coking wastewater is adjusted to 7.5-8.5, and compound common biological enzyme is added into the anoxic tank; the effluent of the anoxic tank enters an aerobic tank for nitration reaction, and the aerobic tank is added with compound common biological enzyme and special enzyme; the effluent of the aerobic tank is delivered by 2 paths through a sludge reflux pump: one path returns to the anoxic section to further remove T-N, and the other path is led into a membrane separation tank; the mixed liquid is subjected to solid-liquid separation by a water producing pump in a suction filtration mode, activated sludge is retained in a biochemical system, and the subsequent process of filtered effluent enables the effluent to reach the standard and be discharged outside. The invention can degrade the COD of the effluent to below 70mg/l, degrade the T-CN to below 0.5mg/l, reduce the turbidity to below 1NTU, and achieve the direct discharge standard of the discharge Standard of pollutants for coking chemical industry (GB16171-2012) through subsequent simple materialization.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a novel and efficient method for treating coking wastewater.
Background
The coking wastewater is wastewater formed in the processes of high-temperature and medium-temperature dry distillation, coal gas purification and chemical product refining of coal, contains organic pollutants such as phenols, benzene series, polycyclic aromatic hydrocarbons, nitrogen-containing heterocyclic compounds and the like and inorganic pollutants such as ammonia, cyanogen, thiocyanide and the like, has complex components, various component types, high organic pollutant concentration and sewage chromaticity, high toxicity and very stable property, and is typical refractory complex toxic industrial organic wastewater. The treatment difficulty for meeting the emission standard is high, the cost is high, and if the treatment is improper, the national water environment is seriously damaged.
At present, most domestic enterprises implement the emission standard GB13456-92 of the steel industry (including the coking industry). On day 1/10 of 2012, the state promulgates the emission standard of pollutants for the coking chemical industry (GB16171-2012), which is hereinafter referred to as new standard. The new standard is stricter in pollutant discharge concentration and monitoring range, the discharge requirements on suspended matters, COD, ammonia nitrogen, petroleum and cyanides are obviously improved, and the discharge requirements on BOD5, T-N, benzene and polycyclic aromatic hydrocarbon are increased; meanwhile, the new standard correspondingly improves the water consumption requirement of the ton product. In view of the current situation of water treatment in the domestic coking industry, strict enforcement of the standards will be a great challenge for the coking industry. Basically, all domestic coking wastewater treatment devices need to be upgraded and modified to possibly meet the discharge requirement; at the same time the level of management of the processing facilities must be further increased.
However, the existing mature coking wastewater treatment technology needs to pay expensive operation cost if the technology stably reaches the latest national discharge standard, and most domestic coking enterprises cannot bear the cost, so that research on a coking wastewater treatment system and a special technology with lower life cycle cost and less environmental risk is developed, and the important significance is realized for realizing the sustainable development of the enterprises and improving the comprehensive competitiveness.
A Membrane Bioreactor (MBR) is a novel state wastewater treatment system which organically combines membrane separation technology and biological treatment technology. The membrane component replaces a secondary sedimentation tank at the tail end of the traditional biological treatment technology, the concentration of high-activity sludge is kept in a bioreactor, the organic load of biological treatment is improved, the floor area of a sewage treatment facility is reduced, and the excess sludge amount is reduced by keeping low sludge load, so that the purposes of reducing the investment of the sewage treatment facility and reducing the operation cost are achieved. But when the method is applied to the field of coking wastewater treatment, the effluent COD is still high and the effluent cannot be directly discharged; the membrane component is easy to be polluted and blocked, and the operation cost is increased.
