CN101497470A - Coagulant treating coking wastewater and use technology thereof - Google Patents
Coagulant treating coking wastewater and use technology thereof Download PDFInfo
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- CN101497470A CN101497470A CNA2009100959807A CN200910095980A CN101497470A CN 101497470 A CN101497470 A CN 101497470A CN A2009100959807 A CNA2009100959807 A CN A2009100959807A CN 200910095980 A CN200910095980 A CN 200910095980A CN 101497470 A CN101497470 A CN 101497470A
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- coagulant
- coking wastewater
- raw material
- mass concentration
- treating coking
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Abstract
The invention discloses a coagulating agent for coking wastewater treatment and a process for applying the same. The coagulating agent for coking wastewater treatment is compounded by using ferrous sulfate, aluminium sulfate, ferric chloride, polysilicate and zeolite powder as raw materials; and the coagulating agent comprises the following raw materials in percentage by mass: 30 to 70 percent of the ferrous sulfate, 20 to 60 percent of the aluminium sulfate, 3 to 10 percent of the ferric chloride, 1 to 5 percent of the polysilicate and 1 to 5 percent of the zeolite powder. The application process comprises that: in a coagulating treatment stage after coking wastewater is subjected to A/O biological treatment, the PH value of the coking wastewater subjected to A/O biological treatment is regulated to be between 6 and 9; and the coagulating agent for coking wastewater treatment is added into the coking wastewater for coagulation treatment so that the final concentration of the coagulating agent for coking wastewater treatment in the coking wastewater is between 900 and 1,500 mg/L. Compared with the other coagulating agents, the coagulating agent has high efficiency, economization and excellent coagulating effect; and the application process is simple and has low investment cost.
Description
(1) technical field
The present invention relates to a kind of coagulant treating coking wastewater and application art thereof.
(2) background technology:
Coking chemical waste water is coal system Jiao, gas purification, the refining waste water that produces in the coke chemicals removal process that reaches of chemical products, contain that phenol, biphenyl, pyridine, indoles and quinoline etc. encircle tens kinds more, hazardous contaminant such as heterocyclic bio-refractory organism and inorganic fluorion, ammonia nitrogen ion, cyanide ion, complicated component, Pollutant levels height, colourity height, toxicity are big, in water, exist with true solution or accurate colloidal form, character is highly stable, is a kind of typical organic wastewater with difficult degradation thereby.To the processing of coking chemical waste water, at present domesticly generally carry out in two steps, at first with A/O or A
2Denitrogenation of/O biochemical process and removal most COD
Cr, the biochemical stage water outlet is further handled with absorption or Coagulation Method again.Contain the large number of biological hardly degraded organic substance in the coking chemical waste water and make COD in the biochemical stage water outlet
CrStill can reach 200～500mg./L, colourity reaches discharging standards far away up to thousands of times.Therefore, follow-up absorption and Coagulation Method just seem particularly important.In the absorption method, often adopt activated carbon, flyash etc. to make sorbent material, but have problems such as cost height or residue be difficult, seldom adopt in the at present domestic producer.And the key of Coagulation Method is used coagulating agent, in the processing to coking chemical waste water, generally adopts bodied ferric sulfate or polymerize aluminum chloride to make coagulating agent, though easy for operation, to COD
Cr, colourity, total CN
-Clearance etc. main contamination index is not high, causes water outlet not reach country or the local emission standard that allows far away.And on the other hand, along with expanding economy, market is to the increase of demands such as iron and steel, and domestic most coke-oven plants, producer gas plant coking chemical waste water quantity discharged are increasing, and these waste water are but day and night polluting our environment.Therefore, develop a kind of coagulant special, remove COD wherein effectively at coking chemical waste water
Cr, colourity and total CN
-Deng pollutent, make the wastewater effluent index reach emission standard and seemed very important.
(3) summary of the invention:
Primary and foremost purpose of the present invention is will be at the coking chemical waste water stable in properties, be difficult to biodegradable water quality characteristics, and a kind of efficient, economic coagulant treating coking wastewater is provided.
For solving the problems of the technologies described above, the present invention mainly is in the building-up process of this composite inorganic coagulating agent, by optimizing processing condition, promptly regulate proportioning raw materials, temperature, basicity, stirring intensity, synthetic a kind of more efficient, economic coagulant treating coking wastewater.
