CN103113000A - Efficient coking wastewater treatment method - Google Patents
Efficient coking wastewater treatment method Download PDFInfo
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- CN103113000A CN103113000A CN 201310060485 CN201310060485A CN103113000A CN 103113000 A CN103113000 A CN 103113000A CN 201310060485 CN201310060485 CN 201310060485 CN 201310060485 A CN201310060485 A CN 201310060485A CN 103113000 A CN103113000 A CN 103113000A
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Abstract
The invention provides an efficient coking wastewater treatment method. The efficient coking wastewater treatment method comprises the following steps of: pretreatment, nitrogen removal, biological treatment, electrocoagulation treatment and reverse osmosis treatment; and the method is characterized in that the original problem that a biological nitrogen source is redundant is solved through early efficient nitrogen removal, so that the effect and efficiency of later biochemical treatment is ensued.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment, relate to especially a kind for the treatment of process of coking chemical waste water.
Background technology
Coking chemical waste water refers generally to from the generation water in coke oven gas primary-cooling and coking production process and vapor condensation waste water.China is global coke production and consumes big country, Coke Industry is when satisfying the every profession and trade development needs such as iron and steel, chemical industry, machinery, and the three industrial wastes that it brings are processed problem, also become increasingly conspicuous, especially the processing of coking chemical waste water, focus and the difficult point of research in industry especially.Coking chemical waste water contains multiple environmental pollutant on the one hand, also contains on the other hand multiple strong carcinogen, so coking chemical waste water on the one hand can cause severe contamination to environment, also can directly threaten human health on the other hand.
Contain a large amount of ammonia nitrogens in coking chemical waste water, take phenols as main organic pollutant, also contain the hazardous and noxious substances such as cyanogen, inorganic fluorion and chlorion, also comprise in addition a large amount of suspended particles, pollutent colourity is high.In the treating processes to coking chemical waste water, except ammonia nitrogen, except phenol, except cyanogen and except suspended particle be several most important be also the link that affects most efficient.And because the high characteristics of nitrogen content in coking chemical waste water cause the required nitrogenous source of biopurification superfluous, can't obtain good result when causing using biochemical process to remove the pollutent such as phenol, cyanogen.
Summary of the invention
The invention provides a kind for the treatment of process of efficient coking chemical waste water, the method comprises pre-treatment, denitrogenates, carries out a biological disposal upon, the step of electric flocculation treatment and reverse-osmosis treated, its key point is by early stage efficiently except the ammonia step, the problem of the biological nitrogenous source surplus that originally exists has not been existed, thereby guaranteed effect and the efficient of later stage biochemical treatment.Specifically, the method includes the steps of:
(1) pre-treatment mainly is comprised of oil removal and pH regulator, and at first the waste water that gives off pass through oil trap, adopts the dull and stereotyped oil wiper in top layer to remove the top layer greasy dirt in oil trap, with hydrochloric acid or sodium hydroxide, the pH value of waste water is adjusted to 7.5～8.5 subsequently;
(2) denitrogenate, the waste water after step (1) is processed enters the column nitrogen removing device, wherein is filled with except the ammonia agent, and waste water enters biological treatment step after by this column nitrogen removing device, and the hydraulic detention time of waste water in nitrogen removing device is 3～6 hours;
(3) biological treatment, mainly consisted of by bio anaerobic, the oxygen of holding concurrently, oxygen consumption, MBR separate tank, utilize traditional anaerobism, double oxygen, oxygen consumption biologic treating technique to remove the most of inorganic and organic pollutant in coking chemical waste water, reduce the colourity of COD, BOD, prussiate, phenol and sewage, utilize simultaneously the MBR membrane separation technique to separate completely water outlet, in the reservation biological treatment system of maximum possible, effective bacterium, improve sludge concentration, and then improve the efficient of biological treatment;
(4) electric flocculation treatment makes the electricity consumption flocculation reactor process the waste water after biological treatment, and flocculation sediment is discharged from lower floor's mud relief outlet, and supernatant liquor enters next treatment step;
(5) reverse osmosis (RO) is processed, and the supernatant liquor that obtains after electric flocculation treatment is for further processing, and utilizes the SS in reverse osmosis unit desalination reduction water, makes the processing water outlet reach discharging or reuse standard.
