CN103058426A - Treatment process for polyvinyl chloride (PVC) production wastewater - Google Patents
Treatment process for polyvinyl chloride (PVC) production wastewater Download PDFInfo
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- CN103058426A CN103058426A CN2012105796494A CN201210579649A CN103058426A CN 103058426 A CN103058426 A CN 103058426A CN 2012105796494 A CN2012105796494 A CN 2012105796494A CN 201210579649 A CN201210579649 A CN 201210579649A CN 103058426 A CN103058426 A CN 103058426A
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Abstract
The invention proposes a treatment process for polyvinyl chloride (PVC) production wastewater. The treatment process includes adjusting the pH of the PVC production wastewater to be 4 to 5; micro-electrolyzing the PVC production wastewater, wherein the electrolysis time is 42 ~ 48min and the weight ratio of a filler layer and the PVC production wastewater is 1:1 to 3:1; oxidizing the micro-electrolyzed PVC production wastewater, wherein adding hydrogen peroxide with a mass concentration of 27 to 33% is added in to make the molar ratio of H2O2 to Fe2 + to be 4:1 to 6: 1, the stirring speed is 150 ~ 250r/min, and the reaction time is 15 ~ 25min; precipitating the oxidized PVC production wastewater, adjusting the pH of the PVC production wastewater to pH 9.7 to 10.3 by using alkali, wherein the residence time is 8 ~ 12min; and discharging the precipitate, and performing dehydration in a centrifugal separator. By adopting the treatment process of the present invention, COD and turbidity are enabled to meet the requirements, cost is reduced, and reaction time and area are decreased.
Description
Technical field
The present invention relates to petrochemical industry disposal of waste gas, water and industrial residue technical field, relate in particular to a kind for the treatment of process of waste water of PVC production.
Background technology
At present, the Production of PVC of China and market demand are and increase situation rapidly, yet in the production process of polyvinyl chloride, can give off a large amount of waste water, water quality characteristics is that the water yield is large, turbidity is high, organic concentration is low, difficult degradation etc., and the residual product that has after vinyl chloride monomer reaches a small amount of other additives (dihydroxyphenyl propane, Resorcinol, methyl alcohol) and these substance reactions or decay in the reaction process, these materials have toxicity and difficult for biological degradation more, can cause great harm to environment, could discharge after the palpus processing is up to standard.
The main technique of processing such waste water both at home and abroad has: Coagulation Method, ultrafiltration process, activated sludge process, By Ozone, biochemical process etc., because waste strength is lower, the water yield is large, and on ultrafiltration material and facility and processing cost, ultrafiltration technology is difficult to technology commercialization; For ozone process, (Chemical Oxygen Demand is abbreviated as COD or COD owing to pretreated chemical oxygen demand (COD)
Cr) still higher, over-burden in the ozone unit, adds present ozone generating apparatus energy consumption high, and the ozonize cost has restricted the application of ozonation technology on producing; Organic concentration is very low in the waste water, also should not adopt activated sludge process to process.
At present domestic and international processing to such waste water, the method that generally adopts catalytic oxidation and ozonize to combine, contact oxidation technology is removed first partial organic substances in the waste water, and bio-chemical effluent is processed through the ozone oxidation even depth again, and water quality reaches reuse standard.
In view of this, how to design a kind of waste water treatment process, large with floor space in the solution production polyvinyl chloride process, long reaction time, cost is higher and can not reduce simultaneously turbidity, and water outlet chemical oxygen demand (COD) (COD) can not reach the problem of reuse standard, is the problem that the insider needs solution badly.
Summary of the invention
In prior art, floor space is large in the production polyvinyl chloride process, long reaction time, and cost is higher and can not reduce simultaneously turbidity, water outlet chemical oxygen demand (COD) (COD) can not reach the defectives such as reuse standard, the invention provides a kind for the treatment of process of waste water of PVC production.
