CN104150682B - A kind for the treatment of process of process for oxychlorination of ethylene vinylchlorid factory effluent - Google Patents
A kind for the treatment of process of process for oxychlorination of ethylene vinylchlorid factory effluent Download PDFInfo
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- CN104150682B CN104150682B CN201410301033.XA CN201410301033A CN104150682B CN 104150682 B CN104150682 B CN 104150682B CN 201410301033 A CN201410301033 A CN 201410301033A CN 104150682 B CN104150682 B CN 104150682B
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Abstract
A kind for the treatment of process of process for oxychlorination of ethylene vinylchlorid factory effluent: waste water removes the pollutent in waste water by flocculation sediment effect; Waste water enters gas stripping column and the volatile hydrochloric ether in waste water is transferred to gas phase from tower top stripping out from aqueous phase, introduces ozone simultaneously and carry out catalytic oxidation treatment to the pollutent in waste water under catalyst action; Waste water is sent into biochemistry pool and is removed organic pollutant through biochemical treatment; Waste water enters second pond to carry out entering intermediate pool after solid-liquid separation removes suspended sludge; Waste water enters microprocessing unit and carries out advanced treatment, further except the organic pollutant of not easily degrading in anhydrating, and final outflow water qualified discharge or reuse.The present invention is all applicable with balance process for oxychlorination vinylchlorid factory effluent to process for oxychlorination of ethylene, and without the need to introducing other waste water as dilution water, water outlet COD is less than 50mg/L.
Description
Technical field
The invention belongs to chemical wastewater treatment field, be specifically related to a kind for the treatment of process of process for oxychlorination of ethylene vinylchlorid factory effluent.
Background technology
Vinylchlorid (VCM) has another name called vinyl chloride, is colourless, easy liquefied gas.VCM is a kind of important monomer of macromolecule chemical industry, is also the main raw material that polyvinyl chloride (PVC) RESINS (PVC) is produced.Current domestic VCM produces and mainly contains two lines, is the carbide acetylene method based on Coal Chemical Industry and the ethylene process based on petrochemical complex respectively.In ethylene process VCM production technique, first ethene through chlorination or oxi-chlorination synthesis 1,2-ethylene dichloride (EDC), then generate VCM monomer by EDC cracking.
Process for oxychlorination of ethylene vinylchlorid factory effluent mainly comprises waste water at the bottom of quench tower (or water quenching tower) tower, and the sealing waste water produced in production process, equipment wash-down water etc.This waste water contains the ethylene dichloride of higher concentration and a large amount of building-up reactions by product, and salts contg is high, and intractability is large.Current most domestic producer generally introduces other waste water and dilutes it, and then carries out biochemical treatment, but water outlet COD is general still up to 100-150mg/L, only can meet national secondary discharge standard.Along with the pay attention to day by day of Environmental protection work; current contamination emission standard improves day by day (emission standard as basin, the peninsula, Shandong Province executed COD<60mg/L from 1 day January in 2010); under these circumstances, the treatment process of process for oxychlorination of ethylene vinylchlorid factory effluent is badly in need of improving.
Summary of the invention
The object of the present invention is to provide a kind for the treatment of process of process for oxychlorination of ethylene vinylchlorid factory effluent, the method can adapt to the emission standard of increasingly stringent.
For achieving the above object, treatment process provided by the invention, comprises following process:
Process for oxychlorination of ethylene vinylchlorid factory effluent removes the pollutent in waste water by flocculation sediment effect in preliminary sedimentation tank, and wherein flocculating settling agent is by iron, calcium ion and gac 1:(0.6-2.3 in mass ratio): (1.6-3.8) is composite to be formed;
The waste water of preliminary sedimentation tank enters gas stripping column through promoting, and is filled with activated carbon supported catalyst of transition metal oxide in gas stripping column; As stripping medium, stripping process is carried out to waste water using the gas mixture of ozone and air in gas stripping column, by gas stripping, the volatile hydrochloric ether in waste water is transferred to gas phase from aqueous phase, from tower top stripping out, in air lift process there is catalytic oxidation in ozone under catalyst action simultaneously, carries out oxide treatment to the pollutent in waste water;
The waste water feeding biochemistry pool of gas stripping column enters second pond and carries out solid-liquid separation removal suspended sludge after biochemical treatment removal organic pollutant, enters intermediate pool subsequently;
The waste water of intermediate pool enters microprocessing unit and carries out advanced treatment, further except the organic pollutant of not easily degrading in anhydrating, and final outflow water qualified discharge or reuse.
Described treatment process, wherein, regulates waste water ph to be 7-9 before flocculation sediment.
