CN102153231A - Method and device for treating high-concentration organic chemical-industrial sewage - Google Patents

Abstract

The invention provides a treatment method and device for high-concentration organic chemical sewage. Specifically, the present invention provides an integrated sewage treatment method and device of "physical and chemical pretreatment + biological enhancement treatment + flocculation and air flotation post-treatment", which can realize high-efficiency and low-cost treatment of high-COD and refractory chemical sewage.

Description

A treatment method and device for high-concentration organic chemical wastewater

technical field

The invention relates to the technical field of high-concentration chemical sewage treatment, in particular to a treatment method and device for high-concentration refractory fine chemical sewage.

Background technique

The organic chemical factories and organic additive factories of petrochemical enterprises occupy an important position in petroleum enterprises, and their products are mainly some important chemical reagents, chemical intermediate products, or monomers for the production of synthetic materials, which are not available in the petrochemical product chain. Or missing. The products of these enterprises are characterized by high added value, variety of products, intermittent production of devices, and small investment in production equipment. Therefore, in the process of product production, the water quality of the discharged sewage is relatively complex, with a wide variety of pollutants, high COD content of sewage (up to hundreds of thousands), large changes in pH value, and intermittent discharge, large changes in water quality and quantity, traditional physical and chemical , Biochemical treatment technology is difficult to make the effluent meet the standard. Therefore, the treatment of high-concentration organic chemical sewage has always been a difficult problem for petrochemical enterprises in sewage treatment, and it is also a bottleneck for achieving stable discharge of sewage from enterprises.

At present, the treatment methods and devices used for organic chemical sewage mainly include:

The Chinese invention patent of application number CN200610201494.5 "A Method for Treating Organic Chemical Wastewater" (Notice No.: CN1994915) discloses a method for treating organic chemical wastewater. The coagulant is added to the pipeline, and the compound element (or compound substance) used to improve the efficiency of the coagulant is added to the coagulant through an additional pipeline. After the compound element is mixed with the coagulant, it enters the sewage pipe or at the outlet In sewage; the coagulant is polyferric sulfate or polyaluminum chloride; the composite element is calcium chloride, magnesium chloride, magnesium sulfate, zinc sulfate, zinc chloride, polyferric sulfate, polyaluminum chloride, Activated silicic acid, cationic polyacrylamide, diallyldimethylammonium chloride or acrylamine copolymer.

The Chinese invention patent "A Method for Treating Organic Chemical Wastewater" (Notice No.: CN101734817A) with application number CN200910186882.4 discloses a method for treating organic chemical wastewater. In this method, after the pH value of the wastewater is adjusted to 2.5-3.0, Through the aeration micro-electrolysis, Fenton oxidation and coagulation sedimentation process, the refractory organic matter in the wastewater can be effectively removed, and the biochemical properties of the wastewater can be improved, and the Fe ²⁺ produced after the micro-electrolysis reaction can be used for the subsequent Fenton oxidation reaction. In order to reduce the treatment cost, the present invention can treat low-concentration organic wastewater such as chemical industry and pharmaceutical industry, and the treated wastewater can be directly discharged up to the standard, and can also be used as a pretreatment method for high-concentration organic wastewater to improve the biochemical properties of refractory biodegradable wastewater. sex.

Patent No. CN201010174616.2 Chinese Invention Patent "A High COD, High Concentration Sulfate Group Acidic Organic Chemical Wastewater Treatment Method" (Notice No.: CN101838083A) discloses a high COD, high concentration sulfate radical acidic organic chemical wastewater treatment method, It mainly includes Ca(OH) ₂ pretreatment, anaerobic treatment, two-stage aerobic treatment and other steps. After Ca(OH) ₂ pretreatment of acidic organic chemical wastewater to remove most of the sulfate and H+, by controlling the main body of wastewater treatment microorganisms and operating parameter factors, an anaerobic wastewater treatment method with anaerobic bacteria as the advantage and The aerobic aeration treatment method based on halophilic aerobic microbial treatment. The above method is suitable for treating organic chemical wastewater with a COD range of about 20,000 mg/L, high sulfate radical content, and low pH.

Patent No. CN200810023332.6 Chinese invention patent "A Method for Advanced Treatment of Chemical Wastewater Biochemical Tail Water" (Notice No.: CN101254992) discloses a method for advanced treatment of chemical wastewater biochemical tail water, the steps are: pretreated Under the condition of room temperature and flow rate of 0.5-8BV/h, the biochemical tail water of chemical wastewater passes through the device filled with resin adsorbent, and the adsorbed water can be discharged after being neutralized with alkali; the above resin is desorbed with alkaline desorbent and acid The desorption agent is desorbed and regenerated. The flow rate of the desorbent is 0.5-3.0BV/h. The high-concentration desorption liquid is used for advanced treatment, and the low-concentration desorption liquid can be used to prepare the next batch of desorption agent for recycling. The COD of the original tail water is 120-250mg/L. After treatment, the COD can be reduced to below 75mg/L. After the saturated resin is desorbed and regenerated, the desorption rate is greater than 96%. The high-concentration desorption liquid can be deeply deal with.