Preferably, in step (4), electric flocculation reactor adopts aluminium sheet as anode, adopts stainless steel as negative electrode, and the spacing between the pole plate of anode and negative electrode is 4.0～5.0mm, and the polar plate voltage of anode and negative electrode is 18～20V.
Preferably, use in step (2) except the ammonia agent be a kind of macromolecular material that contains metal, this macromolecular material can make by following step:
A, with p-tert-butylphenol, formalin, inorganic or organic dispersing agent, and pore-creating agent mixes, adding aqueous sodium hydroxide solution to make the pH of system value is 11～12, makes whole mixture be the polymerization suspended state, makes polymkeric substance I,
The weight ratio of described composition is p-tert-butylphenol: formaldehyde: dispersion agent: pore-creating agent=0.7～0.8: 0.1～0.15: 0.05～0.1: 0.05～0.1;
B, to polymkeric substance I and the chloromethylation reagent react of step a, introduce chloromethyl, then product and aminating agent carried out amination reaction;
C, at room temperature, metallic compound is mixed with nitrate or chlorate solution, with the product of this solution stream through step b, carry out the dynamic metal doping, flow rate control is at 3BV/h～4BV/h, wherein metallic element can be Cr, Mn, Fe, Ni, Cu or Zn, and the concentration of metallic compound is 20～60% weight percents.
In described step a, suspension polymerization is specially each composition is added in reactor, pass into nitrogen in reactor, make that in reactor, pressure remains under the barotropic state of gauge pressure less than or equal to 0.4MPa, be warming up to 110 ℃～120 ℃, be incubated 4 hours～8 hours, then be cooled to 60 ℃～80 ℃, be incubated 3 hours～8 hours, then washing, dry, screening, collecting granularity is the spherical matrix polymer of 0.1mm～0.5mm.
Dispersion agent in described step a is one or both in inorganic dispersant or organic dispersing agent, described inorganic dispersant is one or more in silicate, carbonate or phosphoric acid salt, and described organic dispersing agent is a kind of several in polyvinyl alcohol, gelatin, carboxymethyl cellulose or polyacrylate.
Pore-creating agent in described step a is one or more in Tai-Ace S 150, magnesium chloride, sodium bicarbonate or alum.
Preferably, in step (2), can denitrogenate agent with the diluted acid flushing and make it denitrogenate functional regeneration when the ability of denitrogenating of denitrogenating agent descends.
Coking waste water treatment method provided by the invention mainly comprises pre-treatment, denitrogenates, carries out a biological disposal upon, the step of electric flocculation treatment and reverse-osmosis treated.Finally reach processing to coking chemical waste water by series of physical, chemistry and biological method.Inventive point of the present invention is:
1, used the novel agent of denitrogenating, thisly denitrogenate agent to denitrogenate on the one hand efficient high, specificity is high on the other hand, using this effect of denitrogenating the agent acquisition is merely to have reduced nitrogen content, and can be by waste water the time by nitrogen removing device control denitrogenate after the concentration of ammonia-nitrogen content in water, be that good environment is created in follow-up biological treatment.
2, by pre-treatment, denitrogenate, carry out a biological disposal upon, the combination of electricity flocculation and reverse osmosis, improved the processing efficiency of coking chemical waste water, promoted the treatment effect of coking chemical waste water, can effectively remove the nuisance in coking chemical waste water, have it to removing ammonia nitrogen and hardly degraded organic substance, very good effect to be arranged.
