CN108083553B - Method for treating organic chemical wastewater - Google Patents

Method for treating organic chemical wastewater Download PDF

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Publication number
CN108083553B
CN108083553B CN201711202932.4A CN201711202932A CN108083553B CN 108083553 B CN108083553 B CN 108083553B CN 201711202932 A CN201711202932 A CN 201711202932A CN 108083553 B CN108083553 B CN 108083553B
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wastewater
reaction
microorganism
carrier
cod
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CN108083553A (en
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周林成
丁伟军
刘德胜
白彪勇
陈凤娟
丁维东
朱军龙
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Gansu Ruizhiyuan Environmental Protection Engineering Co ltd
Lanzhou University Silver Industry Technology Research Institute
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Gansu Ruizhiyuan Environmental Protection Engineering Co ltd
Lanzhou University Silver Industry Technology Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2806—Anaerobic processes using solid supports for microorganisms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biological Treatment Of Waste Water (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)

Abstract

The invention provides a method for treating organic wastewater, which comprises the steps of S1, adjusting the pH value of the wastewater to 6-8; step S2, contacting the wastewater treated in the step S1 with a polyurethane bioactive carrier to perform a first reaction; step S3, contacting the wastewater treated in the step S2 with immobilized microorganism carriers to perform a second reaction; and step S4, contacting the wastewater treated in the step S3 with a heterogeneous Fenton catalyst and an oxidant to perform a third reaction. The method firstly adopts the immobilization technology of the microorganism to improve the microorganism content in unit volume and accelerate the biological reaction speed, and finally adopts heterogeneous catalytic oxidation to further catalyze, oxidize and degrade refractory organic matters which cannot be treated in the immobilization stage of the microorganism, so that the effluent of the system reaches the discharge standard.

Description

Method for treating organic chemical wastewater
Technical Field
The invention relates to a method for treating organic chemical wastewater.
Background
High-concentration organic chemical wastewater generated in the process of producing synthetic medicaments such as thymopentin and the like, namely COD (chemical oxygen demand) of the wastewatercrThe concentration is as high as 40000mg/L, and the waste water contains a large amount of methanol, acetonitrile and a small amount of amino acid. Wherein, the content of the methanol and the acetonitrile is far greater than the concentration which is tolerated by free organisms, and the methanol and the acetonitrile have strong inhibiting effect on common microorganisms.
CN103253831A discloses a heterogeneous catalysis Fenton reagent oxidation fluidized bed-anaerobe fluidized bed advanced treatment coking wastewater system, can realize coking wastewater economic high-efficient processing, and the sewage after the processing can reach emission standard. However, the technical treatment device is complex, the process cost is high, and the treatment efficiency of the wastewater containing the refractory organic matters is low.
CN102167435A discloses a Fenton catalyst prepared by using active carbon and slag as carriers and used for treating paint production wastewater (COD)cr1500-2000 mg/L). And particularly discloses that the prepared heterogeneous Fenton catalyst is filled into a reaction column with the thickness of 1200-2000 mm, the pH of the wastewater is controlled to be 6-8, and H is added into the wastewater2O2The adding amount is controlled to be H2O2/CODcrThe molar ratio of (A) to (B) is 0.8-1.2, and the water to be treated and H2O2After fully mixing, introducing into a catalytic oxidation reaction column at a flow rate of 3-5 m/h, standing for 15-40 min, discharging water, and measuring CODcrIs 30-40 mg/L. The treatment method has high requirements on the wastewater treatment process and high treatment cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for treating organic chemical wastewater, which comprises the steps of firstly adopting a microorganism immobilization technology, improving the microorganism content in unit volume, accelerating biological reaction, finally installing a heterogeneous catalytic oxidation device, and further catalytically oxidizing and degrading refractory organic matters which cannot be treated in a microorganism immobilization stage, so that the effluent of a system reaches the discharge standard.
In order to solve the problems, the invention aims to research a method for deeply treating thymopentin processing and production wastewater by coupling immobilized microorganisms with heterogeneous catalytic oxidation.
The method for treating the organic chemical wastewater comprises the following steps:
step S1, adjusting the pH value of the wastewater to 6-8, preferably 6.5-7.5, more preferably 6.9-7.1, and most preferably 7.0;
step S2, contacting the wastewater treated in the step S1 with a polyurethane bioactive carrier to perform a first reaction;
step S3, contacting the wastewater treated in the step S2 with immobilized microorganism carriers to perform a second reaction;
and step S4, contacting the wastewater treated in the step S3 with a heterogeneous Fenton catalyst and an oxidant to perform a third reaction.
According to some embodiments of the invention, the wastewater is from a thymopentin production system.
According to some embodiments of the invention, the CODcr concentration of the wastewater is equal to or less than 50000mg/L, preferably equal to or less than 40000mg/L, more preferably equal to or less than 30000 mg/L.
According to some embodiments of the present invention, the wastewater treated in step S1 is homogenized by aeration and then subjected to step S2.