The content of the above invention is mainly to treat low-concentration organic chemical sewage (COD concentration is less than 50,000 mg/L, most of which are less than 10,000 mg/L), but high-concentration organic chemical sewage (COD concentration is greater than 50,000 mg/L) , especially the treatment of refractory fine chemical wastewater has not yet mature and reliable technology.

Contents of the invention

Herein, the specific contents of all publications and patent applications mentioned in this specification are incorporated by reference.

The technical problem to be solved by the present invention is to provide an integrated sewage treatment method of "physical and chemical pretreatment + biological enhancement treatment + flocculation and air flotation post-treatment" for the problem of poor treatment effect of traditional treatment technology for high-concentration refractory fine chemical sewage sewage and The device can realize high-efficiency and low-cost treatment of high-concentration fine chemical sewage.

A first aspect of the present invention relates to a method for treating high-concentration organic chemical sewage, said method is characterized in that it comprises the following steps:

a) One or several types of acidic sewage (pH value 2-2.5, water temperature 25-40°C) with a COD concentration as high as 50,000-300,000 mg/L first enters the "aerated iron-carbon micro-electrolysis + Fenton" after aeration and mixing Oxidation" pretreatment process, the reaction time of aerated micro-electrolysis is 60 minutes to 180 minutes, and the reaction time of Fenton oxidation is 60 minutes to 100 minutes. Both iron-carbon micro-electrolysis and Fenton oxidation adopt the mixed mass transfer method of bottom aeration . After step a), it can effectively remove refractory organic matter in wastewater (COD removal rate reaches 30-45%), and can effectively decompose organic matter with complex macromolecules into simple small molecule organic matter, thereby improving the biodegradability of wastewater , and the Fe2+ produced after the micro-electrolysis reaction can be used for the subsequent Fenton oxidation reaction, thereby reducing the processing cost;

b) Alkaline sewage (pH value 10-12, water temperature 25-40°C) with a COD concentration as high as 50,000-300,000 mg/L is pretreated by coagulation and sedimentation and acidic sewage pretreated by step a) in the neutralization tank Perform mechanical stirring and neutralization, and the insufficient part of acid and alkali is realized by externally adding acidic or alkaline chemicals, so that the pH value of the sewage reaches 6-8 before entering the subsequent biological strong household treatment unit;

c) Make the sewage pretreated in step b) enter the "hydrolytic acidification + contact oxidation I + contact oxidation II" bioaugmentation treatment unit, wherein the hydrolytic acidification tank (that is, the hydrolysis tank in Figure 1 and Figure 2) is added with combined biological Carrier filler (combined filler) and bioaugmentation engineering bacteria, in the contact oxidation pond (that is, the oxygen pond and the oxygen pond in Fig. 1 and Fig. 2, hereinafter also referred to as the primary oxidation pond and the secondary oxidation pond)) Add natural mineral carrier filler and bio-augmented engineering bacteria, and improve the activity and degradation performance of the enhanced engineering bacteria by adding nutrient solution and biological activation solution. If necessary, according to the effluent concentration of step b), a certain proportion of clean sewage is mixed in this step to ensure that the organic load in the bioaugmentation treatment unit is not greater than 15kg COD/(m ³ .d);

d) Make the effluent from step c) enter the flocculation air flotation post-treatment unit, add 200 mg·L ^-1 polyaluminum ferric chloride (PAFC) and 3 mg·L ^-1 polyacrylamide (PAM) to the air flotation tank, and pressurize After dissolved air flotation treatment, most of the particulate matter in the water can be effectively separated, so as to ensure the deep purification effect of the effluent.

The first stage of the method of the present invention involves the physical and chemical pretreatment of high-concentration fine chemical wastewater, that is, the above-mentioned step a) and step b).

High-concentration fine chemical sewage is mostly strong acid or strong alkali waste water. Therefore, the inventive method makes full use of these characteristics of waste water, and one or several acid waste water (pH value 2-2.5 ) after aeration and mixing, carry out integrated pretreatment of "aeration iron-carbon micro-electrolysis + Fenton oxidation" (several kinds of acidic sewage are mixed by aeration in the mixing tank, and the mixed sewage enters aeration iron-carbon micro-electrolysis and Fenton oxidation Oxidation tank, with an iron-carbon bed in the middle of the pool, with a height of 1m, Fe:C ratio of 1:0.5 to 1:3 (weight ratio), Fe ²⁺ produced after micro-electrolysis reaction is used for subsequent Fenton oxidation reaction (H ₂ O ₂ dosage ranges from 4 to 12mL·L ^-1 ), through the integration of micro-electrolysis and Fenton technology, it can effectively remove refractory organic matter in wastewater and improve the biochemical properties of wastewater. About aerated iron-carbon micro-electrolysis and Fenton Oxidation can be referred to Chinese patent application CN200910186882.4.

