CN111453931A - Treatment process of rubber accelerator wastewater - Google Patents
Treatment process of rubber accelerator wastewater Download PDFInfo
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- CN111453931A CN111453931A CN202010347782.1A CN202010347782A CN111453931A CN 111453931 A CN111453931 A CN 111453931A CN 202010347782 A CN202010347782 A CN 202010347782A CN 111453931 A CN111453931 A CN 111453931A
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- 238000000034 method Methods 0.000 title claims abstract description 44
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- 239000010802 sludge Substances 0.000 claims abstract description 26
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- 238000005188 flotation Methods 0.000 claims abstract description 13
- 230000005484 gravity Effects 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 230000020477 pH reduction Effects 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000007667 floating Methods 0.000 claims description 5
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- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000008394 flocculating agent Substances 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000008267 milk Substances 0.000 claims description 3
- 210000004080 milk Anatomy 0.000 claims description 3
- 235000013336 milk Nutrition 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
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- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 244000005700 microbiome Species 0.000 description 4
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
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- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
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- 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
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
- C02F3/305—Nitrification and denitrification treatment characterised by the denitrification
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Abstract
The invention belongs to the field of chemical wastewater treatment, and particularly relates to a treatment process of rubber accelerator wastewater, which utilizes the characteristic that BTs substances are insoluble in water, adopts a pretreatment process of 'gravity sedimentation, neutralization sedimentation and air flotation' to achieve 50% of COD removal rate, and has stronger hydrophobicity and higher biosorptivity because the n-octanol-water distribution coefficient (Kow) of BTs substances is more than 4, so that the process adopts an 'activated sludge adsorption and precipitation method' to further remove BTs substances in the wastewater, has about 20% -40% of COD removal rate, and carries out post-treatment through 'hydrolytic acidification and two-stage A/O', and can ensure that the wastewater reaches the standard and is discharged.
Description
Technical Field
The invention belongs to the field of chemical wastewater treatment, and particularly relates to a treatment process of rubber accelerator wastewater.
Background
The rubber accelerator is an indispensable auxiliary agent in the rubber processing process, and plays an important role in improving the performance of rubber materials, improving the processing efficiency and the like. In recent years, the rubber accelerator industry is developed quickly and is increased rapidly, at present, domestic rubber accelerator manufacturers are nearly hundreds of families, but most rubber accelerator manufacturers are small in scale, backward in process technology and serious in environmental pollution, and waste water of rubber accelerator products is complex in organic matter components, more in toxic and harmful substances, poor in biodegradability and large in salt content, and is waste water which is accepted by the world and is difficult to treat.
The main pollutants of the rubber accelerator wastewater are benzothiazole organic matters (BTs), benzothiazole compounds (BTs) refer to Benzothiazole (BT) and derivatives thereof, and are polycyclic substances with benzene rings and N, S heterocycles in the structure, methods such as evaporative desalination, anaerobic/aerobic treatment (A/O treatment) or resin adsorption and the like are generally adopted for treating the rubber accelerator wastewater in the prior art, but the requirements on the quality of inlet water are strict, the content of BTs in discharged wastewater is high, and the environment is polluted.
Disclosure of Invention
In order to overcome the problems, the invention provides a rubber accelerator wastewater treatment process, which utilizes the characteristic that BTs substances are insoluble in water, adopts a pretreatment process of 'gravity sedimentation, neutralization sedimentation and air flotation' to achieve 50% of COD removal rate, and simultaneously has stronger hydrophobicity and higher biological adsorption because the n-octanol-water distribution coefficient (Kow) of BTs substances is more than 4, so that the process adopts an 'activated sludge adsorption sedimentation method' to further remove BTs substances in wastewater, about 20% -40% of COD removal rate, and then carries out post-treatment through 'hydrolytic acidification and two-stage A/O', and can discharge the wastewater after reaching the standard.
