CN103663630B - A kind of acrylic nitrile waste water electrolytic processing method - Google Patents
A kind of acrylic nitrile waste water electrolytic processing method Download PDFInfo
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- CN103663630B CN103663630B CN201210333301.7A CN201210333301A CN103663630B CN 103663630 B CN103663630 B CN 103663630B CN 201210333301 A CN201210333301 A CN 201210333301A CN 103663630 B CN103663630 B CN 103663630B
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Abstract
The invention discloses a kind of acrylic nitrile waste water electrolytic processing method, be intended to the method by a step airtight intensified electrolysis method process Wastewater from Acrylonitrile Production, can qualified discharge.The present invention adopts: acrylic nitrile waste water, after flocculation, gravity settling, airtight intensified electrolysis process, can reach the water quality standard of directly discharge completely.Solve acrylic nitrile waste water when adopting other technology and technique to be difficult to process a difficult problem up to standard, after as high in burning disposal cost, Fenton oxidation method produces a large amount of solid wastes, wet oxidation process process, high, the biochemical process of ammonia nitrogen concentration accomplishes process up to standard because prussiate toxicity etc. is very difficult.The present invention can be applicable to acrylic nitrile waste water process up to standard, also can be applicable to the field of waste water treatment with toxicity, difficult biochemistry, high ammonia nitrogen, high organic concentration, has important promotional value.
Description
Technical field
The present invention relates to industrial waste water treatment, be specifically related to a kind of acrylic nitrile waste water process and reached calibration method, belonged to field of environment protection.
Background technology
Vinyl cyanide (Acrylonitrile, AN) is important organic synthesis raw material, is one of the main raw material of synthon, synthetic resins, synthetic rubber and organic synthesis industry.Vinyl cyanide is the organic cyanogen of a kind of hypertoxic type that is colourless, Semen Armeniacae Amarum taste, is also common occupational environment pollutent.Be number four in the noxious chemical list of the 52 kinds of priority acccess control determined in China, there is high toxicity and potential genetoxic, be one of noxious pollutant important in environment, not only destroy water ecosystem, also the life and health of harm humans.Trade effluent generation containing vinyl cyanide is large, and water quality is complicated, and containing recalcitrant substance.
The manufacturer in the current whole world 90% all adopts propylene ammmoxidation process to produce vinyl cyanide.The waste water that such device produces aborning has two kinds: reaction waste and refined wastewater, all containing a large amount of vinyl cyanide in these two kinds of waste water, especially in reaction waste.Both at home and abroad the method for high-concentration acrylonitrile wastewater process is mainly contained: burning method, pressurizing hydrolysis, Fenton oxidation method, ferrous sulfate method, fiber embrane method; Have the method for the acrylic nitrile waste water process of lower concentration: evaporation concentration method, biochemical process, active carbon adsorption etc.
Current domestic many employing burning method processing reaction waste water, because reaction waste calorific value is very low, need in burning process to consume a large amount of fuel, processing cost is very high; Fenton oxidation method, the B/C value of waste water has almost no change, and cannot improve biodegradability, and produces a large amount of solid wastes; Wet oxidation process investment is large, cost is high, and after process, ammonia nitrogen concentration is high, produces restraining effect to follow-up biochemistry; All biochemical processs, comprise the strengthening biochemical process adopting engineering bacteria, due to the existence of prussiate, even if the acrylic nitrile waste water of lower concentration, bacterium is difficult to arrive high biological activity, and do not accomplish process up to standard, the organonitrogen in addition due to this water is higher, and the removal effect of most biochemical treatment ammonia nitrogen is all undesirable.
Due to Wastewater from Acrylonitrile Production height COD, high density toxic cyanide, high density organonitrogen and ammonia nitrogen etc., if it is up to standard to adopt processing costs biological process that is low, that be easy to manage to be difficult to process, also there is various problem in additive method.Therefore existing process Wastewater from Acrylonitrile Production technology, be difficult to the object being reached qualified discharge by a kind of technology or single step reaction, if develop one there is lower cost, simple, can the technology of qualified discharge by single step reaction, just there is important promotional value.