At the same time, the alkaline sewage with COD concentration (pH value 10-12) is pretreated by coagulation and sedimentation (adding a compound alkaline flocculant: the coagulant is CaCl ₂ weight: MgCl ₂ weight = 2: 1, and the flocculant is Anionic polyacrylamide; the dosage of coagulant is 260mg/L, and the dosage of anionic polyacrylamide is 10mg/L) After that, it is stirred and neutralized with the pretreated acidic water in the neutralization tank, and the acid-base dosage is adjusted After the pH value of the sewage reaches 6-8, it enters the subsequent biointensive treatment steps. By making full use of the characteristics of the strong acid and strong alkali of the waste water, the purpose of saving treatment costs is achieved, and the biodegradability of the waste water is greatly improved.

Of course, in the neutralization step b), it is also possible to directly use alkaline chemicals instead of alkaline sewage to carry out the neutralization.

The second stage of the method of the present invention involves the bioaugmentation treatment step, ie the aforementioned step c).

The bioaugmentation technology used in the present invention increases the biomass of biochemical ponds (including hydrolysis ponds, primary oxidation ponds and secondary oxidation ponds) by adding and fixing the screened dominant engineering bacteria on the filler carrier to prevent the loss of dominant bacteria , and improve the degradation activity of engineering bacteria by adding nutrients and activation solution, so that they can form an advantage in the biochemical pool and improve the purification efficiency of sewage.

The filler of the bioaugmentation treatment technology adopts combined biological carrier filler (hereinafter also referred to as combined filler) and natural mineral filler. The combined biological carrier filler is purchased under the trade name "combined filler", with a filling rate of 70%. The structure is to change the plastic disc buckle into a double-circle large plastic ring, and press the aldehyde fiber or polyester filament on the ring of the ring. , so that the fiber bundles are evenly distributed; the inner ring is a snowflake-shaped plastic branch, which can not only hang the film, but also effectively cut the air bubbles, and improve the transfer rate and utilization of oxygen. The sheet distance of the combined filler is 5cm, and the plant distance is 10cm. The natural mineral filler is artificially processed volcanic rock after physical screening, rounding, etc. The density is 0.9-1.1g/cm ³ , the diameter of the filler is 3-5cm, and the compressive strength is 6Mpa. The bioaugmented engineering bacteria used can be composed of the following three parts or petrochemical sewage plant sludge plus any part of the other two parts: ①The mixture of GW1, GW2, and GW5 strains screened and domesticated in the laboratory, the three strains grow at a temperature of 40-65 ℃, pH value between 7 and 8, salt-tolerant concentration range of 0.5% to ² %; Bacteria is the abbreviation of effective microbial group); ③ petrochemical sewage plant sludge. When the bioaugmented engineering bacterium is composed of the three parts, the weight ratio of the three is 2:1:50～100; when the bioaugmented engineering bacterium is composed of the first part and the third part, the weight ratio of the two is 2:50～100. 100; when the bioaugmentation engineering bacteria is composed of the second part and the third part, the weight ratio of the two is 1:50-100; the total dosage is 5% of the effective volume of the pool body.

The screening and domestication process of the three high-efficiency thermophilic bacteria strains GW1, GW2, and GW5 of the bioaugmentation technology mainly includes four steps: collecting bacterial samples, enriching culture, pure species isolation, and performance evaluation.

① Sample collection

Sampling from organic chemical sewage so that the liquid occupies 30% of the volume of the container;

②Enrichment of bacterial sources

Take 100mL of complete culture medium and put it into a 250mL Erlenmeyer flask, sterilize under high pressure steam at 121°C and 1.01MPa for 20 minutes, then take 10mL of organic sewage and add it to the above Erlenmeyer flask, wrap the Erlenmeyer flask with 8 layers of gauze, and then Put the Erlenmeyer flask into a constant temperature air bath shaker with a rotation speed of 150r/min and a constant temperature of 30°C for cultivation.

③ domestication process

The culture fluid after the above-mentioned cultivation for three days was taken for inoculation and acclimatization. During acclimatization, the method of increasing the concentration of organic sewage was adopted, and the constant temperature shaking table was cultivated at 30°C for 5 days as a cycle.

When acclimating, first take 5mL enriched culture solution and pour it into the inorganic medium containing 25mL/g (organic chemical sewage is used as carbon source for domestication screening and fermentation of bioenhanced degrading bacteria.), take out 5mL from it after cultivating for one cycle The culture solution was added to the inorganic medium containing 50mL/g and cultured for one cycle. Repeat this for 6 cycles until the final organic chemical wastewater concentration is 300mL/g.

