CN112551816A - Coking wastewater treatment method - Google Patents
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- 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
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- 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
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- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4619—Supplying gas to the electrolyte
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/06—Nutrients for stimulating the growth of microorganisms
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- C02F3/00—Biological treatment of water, waste water, or sewage
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- C02F3/12—Activated sludge processes
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Abstract
The invention discloses a coking wastewater treatment method, which comprises the following steps of adding a flocculating agent into coking wastewater subjected to preliminary precipitation, uniformly stirring and standing, and removing flocculates to obtain pretreated coking wastewater; inoculating activated sludge, adding carbon source, nitrogen source and phosphorus source, performing aeration, collecting supernatant, and introducing direct current to obtain activated sludge by Ti-RuO2/IrO2The titanium plate is used as a cathode material, and iron plates are embedded between the cathode and the anode at equal intervals to construct an electrochemical double-electrolysis reaction system for electrochemical treatment; adjusting pH, adding flocculant, stirring, standing for layering, and separating solid from liquid. The invention realizes the large-scale and large-scale flocculation operation through flocculant treatment before activated sludge treatment, establishment of an electrochemical double-electrolysis reaction system, micro-aeration operation in the electrochemical treatment and activated sludge treatment processes and further flocculation operation after the electrochemical treatmentThe technical purpose of improving the wastewater treatment efficiency is achieved.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a coking wastewater treatment method.
Background
The coking wastewater is a high-concentration, non-ideal system and heterogeneous refractory organic industrial wastewater containing volatile phenol, polycyclic aromatic hydrocarbon and heterocyclic compounds such as oxygen, sulfur, nitrogen and the like generated in the processes of coke making from coal, gas purification and coking product recovery, and the BOD of the wastewater5The COD value is generally 0.28-0.32, the biodegradability is poor, and the biochemical degradation is difficult. The coking wastewater has various pollutants, complex components and a large amount of difficultly degraded substances, the pollutants are mainly inorganic pollutants and organic pollutants, the organic pollutants are various and mainly exist in the forms of phenol, p-cresol, o-xylene and homologues thereof, and in addition, heterocyclic compounds, polycyclic aromatic hydrocarbons, aliphatic compounds and the like.
The organic pollutants contained in the coking wastewater seriously inhibit the growth and normal metabolic activity of microorganisms, so that the biodegradability of the coking wastewater is reduced, and the treatment difficulty is very high; meanwhile, the water-soluble organic fertilizer contains a large amount of carcinogenic polycyclic aromatic hydrocarbon, which not only causes serious pollution to water, but also causes great harm to human health. The activated sludge method and A are commonly adopted in the prior art2The O process treats the coking wastewater, but because the coking wastewater contains organic matters which are difficult to be biodegraded and the nonbiodegradable organic matters with biotoxicity can inhibit the growth of nitrobacteria in a higher concentration range, the activated sludge method and A2The wastewater treated by the O process can not reach the national discharge standard.
Disclosure of Invention
In order to solve the technical problem, the invention provides a coking wastewater treatment method. The method further removes refractory organic matters in the water by performing electrochemical treatment on the biologically treated coking wastewater to ensure that the refractory organic matters meet the discharge standard, thereby realizing the technical purpose of efficient deep degradation treatment of the coking wastewater.
The invention discloses a coking wastewater treatment method, which comprises the following steps:
(1) adding a first flocculating agent into the coking wastewater subjected to preliminary precipitation and solid particle impurity removal, uniformly stirring and standing, and removing flocculates to obtain pretreated coking wastewater;
(2) inoculating activated sludge through pretreated coking wastewater, adding a carbon source, a nitrogen source and a phosphorus source, and performing closed aeration to obtain a supernatant;
(3) the supernatant in the step (2) is connected with direct current and is treated by Ti-RuO2/IrO2The titanium plate is used as a cathode material, and iron plates are embedded between the cathode and the anode at equal intervals to construct an electrochemical double-electrolysis reaction system for electrochemical treatment;
(4) adjusting the pH value to 8.5-9.5, adding a second flocculating agent, stirring uniformly, standing for layering, and carrying out solid-liquid separation.