According to the present invention, a kind for the treatment of process of waste water of PVC production is provided, wherein, may further comprise the steps:
A. the pH that regulates waste water of PVC production is 4～5;
B. the described waste water of PVC production of little electrolysis injects described waste water of PVC production in the little electrolysis post of ternary, reacts under the normal temperature, and electrolysis time is 42～48min, and the weight ratio of packing layer and described waste water of PVC production is 1:1～3:1;
C. the described waste water of PVC production of oxidation after little electrolysis passes into Fenton oxidizing reaction pond with the described waste water of PVC production after little electrolysis, and to add mass concentration be 27～33% hydrogen peroxide, so that Fe
2+With H
2O
2Mol ratio be 4:1～6:1, wherein, stirring velocity is 150～250r/min, the reaction times is 15～25min;
D. precipitate the described waste water of PVC production after oxidation, wherein, utilize alkali to regulate the pH to 9.7 of described waste water of PVC production～10.3, the residence time is 8～12min; And
E. discharge throw out to separating centrifuge and carry out processed, wherein, the rotating speed of described separating centrifuge is 1500r/min～2000r/min, and the centrifugation time is 15～20min.
Preferably, before described step a, also comprise step f: collection, mixing, homogeneous waste water of PVC production.
Preferably, among the described step b, by sump pump described waste water of PVC production is injected in the little electrolysis post of described ternary.
Preferably, among the described step b, the m (Al) in the little electrolysis post of described ternary: m (Fe): m (C) is 1:4:4～3:4:4.
Preferably, among the described step b, the weight ratio of described packing layer and described waste water of PVC production is 1:2.
Preferably, among the described step b, by weight percentage, the proportioning of described packing layer is iron filings: aluminium bits: gac=2:1:1.
Preferably, among the described step c, the mass concentration of described hydrogen peroxide is 30%, described Fe
2+With H
2O
2Mol ratio be 5:1.
Preferably, among the described step a, be the pH that 50% hydrochloric acid is regulated described waste water of PVC production with mass concentration.
Preferably, in the described steps d, described pH is 10, and the residence time is 10min.
Preferably, in the described steps d, described alkali is that mass concentration is 10% NaOH solution.
Advantage of the present invention is: the Fe that utilizes the little electrolysis of ternary to produce
2+, nascent state the redox reaction of [H] and [O], part difficult degradation ring-type is become the small organic molecule of readily biodegradable and improves biodegradability with the long-chain organic substance decomposing, suspension in the flocculation sediment effect of polymeric ferric aluminum and the electric field action absorption waste water or small-particle and the organic polymer of colloidal state, can further reduce the turbidity of waste water, remove simultaneously some organic pollutants matter, realize that finally chemical oxygen demand (COD) (COD) and turbidity satisfy the requirement of quality of reused water standard.The present invention is little except reduced investment, floor space, process and stablely easily control, outside working cost is low, can also " treatment of wastes with processes of wastes against one another ", and realize the resource utilization of refuse.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, the below will do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art, apparently, accompanying drawing in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 shows the processing technological flow figure according to waste water of PVC production of the present invention.
Embodiment
The below is clearly and completely described the technical scheme in the embodiment of the invention, and obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The present invention be with the little electrolysis of Al-Fe-C ternary as pre-treatment, pass through Fe
2+, nascent state the aluminum ions coagulating sedimentation effect of the attached collection of redox reaction, electrochemistry, the iron ion of [H] and [O] remove suspended substance and the organism of part; Utilize packing layer in little electrolysis post, waste water is filtered, reduced the turbidity of waste water; Utilize Fe
2+With H
2O
2Form Fenton (Fenton) reagent, further the organism in the oxidized waste water adds alkali in settling tank, regulates pH to 10, forms precipitation, and supernatant liquor is discharged, and throw out dewaters through separating centrifuge, the unified processing.
Fig. 1 shows the processing technological flow figure according to waste water of PVC production of the present invention.With reference to Fig. 1, its concrete treatment process following steps:
Step a: the pH that regulates waste water of PVC production is 4～5.Beginning, the pH of waste water of PVC production is 6～7, and being 50% hydrochloric acid with mass concentration regulates the pH of waste water of PVC production, and the pH that makes waste water of PVC production is 4～5, and more specifically, can be adjusted to pH is 4.5.