④Purification process

Purification adopts plate streak separation method.

After 6 cycles of acclimatization, under aseptic conditions, use an inoculation loop to dip the acclimation solution of the last cycle and draw a line on the organic chemical sewage plate (used for the separation and purification of organic chemical sewage degrading bacteria), and pour the plate upside down. Put it in a constant temperature incubator and incubate at 30°C for 4 to 5 days. Afterwards, dominant colonies were picked, streaked and isolated on nutrient agar plates, and cultured for 24 hours.

Pick a single colony from the agar plate and put it into the fermentation medium, culture it in a shaking table at 30°C for 4-5 days, and then separate it by streaking on the plate. Repeat the above steps until the purified colonies with consistent morphology are obtained, and then inoculate the purified single strain on the slant and store at 4°C.

Through the above steps, a total of 12 strains were screened out, numbered GW1-GW12, and then screened for temperature and salt tolerance.

Thermophilic bacteria screening scheme: add 50mL of inorganic salts with trace elements to culture base in 250mL conical flask, and add about 50mL of sterilized organic chemical sewage; adjust the pH value to 7.0, inoculate 4% bacterial solution, every Make three parallel samples of strain samples; investigate the growth of the initially screened strains at different culture temperatures of 70°C, 65°C, 60°C, 55°C, 50°C, and 45°C. After 12 hours of cultivation, the clarified inorganic salt culture The base gradually became turbid, indicating that thermophilic bacteria began to multiply.

Salt-tolerant bacteria screening program: In order to investigate the salt-tolerant performance of thermophilic bacteria, three strains of bacteria were inoculated in different salt concentrations (0.5%, 1%, 1.5%, 2%, 5%, 7% and 10%) In the salt medium, shake (150r/min) culture at 65°C.

Through the above steps, three thermophilic and halo-tolerant strains were screened out, namely GW1, GW2 and GW5.

The nutrient formula of the bioaugmentation technology is as follows (each component is based on weight percentage): urea 1%-5%, NH ₄ Cl 0.05-0.2%, amino acid 0.5-1%, Na ₂ HPO ₄ 0.2%-0.5% , MgSO ₄ ·7H ₂ O 0.01%～0.1%, FeSO ₄ ·5H ₂ O 0.05%～0.2%, ZnCl ₂ 0.1%～0.3%, CaCl ₂ 0.05%～0.2%, Molasses 1%～5%, Buckthorn Sugar 0.1-0.5% and alkyl glycoside 1%-5%, the rest is water.

The formula of the activation solution of this bioaugmentation technology is as follows (each component is by weight percentage): Potassium 5%～8%, cobalt 0.05%～0.1%, molybdenum 0.01%～0.05%, nickel 0.01%～0.1%, iron 1% %~3%, sulfur 1%~5%, butyric acid 0.2%~2%, tourmaline 1%, and the rest is water.

The third stage of the method of the present invention involves post-treatment of flocculation and air flotation, ie the aforementioned step d).

The effluent water of the biological enhancement treatment unit contains a large amount of colloids and suspended solids. Because these substances are small in size, it is difficult to form sludge flocs, so it is difficult to separate them from water by the method of gravity sedimentation. 200mg·L ^-1 , the dosage of PAM is 3mg·L ^-1 ) to aggregate colloids and suspended solids, and use dissolved air flotation to carry out air flotation treatment, which can effectively separate most of the water Particulate matter, so as to ensure the deep purification effect of the effluent.

The second aspect of the present invention relates to a device for treating high-concentration organic chemical sewage, said device is an integrated sewage treatment device comprising the following units:

a) Physicochemical pretreatment unit, said physicochemical pretreatment unit includes an iron-carbon pool for aerated iron-carbon micro-electrolysis, a Fenton pool for Fenton oxidation, a flocculation sedimentation tank for alkaline sewage treatment, and a neutralization pool , in which both the iron-carbon pool and the Fenton pool adopt the mixed mass transfer mode of bottom aeration;

b) Bio-augmentation treatment unit, the bio-augmentation treatment unit includes a hydrolysis tank filled with combined fillers and bio-augmented engineering bacteria, a primary oxidation tank filled with natural mineral carrier fillers, bio-enhanced engineering bacteria, nutrient solution and biological activation solution and secondary oxidation pool;

c) A flocculation and air flotation post-treatment unit, which includes an air flotation tank (including an air dissolving tank, an air compressor and a circulation pump).