The invention is realized by the following technical scheme:
a treatment process of rubber accelerator wastewater comprises the following steps:
s1: carrying out gravity settling on the rubber accelerator wastewater to remove larger particles in the wastewater;
s2: adding lime milk into the wastewater treated by the S1 for neutralization and precipitation, neutralizing charges in the wastewater, and further settling;
s3: introducing the wastewater treated by the S2 into an air flotation device, adding a flotation agent for air flotation treatment, wherein a flocculating agent is a macromolecular organic matter in the added flotation agent, most of BTs substances in the wastewater can be removed after the air flotation treatment, the COD removal rate is 50%, the macromolecular organic matter can be selected from cationic polyacrylamide with the ionicity of 60%, and the effect is optimal;
s4: filtering floating slag after air floatation in S3, and performing activated sludge adsorption treatment on the rest wastewater, wherein the BTs substances have a n-octanol-water distribution coefficient (Kow) larger than 4, and have strong hydrophobicity and high biological adsorption, so that the process further removes BTs substances in the wastewater by adopting an activated sludge adsorption precipitation method, the flocculent structure of the activated sludge has good adsorption performance, the designed adsorption retention time is 20-60min, the sludge age is only 0.3-0.5d, and the COD removal rate can reach about 20-40%;
after the wastewater is subjected to front-end treatment, most BTs substances are removed, the COD is reduced to 10000 mg/L, and biochemical treatment can be carried out;
s5: performing hydrolytic acidification and A/O treatment on the wastewater treated by S4, adopting a two-stage A/O process, adopting a biomembrane treatment process for an O tank of the first-stage A/O, and ensuring denitrification to be performed by additionally adding a carbon source into the A tank of the second-stage A/O, so as to ensure that the total nitrogen of the effluent stably reaches the standard, wherein the carbon source is usually methanol or sodium acetate, the cost of the methanol is lower, but explosion-proof treatment is required during use;
s6: and (3) oxidizing the wastewater treated by the S5, and then discharging, wherein the process of ozone oxidation and activated carbon adsorption is usually adopted, and the treated wastewater can reach the standard for discharge.
The invention has the advantages that: (1) the discharged wastewater in the production of the rubber accelerator is directly adopted, and can be directly treated from raw water, and no special requirement is imposed on the quality of process inlet water. (1) BTs substances are effectively removed through the pretreatment process of 'gravity settling + neutralization settling + air flotation', and the operation cost is relatively low; (3) the biofilm method and the activated sludge method are organically combined, so that the sludge concentration and the impact resistance are improved, and BTs-type wastewater can be more effectively treated by utilizing the synergistic effect of different microorganisms.
Drawings
FIG. 1 is a process flow diagram of the present invention
Detailed Description
The invention is further illustrated below with reference to the figures and examples.
Pretreatment section
The method comprises the steps of directly introducing wastewater produced by the rubber accelerator into a primary sedimentation tank from a drainage system, settling BTs wastewater in the primary sedimentation tank by natural gravity, removing larger particles in the wastewater, introducing the wastewater into a neutralization sedimentation tank, adding lime milk into the neutralization sedimentation tank, neutralizing charges in the wastewater, and further settling. And after the sedimentation is finished, adjusting the pH value by the adjusting tank, introducing the wastewater into an air flotation machine for air flotation treatment, adding a flotation agent of which the flocculating agent is cationic polyacrylamide with the ionic degree of 60% into the air flotation machine, filtering floating flocs after the air flotation is finished, pumping the floating slag into a sludge concentration tank for abandonment, introducing the wastewater after the floating slag is removed into an adsorption tank, and finishing the pretreatment. The process utilizes the characteristic that BTs substances are insoluble in water, adopts a pretreatment process of 'gravity sedimentation, neutralization sedimentation and air flotation', and achieves 50% of COD removal rate.
Activated sludge adsorption precipitation fraction
Activated sludge is adsorbed in the adsorption tank, the n-octanol-water distribution coefficient (Kow) of BTs substances is more than 4, and the adsorption tank has stronger hydrophobicity and higher biosorption, so that BTs substances in wastewater are further removed by adopting an activated sludge adsorption precipitation method, and the removal rate of COD is about 20-40%. Since the adsorption tank continuously receives sewage from the drainage system while also being inoculated with the microbial population that survives in the drainage system, i.e., the drainage system functions as a "microbial selector". Where adaptation, elimination, optimization, proliferation, etc. of the microbial population is continuously generated. Thereby being capable of cultivating, domesticating and inducing microbial population adapted to the original sewage. Because the process is not provided with a primary sedimentation tank, the adsorption tank can fully utilize the microbial population optimized by the drainage system, so that the adsorption tank can form an open biodynamic system. The adsorption tank has high load, and provides good environmental conditions for microbial population with high proliferation speed. The microbial population which can survive in the adsorption tank can only be prokaryotic bacteria with strong impact load resistance, and protozoa and metazoa are difficult to survive. The adsorption tank has high sludge yield and certain adsorption capacity, and the adsorption tank mainly depends on the adsorption of biological sludge to remove pollutants. Therefore, certain heavy metals, organic substances degraded by microorganisms, nitrogen, phosphorus and other substances can be removed to a certain extent through the adsorption tank, and the subsequent aerobic biochemical load is greatly reduced. The BOD removal rate of the adsorption tank is approximately between 40 and 70 percent, but the biodegradability of the sewage treated by the adsorption tank is improved to some extent, which is beneficial to the subsequent aerobic biochemical biodegradation.
The adsorption tank has a certain adaptability to the actions of load, temperature, PH, toxicity and the like because the adsorption tank mainly has an adsorption function taking physical and chemical actions as the leading factor for removing pollutants. The flocculent structure of the activated sludge has good adsorption performance, the retention time of the adsorption tank is designed to be 20-60min, and the sludge age is only 0.3-0.5 d.