Step b: little electrolysis waste water of PVC production.Then, above-mentioned waste water of PVC production through regulating pH is injected in the little electrolysis post of ternary by sump pump, so that m (Al): m (Fe): m (C) is 1:4:4～3:4:4, more specifically, m (Al): m (Fe): m (C) is 1:2:2, and wherein, the weight ratio of packing layer and described waste water of PVC production is 1:1～3:1, by weight percentage, the proportioning of packing layer is iron filings: aluminium bits: gac=2:1:1.More specifically, packing layer in the little electrolysis post of ternary and the weight ratio of waste water of PVC production are 2:1, the electrolysis temperature of waste water of PVC production is 18～23 ℃, for example, 20 ℃, and the electrolysis time of waste water of PVC production in little electrolysis post is 42～48min, and more specifically, electrolysis time is 45min.
C. the waste water of PVC production of oxidation after little electrolysis.Continue, waste water of PVC production is through behind the microelectrolysis processing, open the valve of little electrolysis post lower end, waste water of PVC production flows automatically to Fenton (Fenton) oxidizing reaction pond through action of gravity, in Fenton (Fenton) oxidizing reaction pond, add mass concentration and be 27～33% hydrogen peroxide and carry out oxidizing reaction, and so that Fe
2+With H
2O
2Mol ratio be 4:1～6:1, for example 5:1 stirs the reactant in Fenton (Fenton) the oxidizing reaction pond simultaneously, stirring velocity is 150～250r/min, the reaction times is 15～25min;
Steps d: the waste water of PVC production of precipitation after oxidation.Next, open the valve of lower end, Fenton (Fenton) oxidizing reaction pond, waste water adds alkaline solution from flowing to settling tank in settling tank, regulate the pH value of waste water of PVC production in the settling tank, alkali can be that mass concentration is 10% NaOH solution, the pH value of waste water of PVC production is adjusted into 9.7～10.3, more specifically the pH value can be adjusted into 10, stopping in settling tank is 8～12min, for example can be 10min, to forming supernatant liquor and throw out.
E. discharge throw out to separating centrifuge and carry out processed.At last, supernatant liquor is discharged from the lower end valve of settling tank, throw out is discharged from the bottom of settling tank.And throw out is through the whizzer separating and dehydrating, and separating centrifuge dewaters to throw out with the rotating speed of 1500～2000r/min, and centrifugation time is 15～20min.The blob of slag water ratio that throw out forms after dehydration is less than 20%, and a blob of slag is processed by unified.Wherein, the chemical oxygen demand (COD) of supernatant liquor (COD) is less than 30mg/L, turbidity is less than 2NTU, and the average removal rate of chemical oxygen demand (COD) (COD) and turbidity has reached respectively 71.8% and 89.2%, and water quality should reach " low pressure boiler water quality " requirement (GB1576-2001).
Step f: collection, mixing, homogeneous waste water of PVC production.Before step a, can also collect first waste water of PVC production, and mix to carry out subsequent step.