Summary of the invention
The invention discloses a kind of acrylic nitrile waste water electrolytic processing method, be intended to high for its organic content of domestic Wastewater from Acrylonitrile Production, COD is high, and due to containing a large amount of toxic cyanide, high density organonitrogen and ammonia nitrogen etc., cause its intractability very large, a kind of method by a step airtight intensified electrolysis method process Wastewater from Acrylonitrile Production is provided, can qualified discharge.
The technical solution used in the present invention is:
The Wastewater from Acrylonitrile Production line-blending flocculation agent of enterprise's discharge, first through stirring at low speed flocculation tank, flow into gravity settling basin again, remove colloid, solid particulate etc. wherein, supernatant liquor pipe-line blending salt solution after precipitation flows into and is uniformly mixed pond, be uniformly mixed pond water outlet and enter airtight intensified electrolysis reactor through pump lifting, the draining of airtight intensified electrolysis reactor can accomplish process up to standard.Specific as follows:
(1) acrylic nitrile waste water water quality: COD
cr1000 mg/L ~ 10000mg/L, NH
3-N concentration 50 mg/L ~ 200 mg/L, total nitrogen 100 mg/L ~ 500 mg/L, prussiate 1 ~ 50mg/L;
(2) in acrylic nitrile waste water, add flocculation agent and coagulant aids, adding flocculant concentration is 20 mg/L ~ 80 mg/L;
(3) stirring at low speed flocculation tank is entered, reaction times 1 h ~ 4h;
(4) gravity settling basin is entered after coagulating;
(5) supernatant liquor after precipitation is mixed into saturated brine of sodium chloride, and controlling to add rear wastewater chlorination na concn according to Pollutants in Wastewater concentration is 1000 mg/L ~ 6000 mg/L;
(6) mixed waste water enters and is uniformly mixed pond, and waste water is mixed;
(7) be uniformly mixed pond water outlet and enter airtight intensified electrolysis reactor through pump lifting, electrolysis reactor control pressure is less than 0.5MPa, and establishes overvoltage protection, reaction times 3h ~ 10h, electrolysis rear water outlet up to standard.Airtight intensified electrolysis reactor is long strip shape closed structure, inside there is multi-layer electrode plate, battery lead plate is multi-hole type, battery lead plate and the fixing of inside reactor assembly all adopt corrosion resistant metal parts, separation between positive-negative electrode plate adopts corrosion resistant type rubber cradle, battery lead plate material: just very titanium iridium alloy, negative pole are alloy 316L.When in waste water, organic concentration is different, the number by adjustment sodium chloride concentration, battery lead plate voltage and electric current, battery lead plate changes organic removal total amount, and the draining of airtight intensified electrolysis reactor can accomplish process up to standard, COD
cr120 mg/L, total nitrogen 40 mg/L, prussiate 0.5mg/L.
The essential distinction of the present invention and prior art is, the present invention can realize the process up to standard of acrylic nitrile waste water by simple technique and flow process, solves Problems existing when adopting other technology and technique: burning fuel consumption is large, and processing cost is very high; Fenton oxidation method, cannot improve biodegradability, and produces a large amount of solid wastes; Wet oxidation process investment is large, cost is high, and after process, ammonia nitrogen concentration is high, produces restraining effect to follow-up biochemistry; Biochemical process is due to the existence of prussiate, and bacterium is difficult to arrive high biological activity, does not accomplish process up to standard.
According to different electrolytic oxidation mechanism, electrochemical oxidation can be divided into direct anodic oxidation, anodic oxidation indirectly, negative electrode indirect oxidation, the concerted catalysis oxidative degradation of negative and positive the two poles of the earth.The present invention mainly adopts the direct anodic oxidation in electrochemical oxidation, indirect anodic oxidation and negative electrode indirect oxidation.