In the integrated sewage treatment device, the combined filler, natural mineral carrier filler, bioaugmentation engineering bacteria, nutrient formula and activation solution formula are the same as those described in the first aspect of the present invention.

technical effect

The method of the present invention overcomes the defects of poor treatment effect and difficult treatment of high COD sewage in the existing sewage treatment method. Pretreatment + biological enhancement treatment + flocculation air flotation post-treatment" technology integration process:

(1) Enhanced pretreatment technology: The iron-carbon micro-electrolysis and Fenton oxidation of the physical and chemical pretreatment unit are technically integrated to improve the purification effect of the pretreatment unit. At the same time, the Fe ²⁺ produced after the micro-electrolysis reaction is used for the subsequent Fenton oxidation reaction, which can effectively reduce the cost of water treatment.

(2) Bioaugmentation technology: by adding nutrient solution and biological activation solution to improve the activity and degradation performance of enhanced engineering bacteria; in different biochemical reaction stages (hydrolytic acidification stage, contact oxidation stage I, contact oxidation stage II) adopt The biological carrier filler is different from the engineering bacteria added, and the pollutants in the water are degraded through the synergistic effect of the dominant engineering bacteria in each section; at the same time, due to the addition of nutrient solution and biological activation solution, the biomass and biological activity of the reaction unit are guaranteed. Activity, strengthen the degradation performance of dominant bacteria.

(3) Post-treatment technology of flocculation and air flotation: the SS (suspended solids concentration) content in the effluent water after biointensification treatment is still high (30-50mg/L), which will inevitably affect the COD value of the effluent, and some colloids and bacteria in the water The micelles can also be effectively removed by flocculation and air flotation, and the removal rate is between 40-50%. The post-treatment technology of flocculation and air flotation can effectively ensure the reliability of the effluent water quality.

Therefore, through the integration and effective combination of the above pretreatment, intermediate treatment and post-treatment technologies, it is guaranteed that this technology can be more efficient and treat high-concentration, refractory organic chemical wastewater.

The integrated sewage treatment method and device of "physical and chemical pretreatment + biological enhanced treatment + flocculation and air flotation post-treatment" has a wide range of applications, and can well deal with complex water quality, high COD content, large pH value changes, intermittent discharge, Sewage with large changes in water quality and quantity. Moreover, the method is efficient and low in cost, and the quality of the effluent treated by the method and device of the present invention can meet the influent standard (COD≤500mg/L) for discharge into a sewage treatment plant. In addition, in the method of the present invention, alkaline wastewater is used to neutralize acidic wastewater, which can simultaneously treat alkaline wastewater and acidic wastewater, simplify the treatment process, achieve the purpose of saving treatment costs, and are more suitable for the quality of sewage discharged from chemical plants complex features.

Description of drawings

Fig. 1 is the schematic diagram of chemical industry sewage treatment device of the present invention;

Fig. 2 is a schematic flow chart of using the method and device of the present invention to treat sewage.

Detailed ways

A chemical park includes an auxiliary factory and a fine chemical factory. The fine chemical factory mainly produces antioxidants and p-hydroxybenzaldehyde, and the auxiliary factory mainly produces maleic anhydride and methyl ethyl ketone (see the table below for the quality and quantity of wastewater). The high-concentration sewage of this chemical park produces about 135m ³ per day, and the clean sewage produces about 1300m ³ (COD280mg/L or so) per day, with a volume ratio of about 1:10. The direct discharge of high-concentration sewage into the sewage treatment plant will have a great impact on the treatment process, resulting in the effluent of the sewage plant not meeting the standard. Therefore, the quality of the effluent treated by the process and device of the present invention can meet the influent standard (COD≤500mg/L) for discharge into the sewage treatment plant.

Water quality and quantity of wastewater in chemical industry parks

The production wastewater in the park has the following main characteristics:

1. Sewage COD is high and fluctuates greatly.

2. The content of organic matter in sewage is high and its biodegradability is poor. GC-MS analysis determines that the main pollutant in the water is more than 95% (weight ratio) of the solvent DBP (di-n-butyl phthalate) of maleic anhydride, followed by 2.6-di-tert-butyl-4-methylphenol and the same Separate isomers and p-hydroxybenzaldehyde.

3. The pH value of high-concentration sewage changes greatly. The pH values of the wastewater discharged from the p-hydroxybenzaldehyde plant and the maleic anhydride plant are 14 and 2, respectively, which are strongly acidic and alkaline, and are discharged intermittently.

The high-concentration sewage from the four installations of antioxidant, p-hydroxybenzaldehyde, maleic anhydride, and methyl ethyl ketone is treated as raw water according to the proportion of its displacement. The processing conditions are as follows:

Process conditions:

1. Raw water: 200L/h, antioxidant: p-hydroxybenzaldehyde: maleic anhydride: methyl ethyl ketone = 4:40:72:9 (volume ratio); clean sewage 2m ³ /h.