The biological enzyme is a protein with catalytic function. Compared with the common chemical catalyst, the method has the advantages of specificity, high efficiency, mild reaction conditions and the like. There are hundreds of millions of enzymes in nature, and different enzymes are capable of catalyzing a single substrate for a particular chemical reaction. The water quality characteristics of the coking wastewater determine the types and the number of flora which can be enriched by a coking wastewater biochemical system, wherein a part of the flora is in a dominant position, and microorganisms which can degrade polycyclic and heterocyclic aromatic organic compounds such as diazabenzene, pyridine, quinoline, indole, naphthalene, kazaine, phenanthrene and the like are in a relatively weak position. By analyzing the components and properties of the coking wastewater, biological enzymes capable of specifically degrading polycyclic and heterocyclic aromatic substances are found and added into a biochemical treatment system to develop the weak flora so as to improve the activity of the flora and enrich more quantity, so that the weak flora becomes dominant bacteria. The improvement of the activity and the increase of the number of the florae mean the improvement of the treatment load and the treatment efficiency, and the part of organic matters which are difficult to biodegrade originally are degraded to different degrees due to the improvement of the activity of the florae, so that the COD of the effluent is greatly reduced. Meanwhile, biological enzymes with salt resistance and cyanide resistance are added to enhance the antitoxic capacity and the impact resistance of the microorganisms of the biochemical system and improve the stability of the system.
Disclosure of Invention
In order to solve the problems, the invention provides a method for treating coking wastewater.
The technical scheme of the invention is as follows:
a method for treating coking wastewater is characterized by comprising the following steps:
(1) the coking wastewater enters an anoxic tank for denitrification reaction, water quality is uniformly mixed by stirring and activated sludge deposition is prevented, compound common biological enzyme is added into the anoxic tank, the pH of the coking wastewater is adjusted to be 7.5-8.5, the temperature is controlled to be 25-35 ℃, DO is controlled to be below 0.5mg/l, and the reaction retention time is 16-25 hours;
(2) and the effluent of the anoxic tank enters the aerobic tank for nitration through overflow, the aerobic tank is added with compound common biological enzyme and special enzyme, the pH of the nitration system is adjusted to 6.5-7.5, the temperature is controlled to be 25-35 ℃, and the reflux ratio of the mixed solution is controlled to be 1: 1-5 times of the original water amount, controlling DO at 3-5 mg/l, controlling MLSS at 4000-6000 mg/l, and controlling the reaction retention time to be 40-55 hours;
(3) the effluent of the aerobic tank is delivered by 2 paths through a sludge reflux pump: one path returns to the anoxic section to further remove T-N, and the other path is led into a membrane separation tank;
(4) the pH value of the wastewater in the membrane separation tank is kept at 6.5-7.5, the temperature is controlled at 25-35 ℃, the DO is controlled at 3-5 mg/l, the MLSS is controlled at 6000-10000 mg/l, and the reaction retention time is 10-25 hours;
(5) the mixed liquid is subjected to solid-liquid separation by a water producing pump in a suction filtration mode, activated sludge is retained in a biochemical system, and the filtered effluent can be subjected to physicochemical or advanced oxidation treatment process subsequently, so that the effluent reaches the standard and is discharged outside or is further subjected to deepening treatment by a depth recycling system.
According to the method for treating coking wastewater of the invention, preferably, the compound type common biological enzymes in the anoxic tank in the step (1) comprise lipase, cellulase, hemicellulase, amylase and cyanobhydratase.
Furthermore, the adding amount of the compound type common biological enzyme in the step (1) is 0.1 g-0.2 g per ton of water.
According to the method for treating coking wastewater of the invention, preferably, the compound type common biological enzymes in the step (2) comprise lipase, cellulase, hemicellulase, amylase and cyanogen hydratase, and the special enzyme is naphthalene dioxygenase.
Furthermore, the adding amount of the compound type common biological enzyme in the step (2) is 0.2 g-0.4 g/ton of water, and the adding amount of the special enzyme is 0.1 g-0.3 g/ton of water.
According to the method for treating the coking wastewater, preferably, in the step (2), a fluidized bed type suspension filler is added into the aerobic tank to serve as a carrier for attaching aerobic biological enzyme and activated sludge.
According to the method for treating coking wastewater, the fluidized bed type suspension filler is preferably polyethylene, and the specific surface area of the fluidized bed type suspension filler is 300-1000 square meters per m3The adding proportion is 10-20% of the volume of the aerobic tank.
