CN102775011B - Treating and recycling method for PVC mother liquor wastewater - Google Patents
Treating and recycling method for PVC mother liquor wastewater Download PDFInfo
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- CN102775011B CN102775011B CN201210251800.1A CN201210251800A CN102775011B CN 102775011 B CN102775011 B CN 102775011B CN 201210251800 A CN201210251800 A CN 201210251800A CN 102775011 B CN102775011 B CN 102775011B
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- mother liquor
- waste water
- polychloroethylene
- liquor waste
- baf
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Abstract
The invention belongs to the field of treating method for wastewater, and specifically relates to a treating method for PVC (polyvinyl chloride) mother liquor wastewater. The treating and recycling method for PVC mother liquor wastewater comprises the following steps: conducting cooling treatment, flotation settlement processing, microbial degradation hydrolytic acidification, oxidation in an oxidation pond, treatment by an aerated biofilter, filtering, ozonation and refiltering to PVC mother liquor wastewater. By using the technical scheme provided by the invention, the complete recovery of mother liquor wastewater is achieved, the operating cost is reduced, and guarantee of the safe, stable and efficient operation of the system is the key point of the invention in the technical scheme. A coagulative precipitation tank which is high in operating cost and large in floor area is replaced by the flotation sedimentation tank, and the flotation sedimentation tank also plays a role for decreasing water temperature auxiliarily, thereby improving the cooling efficiency.
Description
Technical field
The invention belongs to method for treating waste liquid field, be specifically related to a kind of processing and recovery method of polychloroethylene mother liquor waste water.
Background technology
Polyvinyl chloride (PVC) mother liquor waste water belongs to the wastewater from chemical industry of lower concentration difficult degradation, though organic content is lower in such waste water, but has toxicity or difficult for biological degradation more, and its pollution problem comes into one's own day by day, COD in this waste water
crbe generally 100～400mg/L, BOD/COD is approximately 0.04, is characterized in: the water yield is large, and turbidity is large, and hardness is low, and polyvinyl alcohol is principal pollutant, contains in addition residual vinyl chloride monomer and other additives, as dihydroxyphenyl propane, Resorcinol, methyl alcohol etc.Polyvinyl alcohol all can produce stimulation to eyes and skin; Polyvinyl monomer to human health damage is: acute toxicity shows as anesthetic action; Long Term Contact can cause vinyl chloride disease.Acute poisoning: during calomel poisoning patient occur dizzy, uncomfortable in chest, drowsiness, lurch etc.; Serious poisoningly go into a coma, twitch, even cause death, skin contact vinylchlorid liquid can cause erythema, oedema or necrosis, chronic poisoning: show as neurasthenia syndrome, hepatomegaly, dysfunction of liver, digestive functional disturbance, Raynaud's phenomenon and acroosteolysis, skin can occur being dried, chaps, furfur, eczema etc., polyethylene is carcinogens, can cause HAS; The harm of dihydroxyphenyl propane is: long-time inspiration dihydroxyphenyl propane powder is harmful to liver function and renal function; Especially severe be the content that it can reduce protoheme in blood; Resorcinol toxicity is very large, and adult wrongly takes 1g, just occur headache, dizzy, feel sick, the toxicity symptom such as vomiting, it has carcinogenic and causes mutagenicity.Therefore need process various pollutents in polychloroethylene mother liquor waste water, reduce the toxicity of this waste water.
In view of the feature that the polychloroethylene mother liquor waste water water yield is large, pollutant load is low, method to its processing is: it is mixed with other industry waste water, discharge after treatment, or use as all kinds of wash-down waters through simple process, in recent years, many enterprises start to pay attention to the reuse of PVC mother liquor waste water, but mostly use the method for the medicines such as coagulating sedimentation, ion-exchange and reverse osmosis or high material consumption, cause waste water recycling running cost high.
The main methods of PVC mother liquor waste water has following several at present:
Coagulation Method: the method can be removed a small amount of PVC suspended particle, but lower for the clearance of soluble COD;
Biochemical process: adopt conventional biological treatment, the growth velocity of PVA degradation bacteria is lower, pollutes in the processing of mud method and is easily washed out in traditional activity, thereby makes the processing of such waste water comparatively difficult;
Ultrafiltrationmembrane process: for a certain reason in ultra-filtration process, PVA colloid stops up filter pore, filter membrane cannot backwash and regeneration, and the cost of the method is higher.
