CN109534498B - Organic acid-containing SO4 for biochemical treatment2-Method for treating waste water - Google Patents
Organic acid-containing SO4 for biochemical treatment2-Method for treating waste water Download PDFInfo
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Abstract
The invention discloses a biochemical treatment method for organic acid-containing and SO-containing substances4 2‑The wastewater treatment method comprises the steps of adjusting the pH value of wastewater in a homogenizing tank, adding sodium carbonate in a water distribution tank, mixing domestic wastewater and saline wastewater, performing biochemical reaction by two-stage series anaerobic reactors, and controlling alkalinity, oxidation-reduction potential and SO4 2‑Salt and other technological parameters to realize biochemical treatment of organic acid, acid and SO4 2‑And (5) stable operation of the wastewater. The process for treating the wastewater disclosed by the invention is simple in process flow, high in treatment efficiency and low in investment cost, realizes the cyclic utilization of the wastewater, saves energy, reduces emission and is beneficial to the realization of sustainable development of enterprises.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for biochemically treating organic acid-containing and SO-containing wastewater4 2-A method for treating waste water.
Background
In industrial production, esterification is the reaction of an alcohol with a carboxylic acid or an oxygen-containing mineral acid to form an ester and water. The method is divided into three types of reactions, namely a reaction of carboxylic acid and alcohol, a reaction of inorganic oxyacid and alcohol and a reaction of inorganic strong acid and alcohol. The esterification of carboxylic acids with alcohols is reversible and generally very slow, so concentrated sulfuric acid is often used as a catalyst. The reaction of a polycarboxylic acid with an alcohol produces a variety of esters. A typical esterification reaction is a reaction of ethanol and acetic acid to produce ethyl acetate having an aromatic odor, which is a raw material for producing dyes and medicines. Wherein the high COD wastewater generated by esterification and the SO-containing wastewater generated by washing the kettle4 2-The waste water is treated biochemically in anaerobic and aerobic mode. But the acetic acid content of the esterification wastewater in industrial production is high and SO is generated in the kettle washing4 2-The effect of anaerobic biochemical treatment is influenced, and anaerobic sludge acidification often occurs, so that the operation of the biochemical device is unstable.
Disclosure of Invention
The invention aims to solve the problems and provide a method for biochemically treating organic acid-containing and SO-containing materials4 2-The wastewater treatment method ensures that the biochemical device can operate stably.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problem is as follows:
biochemical treatment of organic acid-containing and SO-containing substances4 2-A method of treating wastewater comprising the steps of:
step (1): conveying the esterification wastewater into a homogenizing pool, and adjusting the pH value of the wastewater to 6.5-7.5 in the homogenizing pool;
step (2): and (2) conveying the wastewater obtained by the treatment in the step (1) into a distribution pool, further adjusting COD (chemical oxygen demand) of the wastewater to 10000-12000mg/L, stabilizing the pH value to 6.5-7.5, controlling the water temperature to 47 +/-3 ℃, properly adding sodium carbonate to ensure the alkalinity of a subsequent anaerobic reactor, mixing a part of domestic wastewater to ensure the nutrition balance of C, N, P in the wastewater, and mixing a part of salt-containing wastewater to ensure that metal ions in the water are beneficial to the growth of subsequent anaerobic microorganisms. Because the anaerobic microorganisms have a narrow suitable range for acid-base environments and are sensitive to pH fluctuation, especially methanogens, the optimum pH range of which is 6.6-7.5, the pH is ensured to be 6.5-7.5.