According to the method for treating the coking wastewater, the pH is preferably adjusted by adding one of NaOH solution, KOH solution or ammonia solution.
Further, the pH is adjusted by adding NaOH solution.
According to the method for treating the coking wastewater, the membrane separation tank in the step (4) is preferably in a form of an internal organic flat membrane, and the membrane is made of PVDF (polyvinylidene fluoride) and has a pore diameter of 0.04-0.1 μm.
According to the method for treating coking wastewater of the invention, preferably, in the step (4), the membrane system of the membrane separation tank adopts a batch filtration operation mode: the water producing pump stops running for 1-2 min after every 8-10 min of pumping, and the water producing pump is used as a cycle for continuous running.
Further, the water production pump stops running for 1min after every 9min of pumping, and the water production pump is used as a cycle to continuously run in a circulating mode.
Detailed description of the invention:
aiming at the component characteristics and the treatment difficulty of the coking wastewater, the invention creatively adds the compound bio-enzyme related to the difficultly treated components of the coking wastewater into an AO + MBR system which replaces the traditional biochemical sedimentation tank by using a membrane separation technology, increases the efficiency of biochemical reaction, strengthens the action of microorganisms and the impact resistance, and continuously reduces the COD (chemical oxygen demand) of the effluent and the total cyanogen index; after the biological enzyme system is established, the micelle bacteria have advantages, the soluble oil is effectively degraded, the viscosity of the activated sludge is reduced, the possibility of membrane fouling is reduced, and the advantages of low sludge yield, low operation cost, good effluent quality and small occupied area of a membrane separation technology system are kept. The invention furthest exerts the complementary action of MBR and biological enzyme technology, and is a low-cost comprehensive treatment technology developed aiming at coking wastewater treatment.
The device adopted by the invention comprises an anoxic tank, an aerobic tank, a sludge reflux pump, a membrane separation tank, a membrane component and a water production pump. The processing system comprises the following specific operation steps:
(1) the wastewater in the adjusting tank is sent into the anoxic tank through a water delivery pump to carry out denitrification reaction. The anaerobic tank plays a role in uniformly mixing water quality and preventing activated sludge deposition through stirring blades, the PH is kept between 7.5 and 8.5, the temperature is controlled between 25 and 35 ℃, the DO is controlled below 0.5mg/l, and the reaction retention time is 16 to 25 hours.
(2) The effluent of the anoxic tank enters the aerobic tank through overflow for nitration reaction. Adjusting the pH value of a nitration system to 6.5-7.5, controlling the temperature at 25-35 ℃, and controlling the reflux ratio of a mixed solution at 1: 1-5 times of the original water amount, DO (dissolved oxygen) is controlled to be 3-5 mg/l, MLSS (sludge concentration) is controlled to be 4000-6000 mg/l, and the reaction retention time is 40-55 hours.
(3) The effluent of the aerobic tank is delivered by 2 paths through a sludge reflux pump: one path returns to the anoxic section to further remove T-N, and the other path is led into a membrane separation tank.
(4) The PH value of the membrane separation tank is kept at 6.5-7.5, the temperature is controlled at 25-35 ℃, the DO is controlled at 3-5 mg/l, the MLSS is controlled at 6000-10000 mg/l, and the reaction retention time is 10-25 hours.
(5) The mixed liquid is subjected to solid-liquid separation by a water producing pump in a suction filtration mode, activated sludge is retained in a biochemical system, and the filtered effluent can be subjected to physicochemical or advanced oxidation treatment process subsequently, so that the effluent reaches the standard and is discharged outside or is further subjected to deepening treatment by a depth recycling system.
In the step (1), compound common biological enzymes (including lipase, cellulase, hemicellulase, amylase and cyanohydratase) are added into an anoxic tank, wherein the adding amount is 0.1-0.2 g per ton of water.
And (2) adding compound common biological enzyme (comprising lipase, cellulase, hemicellulase, amylase and cyanohydratase) and special enzyme-naphthalene dioxygenase into the aerobic tank, wherein the adding amount of the compound common biological enzyme is 0.2-0.4 g/ton of water, and the adding amount of the special enzyme is 0.1-0.3 g/ton of water.