CN101392852 discloses a kind for the treatment of process of polyvinyl chloride centrifugation mother liquid waste water, the method comprises the following steps: the processing of self-stip filter, and the backwash liquor of self-stip filter is carried out to the recovery of PVC pellet, cooling processing, coagulant precipitation processing, the processing of one-level BAF, ozone oxidation, aeration reduction, the processing of secondary BAF, uf processing, reverse-osmosis treated, ion-exchange; Adopt its COD of waste water after the method is processed
mncontent be 1.5mg/L; But the shortcoming of the method is: this method is used BAF, membrane technique and ion exchange technique in a large number, needs lot of energy to come back flushing filter tank and film, and will change in time resin, and operation easier is high, and cost is high.
CN101525198A has disclosed a kind of method for the treatment of and recovering polyvinyl chloride mother liquid waste water, the step of the method is to reclaim polyvinyl chloride particles, cooling mother liquor waste water, acidication, Air Exposure, ozonize, organic matter degradation, sterilization and disinfection, ion-exchange, reuse; The COD index of the mother liquor waste water after the method is processed is less than 10mg/L, and the shortcoming of the method is: this method lacks necessary filtration measure, after Air Exposure, does not filter, and remaining bacterium corpse or micelle can consume ozone; After sterilization and disinfection, do not filter, dead thalline still can impact follow-up ion-exchange.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of method for the treatment of process of polychloroethylene mother liquor waste water.
The present invention realizes by following technical scheme:
The processing of polychloroethylene mother liquor waste water and recovery method, it is characterized in that, the method comprises following step: to oxidation in polychloroethylene mother liquor waste water cooling processings, air supporting sedimentation processing, microbiological deterioration acidication, oxidation pond, BAF process, filtration, ozone oxidation, refilter; Its concrete step is:
1) processing that cools: regulate cooling pool regulating pondage and water temperature, wherein so that high temperature is reverse-flow, water temperature is dropped to 40 ° of C from 70 ° of C by cooling tower;
2) air supporting sedimentation: the polychloroethylene mother liquor waste water after cooling enters air supporting settling tank, when utilizing small bubbles that air supporting produces to remove the suspended matters such as PVC particle, Xiang Chizhong adds PAC and PAM coagulating sedimentation suspended particle; Reduce the particulate matter in waste water, the bubble that air supporting produces in addition also has the auxiliary effect that reduces water temperature; Therefore, utilize air floatation precipitation device to replace traditional coagulative precipitation tank, load high, take up an area to economize, dosage is few, produce scum silica frost and easily process, and there is the auxiliary effect that reduces water temperature;
3) microbiological deterioration acidication: polychloroethylene mother liquor waste water enters upflowing hydrolyzing sludge bed (UHSB) again, is attached to anaerobion on polypropylene filler to the acidifying that is hydrolyzed of the organism of difficult degradation, makes it to resolve into the material of easy degraded;
4) in oxidation pond, be oxidized: polychloroethylene mother liquor waste water enters two-stage series connection contact-oxidation pool again, in pond, fill special-purpose aerobic filler, the organism that the metabolism degraded of aerobic microbiological is decomposed; Between acidication and BAF, add two-stage series connection contact-oxidation pool, give full play to biochemical degradation effect, reduce the pressure to follow-up BAF and ozonize, thereby reduce costs;
5) BAF is processed: polychloroethylene mother liquor waste water enters BAF BAF again, special-purpose biologic packing material and the microorganism adsorption and the remaining organism of degraded that are attached to top;
6) filter: polychloroethylene mother liquor waste water enters more medium filter, in strainer, fill homogeneous sea sand, the suspensoids such as the zoogloea in biochemistry pool water outlet, bacterium corpse and particle are trapped in the surface and space of filtrate,
7) ozone oxidation: polychloroethylene mother liquor waste water carries out ozone advanced treatment again, adopts ozone to kill the mushroom in water, and the hard-degraded substance in degradation water, up to standard to guarantee stable water outlet;
8) refilter: polychloroethylene mother liquor waste water enters activated charcoal filter again, and gac adsorbs waste water, make the objectionable impurities in water, as organism, colloid, microorganism, oils, chlorine residue and smell taste etc. and be adsorbed on activated carbon surface and be removed, prevent from polluting.
In step (2), the add-on of PAC and PAM respectively: 20g/m
3and 6g/m
3.
Aerobic filler in oxidation pond is combined stuffing, and the ratio of itself and oxidation pond volume is 1:1.
Special bio filler in BAF is biological ceramic particle, and the ratio of itself and BAF volume is 0.8:1.
The ozone adding in step (7) and the ratio of waste water are 1:30.