And (3): pumping the wastewater obtained after the treatment in the step (2) into a first anaerobic reactor through a lifting pump, carrying out biochemical reaction in the first anaerobic reactor, connecting the first anaerobic reactor and a second anaerobic reactor in series, carrying out biochemical reaction on the wastewater in the first anaerobic reactor, then feeding the wastewater into the second anaerobic reactor, recovering anaerobic biochemical sludge by the second anaerobic reactor, further degrading the wastewater treated by the first anaerobic reactor, and periodically pressing anaerobic sludge recovered from the bottom of the second anaerobic reactor into an anaerobic sludge tank;
and (4): conveying the wastewater treated by the second anaerobic reactor into a mixing tank, and adding part of domestic wastewater and salt-containing wastewater into the mixing tank;
and (5): and the wastewater treated by the mixing tank is conveyed to an aerobic tank and is discharged after reaching the standard after passing through the aerobic tank.
Further, in the step (3), the temperature of the first anaerobic reactor tower is controlled to be 36 +/-2 ℃, the Volatile Fatty Acid (VFA) is controlled to be below 5mmol/L, the oxidation-reduction potential (ORP) is controlled to be-450 mv-600 mv, and the alkalinity is controlled to be 2500mg/L-4500 mg/L. When the first anaerobic device treats the esterification wastewater, the pH value of a microbial system of the anaerobic device is reduced by the instability of acetic acid (acetic acid) components in the wastewater and the formation of a large amount of Volatile Fatty Acid (VFA) in an anaerobic acidification stage, the anaerobic device can be acidified to seriously inhibit the growth of methane bacteria, and the acidification of anaerobic sludge of the first anaerobic device can be well controlled by adding sodium carbonate to ensure that the alkalinity in the first anaerobic device is between 2500mg/L and 4500 mg/L. In addition, the anaerobic microbial cells do not contain high-level cytochrome and cytochrome oxidase, the anaerobic microbial system needs to maintain a reducing environment, and the activity of the anaerobic microorganisms can be controlled by controlling the oxidation-reduction potential (ORP) to be-450 mv-600 mv.
Further, in the case where Oxidation Reduction Potential (ORP) and alkalinity in the first anaerobic reactor are controlled, SO in the wastewater of the first anaerobic reactor is controlled4 2-Less than or equal to 300mg/L, high-concentration sulfate ions are reduced into sulfur ions under the action of sulfate reducing bacteria, and the sulfur ions are easily converted into toxic H2S，H2S has toxicity to methanogens and inhibits the generation of methane. The salt content in the wastewater is controlled to be CL-When the ion content is less than or equal to 600mg/L, the first anaerobic reactor can treat the high COD esterification wastewater (the organic sludge load of the first anaerobic reactor is 2.0 kgCOD/(m)3D)) are stable.
Further, the method also comprises the step (31): collecting the anaerobic sludge in the anaerobic sludge tank in the step (3) into anaerobic sludge internal reflux of which the anaerobic sludge is periodically returned to the first anaerobic device through a sludge pump, wherein the purpose of the anaerobic sludge internal reflux is to contain acid and SO4 2-The wastewater is fully contacted and reacted with the anaerobic sludge.
Further, the method also comprises the step (32): the tower top three-phase separator of the first anaerobic device and the second anaerobic device recovers methane to be collected by the gas collecting box and then recycled or incinerated by the methane combustor.
The invention utilizes the control of alkalinity, oxidation-reduction potential and SO4 2-Salt and the like, and realizes the treatment of organic acid, acid and SO containing by a biochemical device4 2-In addition, the method has the advantages of simple process flow, high treatment efficiency and low investment cost, realizes the cyclic utilization of the wastewater, saves energy, reduces emission and is beneficial to the sustainable development of enterprises.