According to some embodiments of the invention, the method consists of steps S1, S2, S3 and S4.
According to some embodiments of the invention, the NH of the wastewater4 +The concentration of-N is 200-500 mg/L.
According to some embodiments of the invention, the first reaction is carried out at 20-40 ℃, preferably 48-96 hours.
According to some embodiments of the invention, the second reaction is carried out at 15-30 ℃, preferably for 18-36 hours.
According to some embodiments of the invention, the third reaction is carried out at 20-30 ℃, preferably for 0.5-2 hours.
According to some embodiments of the invention, the polyurethane bioactive carrier is a carbon fiber composite polyurethane bioactive carrier. According to some embodiments, the carbon fiber composite polyurethane bioactive carrier is prepared by mixing, foaming and curing a first component, a second component and a third component. The first component consists of polyether (preferably polyether 330) and a microorganism culture medium, the second component consists of toluene diisocyanate and carbon fiber (preferably modified activated carbon fiber), and the third component consists of silicone oil, water, monofluorotrichloromethane, triethylene diamine and stannous octoate. Preferably, the weight parts of the components are as follows: 70.0-75.0 parts of polyether, 1.0-2.0 parts of microorganism culture medium, 25-30 parts of toluene diisocyanate, 2.0-5.0 parts of carbon fiber, 0.3-0.5 part of silicone oil, 0.5-1.5 parts of water, 0.20 part of fluorotrichloromethane, 0.15 part of triethylene diamine and 0.1 part of stannous octoate.
According to one embodiment, the preparation method of the carbon fiber composite polyurethane bioactive carrier comprises the following steps:
the components of (1): polyether 330: 70 to 75 portions of
1.0-2.0 parts of microbial culture medium
The raw materials are sequentially mixed and mechanically stirred for 10min at the temperature of 20 ℃ to obtain the component I.
The component II: 25-30 parts of toluene diisocyanate
2.0-5.0 parts of modified activated carbon fiber
The raw materials are mixed in sequence and then mechanically stirred for 10min at the temperature of 20 ℃ to obtain the component II.
Figure BDA0001483095600000031
Mixing the first component and the second component, mixing the other components, stirring at a high speed, stopping stirring after 5-15 seconds after foaming, foaming at room temperature for 30min, and curing at 60 ℃ for 2 hours. Then, cutting into a block (10X 10mm) was carried out.
According to some embodiments of the present invention, the immobilized microorganism carrier is prepared by impregnating a polyurethane foam carrier with a solution comprising guar gum and a enrichment medium to form a reversible gel with a boric acid crosslinking agent to achieve immobilization.
Preferably, the enrichment culture solution contains trace elements and high-efficiency microorganisms.
According to some embodiments of the invention, the specific method for preparing the immobilized microorganism carrier is: mixing guar gum and deionized water at 80-95 ℃ (preferably 90 ℃), cooling to 30-50 ℃ (preferably 40 ℃), adding a enrichment medium and a composite efficient microbial flora to obtain a macromolecular mixed solution of microorganisms to be immobilized; soaking the polyurethane foam carrier in the high molecular mixed solution of the microorganism to be immobilized for 12-36 hours, preferably 20-28 hours, and then forming reversible gel with a boric acid crosslinking agent to obtain the immobilized microorganism carrier.
Preferably, the concentration of the boric acid crosslinking agent is 0.5 wt% to 3 wt%, preferably 0.8 wt% to 1.5 wt%, more preferably 1 wt%.
According to one embodiment, the immobilized microorganism carrier is prepared by the following steps:
mixing guar gum and deionized water, completely dissolving at 90 ℃, standing and cooling to 40 ℃, adding a bacterium enrichment culture medium containing trace elements and compound efficient microbial floras, and mixing and stirring for 10-30 min to obtain a high-molecular mixed solution of a microorganism to be immobilized;
secondly, soaking the polyurethane foam carrier into the macromolecular mixed solution of the microorganism to be immobilized, stirring for 24 hours, taking out, adding 1 percent of boric acid crosslinking agent to form reversible gel to achieve immobilization, and finally obtaining the immobilized microorganism carrier.
According to some embodiments of the present invention, the heterogeneous Fenton catalyst is prepared by impregnating a porous support, preferably a peanut shell powder or an activated carbon powder, with a solution of ammonium iron oxalate. The concentration of the ammonium iron oxalate solution is preferably 50 to 150g/L, more preferably 80 to 120g/L, and most preferably 100 g/L.
The particle size of the porous carrier is 100-200nm, preferably 150 nm.
According to one embodiment, the preparation method of the heterogeneous Fenton catalyst comprises the following steps:
soaking a porous carrier in an ammonium ferric oxalate solution with the concentration of 100g/L for 10 hours;
drying the soaked porous carrier at the temperature of 80 ℃;
thirdly, putting the dried porous carrier into a rotary tubular furnace, and reacting in N2Under protection, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the heterogeneous Fenton catalyst.