Adopt technique scheme of the present invention, realize the recovery completely of mother liquor waste water, in technical scheme, reduce running cost, guarantee that security of system stable and high effective operation is center of gravity of the present invention, therefore adopt air supporting settling tank to replace the coagulative precipitation tank that running cost is high, floor space is large, and play the auxiliary effect that reduces water temperature, improve cooling efficiency.
Two-stage series connection contact bio-oxidation pond, more medium filter and activated charcoal filter are also technical characterictics of the present invention, biochemical degradation organism cost is cheap more than other physico-chemical processes, stability is also very high, therefore this programme expands biochemical action shared proportion in processing, more medium filter and activated charcoal filter efficiency are high, stable, with low cost, do not need to need frequent back flushing or change membrane module as embrane method is filtered.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but does not therefore limit the present invention.
Embodiment 1
1) processing that cools: regulate cooling pool regulating pondage and water temperature, wherein so that high temperature is reverse-flow, water temperature is dropped to 40 ° of C from 70 ° of C by cooling tower;
2) air supporting sedimentation: the polychloroethylene mother liquor waste water after cooling enters air supporting settling tank, when utilizing small bubbles that air supporting produces to remove the suspended matters such as PVC particle, Xiang Chizhong adds PAC and PAM coagulating sedimentation suspended particle; Reduce the particulate matter in waste water, the bubble that air supporting produces in addition also has the auxiliary effect that reduces water temperature; Therefore, utilize air floatation precipitation device to replace traditional coagulative precipitation tank, load high, take up an area to economize, dosage is few, produce scum silica frost and easily process, and there is the auxiliary effect that reduces water temperature; The add-on of PAC and PAM is respectively: 20g/m
3and 6g/m
3;
3) microbiological deterioration acidication: polychloroethylene mother liquor waste water enters upflowing hydrolyzing sludge bed (UHSB) again, is attached to anaerobion on polypropylene filler to the acidifying that is hydrolyzed of the organism of difficult degradation, makes it to resolve into the material of easy degraded;
4) in oxidation pond, be oxidized: polychloroethylene mother liquor waste water enters two-stage series connection contact-oxidation pool again, in pond, fill special-purpose aerobic filler, the organism that the metabolism degraded of aerobic microbiological is decomposed; Between acidication and BAF, add two-stage series connection contact-oxidation pool, give full play to biochemical degradation effect, reduce the pressure to follow-up BAF and ozonize, thereby reduce costs; Aerobic filler in oxidation pond is combined stuffing, and the ratio of itself and oxidation pond volume is 1:1;
5) BAF is processed: polychloroethylene mother liquor waste water enters BAF BAF again, special-purpose biologic packing material and the microorganism adsorption and the remaining organism of degraded that are attached to top; Special bio filler in BAF is biological ceramic particle, and the ratio of itself and BAF volume is 0.8:1;
6) filter: polychloroethylene mother liquor waste water enters more medium filter, in strainer, fill homogeneous sea sand, the suspensoids such as the zoogloea in biochemistry pool water outlet, bacterium corpse and particle are trapped in the surface and space of filtrate;
7) ozone oxidation: polychloroethylene mother liquor waste water carries out ozone advanced treatment again, adopts ozone to kill the mushroom in water, and the hard-degraded substance in degradation water, up to standard to guarantee stable water outlet; The ratio of ozone and waste water is 1:30;
8) refilter: polychloroethylene mother liquor waste water enters activated charcoal filter again, and gac adsorbs it, make the objectionable impurities in water, as organism, colloid, microorganism, oils, chlorine residue and smell taste etc. and be adsorbed on activated carbon surface and be removed, prevent from polluting.
Adopt present method to process mother liquor waste water, particular case, influent quality is in Table 1:
Table 1. influent quality
The standard that waste water reclamation will reach, as shown in table 2:
Table 2. design effluent quality
| Project | pH | COD Cr（mg/L） | Turbidity (NTU) |
| Numerical value | 6～9 | ≤20 | ≤5 |
The treatment effect of each equipment is in Table 3:
Each device processes effect of table 3.