Description of the drawings:
FIG. 1: the invention relates to a biochemical treatment method for organic acid-containing and SO-containing substances4 2-A process flow diagram of a wastewater treatment process.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
As shown in fig. 1Biochemically treating organic acid-containing and SO-containing substances4 2-A method of treating wastewater comprising the steps of:
step (1): conveying esterification wastewater into a homogenizing tank, and adjusting the pH value of the wastewater to 6.5 in the homogenizing tank;
step (2): and (2) conveying the wastewater treated in the step (1) into a distribution tank to further adjust COD (chemical oxygen demand) of the wastewater to 10000mg/L, stabilizing the pH value to 6.5, controlling the water temperature to 47 ℃, properly adding sodium carbonate to ensure the alkalinity of a subsequent anaerobic reactor, mixing a part of domestic wastewater to ensure the nutrition balance of C, N, P in the wastewater, and mixing a part of salt-containing wastewater to ensure that metal ions in the water are beneficial to the growth of subsequent anaerobic microorganisms. Because the anaerobic microorganisms have a narrow suitable range for acid-base environments and are sensitive to pH value fluctuation, especially methanogens, the optimum pH value range of the methanogens is 6.6-7.5, and the pH value is ensured to be 6.5.
And (3): and (3) pumping the wastewater obtained after the treatment in the step (2) into a first anaerobic reactor through a lifting pump, carrying out biochemical reaction in the first anaerobic reactor, connecting the first anaerobic reactor and a second anaerobic reactor in series, carrying out biochemical reaction on the wastewater in the first anaerobic reactor, then feeding the wastewater into the second anaerobic reactor, recovering anaerobic biochemical sludge by the second anaerobic reactor, further degrading the wastewater treated by the first anaerobic reactor, and periodically pressing the anaerobic sludge recovered from the bottom of the second anaerobic reactor into an anaerobic sludge tank. In this step, the temperature of the first anaerobic reactor tower was controlled at 36 ℃, Volatile Fatty Acid (VFA) at 5mmol/L, oxidation-reduction potential (ORP) at-450 mv, and basicity at 2500 mg/L. When the first anaerobic device treats the esterification wastewater, the pH value of a microbial system of the anaerobic device is reduced together with the instability of acetic acid (acetic acid) components in the wastewater and a large amount of Volatile Fatty Acid (VFA) formed in an anaerobic acidification stage, the anaerobic device can be acidified to seriously inhibit the growth of methane bacteria, and the acidification of anaerobic sludge of the first anaerobic device can be well controlled by adding sodium carbonate to ensure that the alkalinity in the first anaerobic device is 2500 mg/L. In addition, the anaerobic microbial cells do not contain high-level cytochrome and cytochrome oxidase, the anaerobic microbial system needs to maintain a reducing environment, and the activity of anaerobic microorganisms can be controlled by controlling the oxidation-reduction potential (ORP) to-450 mv. Is controlled to be the firstControlling SO in wastewater of the first anaerobic reactor under the conditions of oxidation-reduction potential (ORP) and alkalinity in the anaerobic reactors4 2-300mg/L, high concentration sulfate ion is reduced into sulfur ion under the action of sulfate reducing bacteria, and the sulfur ion is easily converted into toxic H2S，H2S has toxicity to methanogens and inhibits the generation of methane. The salt content in the wastewater is controlled to be CL-The ion is 600mg/L, so that the first anaerobic reactor can treat the high COD esterified wastewater (the organic sludge load of the first anaerobic reactor is 2.0 kgCOD/(m)3D)) are stable. Anaerobic sludge is collected in the anaerobic sludge pool and is periodically returned to the anaerobic sludge internal reflux of the first anaerobic device through the sludge pump pressure, and the purpose of the anaerobic sludge internal reflux is to lead acid and SO to be contained4 2-The wastewater is fully contacted and reacted with the anaerobic sludge. The tower top three-phase separators of the first anaerobic device and the second anaerobic device recycle the methane which is collected by the gas collection box and then recycled.
And (4): conveying the wastewater treated by the second anaerobic reactor into a mixing tank, and adding part of domestic wastewater and salt-containing wastewater into the mixing tank;
and (5): and the wastewater treated by the mixing tank is conveyed to an aerobic tank and is discharged after reaching the standard after passing through the aerobic tank.
