CN101172729A - Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant - Google Patents
Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant Download PDFInfo
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- CN101172729A CN101172729A CNA2007101396326A CN200710139632A CN101172729A CN 101172729 A CN101172729 A CN 101172729A CN A2007101396326 A CNA2007101396326 A CN A2007101396326A CN 200710139632 A CN200710139632 A CN 200710139632A CN 101172729 A CN101172729 A CN 101172729A
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Abstract
The invention relates to a physical and chemical treatment process of surplus ammonia in a coke-oven plant. The method comprises the steps as follows: the surplus ammonia is pretreated by steaming, the PH value is adjusted to 11-12, and is delivered to the aeration basin, sufficient NaCLO is added; redox reaction is carried out at the same time of the aeration; the ammonia is delivered through a filter tank, and discharged after the adsorption tank and the depositing tank for the physical treatment. The treatment process of the surplus ammonia provided by the invention can remove the COD and ammonia nitrogen in the ammonia. The result is remarkable, and no three wastes are generated in the treatment. The discharged water highly meets the state first-grade water discharge standard and can be used as other industrial water.
Description
Technical field
The invention belongs to water, waste water or technical field of sewage, be specifically related to the treatment process of a kind of coke-oven plant remained ammonia.Waste water treatment process of the present invention belongs to the waste water multiple-stage treatment technology that contains a chemical treatment step at least.
Background technology
Coking chemical waste water is the high concentrated organic wastewater that the coke-oven plant produces in coal system coke, gas purification and coke chemicals removal process.It forms complicated, contains hazardous and noxious substances such as aromatic series such as a large amount of phenols, biphenyl, pyridine, indoles and quinoline, heterocycle and many ring organic pollutants and prussiate, fluorion, ammonia nitrogen, and pollutent colourity height is than bio-refractory.Therefore the processing of coking chemical waste water is a great problem of domestic and international field of waste water treatment always.Its intractability is that the biodegradability of waste water is very poor, and prussiate, polycyclic aromatic hydrocarbons and heterogeneous ring compound are difficult to biological degradation, and in addition, ammonia nitrogen in high density has very strong restraining effect to the activity of microbial bacterial, and Nitrogen removal effect is not good.
The treatment process of China's present stage coking chemical waste water mainly is divided into three major types such as physico-chemical process, biochemical process and materialization-biochemistry method.Wherein physico-chemical process is simple, has obtained using widely in the processing of coking chemical waste water.
It is one or more solutes that utilize in the porousness adsorbents adsorb waste water that absorption method is handled waste water, and waste water is purified, and sorbent material commonly used has gac, sulphonated coal, slag, diatomite etc.Absorption method is handled waste water cost height, and the adsorbent reactivation difficulty is unfavorable for handling the waste water of high density.Adopt chemical precipitation agent MgCl
26H
2O and Na
2HPO
412H
2O (or MgHPO
43H
2O) treatment of residual coking ammonia water, the NH in precipitation agent and the coking chemical waste water
4 +Reaction generates ammonium magnesium phosphate (MAP) precipitation, can obtain effect preferably, and ammonia-N removal rate is up to more than 99% in the waste water.Coagulation Method is to add coagulating agent and make it hydrolysis to produce hydration coordination ion and hydroxide colloid in waste water, in and in the waste water some material surface with electric charge, make these charge species generation aggegations.The key of Coagulation Method is coagulating agent, and coking producer generally adopts bodied ferric sulfate (PFS) at present, and coagulant aids is polyacrylamide (PDM).
Yet employing physico-chemical process Treatment of Wastewater in Coking also exists COD and ammonia nitrogen can't be handled simultaneously, and process object is single, the problem that processing cost is too high, and simultaneously, ammonia still process also needs to consume the more energy.
Therefore, biochemical process is still at present the main method of wastewater treatment in coke-oven plant mostly, wherein uses at most with activated sludge process (A/O technology) again.A/O Treatment of Wastewater in Coking efficient is lower at present, can't effectively remove aromatic hydrocarbons and nitrogen-containing heterocycle compound in the coking chemical waste water, and water outlet COD and ammonia nitrogen are difficult to qualified discharge, particularly ammonia nitrogen severe overweight simultaneously.Major cause is an aerobic reactor water inlet COD concentration height, with the carbon source organism is that nutraceutical heterotrophic bacteria is a dominant bacteria, suppressed the growth of nitrifier, and contain the higher Biostatic organism of concentration in the water inlet, the activity that has also suppressed nitrifier, the effect of aerobic reactor biological nitration is poor, and the water outlet ammonia nitrogen is difficult to up to standard.
