CN112028318A - Treatment method of petrochemical wastewater - Google Patents
Treatment method of petrochemical wastewater Download PDFInfo
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- CN112028318A CN112028318A CN202010904801.6A CN202010904801A CN112028318A CN 112028318 A CN112028318 A CN 112028318A CN 202010904801 A CN202010904801 A CN 202010904801A CN 112028318 A CN112028318 A CN 112028318A
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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
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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
- 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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- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2103/365—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 from petrochemical industry (e.g. refineries)
Abstract
The invention discloses a petrochemical wastewater treatment method, which comprises two stages of water treatment; the first stage is coagulation treatment, wherein the coagulation treatment is to add a coagulant into the wastewater of the petrochemical secondary effluent, and obtain first-stage treated water through stirring and precipitation; and the second stage is oxidation treatment, wherein the oxidation treatment is to add an oxidant into the first stage treated water obtained by coagulation treatment for oxidation reaction to obtain second stage treated water. According to the invention, the first-stage coagulation pretreatment unit can reduce the load of a subsequent deep oxidation process, reduce the waste of free radicals, improve the oxidation efficiency and reduce the operation cost.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, particularly relates to a treatment method of petrochemical wastewater, and particularly relates to a method for advanced treatment of petrochemical wastewater through sulfate oxidation by coagulation pretreatment.
Background
The petrochemical industry is the national pillar industry and is one of the heavy pollution industries, and the wastewater discharged in the production process contains a large amount of non-degradable organic matters such as petroleum, organic acid, alcohol, amine, phenol, ether and the like, and toxic inorganic matters such as sulfide, cyanide, nitrogen, phosphorus and the like. Multiple refractory organics puncture outfitThe conventional biochemical treatment process of the petrochemical wastewater plant is remained in the petrochemical wastewater generated water. At present, the total amount of industrial wastewater discharged per year in China exceeds 2.1 multiplied by 1010And most of the tons of the waste water are discharged after being treated by a centralized comprehensive sewage treatment plant. For a large petrochemical industrial park, the advanced treatment of the comprehensive sewage treatment plant is the last barrier for ensuring the standard discharge of petrochemical comprehensive wastewater treatment. Along with the improvement of the water body protection requirement, the requirement of China on the drainage standard of the petrochemical industry is more and more strict, the discharge standard of pollutants for the petrochemical industry (GB 31571 2015) (hereinafter referred to as a new standard) is issued by the original environmental protection department of 4, 16 th of 2015, and the new standard not only improves the COD limit of the direct drainage of the petrochemical sewage treatment plant to 60 or 50mg/L, but also adds the concentration discharge limit of 60 characteristic organic pollutants. Based on this, the effluent of many existing petrochemical integrated sewage treatment plants in China can not meet the requirements of new standards, and an advanced treatment process is urgently needed to improve the effluent quality of sewage plants.
The advanced oxidation technology applied to the advanced treatment unit has obvious advantages on the degradation effect of the organic wastewater difficult to degrade. In recent years, persulfate oxidation technology as a novel advanced oxidation technology becomes a research hotspot in the aspect of degrading organic wastewater. The persulfate oxidation technology is to activate persulfate and other sulfur-containing compounds under the conditions of heat, ultrasound, ultraviolet, transition metal, alkali and the like to generate sulfate radicals with strong oxidation capacity to degrade organic matters. Compared with hydroxyl free radical, sulfate radical has stronger oxidation capability, can oxidize organic pollutants which can not be oxidized by OH, has longer service life, better stability and higher organic matter degradation efficiency, and has huge application prospect in the water treatment direction. Persulfate (PS) is an oxidant with good stability, high solubility, strong oxidizing power and easy storage and transportation at room temperature, and includes Peroxomonosulfate (PMS) and Peroxodisulfate (PDS). Compared with hydrogen peroxide and ozone oxidation wastewater organic matters, the persulfate is easier to store, higher in stability, more soluble in water, wider in pH application range, low in price, good in commercial prospect and more suitable for application in laboratories and actual engineering. The persulfate is commonly used and comprises three types of ammonium persulfate, potassium persulfate and sodium persulfate. Among them, ammonium persulfate has poor stability, which causes residual ammonia and secondary pollution, and potassium persulfate has low solubility, thus having poor practicability in water treatment. Sodium persulfate is stable at room temperature, easy to store for a long time, high in solubility and low in price, and is widely concerned.