Described treatment process, wherein, transition metal oxide is one or more in Mn oxide, ferriferous oxide and copper oxide.
Described treatment process, wherein, in gas stripping column, the mass concentration of ozone is 2-60mg/L.
Described treatment process, wherein, biochemical treatment adopts hydrolysis acidification method, contact oxidation method, activated sludge process or its array mode.
Described treatment process, wherein, the hydraulic detention time of biochemical treatment is 6-48 hour.
Described treatment process, wherein, microprocessing unit refers to biological activated carbon filter, sand-bed filter, activated charcoal filter, more medium filter or its array mode.
The present invention is directed to process for oxychlorination of ethylene vinylchlorid factory effluent, but to ethene equilibrium oxygen chlorination process vinylchlorid factory effluent and other similar wastewater from chemical industry containing the volatile halohydrocarbon of high density all applicable, treatment effect is reliable and stable.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Treatment process of the present invention, mainly:
1) waste water removes pollutent by flocculation sediment; Waste water ph is regulated to be 7-9 before flocculation sediment.
2) as stripping medium, stripping process is carried out to waste water using the mixed gas of ozone and air; In gas stripping column, the mass concentration of ozone is 2-60mg/L, and fill activated carbon supported catalyst of transition metal oxide in gas stripping column, transition metal oxide is one or more in Mn oxide, ferriferous oxide and copper oxide.
3) biochemical treatment is carried out; Biochemical treatment adopts hydrolysis acidification method, contact oxidation method, activated sludge process or its array mode, and the hydraulic detention time of biochemical treatment is 6-48 hour.
4) micro-pollution plot is carried out; Micro-pollution plot adopts biological activated carbon filter, sand-bed filter, activated charcoal filter, more medium filter or its array mode.
In detail, treatment process of the present invention, be by from the processing wastewater of each unit of process for oxychlorination of ethylene TOWER OUTLET IN VINYL CHLORIDE UNIT, the sealing factory effluent such as water, wash-down water after wastewater disposal basin is collected, pH to 7-9 is regulated with salkali waste, then preliminary sedimentation tank is entered, removed the pollutents such as cupric ion, colloid and suspended substance in waste water by flocculation sediment effect, wherein flocculating settling agent is by iron, calcium ion and gac 1:(0.6-2.3 in mass ratio): (1.6-3.8) is composite to be formed.Preliminary sedimentation tank water outlet enters gas stripping column through promoting, and fills the catalyst of transition metal oxide (as: Mn oxide, ferriferous oxide, copper oxide etc.) of gac (AC) load in gas stripping column.After waste water enters gas stripping column, carry out stripping process using the gas mixture of ozone and air as stripping medium to waste water, wherein the mass concentration of ozone is 2-60mg/L.In gas stripping column, the volatile hydrochloric ethers such as the ethylene dichloride in waste water can be transferred to gas phase from aqueous phase by gas stripping on the one hand, thus from tower top stripping out; On the other hand, owing to introducing ozone in air lift process, there is catalytic oxidation in ozone under catalyst action, thus carry out oxide treatment to the pollutent in waste water.In air lift process, evenly, oxidation mass-transfer efficiency is high, can improve the biochemical of waste water well in liquid phase contact.Gas stripping column tower reactor waste water sends into biochemistry pool after heat exchange, and biochemistry pool can adopt hydrolysis acidification method, contact oxidation method, activated sludge process or its array mode.According to the needs of technique and water quality, can add a certain amount of N nutritive salt (such as urea, ammonium chloride etc.) and P nutritive salt (such as SODIUM PHOSPHATE, MONOBASIC, tertiary sodium phosphate etc.) when biochemical treatment, the ratio of adding is mass ratio COD:N:P=100:(2-5): (0.3-1).Waste water enters second pond and carries out solid-liquid separation stop 6-48 hour in biochemistry pool after, remove suspended sludge, enter intermediate pool subsequently; Be promoted to microprocessing unit by pump, adopt biological activated carbon filter, sand-bed filter, activated charcoal filter, more medium filter or its array mode to carry out advanced treatment, further except the organic pollutant of not easily degrading in anhydrating, final outflow water qualified discharge or reuse.
Below by embodiment, processing method of the present invention is described in further detail, protection scope of the present invention is not limited to following specific embodiment.