In addition, the biochemical process Treatment of Wastewater in Coking also needs to consume a large amount of diluting waters, has increased cost for wastewater treatment, adds that construction investment is big, running cost is high, and enterprise is difficult to bear.
Summary of the invention
The physical chemistry treatment process that the purpose of this invention is to provide a kind of coke-oven plant remained ammonia adopts this technology can efficiently remove simultaneously COD and ammonia nitrogen in coke-oven plant's remained ammonia and the coking chemical waste water.
Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant of the present invention may further comprise the steps:
A, in remained ammonia, add the Ca (OH) of capacity
2, fully stir, making ammonium salt decomposition and inversion wherein is free ammonia;
B, conversion back waste water feed in the ammonia still, with water vapour it are heated, and free ammonia are separated desorbing from waste water;
C, with NaOH with ammonia still process after the pH value of waste water be adjusted to 11～12, feed in the aeration tank, add the NaClO of capacity, in aeration, carry out redox reaction;
Waste water after d, aeration handle is successively by filtering basin, adsorption tank and settling tank, filters, discharges after absorption and the sedimentary physical treatment.
Coke-oven plant of the present invention remained ammonia treatment process is a kind of based on chemical reaction, physical treatment is the method for assisting, thereby can directly handle waste water after coke-oven plant's remained ammonia or the ammonia still process, be not subjected to ammonia nitrogen, the volatile phenol in the remained ammonia, the influence of prussiate, and make it reach national grade one discharge standard.But the NH in coke-oven plant's remained ammonia or the coking chemical waste water
3-N is except NH
4 +Outside+the OH, also has the considerable part solid ammonium-salt, wherein with NH
4Cl is main.In order to reduce the running cost of wastewater treatment, before handling remained ammonia, preferably earlier it is carried out the ammonia still process pre-treatment with physico-chemical process.NH in the distilled ammonia wastewater after ammonia still process is handled
3The concentration of-N can be reduced to 100～200ppm (deciding on different areas water quality situation).
Owing to will carry out the ammonia still process pre-treatment earlier, how much ammonia-nitrogen content can be unrestricted in the remained ammonia of required processing, when actual treatment, can calculate the minimum dose that adds of needs according to the situation of pending water, remained ammonia thoroughly is degraded in the country-level discharge water standard.
Transform the NH that produces through the NaClO redox reaction
3Gas can major part overflow along with air in the process of aeration, if do not administered, then can form regeneration of contaminated.To this, the present invention is designed to enclosed construction with the aeration tank, and the aeration tank is provided with sealing cover, and blower unit, the NH that produces in the aeration process are installed
3Gas and Air mixing gas are introduced rare H by blower unit
2SO
4In the solution, NH
3Gas is absorbed, and air then enters in the atmosphere.As rare H
2SO
4NH in the solution
3When content reaches finite concentration, then can deliver to ammonium sulfate workshop section and produce ammonium sulfate.
For guaranteeing the serviceability of entire treatment technology, and the minimizing construction investment, the present invention adopts the existing device of technology maturation to carry out wastewater treatment, adopts the upflow filtration method as filtration process, can solve the filtering layer blocking problem effectively, and not need backwash.
If considering when treatment process design of the present invention increases the drainage facility that electrolyzes table salt, produce the oxygenant clorox from producing chlorine, then can reduce the running cost of wastewater treatment greatly.
Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant of the present invention can efficiently remove COD and the ammonia nitrogen in remained ammonia and the coking chemical waste water simultaneously, treatment effect is obvious, not having other three wastes in the treating processes produces, water outlet after the processing reaches country-level discharge water standard fully, can be used as other process waters.
The plant area area that treatment process of the present invention uses is little, less investment, and except that limited several ponds need be provided with in the open, other equipment all can be in indoor setting, and simple to operate, easy to control, working cost is lower.
Description of drawings
Fig. 1 is the process flow sheet of Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant of the present invention.
Embodiment
The concrete treating processes of coke-oven plant's remained ammonia is as shown in Figure 1:
At first remained ammonia is fed in the steel basin, add the Ca (OH) of capacity
2, fully stir, ammonium salt is wherein decomposed, simultaneously the NH in the waste water
4 +Be converted into free ammonia.Waste water after the conversion pumps into one and removes in the tar device, leaves standstill and removes tar, enters in the interchanger, by after waste water preheats after the effusive high temperature ammonia still process of ammonia still, feeds in the ammonia still, heats with water vapour, free ammonia is separated desorbing from waste water.Separate the ammonia of sucking-off and draw, after the condenser cooling, send ammonium sulfate workshop section to produce ammonium sulfate by cat head.Waste water is gone out by tower bottom flow after the ammonia still process, enter in the interchanger with transform back waste water heat-shift after, enter the hypomere operation.Its principal reaction is:
NH
3+H
2O＝NH
4 ++OH
-
2NH
4Cl+Ca(OH)
2＝2NH
3+CaCl
2+2H
2O
Through above-mentioned art breading, the NH after the ammonia still process in the waste water
3-N can be reduced to 100～200ppm.