Adding a fluidized bed type suspended filler into the aerobic tank in the step (2) as a carrier to attach aerobic biological enzyme and activated sludge, wherein the material is polyethylene, and the specific surface area is 300-1000 m2/m3The adding proportion is 10-20% of the volume of the aerobic tank.
The membrane separation tank in the step (4) adopts a built-in organic flat membrane mode, the PVDF material is adopted, and the membrane aperture is 0.04-0.1 mu m. The membrane system adopts an intermittent filtration operation mode: the water producing pump stops running for 1min after every 9min of pumping, and the water producing pump is used as a periodic cycle to continuously run. The aeration without suction can achieve an effective membrane surface cleaning effect.
The diaphragm of dull and stereotyped membrane attaches to the both sides of ABS backup pad, and the diaphragm is the composite construction that the filter layer that has the polyvinyl chloride material and the supporting layer of PET non-woven fabrics material are constituteed. The membrane possessed a concentrated small pore size (0.8 μm) distribution. The area of a single-sheet film element is 1.4 square meters, the number of the film elements is 50, and the total filtering area is 70 square meters. (structural schematic diagram 2) the flat membrane element structure comprises a membrane, a supporting plate, a water production pipe nozzle and the like.
The biochemical system refers to a wastewater treatment process formed by combining oxygen deficiency and aerobic treatment, heterotrophic bacteria in an oxygen deficiency tank hydrolyze suspended pollutants and soluble organic matters in wastewater into organic acid, so that macromolecular organic matters are decomposed into micromolecular organic matters, insoluble organic matters are converted into soluble organic matters, and when products after the anoxic hydrolysis enter an aerobic tank for aerobic treatment, the biodegradability and the oxygen efficiency of sewage can be improved; in an anoxic section, heterotrophic bacteria ammoniate pollutants such as protein, fat and the like (N on an organic chain or amino groups in amino acid) to release ammonia (NH3 and NH4+), under the condition of sufficient oxygen supply, nitrification of the autotrophic bacteria oxidizes NH3-N (NH4+) to NO3-, and the NO 3-is returned to an anoxic pond through reflux control, and under the anoxic condition, denitrification of the heterotrophic bacteria reduces NO3 to molecular nitrogen (N2) to complete ecological circulation of C, N, O, so that harmless treatment of sewage is realized.
The method for treating the coking wastewater provided by the invention has the beneficial technical effects that:
(1) the original biochemical system has large occupied area, and the processing technology of the invention can greatly reduce the structures required by biochemical processing so as to reduce the occupied area and the investment cost.
(2) The COD of the effluent treated by the prior AO process is about 250-350 mg/l, and the T-CN is about 4-5 mg/l, the COD of the effluent can be degraded to be below 80mg/l, the T-CN is degraded to be below 0.5mg/l, the turbidity is reduced to be below 1NTU, and the subsequent simple materialization can reach the direct discharge standard of the emission standard of pollutants for coking chemical industry (GB 16171-2012).
(3) The invention greatly reduces the operation cost of the membrane component, the biological enzyme adding and the subsequent physical and chemical treatment, the operation cost of the technical treatment is less than 7 yuan/ton of water, and the invention has higher economic benefit compared with the prior AO process.
Drawings
FIG. 1 is a flow chart of a method for efficiently treating coking wastewater provided by the invention.
Fig. 2 is a structural view of a flat membrane element to which the present invention is applied.
Wherein: 1-anoxic tank, 2-aeration tank (aerobic tank), 3-membrane separation tank, 4-stirrer, 5-membrane, 6-support plate, and 7-water production pipe nozzle.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. The compound common biological enzyme and the special enzyme applied by the invention are all purchased from the market.