Embodiment
Embodiment 1
The coking chemical waste water that certain coke-oven plant produces is processed with method of the present invention, and step is as follows:
(1) pre-treatment mainly is comprised of oil removal and pH regulator, and at first the waste water that gives off pass through oil trap, adopts the dull and stereotyped oil wiper in top layer to remove the top layer greasy dirt in oil trap, with hydrochloric acid or sodium hydroxide, the pH value of waste water is adjusted to 8 subsequently;
(2) denitrogenate, the waste water after step (1) is processed enters the column nitrogen removing device, wherein is filled with except the ammonia agent, and waste water enters biological treatment step after by this column nitrogen removing device, and the hydraulic detention time of waste water in nitrogen removing device is 4 hours;
(3) biological treatment, mainly consisted of by bio anaerobic, the oxygen of holding concurrently, oxygen consumption, MBR separate tank, utilize traditional anaerobism, double oxygen, oxygen consumption biologic treating technique to remove the most of inorganic and organic pollutant in coking chemical waste water, reduce the colourity of COD, BOD, prussiate, phenol and sewage, utilize simultaneously the MBR membrane separation technique to separate completely water outlet, in the reservation biological treatment system of maximum possible, effective bacterium, improve sludge concentration, and then improve the efficient of biological treatment;
(4) electric flocculation treatment, the electricity consumption flocculation reactor is processed the waste water after biological treatment, the electricity flocculation reactor adopts aluminium sheet as anode, adopt stainless steel as negative electrode, spacing between the pole plate of anode and negative electrode is 4.5mm, the polar plate voltage of anode and negative electrode is 18V, and flocculation sediment is discharged from lower floor's mud relief outlet, and supernatant liquor enters next treatment step;
(5) reverse osmosis (RO) is processed, and the supernatant liquor that obtains after electric flocculation treatment is for further processing, and utilizes the SS in reverse osmosis unit desalination reduction water, makes the processing water outlet reach discharging or reuse standard.
Use in step (2) except the ammonia agent be a kind of macromolecular material that contains metal, it makes by following step:
a, with p-tert-butylphenol, formalin, polyvinyl alcohol and Tai-Ace S 150 mix, adding aqueous sodium hydroxide solution to make the pH of system value is 11, make whole mixture be the polymerization suspended state, make polymkeric substance I, the weight ratio of described composition is p-tert-butylphenol: formaldehyde: polyvinyl alcohol: Tai-Ace S 150=0.7: 0.15: 0.07: 0.08, mentioned component is added in reactor, pass into nitrogen in reactor, make that in reactor, pressure remains under the barotropic state of gauge pressure less than or equal to 0.4MPa, be warming up to 120 ℃, be incubated 8 hours, be cooled to again 80 ℃, be incubated 8 hours, then washing, dry, screening, collecting granularity is the spherical matrix polymer of 0.2mm～0.3mm.
B, to spherical matrix polymer and the chloromethylation reagent react of step a, introduce chloromethyl, then product and aminating agent carried out amination reaction;
C, at room temperature is the cupric nitrate of 30% weight percent with concentration, with the product of this solution stream through step b, carries out the dynamic metal doping, and flow rate control is at 3BV/h.
Water quality situation before and after processing sees the following form.
| ? | COD cr(mg/L) | Ammonia nitrogen (mg/L) | Total phenol (mg/L) | Suspended particle (mg/L) | Total cyanogen (mg/L) |
| Water inlet | 1740 | 423 | 78 | 326 | 4.6 |
| Water outlet | 25 | 6.5 | 0.9 | 6.4 | 0.1 |
Embodiment 2
The coking chemical waste water that certain coke-oven plant produces is processed with method of the present invention, and step is as follows:
(1) pre-treatment mainly is comprised of oil removal and pH regulator, and at first the waste water that gives off pass through oil trap, adopts the dull and stereotyped oil wiper in top layer to remove the top layer greasy dirt in oil trap, with hydrochloric acid or sodium hydroxide, the pH value of waste water is adjusted to 8 subsequently;
(2) denitrogenate, the waste water after step (1) is processed enters the column nitrogen removing device, wherein is filled with except the ammonia agent, and waste water enters biological treatment step after by this column nitrogen removing device, and the hydraulic detention time of waste water in nitrogen removing device is 5 hours;
(3) biological treatment, mainly consisted of by bio anaerobic, the oxygen of holding concurrently, oxygen consumption, MBR separate tank, utilize traditional anaerobism, double oxygen, oxygen consumption biologic treating technique to remove the most of inorganic and organic pollutant in coking chemical waste water, reduce the colourity of COD, BOD, prussiate, phenol and sewage, utilize simultaneously the MBR membrane separation technique to separate completely water outlet, in the reservation biological treatment system of maximum possible, effective bacterium, improve sludge concentration, and then improve the efficient of biological treatment;
(4) electric flocculation treatment, the electricity consumption flocculation reactor is processed the waste water after biological treatment, the electricity flocculation reactor adopts aluminium sheet as anode, adopt stainless steel as negative electrode, spacing between the pole plate of anode and negative electrode is 5mm, the polar plate voltage of anode and negative electrode is 20V, and flocculation sediment is discharged from lower floor's mud relief outlet, and supernatant liquor enters next treatment step;
(5) reverse osmosis (RO) is processed, and the supernatant liquor that obtains after electric flocculation treatment is for further processing, and utilizes the SS in reverse osmosis unit desalination reduction water, makes the processing water outlet reach discharging or reuse standard.