Concrete, the technical solution used in the present invention is as follows:
A kind of coagulant treating coking wastewater, be to be that raw material is composited with ferrous sulfate, Tai-Ace S 150, iron(ic) chloride, poly-silicic acid, zeolite powder, its raw materials quality per-cent consists of: ferrous sulfate 30～70%, Tai-Ace S 150 20～60%, iron(ic) chloride 3～10%, poly-silicic acid 1～5%, zeolite powder 1～5%;
The preparation method of described coagulant treating coking wastewater is as follows: raw material sulphuric acid is ferrous, Tai-Ace S 150, iron(ic) chloride, poly-silicic acid, zeolite powder mix by above-mentioned quality proportioning, be crushed to 50～100 orders, under 70～90 ℃, it is carried out heated and stirred 2～3h, and then the raw material after the above-mentioned processing is carried out following processing: to pulverize, to drip mass concentration be that 0.1～0.5% NaOH solution or mass concentration are 0.05～3% Ca (OH) for raw material after the heated and stirred
2Emulsion makes NaOH or Ca (OH)
2The add-on of quality is 0.1～0.5% of a raw material total mass, promptly obtains coagulant treating coking wastewater liquid-type finished product; Perhaps to pulverize, to drip mass concentration be that 20～30% NaOH solution or mass concentration are 10～15% Ca (OH) for raw material after the heated and stirred
2Emulsion makes NaOH or Ca (OH)
2Quality is 0.1～0.5% of a raw material total mass, dropwise the back drying, sieving promptly obtains coagulant treating coking wastewater powder-type finished product.
Preparation process of the present invention is under agitation carried out, stirring velocity 200～500r/min.
The described mass concentration of general control is that 0.1～0.5% NaOH solution, mass concentration are 0.05～3% Ca (OH) among the present invention
2Emulsion, mass concentration are that 20～30% NaOH solution or mass concentration are 10～15% Ca (OH)
2The dropping time of emulsion is at 0.5～2h.
Ca of the present invention (OH)
2Emulsion is Ca (OH)
2Emulsion with water formation.
The present invention preferably to pulverize, raw material after the heated and stirred to drip mass concentration be 0.1～0.5% NaOH solution with make coagulant treating coking wastewater liquid-type finished product or to pulverize, to drip mass concentration be that 20～30% NaOH solution is to make coagulant treating coking wastewater powder-type finished product for raw material after the heated and stirred.
Among the present invention, the proportioning of Tai-Ace S 150 and ferrous sulfate is bigger in the raw material of described Treatment of Coking Effluent coagulating agent, for reducing cost, the ferrous sulfate of selecting for use comes from the industrial by-products that titanium dioxide or Metal Processing Factory etc. produce, the Tai-Ace S 150 of selecting for use is then from aluminum metallic scrap and acid-respons preparation, and other impurity is removed in these materials process pre-treatment, adjusting concentration promptly can be used to prepare coagulant treating coking wastewater.
Every index of the coking chemical waste water coagulant special that gets according to the inventive method preparation is as follows:
(1), liquid product (reddish-brown): solid content 15-20%, Al
2O
3Content 〉=7.8%, Fe
2O
3Content 〉=7.8%, basicity reach 5～35%, water insoluble matter content≤2.5%, pH value (1% aqueous solution) 1.0～3.0.
(2), solid phase prod (yellow or light brown close grain): Al
2O
3Content 〉=8.0%, Fe
2O
3Content 〉=13.2%, basicity reach 5～35%, water insoluble matter content≤2.5%, pH value (1% aqueous solution) 1.0～3.0, solubility (solid phase prod 45% solution stirring 1h can dissolve fully).
Second purpose of the present invention provides a kind of application art of simple, efficient, economic coagulant treating coking wastewater.The application art of coagulant treating coking wastewater of the present invention comprises the A/O biochemical treatment stage of coking chemical waste water and coagulating agent coagulating treatment stage subsequently, coking chemical waste water is after the A/O biochemical treatment, the pH value of the coking chemical waste water of adjusting after the A/O biochemical treatment, make it to be between 6～9, add described coagulant treating coking wastewater and carry out coagulating treatment, make the final concentration of coagulant treating coking wastewater described in the coking chemical waste water count 900～1500mg/L with its solid content.
Further, above-mentioned coagulating treatment process specifically can adopt following steps: after adding described coagulant treating coking wastewater, stir 30～60s with 300～500r/min earlier, stir 10～15min with 60～120r/min again, leave standstill 30～50min then.