Example 1
The invention provides a method for treating coking wastewater, which comprises the following steps:
taking coking wastewater of a certain steel plant for treatment:
the pH value of the anoxic tank is kept between 7.5 and 8.5, the temperature is controlled between 25 and 35 ℃, DO is controlled below 0.5mg/l, and the reaction retention time is 18 hours; wherein the total adding amount of the biological enzyme is 0.1 g/ton of water,
the pH value of the aerobic tank is controlled to be 6.5-7.5, the temperature is controlled to be 25-35 ℃, and the reflux ratio of the mixed liquid is 1: 3 times of the original water amount, controlling DO at 3-5 mg/l, controlling MLSS at 6000mg/l, and adding the suspended filler at a proportion of 20% of the volume of the aerobic tank; the reaction residence time was 46 hours; the total adding amount of the biological enzyme is 0.3 g/ton of water (the adding amount of the common biological enzyme is 0.2 g/ton of water, the adding amount of the special enzyme is 0.1 g/ton of water),
the membrane system of the membrane separation tank is made of PVDF (polyvinylidene fluoride) organic flat membrane, the membrane aperture is 0.04-0.1 mu m, the pH is kept at 6.5-7.5, the temperature is controlled at 25-35 ℃, the DO is controlled at 3-5 mg/l, and the reaction residence time is 16 hours;
the water quality data before and after wastewater treatment are shown in the following table, and the important indexes of CODcr, total nitrogen, ammonia nitrogen and the like after treatment all reach the direct discharge standard of the coking chemical industry pollutant discharge standard (GB16171-2012) table 2.
| Item | Before treatment | After treatment |
| CODcr | ≤2000mg/l | ≤70mg/l |
| Cyanide compounds | ≤30mg/l | ≤0.5mg/l |
| Total nitrogen | ≤500mg/l | ≤20mg/l |
| Ammonia nitrogen | ≤300mg/l | ≤10mg/l |
| pH | 6～9 | 6～9 |
Example 2
The invention provides a method for treating coking wastewater, which comprises the following steps:
taking coking wastewater of a certain coking plant for treatment:
the pH value of the anoxic tank is kept between 7.5 and 8.5, the temperature is controlled between 25 and 35 ℃, DO is controlled below 0.5mg/l, and the reaction retention time is 21 hours; wherein the total adding amount of the biological enzyme is 0.2 g/ton of water,
the pH value of the aerobic tank is controlled to be 6.5-7.5, the temperature is controlled to be 25-35 ℃, and the reflux ratio of the mixed liquid is 1: 4 times of raw water amount, DO is controlled to be 3-5 mg/l, MLSS is controlled to be 7000mg/l, and the adding proportion of the suspended filler is 20% of the volume of the aerobic tank; the reaction residence time was 52 hours; the total adding amount of the biological enzyme is 0.5 g/ton water (the adding amount of the common biological enzyme is 0.3 g/ton water, the adding amount of the special enzyme is 0.2 g/ton water),
the membrane system of the membrane separation tank is made of PVDF (polyvinylidene fluoride) organic flat membrane, the membrane aperture is 0.04-0.1 mu m, the pH is kept at 6.5-7.5, the temperature is controlled at 25-35 ℃, the DO is controlled at 3-5 mg/l, and the reaction residence time is 21 hours;
the water quality data before and after wastewater treatment are shown in the following table, and the important indexes of CODcr, total nitrogen, ammonia nitrogen and the like after treatment all reach the direct discharge standard of the coking chemical industry pollutant discharge standard (GB16171-2012) table 2.