According to some embodiments of the invention, the oxidizing agent is a hydrogen peroxide solution, preferably the concentration of the hydrogen peroxide solution is between 0.01 wt% and 0.10 wt%, more preferably the concentration of the hydrogen peroxide solution is between 0.3 wt% and 0.7 wt%, most preferably 0.5 wt%.
According to some embodiments of the invention, the microbial culture medium comprises flour, blood meal and bone meal. Preferably, the particle size of the microbial culture medium is 0.1mm or less. Preferably, the microbial culture medium consists of 55-65% of flour, 25-35% of blood meal and 5-15% of bone meal by mass. Preferably, the microorganism culture medium consists of flour 60%, blood meal 30% and bone meal 10% by mass fraction.
According to some embodiments of the invention, the method for preparing the microbial culture medium comprises: mixing dried flour, blood powder, and bone powder at a ratio of 60% flour, 30% blood powder, and 10% bone powder by weight, and sieving to obtain powder with particle size below 0.1 mm.
According to some embodiments of the present invention, the modified activated carbon fiber is prepared by: processing activated carbon fiber to 2-4mm, soaking in 60-68 wt% nitric acid solution for 2-4h, washing with distilled water to neutrality, and oven drying at 100 deg.C.
According to some embodiments of the present invention, the step S2 is preferably performed in an anaerobic reactor, the anaerobic reactor being a 30cm × 300cm × 100cm glass tank, the filling rate of the carrier being 60%.
According to some embodiments of the invention, step S3 is performed in an aerobic reactor. Preferably, the aerobic reactor is a glass tank with the size of 50cm multiplied by 40cm multiplied by 30cm, the bottom of the aerobic reactor is provided with an aeration device, and the filling rate of the carrier is 40-60%.
According to some embodiments of the invention, said step S4 is performed in a heterogeneous catalytic oxidation reactor. Preferably, the heterogeneous catalytic oxidation reactor has a glass groove size of 50cm × 40cm × 30cm, and the filling rate of the catalyst is 80%.
According to some embodiments of the invention, the COD of the wastewater treated in step S2crThe concentration is 1000-1500mg/L, NH4 +The concentration of-N is 100-150 mg/L.
According to some embodiments of the invention, the COD of the wastewater treated in step S3crThe concentration is 800-1000mg/L, NH4 +The concentration of N is 80-120 mg/L.
According to some embodiments of the invention, the COD of the wastewater treated in step S4crThe concentration is 200-500mg/L, NH4 +The concentration of-N is 20-50 mg/L.
According to some embodiments of the invention, the method comprises:
step S1, adjusting the pH value of the wastewater to 6-8, preferably 6.5-7.5, more preferably 6.9-7.1, and most preferably 7.0;
step S2, contacting the wastewater treated in step S1 with polyurethane bioactive carrier and anaerobic microorganism to perform a first reaction;
step S3, the wastewater treated in step S2 is contacted with an immobilized microorganism carrier and a highly effective microorganism (such as microorganism B350 (BIO-SYSTEM, USA)) to perform a second reaction.
And step S4, contacting the wastewater treated in the step S3 with a heterogeneous Fenton catalyst and an oxidant to perform a third reaction.
Compared with the prior art, the invention at least has the following advantages:
1. the method for treating organic wastewater provided by the invention adopts an immobilized microorganism method, is beneficial to improving the concentration of microorganisms in the reactor and solid-liquid separation after reaction, is beneficial to removing high-concentration organic matters, is easy to control the reaction, and avoids the problems of sludge generation, secondary pollution and the like.
2. The method for treating the organic wastewater provided by the invention adopts a heterogeneous catalytic oxidation technology, and the heterogeneous catalyst exists in a solid state form, and has the advantages of high activity, easiness in separation and good stability.
3. The method for treating the organic wastewater provided by the invention adopts the immobilized microorganism technology, improves the microorganism content in unit volume, greatly accelerates the biological reaction speed, and has the characteristics of impact load resistance, strong toxicity resistance, good treatment effect and the like.
4. The method for treating the organic wastewater provided by the invention adopts the immobilized microorganism technology, and finally installs the heterogeneous catalytic oxidation device, so that the organic matters which cannot be treated by the immobilized microorganism technology can be further oxidized, catalytically degraded, and the effluent of the system reaches the discharge standard.
5. According to the method for treating the organic wastewater, provided by the invention, the adopted heterogeneous catalytic oxidation can further degrade organic pollutants in water under a neutral condition, and the whole process is green and environment-friendly and has no secondary pollution.
6. The method for treating the organic wastewater provided by the invention adopts the immobilized microorganism technology and the heterogeneous catalytic oxidation technology to be combined for deeply treating the thymopentin processing and producing wastewater, so that the thymopentin processing and producing wastewater can be economically and efficiently treated, and the treated effluent can reach the discharge standard.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Preparation of microbial culture Medium
Mixing dried flour, blood powder, and bone powder at a ratio of 60% flour, 30% blood powder, and 10% bone powder by weight, and sieving to obtain powder with particle size below 0.1 mm.