Coagulant treating coking wastewater of the present invention is to CN
-, colourity, F
-All can reach satisfied treatment effect etc. index, particularly in the decolouring of coking chemical waste water, remove cyanogen, go aspect effect such as fluorine remarkable.After adopting above-mentioned application art that coking chemical waste water is handled, several main contamination indexs all can reach the permission emission standard.
The invention has the beneficial effects as follows: the Treatment of Coking Effluent coagulating agent that the present invention prepares, its effective constituent contains poly-hydroxyl positively charged ion of a large amount of compound high prices of iron aluminium and iron aluminium silicon composite cation, be with high positive charge, has very strong absorption charge neutrality, compression double electric layer and adsorption bridging ability, after being added in the waste water, can spread out rapidly, have an effect with the pollution components in the coking chemical waste water, make the aromatic ring of the generation colourity in the waste water, cohesion takes place and precipitates in the condensed ring pollutant, simultaneously with the phenols in the waste water, the cyanogen class carries secretly, thereby effectively removes the various pollution components in the coking chemical waste water.In addition, other elements such as the Si that exists in this compound coagulant, Ca, then make above-mentioned these iron, aluminium gather the mutual adhesive effect of hydroxyl positively charged ion and form bigger polymer, thereby make the wadding block of formation long-pending bigger, flco is more closely knit, makes settling velocity fast and complete like this, shortens the settling time, compare with other coagulating agent, coagulation effect is better.In addition, this Treatment of Coking Effluent coagulating agent can be operated in the existing facility system, and need not change equipment increases investment, is a kind of efficient, economic coking chemical waste water special agent.
(4) specific embodiment
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto.
The present invention prepares among the embodiment, and employed each raw material sources are as follows: ferrous sulfate (production of the plentiful chemical industry in Zhuji company limited), Tai-Ace S 150 (production of Hangzhou Tai-Ace S 150 company limited), iron(ic) chloride (sky, Wenzhou is contained electrochemical company limited and produced), poly-silicic acid (production of the Zhejiang Province meticulous auxiliary material of Dongyang City Gao Erte factory), zeolite (the refreshing stone ore industry in Zhejiang company limited produces).
Embodiment 1: the preparation of coagulating agent
Raw material is mixed by following quality proportioning: ferrous sulfate 50%, Tai-Ace S 150 30%, iron(ic) chloride 10%, poly-silicic acid 5%, zeolite 5% mix by the quality proportioning, and total mass is 30 grams.Be crushed to the 50-100 order, under 70～90 ℃, it is heated, stir 2h, and then the raw material after the above-mentioned processing is dripped mass concentration is 6 milliliters of 20% NaOH solution with the speed of 300r/min, 2h drips off, and drying, sieves, packs and promptly obtain the coagulant treating coking wastewater finished product.
Embodiment 2: the preparation of coagulating agent
Raw material is mixed by following quality proportioning: ferrous sulfate 45%, Tai-Ace S 150 40%, iron(ic) chloride 5%, poly-silicic acid 5%, zeolite 5% mix by the quality proportioning, and total mass is 30 kilograms.Be crushed to the 50-100 order, under 70～90 ℃, it is heated, stir 2h, and then the raw material after the above-mentioned processing is dripped mass concentration is 6 liters of 20% NaOH solution with the speed of 300r/min, 1.5h drip off, drying, sieve, pack and promptly obtain the coagulant treating coking wastewater finished product.
Application Example of the present invention, the coking chemical waste water of getting certain coke-oven plant carries out coagulation experiment.This factory's coking chemical waste water last stage after stage processing such as adjustment, neutralization, oil removal by air bubbling, A/O biochemistry, water outlet leading indicator COD
CrBe about 200～400mg/L, mainly by be difficult to biodegradable heterocycle, the aromatic ring pollutent constitutes, colourity about 300 times, total CN
-About 1.0mg/L, F-about 25mg/L, all be much higher than discharging standards.
Embodiment 3: the application of coagulating agent
(1) get the coking chemical waste water that this factory handled through the last stage, its effluent quality is: COD
CrBe 200mg/L, 240 times of colourities, total CN
-Be 1.2mg/L, F
-Be 25mg/L;
(2) regulate the pH value of coking chemical waste water with milk of lime, make it to be between 6～9, start six conjuncted stirrer agitators, drop into the coagulant treating coking wastewater that embodiment 1 makes then, dosage is 900mg/L, to stir 10min with 80r/min behind the 300r/min stirring 30s, leaves standstill 30min, get supernatant liquor, measure COD
Cr, total CN
-, F
-And colourity.