Be equipped with the sedimentation tank behind the adsorption tank, squeeze into the sedimentation tank with the waste water in the adsorption tank, will adsorb a large amount of organic matters mud through gravity precipitation, hold back a large amount of organic matters in the waste water and discharge to the sludge thickening tank along with mud and abandon, upper wastewater in the sedimentation tank can circulate and is beaten back to the adsorption tank and adsorb, until fully adsorbing.
Post-treatment section
BTs the most of BTs kind of substances are removed after the front end treatment, the COD is reduced to 10000 mg/L, and the biochemical treatment can be carried out.
The wastewater in the sedimentation tank is continuously pumped into a hydrolytic acidification tank, BTs substances contain benzene rings, heterocyclic rings and the like, and hydrolytic acidification can effectively open rings and break chains, so that the biodegradability of the wastewater is improved. The hydrolyzed and acidified mixture is pumped into a first-level A/O pool, the first-level A/O pool adopts a biomembrane treatment process, and the biomembrane treatment process are carried out in the same biological treatment unit by the technologyThe activated sludge process is organically combined, the sludge concentration and the impact resistance are improved, and BTs-class wastewater can be more effectively treated by utilizing the synergistic effect of different microorganisms. The volume load of COD can reach 1-3kgCOD/m3D. Meanwhile, the first-level A/O adopts high-ratio backflow, so that the load impact of high-concentration wastewater on microorganisms can be effectively reduced.
After the primary A/O treatment is finished, the wastewater is pumped into a secondary A/O pool, the secondary A/O pool ensures denitrification in a mode of additionally adding a carbon source, so that the stability of the total nitrogen of the effluent reaches the standard, and the carbon source is usually methanol or sodium acetate, wherein the cost of the methanol is lower, but the methanol needs to be subjected to explosion-proof treatment when in use.
And a secondary sedimentation tank is arranged behind the secondary A/O tank, the wastewater after the secondary A/O treatment is pumped into the secondary sedimentation tank for secondary sedimentation, the sludge of the sediment is pumped into a sludge concentration tank for abandoning, and the upper layer wastewater can be pumped back to the hydrolysis acidification tank for circular acidification and A/O treatment again. The surface load of the secondary sedimentation tank is designed to be 0.5m3The lower concentration of suspended solids in the effluent is ensured when the square meter is square meter per hour.
And an advanced oxidation tank is arranged behind the secondary sedimentation tank, the treated wastewater is pumped into the advanced oxidation tank to carry out an advanced treatment process of ozone oxidation and activated carbon adsorption, and the treated wastewater can reach the standard and be discharged.
Claims (9)
1. A treatment process of rubber accelerator wastewater is characterized by comprising the following steps:
s1: performing gravity settling on the rubber accelerator wastewater;
s2: adding lime milk into the wastewater treated by the S1 for neutralization and precipitation;
s3: introducing the wastewater treated by the S2 into an air flotation device, adding a flotation agent, and carrying out air flotation;
s4: filtering the floating slag subjected to air floatation in S3, and performing activated sludge adsorption treatment on the rest wastewater;
s5: carrying out hydrolytic acidification and A/O treatment on the wastewater treated by the S4;
s6: and (4) oxidizing the wastewater treated by the S5, and then discharging.
2. The process of claim 1, wherein in S3, the flocculating agent in the flotation agent is a macromolecular organic substance.
3. The process for treating rubber accelerator wastewater as claimed in claim 2, wherein the macromolecular organic substance is cationic polyacrylamide with an ionic degree of 60%.
4. The process for treating rubber accelerator wastewater as claimed in claim 1, wherein the adsorption retention time is 20-60min and the sludge age is 0.3-0.5d in the adsorption treatment of activated sludge in S4.
5. The process for treating waste water containing a rubber accelerator as claimed in claim 1 or 4, wherein in the step of adsorption treatment of activated sludge in S4, precipitation is carried out after adsorption of activated sludge.
6. The process for treating rubber accelerator wastewater as claimed in claim 1, wherein the A/O treatment in S5 is a secondary A/O treatment.
7. The process for treating rubber accelerator wastewater as recited in claim 6, wherein in the secondary A/O treatment, a biofilm treatment process is adopted for the first stage A/O.
8. The process for treating rubber accelerator wastewater as claimed in claim 6, wherein in the secondary A/O treatment, a carbon source is added to the secondary A/O.
9. The process for treating rubber accelerator wastewater as claimed in claim 8, wherein the carbon source is methanol or sodium acetate.
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2020
- 2020-05-07 CN CN202010347782.1A patent/CN111453931A/en active Pending
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| CN102730862A (en) * | 2011-04-01 | 2012-10-17 | 中国石油化工股份有限公司 | Sewage treatment method in synthetic rubber production |
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