Further, the first flocculating agent in the step (1) is prepared by mixing the first flocculating agent and the second flocculating agent in a molar ratio of 1: 1, the dosage of the mixture of magnesium salt and phosphate is 20-40mg/L of coking wastewater.
Further, the volume ratio of the activated sludge to the coking wastewater in the step (2) is (1-2): (5-10), the aeration time is 12-24h, and the dissolved oxygen in the environment is controlled to be 5-10mg/L in the aeration process.
Further, in the step (2), according to C: n: p is 100: 5: 1, adding a carbon source, a nitrogen source and a phosphorus source.
Further, in the step (3), the current density is 10-20mA/cm2And the electrolysis time is 30-60 min.
Further, in the electrochemical treatment process in the step (3), 2-10mmol/L of potassium persulfate is added into the solution.
Further, oxygen and ozone are introduced into the electrochemical treatment process in the step (3) through micro-aeration, the flow rate is 3-5 g/(L.h), and the mass ratio of the oxygen to the ozone is 2-4: 1.
Further, the second flocculating agent in the step (4) is selected from one or more of activated carbon, polyacrylamide, polyaluminium chloride, polyaluminium sulfate and potassium aluminium sulfate dodecahydrate.
Further, the adding amount of the second flocculating agent in the step (4) is 3-5% of the total mass of the liquid.
Compared with the prior art, the invention has the following beneficial effects:
before activated sludge treatment, magnesium salt and phosphate are added, and can perform chemical reaction with ammonia nitrogen in wastewater to generate precipitates, so that the ammonia nitrogen value in the wastewater is reduced, and the subsequent activated sludge is ensured to have higher degradation activity. In the activated sludge treatment process, aeration is adopted and the dissolved oxygen in the environment is controlled to be 5-10mg/L, so that an aerobic environment and a facultative environment can be provided, and the nitrifying bacteria in the activated sludge have higher activity.
The electrochemical double-electrolysis reaction system is adopted for electrochemical treatment, the coking wastewater is degraded mainly by oxidizing water at the anode, so that a certain amount of hydroxyl free radicals are generated, however, the amount of the hydroxyl free radicals is not enough to achieve the purpose of quickly and effectively degrading pollutants, potassium persulfate is added, the iron plate is used as an induction electrode, the iron plate serves as an anode material and simultaneously has the function of a cathode material, the activity of the potassium persulfate can be excited in the anode reaction process, and Fe is released from the surface of the iron plate2+Activating potassium persulfate by coupling electrochemical oxidation to generate SO with strong oxidant and chemical stability4-The organic pollutants are extremely destructive, so that the degradation of the organic matters is accelerated, and the organic matters which are difficult to be biodegraded by the activated sludge are removed.
The contact probability of active particles such as free radicals and the like with pollution molecules influences the reaction rate and the degradation rate of organic matters to a great extent, and oxygen and ozone are introduced in the electrochemical treatment process through the aeration process, so that on one hand, the concentration of the active particles in an electrolytic system is increased by the oxygen and the ozone, and the degradation effect of the electrochemical treatment on the organic matters is improved; on the other hand, free radicals generated by electrolysis can enter liquid in the form of microbubbles, so that the contact probability of active ions such as the free radicals in bubbles and the like and pollution molecules is increased, the reaction rate is increased, and the degradation rate is increased.