Detection method is to adopt " integrated wastewater discharge standard (GB8978-1996) "; COD measures and adopts potassium dichromate process; Determination of colority adopts platinum cobalt colorimetry; F
-Mensuration adopt ion specific electrode method, CN
-Mensuration with the distillation colorimetric method for determining.
(3) effluent index: COD after measured
CrBe 80mg/L, 50 times of colourities, total CN
-Be 0.36mg/L, F
-Be 7mg/L.According to " integrated wastewater discharge standard (GB8978-1996) ", but these several the equal qualified discharges of leading indicator.
Embodiment 4: the application of coagulating agent
Because coagulation experiment carries out, and near practical situation, investigates the coagulation effect of this coagulant treating coking wastewater under the actually operating situation for further, under cooperating, manufacturer carried out on-the-spot coagulation simulation dynamic experiment under static conditions.
(1) device of on-the-spot coagulation simulated experiment designs by the size and the shape of existing real reaction groove of manufacturer and settling tank, but size is dwindled 1000 times model for physical size, and controlling the influent waste water flow by valve is 5L/min.Waste water quality is: COD
CrBe 180～220mg/L, 200～260 times of colourities, total CN
-Be 1.2～1.6mg/L, F
-Be 20-30mg/L;
(2) after the each start of simulated experiment, move 2～4 days continuously, 24 hours every days are uninterrupted.Start air compressor, logical pressurized air bubbling stirs, and accurately adds the coagulant treating coking wastewater that embodiment 2 makes by peristaltic pump then, and dosage is about 900mg/L.
Treat system's operation for some time that (3) water sampling is analyzed water-quality guideline after the stable effluent quality, detection method is with embodiment 4.Through continuous several days mensuration, effluent quality COD
CrAbout 60～80mg/L, total CN
-About 0.3～0.6mg/L, colourity about 50～70 times, F
-4 concentration are about 5.0～7.0mg/L, and water outlet pH is 6～7, and several main contamination indexs all can reach the permission emission standard.
Claims (6)
1, a kind of coagulant treating coking wastewater, described coagulant treating coking wastewater is to be that raw material is composited with ferrous sulfate, Tai-Ace S 150, iron(ic) chloride, poly-silicic acid, zeolite powder, its raw materials quality per-cent consists of: ferrous sulfate 30～70%, Tai-Ace S 150 20～60%, iron(ic) chloride 3～10%, poly-silicic acid 1～5%, zeolite powder 1～5%;
Described coagulant treating coking wastewater is prepared as follows: raw material sulphuric acid is ferrous, Tai-Ace S 150, iron(ic) chloride, poly-silicic acid, zeolite powder mix by above-mentioned quality proportioning, be crushed to 50～100 orders, under 70～90 ℃, it carried out heated and stirred 2～3h; And then the raw material after the above-mentioned processing carried out following processing: to pulverize, to drip mass concentration be that 0.1～0.5% NaOH solution or mass concentration are 0.05～3% Ca (OH) for raw material after the heated and stirred
2Emulsion makes NaOH or Ca (OH)
2Add-on be 0.1～0.5% of raw material total mass, promptly obtain coagulant treating coking wastewater liquid-type finished product; Perhaps to pulverize, to drip mass concentration be that 20～30% NaOH solution or mass concentration are 10～15% Ca (OH) for raw material after the heated and stirred
2Emulsion makes NaOH or Ca (OH)
2Quality is 0.1～0.5% of a raw material total mass, dropwise the back drying, sieving promptly obtains coagulant treating coking wastewater powder-type finished product.
2, coagulant treating coking wastewater as claimed in claim 1 works to be characterised in that described preparation process under agitation carries out, and stirring velocity is at 200～500r/min.
3, coagulant treating coking wastewater as claimed in claim 1 is characterized in that controlling described mass concentration and is 0.1～0.5% NaOH solution, mass concentration and be 0.05～3% Ca (OH)
2Emulsion, mass concentration are that 20～30% NaOH solution or mass concentration are 10～15% Ca (OH)
2The dropping time of emulsion is 0.5～2h.
4, as the described coagulant treating coking wastewater of one of claim 1～3, it is characterized in that to pulverize, raw material after the heated and stirred to drip mass concentration be 0.1～0.5% NaOH solution with make coagulant treating coking wastewater liquid-type finished product or to pulverize, to drip mass concentration be that 20～30% NaOH solution is to make coagulant treating coking wastewater powder-type finished product for raw material after the heated and stirred.