Processing the activated carbon fiber to 2-4mm, soaking the activated carbon fiber in a 60-68% nitric acid solution for 2-4h, washing the activated carbon fiber with distilled water to be neutral, and drying the activated carbon fiber at 100 ℃ to obtain the modified activated carbon fiber.
Preparation of polyurethane bioactive carrier A
The components of (1): polyether 330: 70 to 75 portions of
1.0-2.0 parts of microbial culture medium
The raw materials are sequentially mixed and mechanically stirred for 10min at the temperature of 20 ℃ to obtain the component I.
The component II: 25-30 parts of toluene diisocyanate
2.0-5.0 parts of modified activated carbon fiber
The raw materials are mixed in sequence and then mechanically stirred for 10min at the temperature of 20 ℃ to obtain the component II.
Figure BDA0001483095600000061
Mixing the first component and the second component, mixing the other components, stirring at a high speed, stopping stirring after 5-15 seconds after foaming, foaming at room temperature for 30min, and curing at 60 ℃ for 2 hours. Then, cutting into a block (10X 10mm) was carried out.
Preparation of polyurethane bioactive carrier B
The components of (1): polyester: 70 to 75 portions of
1.0-2.0 parts of microbial culture medium
The raw materials are sequentially mixed and mechanically stirred for 10min at the temperature of 20 ℃ to obtain the component I.
The component II: 25-30 parts of toluene diisocyanate
2.0-5.0 parts of modified activated carbon fiber
The raw materials are mixed in sequence and then mechanically stirred for 10min at the temperature of 20 ℃ to obtain the component II.
Figure BDA0001483095600000071
Mixing the first component and the second component, mixing the other components, stirring at a high speed, stopping stirring after 5-15 seconds after foaming, foaming at room temperature for 30min, and curing at 60 ℃ for 2 hours. Then, cutting into a block (10X 10mm) was carried out.
Preparation of immobilized microorganism carrier A
Mixing guar gum with deionized water, dissolving completely at 90 deg.C, standing, cooling to 40 deg.C, adding into enrichment medium containing trace elements and high-efficiency microorganisms, mixing and stirring
Obtaining a polymer mixed solution of the microorganism to be immobilized for 10-30 min;
soaking the polyurethane foam carrier into the high-molecular mixed solution of the microorganism to be immobilized, stirring for 24 hours, taking out, adding a boric acid crosslinking agent with the mass concentration of 1% to form reversible gel, and achieving immobilization to finally obtain the immobilized microorganism carrier A.
Preparation of immobilized microorganism carrier B
The preparation process is the same as that of the immobilized microorganism carrier A, and only differs from that of the immobilized microorganism carrier A in that a boric acid crosslinking agent with the mass concentration of 3% is adopted.
Preparation of heterogeneous Fenton catalyst A
Soaking peanut shell powder (with the particle size of 150nm) into 100g/L ammonium ferric oxalate solution for 10 h;
drying the soaked peanut shell powder at the temperature of 80 ℃;
placing the dried peanut shell flour in a rotary tube furnace under N2Under protection, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the heterogeneous Fenton catalyst A.
Preparation of heterogeneous Fenton catalyst B
The same procedure as for the preparation of heterogeneous Fenton catalyst A was followed except that the peanut shell powder was replaced with activated carbon particles (150 nm in size).
The apparatus used in the examples is as follows:
the anaerobic reactor is a glass tank with the volume of 30cm multiplied by 100cm, and the filling rate of the carrier is 60 percent; the aerobic reactor is a glass tank with the size of 50cm multiplied by 40cm multiplied by 30cm, the bottom is provided with an aeration device, and the filling rate of the carrier is 40-60%; the heterogeneous catalytic oxidation reactor is a glass groove with the size of 50cm multiplied by 40cm multiplied by 30cm, and the filling rate of the catalyst is 80 percent.
Example 1
Adding polyurethane bioactive carrier A and anaerobic microorganism into anaerobic reactor, starting for 2 months, and adding CODcrIs 30000mg/L, NH4 +Adjusting the thymopentin processing production wastewater with-N of 200mg/L to be neutral in adjustment, feeding the homogenized production wastewater into an anaerobic reactor, reacting at 40 ℃ for 72 hours, and measuring the COD of effluentcrIs 800mg/L, NH4 +-N is 150 mg/L. In this step, CODcrThe removal rate was 97.33%, NH4 +the-N removal rate was 25%.
The water treated in the anaerobic reactor is fed into the aerobic reactor, and the immobilized microorganism is added into the aerobic reactorCarrier A and microorganism B350 (BIO-SYSTEM, USA) were reacted at 30 deg.C for 24h, and COD of effluent was measuredcrIs 100mg/L, NH4 +-N is 20 mg/L. In this step, CODcrThe removal rate was 87.5%, NH4 +the-N removal rate was 86.67%.