Embodiment 1
The present embodiment process be at the bottom of ethylene oxychlorination unit quench tower tower discharge VCM waste water, wherein COD
crfor 3680mg/L, copper ion concentration is 3.5mg/L.Concrete treatment step is as follows: first waste water add alkali adjust ph to 8-9, after preliminary sedimentation tank flocculating settling, and waste water COD
crbe down to 3000-3300mg/L, copper ion concentration is lower than 1mg/L.Preliminary sedimentation tank water outlet enters and is filled with MnO
2the gas stripping column of/AC catalyzer.In gas stripping column, waste water from top to bottom, and ozone mixes stripping medium from bottom to top with air, and wherein ozone concn is 25-30mg/L.Waste water COD after air lift and catalytic ozonation double effects
crbe down to 200-250mg/L.The water outlet of gas stripping column tower reactor is through heat exchange, and temperature enters contact-oxidation pool after being down to 25-35 DEG C, hydraulic detention time 36h.Bio-chemical effluent is removed after suspended sludge through second pond, enters intermediate pool, is in succession promoted to sand-bed filter and activated charcoal filter subsequently, final outflow water COD by pump
crfor 40-50mg/L, cupric ion does not detect, water quality reaches " peninsula, Shandong Province water pollutants of water basin comprehensive discharge standard " primary standard.
Claims (7)
1. a treatment process for process for oxychlorination of ethylene vinylchlorid factory effluent, comprises following process:
Process for oxychlorination of ethylene vinylchlorid factory effluent removes the pollutent in waste water by flocculation sediment effect in preliminary sedimentation tank, and wherein flocculating settling agent is by iron, calcium ion and gac 1:(0.6-2.3 in mass ratio): (1.6-3.8) is composite to be formed;
The waste water of preliminary sedimentation tank enters gas stripping column through promoting, and is filled with activated carbon supported catalyst of transition metal oxide in gas stripping column; As stripping medium, stripping process is carried out to waste water using the gas mixture of ozone and air in gas stripping column, by gas stripping, the volatile hydrochloric ether in waste water is transferred to gas phase from aqueous phase, from tower top stripping out, in air lift process there is catalytic oxidation in ozone under catalyst action simultaneously, carries out oxide treatment to the pollutent in waste water;
The waste water feeding biochemistry pool of gas stripping column enters second pond and carries out solid-liquid separation removal suspended sludge after biochemical treatment removal organic pollutant, enters intermediate pool subsequently;
The waste water of intermediate pool enters microprocessing unit, further except the organic pollutant of not easily degrading in anhydrating, and final outflow water qualified discharge or reuse.
2. treatment process according to claim 1, wherein, regulates waste water ph to be 7-9 before flocculation sediment.
3. treatment process according to claim 1, wherein, transition metal oxide is one or more in Mn oxide, ferriferous oxide and copper oxide.
4. treatment process according to claim 1, wherein, in gas stripping column, the mass concentration of ozone is 2-60mg/L.
5. treatment process according to claim 1, wherein, biochemical treatment adopts hydrolysis acidification method, contact oxidation method, activated sludge process or its array mode.
6. treatment process according to claim 1 or 5, wherein, the hydraulic detention time of biochemical treatment is 6-48 hour.
7. treatment process according to claim 1, wherein, microprocessing unit refers to biological activated carbon filter, sand-bed filter, activated charcoal filter, more medium filter or its array mode.
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| WO2022109765A1 (en) * | 2020-11-24 | 2022-06-02 | 万华化学集团股份有限公司 | Method for advanced treatment and reuse of vinyl chloride high-salt wastewater |
| CN112607896B (en) * | 2020-11-24 | 2022-11-08 | 万华化学集团股份有限公司 | Advanced treatment and recycling method of chloroethylene high-salt wastewater |
| CN114804456A (en) * | 2022-04-11 | 2022-07-29 | 天津大沽化工股份有限公司 | Recovery system and method for alkaline washing wastewater generated in chloroethylene production by oxychlorination method |
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| CN101774731A (en) * | 2010-01-27 | 2010-07-14 | 四川大学 | Enhanced coagulation-gas stripping-membrane integration method and device for lightening membrane pollution |
| CN102303939A (en) * | 2011-08-12 | 2012-01-04 | 华南理工大学 | Front, middle and rear ozone and central aerated biological activated carbon water supply treatment method |
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| US20040261495A1 (en) * | 2003-06-27 | 2004-12-30 | Kilham Lawrence B. | Method and apparatus for determining the amount of gas contained in a liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101774731A (en) * | 2010-01-27 | 2010-07-14 | 四川大学 | Enhanced coagulation-gas stripping-membrane integration method and device for lightening membrane pollution |
| CN102303939A (en) * | 2011-08-12 | 2012-01-04 | 华南理工大学 | Front, middle and rear ozone and central aerated biological activated carbon water supply treatment method |
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