5, a kind of application art of coagulant treating coking wastewater as claimed in claim 1, described application art comprises the A/O biochemical treatment stage of coking chemical waste water and coagulating agent coagulating treatment stage subsequently, it is characterized in that coking chemical waste water is after the A/O biochemical treatment, regulate the pH value of the coking chemical waste water after the A/O biochemical treatment earlier with milk of lime, make it to be between 6～9, add described coagulant treating coking wastewater and carry out coagulating treatment, make coagulant treating coking wastewater described in the coking chemical waste water final concentration count 900～1500mg/L with its solid content.
6, application art as claimed in claim 5, it is characterized in that described coagulating treatment is: after adding described coagulant treating coking wastewater, stir 30～60s with 300～500r/min earlier, stir 10～15min with 60～120r/min again, leave standstill 30～50min then.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830547A (en) * | 2010-05-17 | 2010-09-15 | 潘泽生 | Specific treating agent for carbonated water and preparation method thereof |
| CN102030401A (en) * | 2010-11-12 | 2011-04-27 | 中冶焦耐(大连)工程技术有限公司 | Method for decyanating coking wastewater |
| CN103449589A (en) * | 2013-09-02 | 2013-12-18 | 苏州富奇诺水治理设备有限公司 | Wastewater treatment agent containing polyhexamethylene adipamide |
| CN103771571A (en) * | 2014-01-20 | 2014-05-07 | 南通华新环保设备工程有限公司 | Sewage treatment flocculating agent and application thereof |
| CN104528899A (en) * | 2014-12-15 | 2015-04-22 | 刘树芹 | Coking wastewater purifying agent as well as preparation method and application thereof |
| CN104891623A (en) * | 2015-06-23 | 2015-09-09 | 杜普利 | Coagulant for wastewater treatment and preparing method thereof |
| CN105016445A (en) * | 2015-07-31 | 2015-11-04 | 石家庄开发区德赛化工有限公司 | Coking wastewater coagulation adsorbent and application thereof |
| CN106423111A (en) * | 2016-10-13 | 2017-02-22 | 北京北方节能环保有限公司 | BF type adsorption precipitant for treating organic wastewater |
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2009
- 2009-02-26 CN CN2009100959807A patent/CN101497470B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830547A (en) * | 2010-05-17 | 2010-09-15 | 潘泽生 | Specific treating agent for carbonated water and preparation method thereof |
| CN101830547B (en) * | 2010-05-17 | 2014-04-02 | 王冠红 | Specific treating agent for carbonated water and preparation method thereof |
| CN102030401A (en) * | 2010-11-12 | 2011-04-27 | 中冶焦耐(大连)工程技术有限公司 | Method for decyanating coking wastewater |
| CN103449589A (en) * | 2013-09-02 | 2013-12-18 | 苏州富奇诺水治理设备有限公司 | Wastewater treatment agent containing polyhexamethylene adipamide |
| CN103449589B (en) * | 2013-09-02 | 2015-01-14 | 苏州富奇诺水治理设备有限公司 | Wastewater treatment agent containing polyhexamethylene adipamide |
| CN103771571A (en) * | 2014-01-20 | 2014-05-07 | 南通华新环保设备工程有限公司 | Sewage treatment flocculating agent and application thereof |
| CN104528899A (en) * | 2014-12-15 | 2015-04-22 | 刘树芹 | Coking wastewater purifying agent as well as preparation method and application thereof |
| CN104528899B (en) * | 2014-12-15 | 2016-08-17 | 新昌县镜岭镇康柳电子元件厂 | A kind of coking chemical waste water cleanser and preparation method and application |
| CN104891623A (en) * | 2015-06-23 | 2015-09-09 | 杜普利 | Coagulant for wastewater treatment and preparing method thereof |
| CN104891623B (en) * | 2015-06-23 | 2017-12-29 | 杜普利 | Use in waste water treatment coagulant and preparation method thereof |
| CN105016445A (en) * | 2015-07-31 | 2015-11-04 | 石家庄开发区德赛化工有限公司 | Coking wastewater coagulation adsorbent and application thereof |
| CN106423111A (en) * | 2016-10-13 | 2017-02-22 | 北京北方节能环保有限公司 | BF type adsorption precipitant for treating organic wastewater |
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