The water quality treated in the aerobic reactor enters a heterogeneous catalytic oxidation reactor again, a heterogeneous Fenton catalyst A and a hydrogen peroxide solution with the concentration of 0.5 wt% are added into the heterogeneous catalytic oxidation reactor, the heterogeneous Fenton catalyst A and the hydrogen peroxide solution are fully mixed with the wastewater at 20 ℃, the mixture stays for 30min, effluent water after the heterogeneous Fenton reaction is obtained, and the COD of the treated water in the heterogeneous catalytic oxidation reactor is measuredcrAnd NH4 +N, determination of the COD of the effluentcrIs 40mg/L, NH4 +-N is 5 mg/L. In this step, CODcrRemoval rate of 60% NH4 +the-N removal rate was 75%.
Final CODcrThe total removal rate reaches 99.87 percent, and NH is removed4 +The total removal rate of-N reaches 97.5 percent.
Example 2
Adding a polyurethane bioactive carrier B into an anaerobic reactor, adding a polyurethane bioactive carrier A and anaerobic microorganisms into the anaerobic reactor, starting up after 2 months, and adding COD (chemical oxygen demand)crIs 30000mg/L, NH4 +Adjusting the thymopentin processing production wastewater with-N of 200mg/L to be neutral in adjustment, feeding the homogenized production wastewater into an anaerobic reactor, reacting at 40 ℃ for 72 hours, and measuring the COD of effluentcrIs 1200mg/L, NH4 +-N is 150 mg/L. In this step, CODcrThe removal rate is 96 percent, NH4 +the-N removal rate was 25%.
Feeding the water treated in the anaerobic reactor into an aerobic reactor, adding immobilized microorganism carrier A and microorganism B350 (BIO-SYSTEM) into the aerobic reactor, reacting at 30 deg.C for 24 hr to obtain effluent CODcrIs 500mg/L, NH4 +-N is 100 mg/L. In this step, CODcrThe removal rate is 58.33%, NH4 +the-N removal rate was 30%.
The water quality treated in the aerobic reactor enters a heterogeneous catalytic oxidation reactor again, a heterogeneous Fenton catalyst A and a hydrogen peroxide solution with the concentration of 0.5 wt% are added into the heterogeneous catalytic oxidation reactor, the heterogeneous Fenton catalyst A and the hydrogen peroxide solution are fully mixed with the wastewater at 20 ℃, the mixture stays for 30min, effluent water after the heterogeneous Fenton reaction is obtained, and the COD of the treated water in the heterogeneous catalytic oxidation reactor is measuredcrAnd NH4 +N, determination of the COD of the effluentcrIs 200mg/L, NH4 +-N is 20 mg/L. In this step, CODcrRemoval rate of 60% NH4 +the-N removal rate was 80%.
Final CODcrThe total removal rate reaches 99.33 percent, NH4 +The total removal rate of-N reaches 90 percent.
Example 3
Adding polyurethane bioactive carrier A and anaerobic microorganism into anaerobic reactor, starting for 2 months, and adding CODcrIs 30000mg/L, NH4 +Adjusting the thymopentin processing production wastewater with-N of 200mg/L to be neutral in an adjusting tank, feeding the production wastewater homogenized by the adjusting tank into an anaerobic reactor, reacting for 72 hours at 40 ℃, and measuring the COD of effluentcrIs 800mg/L, NH4 +-N is 150 mg/L. In this step, CODcrThe removal rate was 97.33%, NH4 +the-N removal rate was 25%.
Feeding the water treated in the anaerobic tank reactor into an aerobic reactor, adding immobilized microorganism carrier B and microorganism B350 (BIO-SYSTEM) into the aerobic reactor, reacting at 30 deg.C for 24 hr to obtain effluent CODcrIs 400mg/L, NH4 +-N is 80 mg/L. In this step, CODcrRemoval rate of 50% NH4 +the-N removal rate was 46.67%.
The water treated in the aerobic reactor enters a heterogeneous catalytic oxidation reactor again, and a heterogeneous Fenton catalyst A and a hydrogen peroxide solution with the concentration of 0.5 wt% are added into the heterogeneous catalytic oxidation reactor to be filled with the wastewater at 20 DEG CMixing, and staying for 30min to obtain water after heterogeneous Fenton reaction. Measuring COD of the treated water in the heterogeneous catalytic oxidation reactorcrAnd NH4 +N, determination of the COD of the effluentcrIs 300mg/L, NH4 +-N is 30 mg/L. In this step, CODcrRemoval rate of 25% NH4 +the-N removal rate was 62.5%.
Final CODcrThe total removal rate reaches 99.0 percent, and NH4 +The total removal rate of-N reaches 85 percent.
