CN106554127B - Treatment method of rubber wastewater - Google Patents
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- CN106554127B CN106554127B CN201510640984.4A CN201510640984A CN106554127B CN 106554127 B CN106554127 B CN 106554127B CN 201510640984 A CN201510640984 A CN 201510640984A CN 106554127 B CN106554127 B CN 106554127B
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Abstract
The invention belongs to the field of chemical engineering environmental protection, and particularly relates to a treatment method of rubber wastewater. Mixing rubber wastewater and ethylene high-salt sewage, wherein the treatment process comprises the following steps: in thatHydrolyzing and acidifying under the action of facultative bacteria, aerating, contacting and oxidizing with a biological film attached to the semi-soft filler, and finally treating by an aeration biological filter. The invention makes full use of the nutrient substances such as nitrogen, phosphorus and the like in the high-salinity sewage, thereby greatly saving the operation cost; the treatment process adopts air aeration, thereby not only saving the operating cost, but also being beneficial to the establishment of nitrification and thoroughly removing ammonia nitrogen in the wastewater; rubber wastewater COD 400-500 mg/L, NH3The concentration of N is 50-55 mg/L, the COD of the effluent after the treatment of the invention is 34.2-48.4 mg/L, the effluent stably reaches the discharge standard of less than 50mg/L, and the effluent simultaneously reaches NH3-N < 5 mg/L.
Description
Technical Field
The invention belongs to the field of chemical engineering environmental protection, and particularly relates to a treatment method of rubber wastewater.
Background
The rubber wastewater contains a large amount of organic matters which are difficult to biodegrade, such as benzene series, polymerization inhibitor, initiator, diffusant, emulsion coagulant and the like, has complex water quality and poor biodegradability, and is wastewater which is difficult to treat. At present, the rubber wastewater treatment methods mainly comprise a coagulating sedimentation method, a coagulating air floatation method, an electrochemical method, a biological method, an advanced oxidation method for advanced treatment, an adsorption method, a reverse osmosis method and the like. The processing method adopted is different because the processing requirements and targets are different. But the COD concentration in the rubber wastewater is difficult to be reduced to below 50mg/L by a single treatment method and the existing treatment process. A certain rubber factory adopts pretreatment, biochemistry and advanced oxidation processes to independently treat 400-500 mg/L COD and NH3The rubber wastewater with the N of 40-60 mg/L, the COD of the biochemical treatment effluent of 80-100 mg/L and the COD of the advanced oxidation treatment effluent of about 70mg/L cannot reach the index of less than or equal to 50mg/L, and the increasingly strict standard discharge requirements of sewage are difficult to meet. Therefore, the exploration of an efficient, practical and economic treatment method becomes the key for reaching the standard of rubber wastewater treatment.
Patent CN102010094B discloses a method for treating high-calcium and high-salt industrial wastewater, which adopts the following technical route: pretreatment, hydrolytic acidification, pure oxygen aeration, contact oxidation and aeration biomembrane when the salinity of the wastewater to be treated is 3.0 percent (by CaCl)2Calculated) at COD 1250mg/L, NH3Under the condition of-N41.3 mg/L, the quality of the treated effluent can reach COD<60mg/L，NH3-N<5mg/L technical index. However, the pure oxygen aeration unit can not establish normal ammonia nitrogen nitrification and denitrification, and 5-10mg/L of nitrobacteria must be added in the contact oxidation unit in an impact manner to achieve the purpose of meeting the standard of the treated ammonia nitrogen.
Patent CN103723878B discloses a styrene butadiene rubber industrial wastewater advanced treatment method, which adopts the following processes: pretreatment, sludge adsorption, aerobic biochemical treatment, flocculation filtration, advanced oxidation and solid-liquid separation. COD of the discharged wastewater after treatment is less than or equal to 40mg/L, NH3-N is less than or equal to 5 mg/L. The invention provides the advanced treatment method which is stable in operation, safe and reliable and high in pollutant removal rate, and can realize the stable standard discharge of the discharged industrial wastewater of the styrene butadiene rubber production device. But flocculation filtration and advanced oxidation generate a large amount of sediments, which increases the cost of the medicament and the cost of sludge treatment.
Patent CN102134144B discloses a styrene butadiene rubber sewage treatment process, the main process of the process is air flotation, adsorption, hydrolysis, CBR (carrier fluidized bed) and filtration, and finally, the COD of the effluent after filtration is 45-60mg/l, which meets the first-level discharge requirement of petrochemical industry in the integrated sewage discharge standard (GB 102134144B-1996). But can not meet the standard requirement that COD is less than or equal to 50mg/L stably.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for treating rubber wastewater, wherein the COD of effluent treated by the method stably reaches the discharge standard of less than 50 mg/L; organic matter and ammonia nitrogen in the rubber wastewater reach NH3-N < 5 mg/L.