Flocculating agent is added into the sewage after electrochemical treatment for flocculation and precipitation again, and part of the sewage is decomposed into low molecular organic matters, and the organic matters which are not completely degraded and suspended solid particles can be adsorbed and coagulated by the flocculating agent for removal. Due to the bridging action of hydroxide ions and the polymerization action of polyvalent anions, the polyaluminium chloride has larger relative molecular mass and higher charge, can realize the bridging action on colloids and particles in the wastewater, and can effectively remove flocculates in the wastewater under the synergistic action with the polyaluminium chloride. The amido of polyacrylamide can form hydrogen bond with a plurality of substances through affinity and adsorption, and simultaneously, polyacrylamide forms 'bridging' among adsorbed particles to generate floccules, which is beneficial to the sedimentation of particles.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The coking wastewater used in the following examples of the invention has the components shown in table 1 after removing solid particle impurities through preliminary precipitation;
TABLE 1
| COD | NH3-N | |
| Concentration, mg/L | 2535 | 278 |
Example 1
(1) Adding flocculating agents (magnesium chloride and potassium dihydrogen phosphate with a molar ratio of 1: 1) into the coking wastewater, wherein the concentration of the flocculating agents is 30mg/L, uniformly stirring and standing for 8 hours, and removing flocculates to obtain pretreated coking wastewater;
(2) activated sludge is inoculated to the pretreated coking wastewater (the volume ratio of the coking wastewater to the activated sludge is 5: 1), and the ratio of the coking wastewater to the activated sludge is as follows: n: p is 100: 5: 1, adding glucose, ammonium chloride and potassium dihydrogen phosphate according to the proportion for aeration for 12 hours, controlling the dissolved oxygen in the environment to be 5mg/L in the process, and taking supernatant;
(3) the supernatant in the step (2) is connected with direct current and is treated by Ti-RuO2/IrO2Is used as an anode material, a titanium plate is used as a cathode material, and an iron plate is embedded between the cathode and the anode at equal intervals to construct an electrochemical double-electrolysis reaction system for carrying out electricityChemical treatment at a current density of 15mA/cm2Electrolyzing for 30 min;
(4) adjusting pH to 9, adding flocculant (polyaluminium chloride mixture of polyacrylamide with mass ratio of 1: 1) to make mass fraction of the flocculant in the solution be 5%, stirring, mixing, standing for layering, and performing solid-liquid separation.
Example 2
(1) Adding flocculating agents (magnesium chloride and potassium dihydrogen phosphate with a molar ratio of 1: 1) into the coking wastewater, wherein the concentration of the flocculating agents is 20mg/L, stirring and uniformly mixing, standing for 12 hours, and removing flocculates to obtain pretreated coking wastewater;
(2) activated sludge is inoculated to the pretreated coking wastewater (the volume ratio of the coking wastewater to the activated sludge is 5: 1), and the ratio of the coking wastewater to the activated sludge is as follows: n: p is 100: 5: 1, adding glucose, ammonium chloride and potassium dihydrogen phosphate according to the proportion for aeration for 12 hours, controlling the dissolved oxygen in the environment at 10mg/L in the process, and taking supernatant;
(3) the supernatant in the step (2) is connected with direct current and is treated by Ti-RuO2/IrO2Is used as an anode material, a titanium plate is used as a cathode material, an iron plate is embedded between the cathode and the anode at equal intervals to construct an electrochemical double-electrolysis reaction system for electrochemical treatment, and the current density is 20mA/cm2Electrolyzing for 50 min;
(4) adjusting the pH value to 8.5, adding a flocculating agent (a mixture of activated carbon and polyacrylamide with the mass ratio of 1: 1) to enable the mass fraction of the flocculating agent in the solution to be 3%, stirring, uniformly mixing, standing, layering and carrying out solid-liquid separation.
Example 3
(1) Adding flocculating agents (magnesium chloride and potassium dihydrogen phosphate with a molar ratio of 1: 1) into the coking wastewater, wherein the concentration of the flocculating agents is 40mg/L, uniformly stirring and standing for 8 hours, and removing flocculates to obtain pretreated coking wastewater;
(2) activated sludge is inoculated to the pretreated coking wastewater (the volume ratio of the coking wastewater to the activated sludge is 5: 1), and the ratio of the coking wastewater to the activated sludge is as follows: n: p is 100: 5: 1, adding glucose, ammonium chloride and potassium dihydrogen phosphate according to the proportion for aeration for 12 hours, controlling the dissolved oxygen in the environment to be 8mg/L in the process, and taking supernatant;
(3) the supernatant in the step (2) is connected with direct current and is treated by Ti-RuO2/IrO2Is used as an anode material, a titanium plate is used as a cathode material, an iron plate is embedded between the cathode and the anode at equal intervals to construct an electrochemical double-electrolysis reaction system for electrochemical treatment, and the current density is 10mA/cm2Electrolyzing for 60 min;
(4) adjusting the pH value to 9.5, adding a flocculating agent (activated carbon) to ensure that the mass fraction of the flocculating agent in the solution is 5 percent, stirring and uniformly mixing, standing for layering, and carrying out solid-liquid separation.