However, particulate matter formed by mixing microbial floc, metabolites, colloids and other substances in petrochemical wastewater consumes a large amount of oxides in the advanced treatment oxidation process, reduces the treatment efficiency of wastewater organic matters, and increases the cost. Therefore, in order to improve the oxidation effect, the pretreatment technology of the sulfate oxidation research needs to be combined for synergistic research. A common pretreatment technique is coagulation. Coagulation process includes coagulation and flocculation, which means that under the action of a coagulant, colloidal particles and tiny suspended matters in water are gathered through the actions of double-electric-layer compression, adsorption and electrical neutralization, adsorption bridging, sediment net-catching and the like, and suspended matters and colloidal particles are removed, and the coagulation process is a common water treatment mode. In the advanced wastewater treatment unit, coagulation is often used as pretreatment in combination with other oxidation processes, and the coagulation pretreatment unit can reduce the load of the subsequent advanced oxidation process, reduce the waste of free radicals, improve the oxidation efficiency and reduce the operation cost.
Disclosure of Invention
The sulfate oxidation technology is less applied to water pollution treatment at present, the current research is mainly used for simulating wastewater in a laboratory and is only applied to actual wastewater, particularly secondary effluent of petrochemical wastewater, and the invention aims to research the persulfate oxidation technology in advanced treatment and application process of the petrochemical wastewater.
The technical scheme of the invention is as follows:
the invention discloses a method for advanced treatment of sulfate in petrochemical wastewater coagulation, which comprises a first-stage coagulation pretreatment stage and a second-stage persulfate oxidation treatment stage.
In the first stage, in the coagulation pretreatment stage, the coagulant is polyaluminium chloride, and the dosage of the coagulant is 15-25 mg/L; rapidly stirring for 2 min; slowly stirring for 20min, standing for 20min, wherein the rapid stirring is 300r/min, and the slow stirring is 50 r/min. .
In the second stage, a persulfate oxidation treatment stage, wherein the persulfate is sodium Persulfate (PS) and the addition amount of the persulfate is 6 mmol/L; the initiator is ferrous sulfate heptahydrate, and the adding amount is 6 mmol/L; the order of addition is ferrous sulfate heptahydrate and then sodium persulfate.
The initial COD concentration of the petrochemical wastewater treated by the method is 80-120mg/L, the optimal amount of the peroxysulfuric acid is determined by the molar ratio of sodium persulfate to COD, and the molar ratio of the sodium persulfate to the COD, namely PS/12COD, is 1.0-1.5.
The petrochemical wastewater is industrial wastewater discharged in the petrochemical industry, and particularly relates to secondary effluent of the petrochemical wastewater.
In the second stage, persulfate is oxidized, wherein in the oxidation reaction, the reaction temperature is 23-28 ℃, the reaction pH is 3-11, and the reaction time is 30-60 min.
In the oxidation reaction, the reaction pH regulator is H2SO4And NaOH. Said H2SO4The mass fraction of (2) is 10%, and the mass fraction of the NaOH is 10%.