| Item | Before treatment | After treatment |
| CODcr | ≤5000mg/l | ≤70mg/l |
| Cyanide compounds | ≤50mg/l | ≤0.5mg/l |
| Total nitrogen | ≤800mg/l | ≤20mg/l |
| Ammonia nitrogen | ≤500mg/l | ≤10mg/l |
| pH | 6～9 | 6～9 |
Of course, those skilled in the art should recognize that the above-described embodiments are illustrative only, and not limiting, and that changes and modifications can be made within the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A method for treating coking wastewater is characterized by comprising the following steps:
(1) the coking wastewater enters an anoxic tank for denitrification reaction, water quality is uniformly mixed by stirring and activated sludge deposition is prevented, compound common biological enzyme is added into the anoxic tank, the pH value of the coking wastewater is adjusted to be 7.5-8.5, the temperature is controlled to be 25-35 ℃, DO is controlled to be below 0.5mg/L, and the reaction retention time is 16-25 hours;
(2) and the effluent of the anoxic tank enters the aerobic tank for nitration through overflow, the aerobic tank is added with compound common biological enzyme and special enzyme, the pH value of a nitration system is adjusted to 6.5-7.5, the temperature is controlled to be 25-35 ℃, and the reflux ratio of the mixed solution is controlled to be 1: 1-5 times of the original water amount, controlling DO at 3-5 mg/L, controlling MLSS at 4000-6000 mg/L, and controlling the reaction retention time at 40-55 hours;
(3) the effluent of the aerobic tank is delivered by 2 paths through a sludge reflux pump: one path returns to the anoxic section to further remove T-N, and the other path is led into a membrane separation tank;
(4) the pH value of the wastewater in the membrane separation tank is kept at 6.5-7.5, the temperature is controlled at 25-35 ℃, the DO is controlled at 3-5 mg/L, the MLSS is controlled at 6000-10000 mg/L, and the reaction retention time is 10-25 hours;
(5) the mixed liquid is subjected to solid-liquid separation by a water producing pump in a suction filtration mode, activated sludge is retained in a biochemical system, and the filtered effluent is subjected to a physicochemical or advanced oxidation treatment process to ensure that the effluent reaches the standard and is discharged outside or is further subjected to deepening treatment by a depth recycling system;
in the step (1), the compound common biological enzyme in the anoxic tank comprises lipase, cellulase, hemicellulase, amylase and cyanohydratase;
the adding amount of the compound type common biological enzyme in the step (1) is 0.1 g-0.2 g per ton of water;
in the step (2), the compound common biological enzyme comprises lipase, cellulase, hemicellulase, amylase and cyanide hydratase, and the special enzyme is naphthalene dioxygenase;
the adding amount of the compound type common biological enzyme in the step (2) is 0.2 g-0.4 g/ton of water, and the adding amount of the special enzyme is 0.1 g-0.3 g/ton of water.
2. The method for treating coking wastewater according to claim 1, characterized in that in the step (2), a fluidized bed type suspension filler is added into the aerobic tank as a carrier for attaching aerobic biological enzyme and activated sludge.
3. The method for treating coking wastewater according to claim 2, characterized in that the fluidized bed type suspended filler is polyethylene and has a specific surface area of 300-1000 m2/m3The adding proportion is 10-20% of the volume of the aerobic tank.
4. The method of claim 1, wherein the pH is adjusted by adding one of NaOH solution, KOH solution, or ammonia solution.
5. The method for treating coking wastewater according to claim 1, characterized in that the membrane separation tank in the step (4) is in a form of a built-in organic flat membrane, and the membrane is made of PVDF and has a pore size of 0.04-0.1 μm.
6. The method for treating coking wastewater according to claim 1, characterized in that in the step (4), the membrane system in the membrane separation tank adopts a batch filtration operation mode: the water producing pump stops running for 1-2 min after every 8-10 min of pumping, and the water producing pump is used as a cycle for continuous running.
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| CN102268394A (en) * | 2011-07-14 | 2011-12-07 | 北京赛富威环境工程技术有限公司 | Method of amplification culture of microorganism for waste water treatment and method of microorganism waste water treatment |
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| CN102268394A (en) * | 2011-07-14 | 2011-12-07 | 北京赛富威环境工程技术有限公司 | Method of amplification culture of microorganism for waste water treatment and method of microorganism waste water treatment |
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Address after: 200942 three chemical engineering office building, Baoshan Iron and steel factory, Shanghai, Baoshan District Patentee after: Baowu Carbon Technology Co.,Ltd. Address before: 200942 three chemical engineering office building, Baoshan Iron and steel factory, Shanghai, Baoshan District Patentee before: BAOWU CARBON MATERIAL TECHNOLOGY Co.,Ltd. |
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