The rubber wastewater treatment method provided by the invention is used for mixing and treating rubber wastewater and ethylene high-salt wastewater, wherein the ethylene high-salt wastewater is wastewater generated in an ethylene production process.
Wherein: the ethylene high-salinity sewage is sewage generated in the ethylene production process and is a known substance in the field, preferably, the calcium ion content in the ethylene high-salinity sewage is 2700-5300 mg/L, and the chloride ion content is 4000-8000 mg/L.
Wherein:
the volume ratio of the rubber wastewater to the ethylene high-salt wastewater is 1: 4-16.
Mixing rubber wastewater and ethylene high-salt sewage, wherein the treatment process comprises the following steps: hydrolyzing and acidifying under the action of facultative bacteria, aerating, contacting and oxidizing with a biological film attached to the semi-soft filler, and treating by an aeration biological filter.
The treatment method of the rubber wastewater comprises the following steps:
(1) mixing rubber sewage and high-salinity sewage, stirring the mixture under liquid in a hydrolysis acidification tank to realize sludge-water mixing, degrading organic pollutants into small molecular substances under the action of facultative bacteria, separating the sludge from the effluent, refluxing the precipitated sludge to the hydrolysis acidification tank, and allowing the supernatant to enter an activated sludge air aeration tank;
(2) the activated sludge air aeration tank is used for air aeration, the supernatant obtained in the step (1) and the precipitated sludge refluxed in the step are fully mixed and then treated, the sludge and the water are separated after the treatment is finished, the precipitated sludge partially refluxes to the front end of the activated sludge air aeration tank, and the effluent enters a contact oxidation tank;
(3) the effluent water in the step (2) enters a contact oxidation tank to further degrade organic pollutants, semi-soft filler is suspended in the contact oxidation tank, a biological membrane is attached to the semi-soft filler, and the effluent water enters an aeration biological filter after solid-liquid separation after the treatment is finished;
(4) and (4) further degrading organic matters which are difficult to degrade in the sewage in the biological aerated filter, removing suspended matters, and finishing the treatment.
Wherein:
the activated sludge air aeration tank is preferably aerated by using a perforated pipe.
The hydraulic retention time of the hydrolysis acidification tank is 11.3h, the dissolved oxygen is less than 0.5mg/L, and the sludge reflux ratio is 50-150%, preferably 80-120%; the sludge concentration is 1.5-4 mg/L, preferably 2-3 mg/L.
The hydraulic retention time of the activated sludge air aeration tank is 16 hours, the dissolved oxygen is 2-15 mg/L, preferably 3-6 mg/L, the sludge reflux ratio is 50-150%, preferably 80-120%, and the sludge concentration is 2-8 mg/L, preferably 3-5 mg/L.
The hydraulic retention time of the contact oxidation pond is 7.8h, and the dissolved oxygen is 3-10 mg/L, preferably 5-8 mg/L. The semi-flexible filler and the biological film are all conventional commercial products in the field.
The hydraulic retention time of the biological aerated filter is 2.0h, and the dissolved oxygen is 2-8 mg/L, preferably 3-6 mg/L. The aeration biological filter is a conventional aeration biological filter on the market in the field.
As a preferable scheme, the method for treating the rubber wastewater comprises the following steps:
(1) mixing rubber sewage and high-salinity sewage in proportion, pumping into a hydrolysis acidification tank, stirring under liquid to realize sludge-water mixing in the hydrolysis acidification tank, degrading organic pollutants into small molecular substances under the action of facultative bacteria, improving the biodegradability of sewage, separating sludge from water, refluxing precipitated sludge to the front end of the hydrolysis acidification tank, and automatically flowing supernatant into an activated sludge air aeration tank;
(2) the activated sludge air aeration tank adopts perforated pipes for aeration, sludge and water are fully mixed, meanwhile, enough dissolved oxygen is provided for microorganisms, most organic matters in water are removed in the unit, a polymer is fully contacted with the sludge for coagulation and sedimentation, part of precipitated sludge flows back to the front end of the activated sludge air aeration tank, part of precipitated sludge is used as residual sludge and is sent to a sludge concentration tank, and effluent enters a contact oxidation tank after sludge and water are separated;
(3) the contact oxidation pond is suspended with semi-soft stuffing, biomembrane is adhered to the semi-soft stuffing, organic pollutant is further degraded depending on rich biological phase in the biomembrane, and effluent is pumped into a biological aerated filter (BAF pond) after solid-liquid separation.