Example 2
Biochemical treatment of organic acid-containing and SO-containing substances4 2-A method of treating wastewater comprising the steps of:
step (1): conveying the esterification wastewater into a homogenizing pool, and adjusting the pH value of the wastewater to 7.5 in the homogenizing pool;
step (2): and (2) conveying the wastewater treated in the step (1) into a distribution tank to further adjust COD (chemical oxygen demand) of the wastewater to 12000mg/L, stabilizing the pH value to 7.5, controlling the water temperature to 50 ℃, properly adding sodium carbonate to ensure the alkalinity of a subsequent anaerobic reactor, mixing a part of domestic wastewater to ensure the nutrition balance of C, N, P in the wastewater, and mixing a part of salt-containing wastewater to ensure that metal ions in the water are favorable for the growth of subsequent anaerobic microorganisms. Because the anaerobic microorganisms have a narrow suitable range for acid-base environments and are sensitive to pH value fluctuation, especially methanogens, the optimum pH value range of the methanogens is 6.6-7.5, and therefore the pH value is ensured to be 7.5.
And (3): and (3) pumping the wastewater obtained after the treatment in the step (2) into a first anaerobic reactor through a lifting pump, carrying out biochemical reaction in the first anaerobic reactor, connecting the first anaerobic reactor and a second anaerobic reactor in series, carrying out biochemical reaction on the wastewater in the first anaerobic reactor, then feeding the wastewater into the second anaerobic reactor, recovering anaerobic biochemical sludge by the second anaerobic reactor, further degrading the wastewater treated by the first anaerobic reactor, and periodically pressing the anaerobic sludge recovered from the bottom of the second anaerobic reactor into an anaerobic sludge tank. In this step, the temperature of the first anaerobic reactor column was controlled at 38 ℃, Volatile Fatty Acid (VFA) 4mmol/L, oxidation-reduction potential (ORP) 600mv, and alkalinity 4500 mg/L. When the first anaerobic device treats the esterification wastewater, the pH value of a microbial system of the anaerobic device is reduced together with the instability of acetic acid (acetic acid) components in the wastewater and a large amount of Volatile Fatty Acid (VFA) formed in an anaerobic acidification stage, the anaerobic device can be acidified to seriously inhibit the growth of methane bacteria, and the acidification of anaerobic sludge of the first anaerobic device can be well controlled by adding sodium carbonate to ensure that the alkalinity in the first anaerobic device is 4500 mg/L. In addition, the anaerobic microbial cells do not contain high-level cytochrome and cytochrome oxidase, the anaerobic microbial system needs to maintain a reducing environment, and the activity of anaerobic microorganisms can be controlled by controlling the oxidation-reduction potential (ORP) to be-600 mv. Controlling SO in wastewater of the first anaerobic reactor under the condition that oxidation-reduction potential (ORP) and alkalinity in the first anaerobic reactor are controlled4 2-280mg/L, high concentration sulfate ion is reduced into sulfur ion under the action of sulfate reducing bacteria, and the sulfur ion is easily converted into toxic H2S，H2S has toxicity to methanogens and inhibits the generation of methane. The salt content in the wastewater is controlled to be CL-The ion is 550mg/L, so that the first anaerobic reactor can treat the high COD esterified wastewater (the organic sludge load of the first anaerobic reactor is 2.0 kgCOD/(m)3D)) are stable. Anaerobic sludge is collected in the anaerobic sludge pool and is periodically returned to the anaerobic sludge internal reflux of the first anaerobic device through the sludge pump pressure, and the purpose of the anaerobic sludge internal reflux is to lead acid and SO to be contained4 2-The wastewater is fully contacted and reacted with the anaerobic sludge. A first anaerobic reactor and a second anaerobic reactorThe top three-phase separator of the anaerobic device recovers the biogas and is recycled after being collected by the gas collection tank.
And (4): conveying the wastewater treated by the second anaerobic reactor into a mixing tank, and adding part of domestic wastewater and salt-containing wastewater into the mixing tank;
and (5): and the wastewater treated by the mixing tank is conveyed to an aerobic tank and is discharged after reaching the standard after passing through the aerobic tank.