The present invention is in the little electrolysis post of ternary, and Fe, C and other impurity are dispersed in the cast iron with the form of minimum particle, because its electropotential is lower than iron, so just form a large amount of microbatterys in electrolyte solution the time.Its electrode reaction is as follows:
Anode: Fe → Fe
2++ 2e E
0=﹣ 0.44V
Negative electrode: 2H+2e → H
2↑ E
0=0.00V (acidic conditions)
O
2+ 2H
2O+4e → 4OH
-E
0=0.41V (alkaline condition)
After adding the aluminium bits in the system, the aluminium bits also can form galvanic cell with gac, and its electrode reaction is as follows:
Anode: Al → A1
3++ 3e E
0=﹣ 1.66V
Negative electrode: 2H+2e → H
2↑ E
0=0.00V (acidic conditions)
O
2+ 2H
2O+4e → 4OH
-E
0=0.41V (alkaline condition)
The nascent state ferrous ion that the anodic reaction of little electrolysis produces has stronger reducing power can make two keys of some unsaturated chromophoric group open, destroy chromophoric group and remove colourity, part difficult degradation ring-type is become the small organic molecule of readily biodegradable and improves biodegradability with the long-chain organic substance decomposing; Cathodic reaction produces a large amount of nascent states [H] and [O], under the condition of slant acidity, these activeconstituentss all can with waste water in many component generation redox reactions, make organic macromolecule generation chain-scission degradation, thereby eliminated the colourity of organic waste water.Fe
2+With H
2O
2Form Fenton reagent (Fenton reagent is the very strong oxygenant of a kind of oxidation capacity, is usually used in the purifying treatment of waste water), under acidic conditions, produce hydroxyl radical free radical (OH), reaction formula is:
Fe
2++ H
2O
2→ Fe
3++ OH
-+ OH, the oxidizing potential of hydroxyl radical free radical (OH) is 2.8V, oxidable most organism, thus further reduce chemical oxygen demand (COD) (COD).
Through regulating pH to 9.7～10.3, reaction produces Fe in settling tank
3+And A1
3+, during the solution alkalize, can form Fe (OH)
3And Al (OH)
3Both synergies form polymeric ferric aluminum, its collection aluminium salt and molysite be advantage separately, form to aluminum ion and iron ion all has clear improvement, extent of polymerization greatly improves, and according to the synergy principle, adds the settleability that it is good, purifying treatment effect to low temperature and low turbidity water is obvious especially, has further reduced chemical oxygen demand (COD) (COD) and turbidity.
Waste water of PVC production can realize that chemical oxygen demand (COD) (COD) and turbidity reach industrial reuse water water quality requirement after above-mentioned processing.
3 embodiment of the present invention below are provided:
Embodiment 1
That the present embodiment is processed is 5m
3Waste water of PVC production: the pH of raw wastewater is 6, and chemical oxygen demand (COD) (COD) concentration is 246.5mg/L, and turbidity is 23NTU.The implementation step is as follows: at first, with waste water of PVC production, be collected in the acid-alkali accommodation pond mix, homogeneous, and to add mass concentration be that 50% hydrochloric acid is 4.5 with its pH regulator.Then, by sump pump waste water of PVC production is injected the little electrolysis post of ternary, m (Al) in the little electrolysis post of ternary: m (Fe): m (C) is 1:2:2, the weight ratio of packing layer and waste water of PVC production is 2:1, by weight percentage, the proportioning of packing layer is iron filings: aluminium bits: gac=2:1:1.The reaction times of waste water of PVC production in the little electrolysis post of ternary is 45min, and it opens the valve of the little electrolysis post of ternary lower end after micro-electrolysis reaction is processed, and waste water of PVC production is in action of gravity flows automatically to Fenton (Fenton) oxidation reactor.Then, adding mass concentration in Fenton (Fenton) the oxidizing reaction pond is 30% H
2O
24L, the speed stirring waste water of PVC production with 200r/min makes its reaction 20min.Then, open the valve of Fenton (Fenton) oxidation reactor lower end, waste water of PVC production is from flowing in the settling tank, add mass concentration in the settling tank and be 10% NaOH solution, the pH value of regulating waste water of PVC production is 10, and stop is 10min, formation supernatant liquor and throw out.Next, open the lower end valve of settling tank supernatant liquor is discharged, and throw out is discharged from the bottom of settling tank.Throw out is by the whizzer separating and dehydrating, and the separating centrifuge rotating speed is 1700r/min, and the centrifugation time is 18min, and throw out forms a blob of slag after dehydration, and the water ratio of a blob of slag is less than 20%, and a blob of slag is processed by unified.