| Equipment | COD Cr（mg/L） | Turbidity (NTU) |
| Regulate cooling pool | 300 | 260 |
| Air supporting settling tank | 250 | 40 |
| Upflowing hydrolysis bed | 240 | 40 |
| Two-stage series connection biological contact oxidation pond | 80 | 40 |
| BAF | 40 | 30 |
| More medium filter | 40 | 20 |
| Ozonize pond | 30 | 20 |
| Activated charcoal filter | 20 | 5 |
Embodiment 2
Adopt present method to process Haijing Chemical Group Co., Ltd., Qingdao's polyvinyl chloride (PVC) RESINS centrifugal mother liquor waste water engineering operation particular case, influent quality is in Table 4:
Table 4. influent quality
The standard that waste water reclamation will reach, as shown in table 5:
Table 5. design effluent quality
The treatment effect of each equipment is in Table 6:
Each device processes effect of table 6.
| Equipment | COD Cr（mg/L） | Turbidity (NTU) | Temperature (° C) |
| Regulate cooling pool | 280 | 260 | 45 |
| Air supporting settling tank | 230 | 40 | 35 |
| Upflowing hydrolysis bed | 210 | 40 | 35 |
| Two-stage series connection biological contact oxidation pond | 60 | 40 | 30 |
| BAF | 40 | 20 | 25 |
| More medium filter | 40 | 15 | 25 |
| Ozonize pond | 30 | 15 | 25 |
| Activated charcoal filter | 20 | 2 | 25 |
After processing through method of the present invention, the COD in waste water
crreach 20mg/L, turbidity is 2NTU, and temperature is reduced to 25 ° of C by 40 ° of C of intaking.
Embodiment 3
Adopt present method to process the PVC of Shouguang Xinlong Electrification Group Polyvinyl Chloride Co., Ltd mother liquor waste water engineering operation particular case, influent quality is in Table 7:
Table 7. influent quality
The standard that waste water reclamation will reach, as shown in table 8:
Table 8. design effluent quality
The treatment effect of each equipment is in Table 9:
Each device processes effect of table 9.
| Equipment | COD Cr（mg/L） | Turbidity (NTU) | Temperature (° C) |
| Regulate cooling pool | 200 | 260 | 45 |
| Air supporting settling tank | 170 | 40 | 35 |
| Upflowing hydrolysis bed | 150 | 40 | 35 |
| Two-stage series connection biological contact oxidation pond | 50 | 40 | 30 |
| BAF | 30 | 20 | 25 |
| More medium filter | 25 | 15 | 25 |
| Ozonize pond | 30 | 15 | 25 |
| Activated charcoal filter | 20 | 2 | 25 |
After processing through method of the present invention, the COD in waste water
crreach 20mg/L, turbidity is 2NTU, and temperature is reduced to 25 ° of C by 40 ° of C of intaking.
Embodiment 4
Adopt present method to process Shandong Hengtong Chemicals Co., Ltd.'s polyvinyl chloride (PVC) RESINS centrifugal mother liquor waste water engineering operation particular case, influent quality is in Table 10:
Table 10. influent quality
The standard that waste water reclamation will reach, as shown in table 11:
Table 11. design effluent quality
The treatment effect of each equipment is in Table 12:
Each device processes effect of table 12.
| Equipment | COD Cr（mg/L） | Turbidity (NTU) | Temperature (° C) |
| Regulate cooling pool | 300 | 260 | 45 |
| Air supporting settling tank | 260 | 40 | 35 |
| Upflowing hydrolysis bed | 220 | 40 | 35 |
| Two-stage series connection biological contact oxidation pond | 70 | 40 | 30 |
| BAF | 50 | 20 | 25 |
| More medium filter | 40 | 15 | 25 |
| Ozonize pond | 30 | 15 | 25 |
| Activated charcoal filter | 20 | 2 | 25 |
After processing through method of the present invention, the COD in waste water
crreach 20mg/L, turbidity is 2NTU, and temperature is reduced to 25 ° of C by 40 ° of C of intaking.