Example 4
The COD is treatedcrIs 30000mg/L, NH4 +Adjusting the thymopentin processing production wastewater with-N of 200mg/L to be neutral in adjustment, introducing the homogenized production wastewater after aeration adjustment into an anaerobic reactor, adding a polyurethane bioactive carrier A into the anaerobic reactor, reacting for 72h at 40 ℃, and measuring the COD (chemical oxygen demand) of effluentcrIs 800mg/L, NH4 +-N is 150 mg/L. In this step, CODcrThe removal rate was 97.33%, NH4 +the-N removal rate was 25%.
Feeding the water treated in the anaerobic reactor into an aerobic reactor, adding immobilized microorganism carrier A and microorganism B350 (BIO-SYSTEM) into the aerobic reactor, reacting at 30 deg.C for 24 hr to obtain effluent CODcrIs 100mg/L, NH4 +-N is 5 mg/L. In this step, CODcrThe removal rate was 87.5%, NH4 +the-N removal rate was 96.67%.
And (2) the water treated in the aerobic reactor enters a heterogeneous catalytic oxidation reactor, a homogeneous Fenton catalyst B and a hydrogen peroxide solution with the concentration of 0.5 wt% are added into the heterogeneous catalytic oxidation reactor, the heterogeneous Fenton catalyst B and the hydrogen peroxide solution are fully mixed with the wastewater at the temperature of 20 ℃, and the mixture stays for 30min to obtain effluent after the heterogeneous Fenton reaction. Measuring COD of the treated water in the heterogeneous catalytic oxidation reactorcrAnd NH4 +N, determination of the COD of the effluentcrIs 60mg/L, NH4 +-N is 4 mg/L. In this step, CODcrRemoval rate of 40% NH4 +the-N removal rate was 20%.
Final CODcrThe total removal rate reaches 95.67 percent, NH4 +The total removal rate of-N reaches 88 percent.
Example 5
Adding carbon fiber composite polyurethane bioactive carrier and anaerobic microorganism into anaerobic reactor, starting for 2 months, and adding CODcrIs 40000mg/L, NH4 +Adjusting the thymopentin processing production wastewater with-N of 300mg/L to be neutral in the adjustment, feeding the homogenized production wastewater into an anaerobic reactor, reacting for 72h, and measuring the COD of effluentcrIs 1200mg/L, NH4 +N is 200 mg/L. In this step, CODcrThe removal rate was 97% NH4 +the-N removal rate was 33.33%.
Feeding the water treated in the anaerobic reactor into an aerobic reactor, adding immobilized microorganism carrier and microorganism B350 (BIO-SYSTEM) into the aerobic reactor, reacting for 24 hr to obtain effluent CODcrIs 300mg/L, NH4 +-N is 50 mg/L. In this step, CODcrRemoval rate of 75% NH4 +the-N removal rate was 75%.
And (2) the water treated in the aerobic reactor enters a heterogeneous catalytic oxidation reactor, a heterogeneous Fenton catalyst B and a hydrogen peroxide solution with the concentration of 0.5 wt% are added into the heterogeneous catalytic oxidation reactor, the heterogeneous Fenton catalyst B and the hydrogen peroxide solution are fully mixed with the wastewater, and the mixture stays for 30min to obtain effluent after the heterogeneous Fenton reaction. Measuring COD of the treated water in the heterogeneous catalytic oxidation reactorcrAnd NH4 +N, determination of the COD of the effluentcrIs 80mg/L, NH4 +-N is 5 mg/L. In this step, CODcrThe removal rate was 73.33%, NH4 +the-N removal rate was 90%.
Final CODcrThe total removal rate reaches 97.78 percent, and NH is removed4 +The total removal rate of-N reaches 93 percent.
Example 6
Adding carbon fiber composite polyurethane biological activity into anaerobic reactorThe carrier and anaerobic microorganism are started after 2 months, and the COD is obtainedcrIs 20000mg/L, NH4 +Adjusting the thymopentin processing production wastewater with-N of 100mg/L to be neutral in the adjustment, feeding the homogenized production wastewater after aeration adjustment into an anaerobic reactor, reacting for 48h, and measuring the COD of effluentcrIs 700mg/L, NH4 +-N is 50 mg/L. In this step, CODcrThe removal rate is 96.5 percent, NH4 +the-N removal rate was 50%.
Feeding the water treated in the anaerobic reactor into an aerobic reactor, adding immobilized microorganism carrier and microorganism B350 (BIO-SYSTEM) into the aerobic reactor, reacting for 24 hr to obtain effluent CODcrIs 200mg/L, NH4 +-N is 8 mg/L. In this step, CODcrThe removal rate was 71.43%, NH4 +the-N removal rate was 84%.