(4) The aeration biological filter has the functions of biological adsorption, biological oxidation and filtration, organic matters which are difficult to degrade in sewage are further degraded through the co-metabolism under the action of the co-matrix, suspended matters are removed, and then an excellent treatment effect is obtained.
The invention has the following advantages:
(1) the invention is different from other independent treatment modes of rubber wastewater, and adopts the mixed treatment of the rubber wastewater and the ethylene high-salinity sewage. Rubber wastewater COD 400-500 mg/L, NH3-N 50～55mg/L, COD of the mixed ethylene high-salt sewage is 210-260 mg/L, and NH is3N is 10-20 mg/L, COD of the effluent after treatment by the method is 34.2-48.4 mg/L, and the COD of the effluent stably reaches the discharge standard of less than 50 mg/L; organic matters and ammonia nitrogen in the rubber wastewater are removed after the treatment of the invention to achieve NH3-N < 5 mg/L.
(2) According to the invention, the rubber sewage and the high-salinity sewage are mixed for treatment, so that the nutrient substances such as nitrogen, phosphorus and the like in the high-salinity sewage can be fully utilized, no additional nutrient agent is required to be added in the biochemical treatment process, and the operation cost can be greatly saved; the treatment process changes pure oxygen aeration of a high-salinity sewage treatment system into air aeration, so that the operation cost is saved, the establishment of nitrification is facilitated, and ammonia nitrogen in the wastewater is thoroughly removed; after the two are mixed, the original rubber wastewater single treatment facility can stop running, thus obviously saving the maintenance and running cost.
(3) The activated sludge air aeration tank adopts air aeration, the system establishes normal nitration reaction, the deamination and denitrification efficiency is high, the embarrassment that the nitration reaction is difficult to establish due to over oxidation of pure oxygen aeration is avoided, and efficient nitrobacteria do not need to be added.
(4) The invention has mild operation condition, does not relate to high temperature and high pressure, utilizes the existing sewage treatment facility and does not need to add new treatment equipment; after the rubber wastewater and the ethylene high-salt wastewater are mixed and treated, the original rubber wastewater treatment facility can stop running, land is saved, and meanwhile, the maintenance and operation cost can be saved by more than 600 ten thousand yuan per year.
Drawings
FIG. 1 is a process flow diagram of the method for treating rubber wastewater according to the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The mixing volume ratio of the rubber wastewater and the high-salinity sewage in the inlet water is 1:16, the COD of the rubber wastewater is 210-240 mg/L, and NH is added3N is 8.0-12.0 mg/L.
The following treatment methods are adopted for treatment:
(1) mixing rubber sewage and ethylene high-salt sewage (the ethylene high-salt sewage is sewage generated in the ethylene production process) in proportion, pumping the mixture into a hydrolysis acidification tank, stirring the mixture under liquid to realize mud-water mixing in the hydrolysis acidification tank, degrading organic pollutants into small molecular substances under the action of facultative bacteria, improving the biodegradability of the sewage, ensuring that the hydraulic retention time of the hydrolysis acidification tank is 11.3 hours, the dissolved oxygen is less than 0.5mg/L, the sludge reflux ratio is 100 percent, and the sludge concentration is 3 mg/L; after the effluent is subjected to mud-water separation, the precipitated sludge flows back to the front end of the hydrolysis acidification tank, and the supernatant automatically flows into an activated sludge air aeration tank;
(2) the activated sludge air aeration tank adopts perforated pipes for aeration, sludge and water are fully mixed and simultaneously sufficient dissolved oxygen is provided for microorganisms, the hydraulic retention time of the activated sludge air aeration tank is 16h, the dissolved oxygen is 6mg/L, the sludge reflux ratio is 100%, the sludge concentration is 4mg/L, most organic matters in water are removed in the unit, a polymer is fully contacted with the sludge for coagulation and sedimentation, part of precipitated sludge flows back to the front end of the activated sludge air aeration tank, part of precipitated sludge is used as residual sludge and is sent to the sludge concentration tank, and effluent enters the contact oxidation tank after sludge and water are separated.