Anode: the 1) OH2 of electrode surface accumulation) directly utilize negatively charged ion, chlorion Electrocatalytic Oxidation on anode is produced the chlorine of nascent state or forms hypochlorite further, thus makes the organism in water strong oxidation occur and degrade.
2C1
-→C1
2+2e
C1
2+H
2O→HOC1+H
++C1
-
HOC1→H
++C1
-
Negative electrode: the indirect degradation of organic substances of hydrogen peroxide that reduction produces.
O
2+2H
++2e→H
2O
2
Beneficial effect of the present invention:
The invention provides a kind of lower cost, simple airtight intensified electrolysis method process Wastewater from Acrylonitrile Production, this type of waste water can be made to accomplish qualified discharge.By simple method, lower cost and investment, achieve the process up to standard of acrylic nitrile waste water, is a kind of effective, economically viable technology.
Accompanying drawing explanation
Fig. 1 is process flow diagram;
Fig. 2 is electrolysis reactor schematic diagram;
Be labeled as in figure: 1-closed reactor, 2-positive pole, 3-negative pole, 4-rubber cradle
Fig. 3 is porous electrolytic zinc-coated steel sheet pore distribution schematic diagram.
Embodiment
Below, by reference to the accompanying drawings and specific embodiment, the X kind embodiment of invention is further described.
In acrylic nitrile waste water transport pipe, add flocculation agent and coagulant aids, adding flocculant concentration is 20 mg/L ~ 80 mg/L;
Flow into stirring at low speed flocculation tank, reaction times 1 h ~ 4h;
Gravity settling basin is flowed into after coagulating;
Supernatant liquor pipe-line blending saturated brine of sodium chloride after precipitation, controlling to add rear wastewater chlorination na concn according to Pollutants in Wastewater concentration is 1000 mg/L ~ 6000 mg/L;
Mixed waste water flows into and is uniformly mixed pond, and waste water is mixed;
Be uniformly mixed pond water outlet and enter airtight intensified electrolysis reactor through pump lifting, electrolysis reactor control pressure is less than 0.5MPa, and establishes overvoltage protection, reaction times 3h ~ 10h, water outlet after electrolysis.
Airtight intensified electrolysis reactor is long strip shape closed structure, inside there is multi-layer electrode plate, battery lead plate is multi-hole type, battery lead plate and the fixing of inside reactor assembly all adopt corrosion resistant metal parts, separation between positive-negative electrode plate adopts corrosion resistant type rubber cradle, battery lead plate material: just very titanium iridium alloy, negative pole are alloy 316L.When in waste water, organic concentration is different, the number by adjustment sodium chloride concentration, battery lead plate voltage and electric current, battery lead plate changes organic removal total amount, and the draining of airtight intensified electrolysis reactor can accomplish process up to standard, COD
cr120 mg/L, total nitrogen 40 mg/L, prussiate 0.5mg/L.
Embodiment 1
As above, parameter is as table 1 for step.
Table 1 embodiment 1 water quality and controling parameters situation
Embodiment 2
As above, parameter is as table 2 for step.
Table 2 embodiment 2 water quality and controling parameters situation
Embodiment 3
Table 3 embodiment 3 water quality and controling parameters situation
The foregoing is only better possible embodiments of the present invention, not thereby limit to the scope of the claims of the present invention, therefore the equivalent structure change that every utilization specification sheets of the present invention and accompanying drawing content are done, be all contained in protection scope of the present invention.
Claims (4)
1. an acrylic nitrile waste water electrolytic processing method, comprises the following steps:
(1) in acrylic nitrile waste water, add flocculation agent and coagulant aids, adding flocculant concentration is 20mg/L ~ 80mg/L;
(2) stirring at low speed flocculation tank is entered again, reaction times 1h ~ 4h;
(3) gravity settling basin is entered again after coagulating;
(4) supernatant liquor after precipitation is mixed into saturated brine of sodium chloride, and controlling to add rear wastewater chlorination na concn according to Pollutants in Wastewater concentration is 1000mg/L ~ 6000mg/L;
(5) mixed waste water enters and is uniformly mixed pond, and waste water is mixed;
(6) be uniformly mixed pond water outlet and enter airtight intensified electrolysis reactor through pump lifting, electrolysis reactor control pressure is less than 0.5MPa, and establishes overvoltage protection, reaction times 3h ~ 10h, electrolysis rear water outlet up to standard.