Use in step (2) except the ammonia agent be a kind of macromolecular material that contains metal, it makes by following step:
a, with p-tert-butylphenol, formalin, water glass and magnesium chloride mix, adding aqueous sodium hydroxide solution to make the pH of system value is 12, make whole mixture be the polymerization suspended state, make polymkeric substance I, the weight ratio of described composition is p-tert-butylphenol: formaldehyde: water glass: magnesium chloride=0.75: 0.13: 0.06: 0.06, mentioned component is added in reactor, pass into nitrogen in reactor, make that in reactor, pressure remains under the barotropic state of gauge pressure less than or equal to 0.4MPa, be warming up to 110 ℃, be incubated 7 hours, be cooled to again 70 ℃, be incubated 5 hours, then washing, dry, screening, collecting granularity is the spherical matrix polymer of 0.3mm～0.5mm,
B, to spherical matrix polymer and the chloromethylation reagent react of step a, introduce chloromethyl, then product and aminating agent carried out amination reaction;
C, at room temperature is the zinc chloride of 35% weight percent with concentration, with the product of this solution stream through step b, carries out the dynamic metal doping, and flow rate control is at 4BV/h.
Water quality situation before and after processing sees the following form.
| ? | COD cr(mg/L) | Ammonia nitrogen (mg/L) | Total phenol (mg/L) | Suspended particle (mg/L) | Total cyanogen (mg/L) |
| Water inlet | 1540 | 360 | 72 | 348 | 5.6 |
| Water outlet | 27 | 5.7 | 0.8 | 7.1 | 0.08 |
Embodiment 3
The coking chemical waste water that certain coke-oven plant produces is processed with method of the present invention, and step is as follows:
(1) pre-treatment mainly is comprised of oil removal and pH regulator, and at first the waste water that gives off pass through oil trap, adopts the dull and stereotyped oil wiper in top layer to remove the top layer greasy dirt in oil trap, with hydrochloric acid or sodium hydroxide, the pH value of waste water is adjusted to 8 subsequently;
(2) denitrogenate, the waste water after step (1) is processed enters the column nitrogen removing device, wherein is filled with except the ammonia agent, and waste water enters biological treatment step after by this column nitrogen removing device, and the hydraulic detention time of waste water in nitrogen removing device is 6 hours;
(3) biological treatment, mainly consisted of by bio anaerobic, the oxygen of holding concurrently, oxygen consumption, MBR separate tank, utilize traditional anaerobism, double oxygen, oxygen consumption biologic treating technique to remove the most of inorganic and organic pollutant in coking chemical waste water, reduce the colourity of COD, BOD, prussiate, phenol and sewage, utilize simultaneously the MBR membrane separation technique to separate completely water outlet, in the reservation biological treatment system of maximum possible, effective bacterium, improve sludge concentration, and then improve the efficient of biological treatment;
(4) electric flocculation treatment, the electricity consumption flocculation reactor is processed the waste water after biological treatment, the electricity flocculation reactor adopts aluminium sheet as anode, adopt stainless steel as negative electrode, spacing between the pole plate of anode and negative electrode is 4mm, the polar plate voltage of anode and negative electrode is 18V, and flocculation sediment is discharged from lower floor's mud relief outlet, and supernatant liquor enters next treatment step;
(5) reverse osmosis (RO) is processed, and the supernatant liquor that obtains after electric flocculation treatment is for further processing, and utilizes the SS in reverse osmosis unit desalination reduction water, makes the processing water outlet reach discharging or reuse standard.