2. Iron-carbon micro-electrolytic cell Fe:C=1:1.5~4 (weight ratio)

3. The dosage of H ₂ O ₂ ranges from 2 to 10mL·L ^-1

4. High concentration sewage: clean sewage = 1:5~15 (volume ratio)

5. The dosage of flocculant in the post-treatment of flocculation and air flotation: the dosage of PAFC is 100mg·L ^-1 ~ 200mg·L ^-1 , the dosage of PAM is 1mg·L ^-1 ~ 5mg·L ^-1

6. Air-to-water ratio (volume ratio of aeration rate to water intake): 2～10:1 (volume ratio)

The best process conditions:

1. Raw water: 200L/h, antioxidant: p-hydroxybenzaldehyde: maleic anhydride: methyl ethyl ketone = 4:40:72:9 (volume ratio); clean sewage 2m ³ /h.

2. Iron carbon micro electrolytic cell

3. The dosage of H ₂ O ₂ is 6mL·L ^-1

4. High concentration sewage: clean sewage = 1:10 (volume ratio)

5. The dosage of flocculant in post-treatment of flocculation and air flotation: the dosage of PAFC is 200mg·L ^-1 , the dosage of PAM is 3mg·L ^-1

6. Air-water ratio: 6:1 (volume ratio)

Example 1:

1. The total inflow of high-concentration organic chemical sewage is 200L/h, and the antioxidant: p-hydroxybenzaldehyde: maleic anhydride: methyl ethyl ketone is influent at a ratio of 4:40:72:9, that is, the antioxidant is 6.4L/h. p-hydroxybenzaldehyde 64L/h, maleic anhydride 115L/h, methyl ethyl ketone 14.6L/h;

2. Antioxidant, maleic anhydride, methyl ethyl ketone three kinds of acidic (pH2.0) sewage are lifted from the sewage storage tank by the metering pump to the iron carbon pool according to the flow rate (Fe: C = 1: 1.5 (weight ratio), the iron carbon bed is high 500mm) for micro-electrolysis reaction, the COD value of the mixed sewage is 53,000 mg/L, and the bottom of the iron-carbon pool is aerated and stirred at the same time, and the total reaction time is 150 minutes;

3. After the reaction in the iron-carbon tank, the effluent enters the Fenton oxidation tank for oxidation reaction. The dosage of H ₂ O ₂ is 6mL·L ^-1 , and the bottom aeration method is used for mass transfer and stirring. The Fenton oxidation reaction time is 90 Minutes, the sewage after "iron-carbon micro-electrolysis-Fenton oxidation" and the treated p-hydroxybenzaldehyde alkaline sewage merge into the neutralization pool;

4. The p-hydroxybenzaldehyde alkaline sewage (pH value 10-12) with a COD concentration of 240,000 mg/L is lifted from the sewage storage tank to the flocculation tank by the metering pump according to the flow rate, and the dosage of the basic flocculant is respectively Coagulant 260mg/L, anionic polyacrylamide 10mg/L (the coagulant is CaCl ₂ weight: MgCl ₂ weight = 2: 1), after putting in the flocculant, stir it with a mixer, and the effluent enters the sedimentation tank for precipitation. The supernatant and the above-mentioned pretreated acidic water are merged into the neutralization tank;

5. After the acid-base sewage is treated by "iron-carbon micro-electrolysis-Fenton oxidation" and "flocculation sedimentation" respectively, it can remove some refractory organic matter in the wastewater (COD removal rate can reach 40-55%), and can make the complex structure Macromolecular organic matter is effectively decomposed into simple small molecular organic matter, thereby improving the biodegradability of wastewater. The acid-base wastewater is neutralized in the neutralization tank. If the acid-base cannot be completely neutralized, it can be neutralized by adding NaOH or H ₂ SO ₄ to make the pH value of the sewage reach 6-9. The mixing method is mechanical stirring;

6. The pretreated acid-base sewage (flow rate 200L/h) and clean sewage (flow rate 2m ³ /h, COD280mg/L) are diluted at a ratio of 1:10 and enter the subsequent "hydrolysis acidification + contact oxidation I + contact oxidation II "Biochemical section. Among them, the combined biological carrier filler (suspension mode, filling rate 70%) and bio-augmented engineering bacteria (10 kg of mixed bacterial solution of GW1, GW2 and GW5 strains of ^{10 8} -10 ⁹ colonies/mL were added respectively in the hydrolytic acidification tank; ② market purchase Jiangsu Lvke Biotechnology Co., Ltd. EM bacteria freeze-dried powder 5kg (effective live bacteria ≥ 5 × 10 ⁹ CFU/g); ③ petrochemical sewage plant sludge 500kg), using submersible mixer for mud-water mixing and mass transfer; contact oxidation tank Add natural mineral carrier filler (stacking method, filling rate 60%) and bio-augmented engineering bacteria (①16kg of mixed bacterial solution of GW1, GW2, and GW5 strains with 10 ⁸ -10 ⁹ colonies/mL; ② 8kg of EM bacteria freeze-dried powder (effective Viable bacteria ≥5×10 ⁹ CFU/g); ③Sludge from petrochemical sewage plant 500kg), use bottom aeration for oxygen supply and mass transfer (dissolved oxygen concentration 2mg/L, keep air-water ratio 6:1) ); at the same time, according to the growth of the sludge, the method of adding nutrient solution and biological activation solution (generally adding 1L per pool every 5 days) improves the activity and degradation performance of the enhanced engineering bacteria. The reaction time of the biochemical section is 24 hours for the hydrolytic acidification tank, 20 hours for the primary oxidation tank and 18 hours for the secondary oxidation tank. The effluent after treatment by the bioaugmentation unit enters the post-treatment unit of flocculation and air flotation.