Embodiment 2
That the present embodiment is processed is 1m
3Waste water of PVC production: the pH of raw wastewater is 7, and chemical oxygen demand (COD) (COD) concentration is 128.6mg/L, and turbidity is 19NTU.The implementation step is as follows: at first, with waste water of PVC production, be collected in the acid-alkali accommodation pond mix, homogeneous, and to add mass concentration be that 50% hydrochloric acid is 4 with its pH regulator.Then, by sump pump waste water of PVC production is injected the little electrolysis post of ternary, m (Al) in the little electrolysis post of ternary: m (Fe): m (C) is 1:4:4, the weight ratio of packing layer and waste water of PVC production is 1:1, by weight percentage, the proportioning of packing layer is iron filings: aluminium bits: gac=2:1:1.The reaction times of waste water of PVC production in the little electrolysis post of ternary is 42min, and it opens the valve of the little electrolysis post of ternary lower end after micro-electrolysis reaction is processed, and waste water of PVC production is in action of gravity flows automatically to Fenton (Fenton) oxidation reactor.Then, adding mass concentration in Fenton (Fenton) the oxidizing reaction pond is 27% H
2O
24L, the speed stirring waste water of PVC production with 150r/min makes its reaction 15min.Then, open the valve of Fenton (Fenton) oxidation reactor lower end, waste water of PVC production is from flowing in the settling tank, add mass concentration in the settling tank and be 10% NaOH solution, the pH value of regulating waste water of PVC production is 9.7, and stop is 8min, formation supernatant liquor and throw out.Next, open the lower end valve of settling tank supernatant liquor is discharged, and throw out is discharged from the bottom of settling tank.Throw out is by the whizzer separating and dehydrating, and the separating centrifuge rotating speed is 1500r/min, and the centrifugation time is 15min, and throw out forms a blob of slag after dehydration, and the water ratio of a blob of slag is less than 20%, and a blob of slag is processed by unified.
Embodiment 3
That the present embodiment is processed is 10m
3Waste water of PVC production: the pH of raw wastewater is 6.5, and chemical oxygen demand (COD) (COD) concentration is 71.3mg/L, and turbidity is 12NTU.The implementation step is as follows: at first, waste water of PVC production is collected in the acid-alkali accommodation pond mix, homogeneous, and to add mass concentration be that 50% hydrochloric acid is 4.5 with its pH regulator.Then, by sump pump waste water of PVC production is injected the little electrolysis post of ternary, m (Al) in the little electrolysis post of ternary: m (Fe): m (C) is 3:4:4, the weight ratio of packing layer and waste water of PVC production is 3:1, by weight percentage, the proportioning of packing layer is iron filings: aluminium bits: gac=2:1:1.The reaction times of waste water of PVC production in the little electrolysis post of ternary is 48min, and it opens the valve of the little electrolysis post of ternary lower end after micro-electrolysis reaction is processed, and waste water of PVC production is in action of gravity flows automatically to Fenton (Fenton) oxidation reactor.Then, adding mass concentration in Fenton (Fenton) the oxidizing reaction pond is 33% H
2O
24L, the speed stirring waste water of PVC production with 250r/min makes its reaction 25min.Then, open the valve of Fenton (Fenton) oxidation reactor lower end, waste water of PVC production is from flowing in the settling tank, add mass concentration in the settling tank and be 10% NaOH solution, the pH value of regulating waste water of PVC production is 10.3, and stop is 12min, formation supernatant liquor and throw out.Next, open the lower end valve of settling tank supernatant liquor is discharged, and throw out is discharged from the bottom of settling tank.Throw out is by the whizzer separating and dehydrating, and the separating centrifuge rotating speed is 2500r/min, and the centrifugation time is 20min, and throw out forms a blob of slag after dehydration, and the water ratio of a blob of slag is less than 20%, and a blob of slag is processed by unified.