The invention has the beneficial effects that:
(1) in the method, the organic matters in the petrochemical wastewater are removed by adopting a coagulation pretreatment combined sulfate advanced treatment combined technology. In the first stage, polyaluminium chloride is used as a flocculating agent, and colloid floc substances in the wastewater are removed through pretreatment; second stage of, Fe2+The persulfate is activated to generate sulfate radicals which are used as a strong oxidizer to decompose organic matters in the wastewater so as to achieve the effect of reducing COD in the wastewater. Under the optimized process conditions, the effluent TOC removal rate is higher than 50%, the COD removal rate is higher than 60.8%, the effluent TOC concentration is 9.34mg/L and the effluent COD concentration is 30.82mg/L, and the special emission limit value required by the petrochemical industry pollutant emission Standard (GB 31571-2015) is met.
(2) The method can effectively remove colloidal substances and fluorescent substances in the wastewater. Wherein, the protein is reduced to 3.10mg/L, the polysaccharide is reduced to 1.2mg/L, the protein removal rate is higher than 50%, the polysaccharide is higher than 70%, and the removal effect on colloidal substances in the wastewater is remarkable. The removal rate of the fluorescence intensity of the fluorescence peak of the soluble microbial product and the fluorescence peak of the tryptophan aromatic protein is respectively higher than 39.0 percent and 42.0 percent. The removal rate of organic matters with the molecular weight of less than 3000 is higher than 90 percent.
(3) The sulfate radical free radical of the invention has long survival time in water, low selectivity to organic matters, wider pH range and wide application prospect in treating complex practical industrial wastewater.
(4) The method has strong pH adaptability, can realize better sewage purification effect within a wider pH value range, and achieves good DOC removal rate.
The sulfate advanced treatment method of the coagulation pretreatment of the invention is further explained by combining the attached drawings.
Description of the drawings:
FIG. 1: influence of pH on the effluent effect of the petrochemical wastewater persulfate oxidation test on the effluent DOC.
FIG. 2: the concentrations of DOC, COD, protein and polysaccharide in raw petrochemical wastewater and persulfate oxidized water are changed. FIG. 3: the concentrations of DOC, COD, protein and polysaccharide in raw petrochemical wastewater and coagulation pretreatment-persulfate oxidation effluent are changed.
The specific implementation mode is as follows:
example 1
Placing 100mL petrochemical secondary effluent in a 250mL conical flask, and adding H2SO4(10 percent by mass) and NaOH (10 percent by mass) to regulate pH, adding a certain amount of ferrous sulfate heptahydrate, and then quickly adding a certain amount of Na2S2O8Mixing rapidly, stirring with a magnetic stirrer (200rmp), reacting for a certain time, adjusting pH to 9-9.5, filtering with 0.45 μm filter membrane to stop reaction, and measuring supernatant COD.
Example 2
100mL of petrochemical secondary effluent is put into a 250mL conical flask, and a certain amount of heptahydrate sulfuric acid is addedFerrous iron, then adding a certain amount of Na rapidly2S2O8The reaction was stopped by rapid mixing and filtration through a 0.45 μm filter, and the COD of the supernatant was determined. The removal effect of DOC, COD, polysaccharide and protein after the petrochemical secondary effluent is subjected to sulfate oxidation is shown in figure 2, the DOC is reduced from 20.73mg/L to 11.7mg/L, the removal rate reaches 44%, the COD is reduced from 85mg/L to 41.49mg/L, the removal rate reaches 51.2%, the protein is reduced from 6.21mg/L to 4.39mg/L, the removal rate is 29.3%, the polysaccharide is reduced from 3.61mg/L to 1.28mg/L, and the removal rate reaches 64.5%. Thus, Fe2+The PS peroxydisulfate oxygen oxidation system has a good treatment effect on petrochemical secondary effluent, and the effluent reaches the discharge standard required by petrochemical industry pollutant discharge standard (GB 31571-2015).