7. The effluent of the bioaugmentation unit contains colloids and biofilm flocs, which are removed by pressurized dissolved air flotation. The dosage of flocculants in this unit is: PAFC200mg·L ^-1 , PAM3mg·L ^-1 , Air flotation and flocculation can effectively separate most of the particulate matter in the water, so as to ensure the deep purification effect of the effluent.

The treatment effect under the optimal process conditions is as follows:

Example 2:

Adopt the same method as Example 1 to carry out sewage treatment, the difference is that in the hydrolytic acidification tank in step 6, the bioaugmentation engineering bacteria are added (10 ⁸ -10 ⁹ colonies/mL of GW1, GW2, GW5 bacterial strain mixed bacterial solution 10kg ; ②Petrochemical sewage plant sludge 500kg); in the contact oxidation tank, add bio-enhanced engineering bacteria (①10 ⁸ -10 ⁹ colonies/mL of GW1, GW2, GW5 strain mixed bacterial solution 16kg; ②Petrochemical sewage plant sludge 500kg) . Obtained the sewage treatment effect identical with embodiment 1.

Example 3:

Adopt the same method as Example 1 to carry out sewage treatment, the difference is that in the hydrolytic acidification tank in step 6, add bio-augmentation engineering bacteria as (1. Jiangsu Lvke Biotechnology Co., Ltd. EM bacteria freeze-dried powder 5kg (effective Viable bacteria ≥5×10 ⁹ CFU/g); ② petrochemical sewage plant sludge 500kg); adding bio-enhanced engineering bacteria to the contact oxidation tank is (① 5kg of freeze-dried powder of EM bacteria purchased from the market from Jiangsu Lvke Biotechnology Co., Ltd. (Effective live bacteria ≥5×10 ⁹ CFU/g); ②Petrochemical sewage plant sludge 500kg). Obtained the sewage treatment effect identical with embodiment 1.

Claims (8)

1. method of handling the high density organic chemical industry sewage said method comprising the steps of:

A) COD concentration at first enters " the little electrolysis of aeration iron charcoal+Fenton oxidation " pretreatment technology after the mixing of process aeration up to one or more sour waters of 5-30 ten thousand mg/L, little electrolytic reaction times of aeration is 60 minutes～180 minutes, the Fenton oxidation time is 60 minutes～100 minutes, and the mixing mass transfer mode of bottom aeration is all adopted in little electrolysis of iron charcoal and Fenton oxidation;

B) COD concentration up to the alkaline sewage of 5-30 ten thousand mg/L through the coagulating sedimentation pre-treatment after with carry out the mechanical stirring neutralization through the pretreated sour water of step a) at neutralization tank, the soda acid insufficient section adds acidic chemical by the outside or alkaline chemical is realized, thereby enters follow-up biological intensive treatment unit again after making sewage pH value reach 6～8;

C) make through the pretreated sewage of step b) and enter " acidication+catalytic oxidation I+ catalytic oxidation II " biological reinforced processing unit, wherein add combined bio carrier filler and biological reinforced engineering bacteria in the hydrolysis acidification pool, add natural mineral carrier filler and biological reinforced engineering bacteria in the contact-oxidation pool, and improve to strengthen the activity and the degradation property of engineering bacteria by the method that adds nutritive medium and bioactivation liquid, if desired, go out the water concentration situation according to step b), in this step, sneak into water under a certain proportion of cleaning, be not more than 15kg COD/ (m to guarantee the organic loading in the biological reinforced processing unit ³D);

D) make the water outlet of step c) enter the flocculation-air floating post-processing unit.

2. the flocculation agent in the method for claim 1, wherein described biological reinforced unit is polymerization oxidation ferro-aluminum and polyacrylamide.