Claims (5)
1. the processing of polychloroethylene mother liquor waste water and recovery method, it is characterized in that, the method comprises following step: to oxidation in polychloroethylene mother liquor waste water cooling processings, air supporting sedimentation processing, microbiological deterioration acidication, oxidation pond, BAF process, filtration, ozone oxidation, refilter; Its concrete step is:
1) processing that cools: the water temperature of polychloroethylene mother liquor waste water is dropped to 40 ℃ from 70 ℃;
2) air supporting sedimentation: the polychloroethylene mother liquor waste water after cooling enters air supporting settling tank, when the small bubbles that air supporting produces are removed the suspended matters such as PVC particle, Xiang Chizhong adds PAC and PAM coagulating sedimentation suspended particle;
3) microbiological deterioration acidication: polychloroethylene mother liquor waste water enters upflowing hydrolyzing sludge bed again, is attached to anaerobion on polypropylene filler to the acidifying that is hydrolyzed of the organism of difficult degradation, makes it to resolve into the material of easy degraded;
4) in oxidation pond, be oxidized: polychloroethylene mother liquor waste water enters two-stage series connection contact-oxidation pool again, in pond, fill special-purpose aerobic filler, the organism that the metabolism degraded of aerobic microbiological is decomposed;
5) BAF is processed: polychloroethylene mother liquor waste water enters BAF BAF again, special-purpose biologic packing material and the microorganism adsorption and the remaining organism of degraded that are attached to top;
6) filter: polychloroethylene mother liquor waste water enters more medium filter, in strainer, fill homogeneous sea sand, the suspensoids such as the zoogloea in biochemistry pool water outlet, bacterium corpse and particle are trapped in the surface and space of filtrate;
7) ozone oxidation: polychloroethylene mother liquor waste water carries out ozone advanced treatment again, adopts ozone to kill the mushroom in water, and the hard-degraded substance in degradation water;
8) refilter: polychloroethylene mother liquor waste water enters activated charcoal filter again, and gac adsorbs waste water.
2. the processing of polychloroethylene mother liquor waste water as claimed in claim 1 and recovery method, is characterized in that, described step 2) in the add-on of PAC and PAM be respectively 20g/m
3and 6g/m
3.
3. the processing of polychloroethylene mother liquor waste water as claimed in claim 1 and recovery method, is characterized in that, the aerobic filler in oxidation pond is combined stuffing, and the ratio of itself and oxidation pond volume is 1:1.
4. the processing of polychloroethylene mother liquor waste water as claimed in claim 1 and recovery method, is characterized in that, the special bio filler in described BAF is biological ceramic particle, and the ratio of itself and BAF volume is 0.8:1.
5. the processing of polychloroethylene mother liquor waste water as claimed in claim 1 and recovery method, is characterized in that, the ozone adding in step 7) and the ratio of waste water are 1:30.
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| CN201210251800.1A CN102775011B (en) | 2012-07-20 | 2012-07-20 | Treating and recycling method for PVC mother liquor wastewater |
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|---|---|---|---|
| CN201210251800.1A CN102775011B (en) | 2012-07-20 | 2012-07-20 | Treating and recycling method for PVC mother liquor wastewater |
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| CN102775011A CN102775011A (en) | 2012-11-14 |
| CN102775011B true CN102775011B (en) | 2014-02-26 |
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| CN103288306A (en) * | 2013-07-01 | 2013-09-11 | 国家电网公司 | Process for treating heavy oil waste water |
| CN103342442A (en) * | 2013-07-18 | 2013-10-09 | 山东太平洋环保有限公司 | Integrated biotreatment system and method for PVC (poly vinyl chloride) industrial wastewater |
| CN106145565A (en) * | 2016-09-06 | 2016-11-23 | 苏州方舟环保科技有限公司 | A kind of efficient laboratory waste liquid processing method and processing device |
| CN106316008A (en) * | 2016-11-22 | 2017-01-11 | 广东石油化工学院 | Efficient resource treatment and reuse system of waste water of hydrogen prepared by Texaco furnace coal |
| CN108002654B (en) * | 2017-03-03 | 2020-11-13 | 北京中科众联新能源技术服务有限公司 | Suspension method polyvinyl chloride polymerization section wastewater treatment method |
| CN107176755A (en) * | 2017-06-06 | 2017-09-19 | 滁州市宏源喷涂有限公司 | A kind of polyvinyl chloride centrifugation mother liquid multi-method combined pretreatment method |
| CN108911259B (en) * | 2018-08-03 | 2024-03-05 | 内蒙古睿达鑫科技有限责任公司 | System and process for treating polyvinyl chloride organic wastewater |
| CN110078318A (en) * | 2019-06-10 | 2019-08-02 | 苏州中色德源环保科技有限公司 | A kind of chemical industry for making chlorine and alkali mother liquor water process and reclaiming system |
| CN111196645A (en) * | 2019-10-08 | 2020-05-26 | 安徽华塑股份有限公司 | Centrifugal mother liquor water recycling system and method thereof |
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2012
- 2012-07-20 CN CN201210251800.1A patent/CN102775011B/en not_active Expired - Fee Related
Patent Citations (3)
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| CN1654374A (en) * | 2005-01-12 | 2005-08-17 | 天津市塘沽区鑫宇环保科技有限公司 | Method for directly treating high temperature and high turbidity PVC mother liquor by using biologic filter |
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