And (2) the water treated in the aerobic reactor enters a heterogeneous catalytic oxidation reactor, a heterogeneous Fenton catalyst B and a hydrogen peroxide solution with the concentration of 0.5 wt% are added into the heterogeneous catalytic oxidation reactor, the heterogeneous Fenton catalyst B and the hydrogen peroxide solution are fully mixed with the wastewater, and the mixture stays for 30min to obtain effluent after the heterogeneous Fenton reaction. Measuring COD of the treated water in the heterogeneous catalytic oxidation reactorcrAnd NH4 +N, determination of the COD of the effluentcrIs 30mg/L, NH4 +-N is 5 mg/L. In this step, CODcrThe removal rate is 85%, NH4 +the-N removal rate was 37.5%.
Final CODcrThe total removal rate reaches 96.68 percent, NH4 +The total removal rate of-N reaches 95 percent.
Comparative example 1
Adding carbon fiber composite polyurethane bioactive carrier and anaerobic microorganism into anaerobic reactor, starting for 2 months, and adding CODcrIs 30000mg/L, NH4 +Adjusting the thymopentin processing production wastewater with-N of 200mg/L to neutral during adjustment, feeding the homogenized production wastewater into an anaerobic reactor, reacting at 40 deg.C for 72 hr, and measuring COD of effluentcrIs 800mg/L, NH4 +-N is 150 mg/L. In this step, CODcrThe removal rate was 97.33%, NH4 +the-N removal rate was 25%.
And (2) the water treated in the aerobic reactor enters a heterogeneous catalytic oxidation reactor, a heterogeneous Fenton catalyst A and a hydrogen peroxide solution with the concentration of 0.5 wt% are added into the heterogeneous catalytic oxidation reactor, the heterogeneous Fenton catalyst A and the hydrogen peroxide solution are fully mixed with the wastewater, and the mixture stays for 30min to obtain effluent after the heterogeneous Fenton reaction.
Measuring COD of the treated water in the heterogeneous catalytic oxidation reactorcrAnd NH4 +N, determination of the COD of the effluentcrIs 600mg/L, NH4 +-N is 50 mg/L. In this step, CODcrRemoval rate of 25% NH4 +the-N removal rate was 66.67%.
Feeding the water treated in the anaerobic reactor into an aerobic reactor, adding immobilized microorganism carrier and microorganism B350 (BIO-SYSTEM) into the aerobic reactor, reacting at 30 deg.C for 24 hr to obtain effluent CODcrIs 400mg/L, NH4 +-N is 40 mg/L. In this step, CODcrThe removal rate was 33.33%, NH4 +the-N removal rate was 25%.
Final CODcrThe total removal rate reaches 98.67 percent, NH4 +The total removal rate of-N reaches 80 percent.
The embodiments described above are exemplary embodiments of the present invention and those skilled in the art may make various modifications thereto without departing from the inventive concept disclosed herein.

Claims (22)

1. A method for treating organic chemical wastewater comprises the following steps:
step S1, adjusting the pH value of the wastewater to 6-8;
step S2, contacting the wastewater treated in the step S1 with a polyurethane bioactive carrier to perform a first reaction;
step S3, contacting the wastewater treated in the step S2 with immobilized microorganism carriers to perform a second reaction;
step S4, contacting the wastewater treated in the step S3 with a heterogeneous Fenton catalyst and an oxidant to perform a third reaction;
the wastewater comes from a thymopentin production system;
the polyurethane bioactive carrier is a carbon fiber composite polyurethane bioactive carrier, and the specific preparation method comprises the following steps: mixing, foaming and curing the first component, the second component and the third component to obtain the carbon fiber composite polyurethane bioactive carrier; wherein the first component consists of polyether and a microorganism culture medium, the second component consists of toluene diisocyanate and carbon fiber, and the third component consists of silicone oil, water, trichlorofluoromethane, triethylene diamine and stannous octoate;
the immobilized microorganism carrier is prepared by impregnating a polyurethane foam carrier with a solution containing guar gum and a enrichment culture medium, and forming reversible gel with a boric acid crosslinking agent to achieve immobilization, wherein the specific preparation method comprises the following steps: mixing guar gum and deionized water at 80-95 ℃, cooling to 30-50 ℃, and adding a bacterium enrichment culture medium containing trace elements and efficient microorganisms to obtain a high-molecular mixed solution of the microorganisms to be immobilized; soaking the polyurethane foam carrier in the high molecular mixed solution of the microorganism to be immobilized for 12-36 hours to form reversible gel with a boric acid crosslinking agent, thereby obtaining the immobilized microorganism carrier.
2. The method of claim 1, wherein the step S1 is performed to adjust the pH value of the wastewater to 6.5-7.5.
3. The method of claim 2, wherein the step S1 is performed to adjust the pH of the wastewater to 6.9-7.1.
4. The method according to any one of claim 3, wherein the step S1 is to adjust the pH value of the wastewater to 7.0.
5. The method of claim 1, wherein the wastewater is from a thymopentin production system and has a CODcr concentration of 50000mg/L or less.
6. The method of claim 5, wherein the wastewater is from a thymopentin production system and has a CODcr concentration of 40000mg/L or less.