Advantage of the present invention is: the Fe that utilizes the little electrolysis of ternary to produce
2+, nascent state the redox reaction of [H] and [O], part difficult degradation ring-type is become the small organic molecule of readily biodegradable and improves biodegradability with the long-chain organic substance decomposing, suspension in the flocculation sediment effect of polymeric ferric aluminum and the electric field action absorption waste water or small-particle and the organic polymer of colloidal state, can further reduce the turbidity of waste water, remove simultaneously some organic pollutants matter, realize that finally chemical oxygen demand (COD) (COD) and turbidity satisfy the requirement of quality of reused water standard.The present invention is little except reduced investment, floor space, process and stablely easily control, outside working cost is low, can also " treatment of wastes with processes of wastes against one another ", and realize the resource utilization of refuse.
Above demonstration and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (10)
1. the treatment process of a waste water of PVC production is characterized in that, may further comprise the steps:
A. the pH that regulates waste water of PVC production is 4～5;
B. the described waste water of PVC production of little electrolysis injects described waste water of PVC production in the little electrolysis post of ternary, reacts under the normal temperature, and electrolysis time is 42～48min, and the weight ratio of packing layer and described waste water of PVC production is 1:1～3:1;
C. the described waste water of PVC production of oxidation after little electrolysis passes into Fenton oxidizing reaction pond with the described waste water of PVC production after little electrolysis, and to add mass concentration be 27～33% hydrogen peroxide, so that Fe
2+With H
2O
2Mol ratio be 4:1～6:1, wherein, stirring velocity is 150～250r/min, the reaction times is 15～25min;
D. precipitate the described waste water of PVC production after oxidation, wherein, utilize alkali to regulate the pH to 9.7 of described waste water of PVC production～10.3, the residence time is 8～12min; And
E. discharge throw out to separating centrifuge and carry out processed, wherein, the rotating speed of described separating centrifuge is 1500r/min～2000r/min, and the centrifugation time is 15～20min.
2. the treatment process of waste water of PVC production as claimed in claim 1 is characterized in that, also comprises step f before described step a: collection, mixing, homogeneous waste water of PVC production.
3. the treatment process of vinylchlorid factory effluent as claimed in claim 1 is characterized in that, among the described step b, by sump pump described waste water of PVC production is injected in the little electrolysis post of described ternary.
4. the treatment process of waste water of PVC production as claimed in claim 1 is characterized in that, among the described step b, the m (Al) in the little electrolysis post of described ternary: m (Fe): m (C) is 1:4:4～3:4:4.
5. the treatment process of waste water of PVC production as claimed in claim 1 is characterized in that, among the described step b, the weight ratio of described packing layer and described waste water of PVC production is 1:2.
6. the treatment process of waste water of PVC production as claimed in claim 5 is characterized in that, among the described step b, by weight percentage, the proportioning of described packing layer is iron filings: aluminium bits: gac=2:1:1.
7. the treatment process of waste water of PVC production as claimed in claim 1 is characterized in that, among the described step c, the mass concentration of described hydrogen peroxide is 30%, described Fe
2+With H
2O
2Mol ratio be 5:1.
8. the treatment process of waste water of PVC production as claimed in claim 1 is characterized in that, among the described step a, is the pH that 50% hydrochloric acid is regulated described waste water of PVC production with mass concentration.
9. such as the treatment process of each described waste water of PVC production of claim 1 to 8, it is characterized in that, in the described steps d, described pH is 10, and the residence time is 10min.
10. such as each the treatment process of waste water of PVC production of claim 1 to 8, it is characterized in that, in the described steps d, described alkali is that mass concentration is 10% NaOH solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105060547A (en) * | 2015-07-23 | 2015-11-18 | 百川化工(如皋)有限公司 | Pretreatment process for toluene-contained wastewater |
| CN114105346A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | PVC mother liquor recycling treatment device and process |
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| CN101525198A (en) * | 2009-04-03 | 2009-09-09 | 寿光新龙电化集团聚氯乙烯有限公司 | Method for treating and recovering polyvinyl chloride mother liquid waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105060547A (en) * | 2015-07-23 | 2015-11-18 | 百川化工(如皋)有限公司 | Pretreatment process for toluene-contained wastewater |
| CN114105346A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | PVC mother liquor recycling treatment device and process |
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Application publication date: 20130424 |