Use in step (2) except the ammonia agent be a kind of macromolecular material that contains metal, it makes by following step:
a, with p-tert-butylphenol, formalin, water glass and magnesium chloride mix, adding aqueous sodium hydroxide solution to make the pH of system value is 12, make whole mixture be the polymerization suspended state, make polymkeric substance I, the weight ratio of described composition is p-tert-butylphenol: formaldehyde: carboxymethyl cellulose: alum=0.7: 0.1: 0.1: 0.1, mentioned component is added in reactor, pass into nitrogen in reactor, make that in reactor, pressure remains under the barotropic state of gauge pressure less than or equal to 0.4MPa, be warming up to 110 ℃, be incubated 8 hours, be cooled to again 60 ℃, be incubated 4 hours, then washing, dry, screening, collecting granularity is the spherical matrix polymer of 0.2mm～0.5mm,
B, to spherical matrix polymer and the chloromethylation reagent react of step a, introduce chloromethyl, then product and aminating agent carried out amination reaction;
C, at room temperature is the iron nitrate of 43% weight percent with concentration, with the product of this solution stream through step b, carries out the dynamic metal doping, and flow rate control is at 4BV/h.
Water quality situation before and after processing sees the following form.
| ? | COD cr(mg/L) | Ammonia nitrogen (mg/L) | Total phenol (mg/L) | Suspended particle (mg/L) | Total cyanogen (mg/L) |
| Water inlet | 1965 | 403 | 107 | 421 | 12.3 |
| Water outlet | 34 | 7.1 | 1.3 | 7.5 | 0.15 |
Can see from above-mentioned several embodiment, the method for Treatment of Wastewater in Coking used in the present invention is effective.In addition, denitrogenate agent for used in the present invention, the applicant has carried out the independent test of denitrogenating, and the agent of denitrogenating of using is the agent of denitrogenating of using in embodiment 1,2 and 3.Get and denitrogenate agent 200g and pack into except the ammonia nitrogen device, the ammonia-nitrogen content that flows into water is respectively 100,200 and 300mg/L, and pH is 8, flow velocity 3BV/h.In mensuration outflow water, the ammonia-nitrogen content result is as follows:
| ? | Denitrogenate agent in embodiment 1 | Denitrogenate agent in embodiment 2 | Denitrogenate agent in embodiment 3 |
| Influent ammonia nitrogen 100mg/L | 15.6mg/L | 18.7mg/L | 14.3mg/L |
| Influent ammonia nitrogen 200mg/L | 16.9mg/L | 18.8mg/L | 14.6mg/L |
| Influent ammonia nitrogen 300mg/L | 17.1mg/L | 19mg/L | 15.1mg/L |
As seen from the above table, used in the present inventionly denitrogenate agent and have the good function of denitrogenating.
Those skilled in the art can make replacement or modification to content of the present invention according to content disclosed by the invention and the art technology of grasping; but these replacements or modification should not be considered as breaking away from the present invention's design, and these replacements or modification are all in the claimed interest field of the present invention.
Claims (6)
1. the high-efficient treatment method of a coking chemical waste water, the method comprise and comprise following steps:
(1) pre-treatment mainly is comprised of oil removal and pH regulator, and at first the waste water that gives off pass through oil trap, adopts the dull and stereotyped oil wiper in top layer to remove the top layer greasy dirt in oil trap, with hydrochloric acid or sodium hydroxide, the pH value of waste water is adjusted to 7.5～8.5 subsequently;
(2) denitrogenate, the waste water after step (1) is processed enters the column nitrogen removing device, wherein is filled with except the ammonia agent, and waste water enters biological treatment step after by this column nitrogen removing device, and the hydraulic detention time of waste water in nitrogen removing device is 3～6 hours;
(3) biological treatment, mainly consisted of by bio anaerobic, the oxygen of holding concurrently, oxygen consumption, MBR separate tank, utilize traditional anaerobism, double oxygen, oxygen consumption biologic treating technique to remove the most of inorganic and organic pollutant in coking chemical waste water, reduce the colourity of COD, BOD, prussiate, phenol and sewage, utilize simultaneously the MBR membrane separation technique to separate completely water outlet, in the reservation biological treatment system of maximum possible, effective bacterium, improve sludge concentration, and then improve the efficient of biological treatment;
(4) electric flocculation treatment makes the electricity consumption flocculation reactor process the waste water after biological treatment, and flocculation sediment is discharged from lower floor's mud relief outlet, and supernatant liquor enters next treatment step;
(5) reverse osmosis (RO) is processed, and the supernatant liquor that obtains after electric flocculation treatment is for further processing, and utilizes the SS in reverse osmosis unit desalination reduction water, makes the processing water outlet reach discharging or reuse standard.