7. The method of claim 5, wherein the wastewater is from a thymopentin production system and has a CODcr concentration of less than 30000 mg/L.
8. The process according to any one of claims 1 to 4, characterized in that the first reaction is carried out at 20-40 ℃; the second reaction is carried out at 15-30 ℃; and/or the third reaction is carried out at 20-30 ℃.
9. The method of claim 8, wherein the first reaction is carried out for 48 to 96 hours; the reaction of the second reaction is carried out for 18 to 36 hours; and/or the reaction of the third reaction is carried out for 0.5 to 2 hours.
10. The method of claim 1, wherein the polyether of the first component is polyether 330.
11. The method of claim 1, wherein the carbon fibers of the second component are modified activated carbon fibers.
12. The method of any one of claims 1-4, wherein the oxidizing agent is a hydrogen peroxide solution.
13. The method of claim 12, wherein the hydrogen peroxide solution has a concentration of 0.01 wt% to 0.010 wt%.
14. The method of claim 12, wherein the hydrogen peroxide solution has a concentration of 0.3 wt% to 0.7 wt%.
15. The method of claim 12, wherein the hydrogen peroxide solution has a concentration of 0.5 wt%.
16. The method according to claim 1, wherein the polyether is 70.0 to 75.0 parts, the microbial culture medium is 1.0 to 2.0 parts, the toluene diisocyanate is 25 to 30 parts, the carbon fiber is 2.0 to 5.0 parts, the silicone oil is 0.3 to 0.5 part, the water is 0.5 to 1.5 parts, the monofluorotrichloromethane is 0.20 part, the triethylene diamine is 0.15 part, and the stannous octoate is 0.1 part by mass.
17. The process according to claim 1, characterized in that (i) guar gum is mixed with deionized water at 90 ℃.
18. The method as claimed in claim 1, wherein the polyurethane foam carrier is soaked in the polymer mixed solution of the microorganism to be immobilized for 20-28 hours.
19. The method of any one of claims 1 to 4, wherein the heterogeneous Fenton catalyst is prepared by impregnating a porous support with a solution of ammonium iron oxalate.
20. The method of claim 19, wherein the concentration of the ammonium iron oxalate solution is 50-150 g/L.
21. The method of claim 19, wherein the porous carrier is a peanut shell powder and/or an activated carbon powder.
22. The method according to any one of claims 1 to 4, wherein the step S2 is performed in an anaerobic reactor; said step S3 is performed in an aerobic reactor; and/or said step S4 is carried out in a heterogeneous catalytic oxidation reactor.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837361A (en) * 2006-04-12 2006-09-27 兰州大学 Preparation and application of bioactive carrier of carbon fiber composite polyurethane
CN102381812A (en) * 2011-09-30 2012-03-21 浙江清华长三角研究院 Advanced treatment method and device for nonbiodegradable organic wastewater by utilizing O3 catalytic oxidation
CN102557328A (en) * 2010-12-10 2012-07-11 新奥科技发展有限公司 Coal gasification wastewater processing method
CN103480331A (en) * 2013-09-10 2014-01-01 兰州大学 Biomass magnetic carbon material for degrading organic dye
CN103951039A (en) * 2014-04-04 2014-07-30 北京工业大学 Preparation and application of nitrifying bacteria immobilized bioactive filler based on polyurethane carrier
CN105601031A (en) * 2015-12-21 2016-05-25 山东省环保产业股份有限公司 Treatment method of waste water produced during production of intermediate compound 4AA
CN205295084U (en) * 2015-12-28 2016-06-08 四川希望环保工程技术有限公司 Processing system of wax printing waste water
CN106007221A (en) * 2016-07-12 2016-10-12 浙江环耀环境建设有限公司 Pharmaceutical wastewater treatment process

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1837361A (en) * 2006-04-12 2006-09-27 兰州大学 Preparation and application of bioactive carrier of carbon fiber composite polyurethane
CN102557328A (en) * 2010-12-10 2012-07-11 新奥科技发展有限公司 Coal gasification wastewater processing method
CN102381812A (en) * 2011-09-30 2012-03-21 浙江清华长三角研究院 Advanced treatment method and device for nonbiodegradable organic wastewater by utilizing O3 catalytic oxidation
CN103480331A (en) * 2013-09-10 2014-01-01 兰州大学 Biomass magnetic carbon material for degrading organic dye
CN103951039A (en) * 2014-04-04 2014-07-30 北京工业大学 Preparation and application of nitrifying bacteria immobilized bioactive filler based on polyurethane carrier
CN105601031A (en) * 2015-12-21 2016-05-25 山东省环保产业股份有限公司 Treatment method of waste water produced during production of intermediate compound 4AA
CN205295084U (en) * 2015-12-28 2016-06-08 四川希望环保工程技术有限公司 Processing system of wax printing waste water
CN106007221A (en) * 2016-07-12 2016-10-12 浙江环耀环境建设有限公司 Pharmaceutical wastewater treatment process

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