Example 3
Biochemical treatment of organic acid-containing and SO-containing substances4 2-A method of treating wastewater comprising the steps of:
step (1): conveying the esterification wastewater into a homogenizing pool, and adjusting the pH value of the wastewater to 7 in the homogenizing pool;
step (2): and (2) conveying the wastewater obtained by the treatment in the step (1) into a distribution tank to further adjust COD (chemical oxygen demand) of the wastewater to 11000mg/L, stabilizing the pH value to 7, controlling the water temperature to be 44 ℃, properly adding sodium carbonate to ensure the alkalinity of the subsequent anaerobic device, mixing a part of the active wastewater to ensure the nutrition balance of C, N, P in the wastewater, and mixing a part of the salt-containing wastewater to ensure that metal ions in the water are beneficial to the growth of the subsequent anaerobic microorganisms. Because the anaerobic microorganisms have a narrow suitable range for acid-base environments and are sensitive to pH value fluctuation, especially methanogens, the optimum pH value range of the methanogens is 6.6-7.5, and the pH value is ensured to be 7.
And (3): and (3) pumping the wastewater obtained after the treatment in the step (2) into a first anaerobic reactor through a lifting pump, carrying out biochemical reaction in the first anaerobic reactor, connecting the first anaerobic reactor and a second anaerobic reactor in series, carrying out biochemical reaction on the wastewater in the first anaerobic reactor, then feeding the wastewater into the second anaerobic reactor, recovering anaerobic biochemical sludge by the second anaerobic reactor, further degrading the wastewater treated by the first anaerobic reactor, and periodically pressing the anaerobic sludge recovered from the bottom of the second anaerobic reactor into an anaerobic sludge tank. In this step, the temperature of the first anaerobic reactor tower was controlled at 34 ℃, Volatile Fatty Acid (VFA) at 3mmol/L, oxidation-reduction potential (ORP) at-500 mv, and alkalinity at 3000 mg/L. When the first anaerobic reactor is used for treating the esterification wastewater, the acetic acid (acetic acid) component in the wastewater is unstable and has anaerobic acidification stageA large amount of Volatile Fatty Acid (VFA) is formed in the section, the PH value of a microbial system of the anaerobic device is reduced, the anaerobic device can be acidified to seriously inhibit the growth of methane bacteria, and the acidification of anaerobic sludge of the first anaerobic device can be well controlled by adding sodium carbonate to ensure that the alkalinity in the first anaerobic device is 3000 mg/L. In addition, the anaerobic microbial cells do not contain high-level cytochrome and cytochrome oxidase, the anaerobic microbial system needs to maintain a reducing environment, and the activity of anaerobic microorganisms can be controlled by controlling the oxidation-reduction potential (ORP) to be-500 mv. Controlling SO in wastewater of the first anaerobic reactor under the condition that oxidation-reduction potential (ORP) and alkalinity in the first anaerobic reactor are controlled4 2-240mg/L, high concentration sulfate ion is reduced into sulfur ion under the action of sulfate reducing bacteria, and the sulfur ion is easily converted into toxic H2S，H2S has toxicity to methanogens and inhibits the generation of methane. The salt content in the wastewater is controlled to be CL-The ion is 500mg/L, so that the first anaerobic reactor can treat the high COD esterified wastewater (the organic sludge load of the first anaerobic reactor is 2.0 kgCOD/(m)3D)) are stable. Anaerobic sludge is collected in the anaerobic sludge pool and is periodically returned to the anaerobic sludge internal reflux of the first anaerobic device through the sludge pump pressure, and the purpose of the anaerobic sludge internal reflux is to lead acid and SO to be contained4 2-The wastewater is fully contacted and reacted with the anaerobic sludge. The tower top three-phase separator of the first anaerobic device and the second anaerobic device recovers biogas, the biogas is collected by the gas collecting box and is burnt by the biogas burner.