2. acrylic nitrile waste water electrolytic processing method according to claim 1, is characterized in that, the water quality of described acrylic nitrile waste water is as follows: COD
cr1000mg/l ~ 10000mg/l, NH
3-N concentration 50mg/L ~ 200mg/L, total nitrogen 100mg/L ~ 500mg/L, prussiate 1 ~ 50mg/L.
3. acrylic nitrile waste water electrolytic processing method according to claim 1, it is characterized in that, described airtight intensified electrolysis reactor is long strip shape closed structure, inside there is multi-layer electrode plate, battery lead plate is multi-hole type, battery lead plate and the fixing of inside reactor assembly all adopt corrosion resistant metal parts, and the separation between positive-negative electrode plate adopts corrosion resistant type rubber cradle, battery lead plate material: just very titanium iridium alloy, negative pole are alloy 316L.
4. acrylic nitrile waste water electrolytic processing method according to claim 1, it is characterized in that, the acrylic nitrile waste water different to organic concentration, the number by adjustment sodium chloride concentration, battery lead plate voltage and electric current, battery lead plate changes organic removal total amount.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104803441B (en) * | 2015-05-05 | 2017-11-17 | 东北石油大学 | A kind of method of solar energy coupled thermomechanics processing acrylonitrile sewage |
| CN111087047A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Treatment method of bromine-containing organic wastewater |
| CN111087049A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Method for treating organic nitrogen wastewater |
| CN111995010B (en) * | 2020-09-10 | 2021-08-20 | 南京理工大学 | Electrochemical tubular treatment device and method applied to high-concentration cyanide-containing wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189381A (en) * | 1978-09-07 | 1980-02-19 | Amax Inc. | Waste water treatment |
| CN1417143A (en) * | 2001-11-09 | 2003-05-14 | 中国石油天然气股份有限公司 | ABS sewage treating method |
| CN101962214A (en) * | 2009-07-23 | 2011-02-02 | 江苏新河农用化工有限公司 | Method for treating cyanide-containing waste water |
| CN201809240U (en) * | 2010-08-13 | 2011-04-27 | 北京神州瑞霖环保科技有限公司 | Chemical fiber wastewater advanced treatment system |
| CN102267772A (en) * | 2010-12-02 | 2011-12-07 | 中国环境科学研究院 | Novel electrocatalytic oxidation method used for pre-treating acrylic fiber polymerization wastewater |
-
2012
- 2012-09-10 CN CN201210333301.7A patent/CN103663630B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189381A (en) * | 1978-09-07 | 1980-02-19 | Amax Inc. | Waste water treatment |
| CN1417143A (en) * | 2001-11-09 | 2003-05-14 | 中国石油天然气股份有限公司 | ABS sewage treating method |
| CN101962214A (en) * | 2009-07-23 | 2011-02-02 | 江苏新河农用化工有限公司 | Method for treating cyanide-containing waste water |
| CN201809240U (en) * | 2010-08-13 | 2011-04-27 | 北京神州瑞霖环保科技有限公司 | Chemical fiber wastewater advanced treatment system |
| CN102267772A (en) * | 2010-12-02 | 2011-12-07 | 中国环境科学研究院 | Novel electrocatalytic oxidation method used for pre-treating acrylic fiber polymerization wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 混凝法预处理丙烯腈废水的研究;张沛存等;《山东化工》;20110331;第40卷(第03期);第58-63页 * |
| 电化学氧化处理丙烯腈废水及对可生化性的提高;褚兆晶等;《生态环境学报》;20100831;第19卷(第08期);第1956-1959页 * |
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