(3) And (3) allowing the effluent water obtained in the step (2) to enter a contact oxidation tank to further degrade organic pollutants, suspending a semi-soft filler in the contact oxidation tank, attaching a biological membrane to the semi-soft filler, further degrading the organic pollutants by depending on rich biological phases in the biological membrane, allowing the water power of the contact oxidation tank to stay for 7.8 hours and dissolved oxygen to be 7mg/L, and pumping the effluent water into a biological aerated filter (BAF tank) through a pump after solid-liquid separation.
(4) And (4) further degrading organic matters which are difficult to degrade in the sewage in the biological aerated filter by using the effluent obtained in the step (3), wherein the hydraulic retention time of the biological aerated filter is 2.0h, the dissolved oxygen is 6mg/L, removing suspended matters, and finishing the treatment.
The COD of the effluent obtained after treatment is 34.2-47.2 mg/L, and NH3N is 0 to 3.4 mg/L.
Example 2
The mixing volume ratio of the rubber wastewater and the high-salinity sewage in the inlet water is 1:8, and the COD of the rubber wastewater is 220～250mg/L，NH3the-N is 9.8-15.6 mg/L.
The following treatment methods are adopted for treatment:
(1) mixing rubber sewage and ethylene high-salt sewage (the ethylene high-salt sewage is sewage generated in the ethylene production process, calcium ions are 3000mg/L, and chloride ions are 4000mg/L) in proportion, pumping the mixture into a hydrolysis acidification tank, and mixing the sludge and water in the hydrolysis acidification tank by adopting submerged stirring, wherein organic pollutants are degraded into small molecular substances under the action of facultative bacteria, so that the biodegradability of the sewage is improved, the hydraulic retention time of the hydrolysis acidification tank is 11.3h, the dissolved oxygen is less than 0.5mg/L, the sludge reflux ratio is 80%, and the sludge concentration is 4 mg/L; after the effluent is subjected to mud-water separation, the precipitated sludge flows back to the front end of the hydrolysis acidification tank, and the supernatant automatically flows into an activated sludge air aeration tank;
(2) the activated sludge air aeration tank adopts perforated pipes for aeration, sludge and water are fully mixed and simultaneously sufficient dissolved oxygen is provided for microorganisms, the hydraulic retention time of the activated sludge air aeration tank is 16h, the dissolved oxygen is 10mg/L, the sludge reflux ratio is 150%, the sludge concentration is 2mg/L, most organic matters in water are removed in the unit, a polymer is fully contacted with the sludge for coagulation and sedimentation, part of precipitated sludge flows back to the front end of the activated sludge air aeration tank, part of precipitated sludge is used as residual sludge and is sent to a sludge concentration tank, and effluent enters a contact oxidation tank after sludge and water are separated.
(3) And (3) allowing the effluent water obtained in the step (2) to enter a contact oxidation tank to further degrade organic pollutants, suspending a semi-soft filler in the contact oxidation tank, attaching a biological membrane to the semi-soft filler, further degrading the organic pollutants by depending on rich biological phases in the biological membrane, allowing the water power of the contact oxidation tank to stay for 7.8h and dissolved oxygen to be 10mg/L, and pumping the effluent water into a biological aerated filter (BAF tank) through a pump after solid-liquid separation.
(4) And (4) further degrading organic matters which are difficult to degrade in the sewage in the biological aerated filter by using the effluent obtained in the step (3), wherein the hydraulic retention time of the biological aerated filter is 2.0h, the dissolved oxygen is 8mg/L, removing suspended matters, and finishing the treatment.
COD of the effluent obtained after treatment is 35.3-47.6 mg/L3N is 0-4.2 mg/L.
Example 3
The mixing volume ratio of the rubber wastewater and the high-salinity sewage in the inlet water is 1:4, the COD of the rubber wastewater is 220-250 mg/L, and NH is added3the-N is 9.8-15.6 mg/L.
The following treatment methods are adopted for treatment:
(1) mixing rubber sewage and ethylene high-salt sewage (the ethylene high-salt sewage is sewage generated in the ethylene production process, calcium ions are 5300mg/L, chloride ions are 8000mg/L) in proportion, pumping into a hydrolysis acidification pool, and stirring under liquid to realize sludge-water mixing in the hydrolysis acidification pool, wherein organic pollutants are degraded into small molecular substances under the action of facultative bacteria, so that the biodegradability of the sewage is improved, the hydraulic retention time of the hydrolysis acidification pool is 11.3h, the dissolved oxygen is less than 0.5mg/L, the sludge reflux ratio is 50%, and the sludge concentration is 4 mg/L; after the effluent is subjected to mud-water separation, the precipitated sludge flows back to the front end of the hydrolysis acidification tank, and the supernatant automatically flows into an activated sludge air aeration tank;
(2) the activated sludge air aeration tank adopts perforated pipes for aeration, sludge and water are fully mixed and simultaneously sufficient dissolved oxygen is provided for microorganisms, the hydraulic retention time of the activated sludge air aeration tank is 16h, the dissolved oxygen is 2mg/L, the sludge reflux ratio is 50%, the sludge concentration is 8mg/L, most organic matters in water are removed in the unit, a polymer is fully contacted with the sludge for coagulation and sedimentation, part of precipitated sludge flows back to the front end of the activated sludge air aeration tank, part of precipitated sludge is used as residual sludge and is sent to the sludge concentration tank, and effluent enters the contact oxidation tank after sludge and water are separated.