Example 3
Adding a certain amount of polyaluminium chloride into a water sample with the volume of 1L as a coagulant, adopting a six-in-one stirrer to carry out a coagulation experiment, and quickly stirring for 2min at the speed of 300 r/min; then stirring at a low speed of 50r/min for 20min, standing for 20min, putting the effluent of the pretreated supernatant into a 250mL conical flask, adding a certain amount of ferrous sulfate heptahydrate, and then quickly adding a certain amount of Na2S2O8The reaction was stopped by rapid mixing and filtration through a 0.45 μm filter, and the COD of the supernatant was determined. The removal effect of DOC, polysaccharide and protein after the petrochemical secondary effluent is treated by the coagulation pretreatment-persulfate oxidation combined process is shown in the attached drawing 3, and the removal rate of the DOC is improved by 17% compared with that of the DOC without the coagulation pretreatment. The removal rate of COD is improved by 1.6 percent compared with the removal rate of the non-coagulation pretreatment. The polysaccharide content is further reduced by 0.08mg/L compared with that of the polysaccharide not subjected to coagulation pretreatment. It can be known that the combined process of coagulation pretreatment and persulfate oxidation has a good effect of removing the organic matters in the petrochemical secondary effluent, and the effluent meets the discharge standard required by the discharge Standard of pollutants for the petrochemical industry (GB 31571-.
The amount of the polymeric alumina added is the amount conventionally used for water coagulation by those skilled in the art.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A treatment method of petrochemical wastewater is characterized in that the treatment method comprises two-stage water treatment; the first stage is coagulation treatment, wherein the coagulation treatment is to add a coagulant into the wastewater of the petrochemical secondary effluent, and obtain first-stage treated water through stirring and precipitation; and the second stage is oxidation treatment, wherein the oxidation treatment is to add an oxidant into the first stage treated water obtained by coagulation treatment for oxidation reaction to obtain second stage treated water.
2. The method for treating petrochemical wastewater according to claim 1, wherein the coagulant is polyaluminium oxide in the first coagulation treatment.
3. The method for treating petrochemical wastewater according to claim 1, wherein in the first-stage coagulation treatment, the input amount of the coagulant is 15-25 mg/L; sequentially stirring rapidly for 2min, stirring slowly for 20min, and standing for 20min to obtain first stage treated water; the rapid stirring is 300r/min, and the slow stirring is 50 r/min.
4. The method for treating petrochemical wastewater according to claim 1, wherein the oxidizing agent is persulfate.
5. The method for treating petrochemical wastewater according to claim 4, wherein the second-stage oxidation treatment comprises the steps of: adding ferrous sulfate heptahydrate into the first stage of treated water obtained by coagulation treatment, wherein the adding amount of the ferrous sulfate heptahydrate is 6 mmol/L; and adding an oxidant under the stirring action, wherein the oxidant is sodium persulfate, and the adding amount of the sodium persulfate is 6 mmol/L.
6. The petrochemical wastewater treatment method according to claim 4, wherein in the second stage oxidation treatment, the initial COD concentration of the petrochemical secondary effluent is in the range of 80-120mg/L, and the molar ratio of persulfate to COD is preferably PS: 12COD is 1.0-1.5.
7. The method for treating petrochemical wastewater according to claim 1, wherein the reaction temperature is 23-28 ℃, the reaction pH is 3-11, and the reaction time is 30-60min in the second-stage oxidation treatment.
8. The method for treating petrochemical wastewater according to claim 1, wherein the reaction pH adjusting agent is H in the oxidation reaction2SO4Solutions or NaOH solutions.
9. The method for treating petrochemical wastewater according to claim 1, wherein the second stage treated water obtained after the second stage oxidation treatment is further filtered through a filter membrane to terminate the reaction.
10. The method for treating petrochemical wastewater according to claim 9, wherein the filter membrane is a 0.45 μm filter membrane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113735319A (en) * | 2021-09-10 | 2021-12-03 | 中煤科工集团南京设计研究院有限公司 | Sewage treatment method and system |
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| CN113735319A (en) * | 2021-09-10 | 2021-12-03 | 中煤科工集团南京设计研究院有限公司 | Sewage treatment method and system |
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