3. method of handling the high density organic chemical industry sewage said method comprising the steps of:

A) COD concentration is promoted to iron charcoal pond by volume pump from sewage storage tank up to one or more sour waters of 5-30 ten thousand mg/L and carries out micro-electrolysis reaction, bottom, iron charcoal pond is carried out aeration agitation, total reaction time 150 minutes simultaneously;

B) water outlet of reaction back, iron charcoal pond enters the Fenton oxidation pond and carries out oxidizing reaction, H ₂O ₂Dosage be 6mLL ^-1, adopt the mode of bottom aeration to carry out the mass transfer stirring, the Fenton oxidation time is 90 minutes;

C) alkaline sewage that will have high COD concentration is promoted to flocculation basin by volume pump from sewage storage tank by flow, and alkali formula flocculation agent comprises flocculation agent and anion-polyacrylamide, and wherein flocculation agent is CaCl ₂Weight: MgCl ₂Weight=2: 1 stirs with stirrer after dropping into flocculation agent, and water outlet enters the settling tank precipitation, and the supernatant liquor of post precipitation enters neutralization tank with converging through the pretreated sour water of step b);

D) after " the little electrolysis of iron charcoal-Fenton oxidation " and " flocculation sediment " handled, acidic and alkaline waste water carried out acid-base neutralisation at neutralization tank to soda acid sewage respectively, and soda acid is not as neutralizing fully then by adding NaOH or H ₂SO ₄Mode neutralize, make sewage pH value reach 6～9, hybrid mode is a mechanical stirring;

E) after diluting in proportion, water enters follow-up " acidication+catalytic oxidation I+ catalytic oxidation II " biochemical section through pretreated soda acid sewage to clean down, wherein add combined bio carrier filler and biological reinforced engineering bacteria in the hydrolysis acidification pool respectively, adopt diving mixer to carry out muddy water and mix and mass transfer; Add natural mineral carrier filler and biological reinforced engineering bacteria in the contact-oxidation pool, adopt the mode of bottom aeration to carry out oxygen supply and mass transfer; Simultaneously, in described hydrolysis acidification pool and contact-oxidation pool, all add nutritive medium and bioactivation liquid, improve activity and the degradation property of strengthening engineering bacteria thus; The biochemical section reaction times is hydrolysis acidification pool 24h, stair oxidation pond 20h, secondary oxidation pond 18h; Water outlet enters the flocculation-air floating post-processing unit after the biological reinforced cell processing;

F) contain colloid and microbial film flco in the biological reinforced unit water outlet, adopt the mode of pressurized dissolved air flotation that it is removed, the flocculation agent that adds in the described unit is polymerization oxidation ferro-aluminum and polyacrylamide.

4. as each described method in the claim 1～3, wherein, described biological reinforced engineering bacteria can be made of following three parts, or is made of first part and third part, or is made of second section and third part: 1. GW1, GW2, GW5 strain mixture; 2. EM bacterium lyophilized powder; 3. petrifaction sewage factory mud.

5. method as claimed in claim 4, wherein, when biological reinforced engineering bacteria was made of described three parts, three's weight ratio was 2: 1: 50～100; When biological reinforced engineering bacteria was made of first part and third part, both weight ratios were 2: 50～100; When biological reinforced engineering bacteria was made of second section and third part, both weight ratios were 1: 50～100; Total dosage is 5% of a pond body useful volume.

6. device of handling the high density organic chemical industry sewage, described device is to comprise following unitary integrated waste disposal plant:

A) physico-chemical pretreatment unit, described physico-chemical pretreatment unit comprises the iron carbon pond of carrying out the aeration iron-carbon micro-electrolysis, the Fenton pond of carrying out the Fenton oxidation, to flocculation sedimentation tank and neutralization tank that alkaline sewage is handled, wherein the mixing mass transfer mode of bottom aeration is all adopted in iron carbon pond and Fenton pond;

B) biological reinforced processing unit, described biological reinforced processing unit comprise the hydrolytic tank that is filled with combined stuffing and biological reinforced engineering bacteria, the stair oxidation pond that is filled with natural mineral carrier filler, biological reinforced engineering bacteria, nutritive medium and bioactivation liquid and secondary oxidation pond;

C) flocculation-air floating post-processing unit, described flocculation-air floating post-processing unit comprises air flotation pool.

7. device as claimed in claim 6, wherein, described biological reinforced engineering bacteria can be made of following three parts, or is made of first part and third part, or is made of second section and third part: 1. GW1, GW2, GW5 strain mixture; 2. EM bacterium lyophilized powder; 3. petrifaction sewage factory mud.

8. device as claimed in claim 7, wherein, when biological reinforced engineering bacteria was made of described three parts, three's weight ratio was 2: 1: 50～100; When biological reinforced engineering bacteria was made of first part and third part, both weight ratios were 2: 50～100; When biological reinforced engineering bacteria was made of second section and third part, both weight ratios were 1: 50～100; Total dosage is 5% of a pond body useful volume.

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