(3) And (3) allowing the effluent water obtained in the step (2) to enter a contact oxidation tank to further degrade organic pollutants, suspending a semi-soft filler in the contact oxidation tank, attaching a biological membrane to the semi-soft filler, further degrading the organic pollutants by depending on rich biological phases in the biological membrane, allowing the water power of the contact oxidation tank to stay for 7.8 hours and dissolved oxygen to be 3mg/L, and pumping the effluent water into a biological aerated filter (BAF tank) through a pump after solid-liquid separation.
(4) And (4) further degrading organic matters which are difficult to degrade in the sewage in the biological aerated filter by using the effluent obtained in the step (3), wherein the hydraulic retention time of the biological aerated filter is 2.0h, the dissolved oxygen is 5mg/L, removing suspended matters, and finishing the treatment.
The COD of the effluent obtained after treatment is 37.1-48.4 mg/L, and NH3N is 0-4.5 mg/L.
Claims (8)
1. A method for treating rubber wastewater is characterized by comprising the following steps: mixing rubber wastewater and ethylene high-salt sewage for treatment, wherein the ethylene high-salt sewage is sewage generated in the ethylene production process;
the method specifically comprises the following steps:
(1) mixing rubber wastewater and ethylene high-salt sewage, stirring the mixture under liquid in a hydrolysis acidification tank to realize sludge-water mixing, degrading organic pollutants into small molecular substances under the action of facultative bacteria, separating the sludge from the effluent, refluxing the precipitated sludge to the hydrolysis acidification tank, and allowing the supernatant to enter an activated sludge air aeration tank;
(2) the activated sludge air aeration tank is used for air aeration, the supernatant obtained in the step (1) and the precipitated sludge refluxed in the step are fully mixed and then treated, the sludge and the water are separated after the treatment is finished, the precipitated sludge partially refluxes to the front end of the activated sludge air aeration tank, and the effluent enters a contact oxidation tank;
(3) the effluent water in the step (2) enters a contact oxidation tank to further degrade organic pollutants, semi-soft filler is suspended in the contact oxidation tank, a biological membrane is attached to the semi-soft filler, and the effluent water enters an aeration biological filter after solid-liquid separation after the treatment is finished;
(4) and (4) further degrading organic matters which are difficult to degrade in the sewage in the biological aerated filter, removing suspended matters, and finishing the treatment.
2. The method for treating rubber waste water according to claim 1, wherein: calcium ions in the ethylene high-salinity sewage are 2700-5300 mg/L, and chloride ions are 4000-8000 mg/L.
3. The method for treating rubber waste water according to claim 1, wherein: the volume ratio of the rubber wastewater to the ethylene high-salt wastewater is 1: 4-16.
4. The method for treating rubber waste water according to claim 1, wherein: the activated sludge air aeration tank adopts perforated pipes for aeration.
5. The method for treating rubber waste water according to claim 1, wherein: the hydraulic retention time of the hydrolysis acidification tank is 11.3h, the dissolved oxygen is less than 0.5mg/L, the sludge reflux ratio is 50-150%, and the sludge concentration is 1.5-4 mg/L.
6. The method for treating rubber waste water according to claim 1, wherein: the hydraulic retention time of the activated sludge air aeration tank is 16 hours, the dissolved oxygen is 2-15 mg/L, the sludge reflux ratio is 50-150%, and the sludge concentration is 2-8 mg/L.
7. The method for treating rubber waste water according to claim 1, wherein: the hydraulic retention time of the contact oxidation pond is 7.8h, and the dissolved oxygen is 3-10 mg/L.
8. The method for treating rubber waste water according to claim 1, wherein: the hydraulic retention time of the biological aerated filter is 2.0h, and the dissolved oxygen is 2-8 mg/L.
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