And (4): conveying the wastewater treated by the second anaerobic reactor into a mixing tank, and adding part of domestic wastewater and salt-containing wastewater into the mixing tank;
and (5): and the wastewater treated by the mixing tank is conveyed to an aerobic tank and is discharged after reaching the standard after passing through the aerobic tank.
By controlling the alkalinity, oxidation-reduction potential, SO, the treatment method of the above example4 2-Salt and the like, realizes the treatment of organic acid, acid and SO containing by a biochemical device4 2-The wastewater can stably run, in addition, the process flow of the embodiment is simple, the treatment efficiency is high, the investment cost is low, and the wastewater treatment method realizes the wastewater treatmentThe recycling, energy conservation and emission reduction of the method are beneficial to the sustainable development of enterprises.
Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (4)
1. Biochemical treatment of organic acid-containing and SO-containing substances4 2-A method for treating wastewater, comprising the steps of:
step (1): conveying the esterification wastewater into a homogenizing tank, and adjusting the p H value of the wastewater to 6.5-7.5 in the homogenizing tank;
step (2): conveying the wastewater obtained by the treatment in the step (1) into a distribution pool to further adjust the COD of the wastewater to 10000-12000mg/L, wherein the p H value is stabilized at 6.5-7.5, the water temperature is controlled at 47 +/-3 ℃, sodium carbonate is properly added to ensure the alkalinity in a subsequent anaerobic reactor, a part of domestic wastewater is mixed to ensure the nutrition balance of C, N, P in the wastewater, and a part of salt-containing wastewater is mixed to ensure that metal ions in the wastewater are beneficial to the growth of subsequent anaerobic microorganisms;
and (3): pumping the wastewater obtained after the treatment in the step (2) into a first anaerobic reactor through a lifting pump, carrying out biochemical reaction in the first anaerobic reactor, connecting the first anaerobic reactor and a second anaerobic reactor in series, carrying out biochemical reaction on the wastewater in the first anaerobic reactor, then feeding the wastewater into the second anaerobic reactor, recovering anaerobic biochemical sludge by the second anaerobic reactor, further degrading the wastewater treated by the first anaerobic reactor, and periodically pressing anaerobic sludge recovered from the bottom of the second anaerobic reactor into an anaerobic sludge tank; wherein the temperature of the first anaerobic reactor tower is controlled to be 36 +/-2 ℃, the Volatile Fatty Acid (VFA) is below 5mmol/L, the oxidation-reduction potential (ORP) is between-450 mv and 600mv, and the alkalinity is between 2500mg/L and 4500 mg/L;
and (4): conveying the wastewater treated by the second anaerobic reactor into a mixing tank, and adding part of domestic wastewater and salt-containing wastewater into the mixing tank;
and (5): and the wastewater treated by the mixing tank is conveyed to an aerobic tank and is discharged after reaching the standard after passing through the aerobic tank.
2. The method of claim 1 for biochemically treating an organic acid-containing SO-containing material4 2-A method for treating wastewater, characterized in that SO in the first anaerobic reactor4 2-≦300mg/L。
3. The method of claim 1 for biochemically treating an organic acid-containing SO-containing material4 2-The method for treating wastewater is characterized by further comprising the step (31): collecting the anaerobic sludge in the anaerobic sludge tank in the step (3) into anaerobic sludge internal reflux of which the anaerobic sludge is periodically returned to the first anaerobic device through a sludge pump, wherein the purpose of the anaerobic sludge internal reflux is to contain acid and SO4 2-The wastewater is fully contacted and reacted with the anaerobic sludge.
4. The method of claim 1 for biochemically treating an organic acid-containing SO-containing material4 2-A method for treating wastewater, characterized by further comprising the step (32): the tower top three-phase separator of the first anaerobic device and the second anaerobic device recovers methane to be collected by the gas collecting box and then recycled or incinerated by the methane combustor.
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