2. the high-efficient treatment method of the coking chemical waste water described in claim 1, it is characterized in that in step (4), the electricity flocculation reactor adopts aluminium sheet as anode, adopt stainless steel as negative electrode, spacing between the pole plate of anode and negative electrode is 4.0～5.0mm, and the polar plate voltage of anode and negative electrode is 18～20V.
3. the high-efficient treatment method of the coking chemical waste water described in claim 1 or 2, it is characterized in that using in step (2) except the ammonia agent be a kind of macromolecular material that contains metal, this macromolecular material can make by following step:
A, with p-tert-butylphenol, formalin, inorganic or organic dispersing agent, and pore-creating agent mixes, adding aqueous sodium hydroxide solution to make the pH of system value is 11～12, makes whole mixture be the polymerization suspended state, makes polymkeric substance I,
The weight ratio of described composition is p-tert-butylphenol: formaldehyde: dispersion agent: pore-creating agent=0.7～0.8: 0.1～0.15: 0.05～0.1: 0.05～0.1;
B, to polymkeric substance I and the chloromethylation reagent react of step a, introduce chloromethyl, then product and aminating agent carried out amination reaction;
C, at room temperature, metallic compound is mixed with nitrate or chlorate solution, with the product of this solution stream through step b, carry out the dynamic metal doping, flow rate control is at 3BV/h～4BV/h, wherein metallic element can be Cr, Mn, Fe, Ni, Cu or Zn, and the concentration of metallic compound is 20～60% weight percents.
In described step a, suspension polymerization is specially each composition is added in reactor, pass into nitrogen in reactor, make that in reactor, pressure remains under the barotropic state of gauge pressure less than or equal to 0.4MPa, be warming up to 110 ℃～120 ℃, be incubated 4 hours～8 hours, then be cooled to 60 ℃～80 ℃, be incubated 3 hours～8 hours, then washing, dry, screening, collecting granularity is the spherical matrix polymer of 0.1mm～0.5mm.
4. the high-efficient treatment method of the coking chemical waste water described in claim 2 or 3, it is characterized in that dispersion agent in described step a is one or both in inorganic dispersant or organic dispersing agent, described inorganic dispersant is one or more in silicate, carbonate or phosphoric acid salt, and described organic dispersing agent is a kind of several in polyvinyl alcohol, gelatin, carboxymethyl cellulose or polyacrylate.
5. the high-efficient treatment method of the coking chemical waste water described in claim 2 or 3 is characterized in that pore-creating agent in described step a is one or more in Tai-Ace S 150, magnesium chloride, sodium bicarbonate or alum.
6. the high-efficient treatment method of the coking chemical waste water described in claim 2 or 3, is characterized in that in step (2), can denitrogenate agent with the diluted acid flushing and make it denitrogenate functional regeneration when the ability of denitrogenating of denitrogenating agent descends.
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| CN 201310060485 CN103113000A (en) | 2013-02-27 | 2013-02-27 | Efficient coking wastewater treatment method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145303A (en) * | 2013-04-02 | 2013-06-12 | 江苏艾特克环境工程有限公司 | Efficient treating method of coking wastewater |
| CN111423050A (en) * | 2018-12-03 | 2020-07-17 | 浙江天地环保科技有限公司 | Sewage purification treatment system and treatment method |
-
2013
- 2013-02-27 CN CN 201310060485 patent/CN103113000A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145303A (en) * | 2013-04-02 | 2013-06-12 | 江苏艾特克环境工程有限公司 | Efficient treating method of coking wastewater |
| CN111423050A (en) * | 2018-12-03 | 2020-07-17 | 浙江天地环保科技有限公司 | Sewage purification treatment system and treatment method |
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Application publication date: 20130522 |