Example 4
The difference from example 1 is that oxygen and ozone are introduced into the electrochemical treatment process in step (3) at a mass ratio of 3:1 by micro-aeration at a flow rate of 3 g/(L.h).
Example 5
The difference from example 1 is that step (1) is omitted.
Example 6
The difference from example 1 is that step (3) is omitted.
Example 7
The difference from example 1 is that step (4) is omitted and the product of electrochemical treatment in step (3) is directly allowed to stand for solid-liquid separation.
Example 8
The same as example 1, except that the step (3) omits the construction of an electrochemical double electrolysis reaction system by inserting an iron plate between the cathode and the anode at equal intervals.
The coking wastewater treated by the examples 1 to 8 is subjected to water quality detection, and the results are shown in a table 2;
TABLE 1
As can be seen from table 2, compared with examples 5 to 8, the coking wastewater treatment method of examples 1 to 4 of the present invention is advantageous to greatly reduce COD and ammonia nitrogen in water, and has significant effects on wastewater treatment effects no matter flocculant treatment before activated sludge treatment, electrochemical treatment by constructing an electrochemical dual electrolysis reaction system, micro-aeration operation in the activated sludge treatment process, or further flocculation operation after electrochemical treatment, and the three synergistic effects in combination with biological treatment of activated sludge can greatly improve wastewater treatment efficiency.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A coking wastewater treatment method is characterized by comprising the following steps:
(1) adding a first flocculating agent into the coking wastewater subjected to preliminary precipitation and solid particle impurity removal, uniformly stirring and standing, and removing flocculates to obtain pretreated coking wastewater;
(2) inoculating activated sludge through pretreated coking wastewater, adding a carbon source, a nitrogen source and a phosphorus source, and performing closed aeration to obtain a supernatant;
(3) the supernatant in the step (2) is connected with direct current and is treated by Ti-RuO2/IrO2The titanium plate is used as a cathode material, and iron plates are embedded between the cathode and the anode at equal intervals to construct an electrochemical double-electrolysis reaction system for electrochemical treatment;
(4) adjusting the pH value to 8.5-9.5, adding a second flocculating agent, stirring uniformly, standing for layering, and carrying out solid-liquid separation.
2. The coking wastewater treatment method according to claim 1, characterized in that the first flocculant in the step (1) is a mixture of a first flocculant and a second flocculant in a molar ratio of 1: 1, the dosage of the mixture of magnesium salt and phosphate is 20-40mg/L of coking wastewater.
3. The coking wastewater treatment method according to claim 1, characterized in that the volume ratio of the activated sludge to the coking wastewater in the step (2) is (1-2): (5-10), the aeration time is 12-24h, and the dissolved oxygen in the environment is controlled to be 5-10mg/L in the aeration process.
4. The coking wastewater treatment method according to claim 1, characterized in that in step (2) the ratio of C: n: p is 100: 5: 1, adding a carbon source, a nitrogen source and a phosphorus source.
5. The coking wastewater treatment method according to claim 1, characterized in that, in the step (3), the current density is 10 to 20mA/cm2And the electrolysis time is 30-60 min.
6. The coking wastewater treatment method according to claim 1, characterized in that 2 to 10mmol/L of potassium persulfate is added to the solution during the electrochemical treatment in the step (3).
7. The coking wastewater treatment method according to claim 1, characterized in that oxygen and ozone are introduced by micro-aeration in the electrochemical treatment process in the step (3), the flow rate is 3-5 g/(L.h), and the mass ratio of oxygen to ozone is 2-4: 1.
8. The coking wastewater treatment method according to claim 1, characterized in that the second flocculant in the step (4) is one or more selected from activated carbon, polyacrylamide, polyaluminum chloride, polyaluminum sulfate and aluminum potassium sulfate dodecahydrate.
9. The coking wastewater treatment method according to claim 1, characterized in that the amount of the second flocculant added in the step (4) is 3-5% of the total mass of the liquid.
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| CN114230106A (en) * | 2021-12-28 | 2022-03-25 | 上海淼清水处理有限公司 | Oil refining wastewater treatment method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114230106A (en) * | 2021-12-28 | 2022-03-25 | 上海淼清水处理有限公司 | Oil refining wastewater treatment method |
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