Waste water feeds earlier in the steel basin after the ammonia still process, stirs to add NaOH down, modulate its pH value to 11～12 after, feed in the aeration tank, in the aeration tank, add strong oxidizer NaClO simultaneously, and bubbling air, under the situation of abundant aeration, carry out the redox chemistry reaction.
Reaction back waste water feeds in the next steel basin again, modulate its pH value to 11～12 equally after, feed again in another aeration tank, adding NaClO and bubbling air carry out secondary aeration redox reaction.Reaction back waste water can turn back in first aeration tank and continue circulating reaction, until thorough degraded, enters subsequent processing again.
The aeration tank is an enclosed construction, and the top is provided with sealing cover, and blower unit, the NH that produces in the aeration process are installed
3Gas and Air mixing gas are introduced a rare H by blower unit
2SO
4In the solution pool, NH
3Gas is absorbed, and air then enters in the atmosphere.As rare H
2SO
4NH in the solution
3When content reaches finite concentration, then can deliver to ammonium sulfate workshop section and produce ammonium sulfate.
Because the oxidisability of NaClO is not subjected to the restriction of medium, under alkaline condition, NaClO and NH
4 +Can be hydrolyzed simultaneously, and can mutually promote, on the one hand NaClO is transformed better towards the HClO direction, on the other hand NH
4 +Be converted into NH more
3In this process, the further promotes oxidn reduction reaction of the HClO of generation is fully decomposed ammonia nitrogen, cyanogen, sulphur cyanogen, phenol, and desorb in the process of aeration is removed from waste water.Principal reaction has:
NaClO+H
2O＝HClO+NaOH
NaOH+NH
4Cl＝NaCl+NH
3+H
2O
NH
3+HClO＝NH
2Cl+H
2O
NH
2Cl+HClO＝NHCl
2+H
2O
NH
2Cl+NHCl
2＝N
2↑+3H
++3Cl
-
CN
-+ClO
-+H
2O＝CNCl+2OH
-
CNCl+2OH
-＝CNO
-+Cl
-+H
2O
2CNO
-+3ClO
-+H
2O＝N
2↑+3Cl
-+H
2O
CH
3COOH+O
2→HCOOH
HCOOH+O
2→CO
2↑+H
2O
NH
3+O
2→H
2O+N
2
NH
4SCN+O
2→N
2+H
2O+H
2SO
4+CO
2
Along with the carrying out of whole redox reaction process, the COD in the remained ammonia has also obtained degraded.Simultaneously, because the generation of acidic substance, alkaline waste water has obtained neutralization, and the pH value of final drainage water directly can reach about 6, substantially without re-adjustment.
Waste water after aeration is handled by cascade filtration pond, adsorption tank and settling tank, filters respectively successively, after absorption and the sedimentary physical treatment, clear water directly discharges or reuse.
Stepwise degradation is adopted in technological design of the present invention, such design both can guarantee sufficient chemical time, can reduce the running cost of wastewater treatment again, in conjunction with a series of physical processes such as aeration, filtration, absorption, precipitations, every technical indicator of discharging waste water all is up to state standards more than the first grade discharging water quality standard.
Water-quality guideline before and after remained ammonia is handled
| Project | The pH value | Ammonia nitrogen (ppm) | Volatile phenol (ppm) | Prussiate (ppm) | COD(ppm) |
| Before the |
8 | ＞1700 | ＞70 | ＞50 | ＞3500 |
| After the processing | 6 | ＜15 | ＜0.5 | ＜0.5 | ＜100 |
Claims (4)
1. Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant may further comprise the steps:
A, in remained ammonia, add the Ca (OH) of capacity
2, fully stir, making ammonium salt decomposition and inversion wherein is free ammonia;
B, conversion back waste water feed in the ammonia still, with water vapour it are heated, and free ammonia are separated desorbing from waste water;
C, with NaOH with ammonia still process after the pH value of waste water be adjusted to 11～12, feed in the aeration tank, add the NaClO of capacity, in aeration, carry out redox reaction;
Waste water after d, aeration handle is successively by filtering basin, adsorption tank and settling tank, filters, discharges after absorption and the sedimentary physical treatment.
2. Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant according to claim 1 is characterized in that described aeration tank is an enclosed construction, and the aeration tank is provided with sealing cover, and blower unit is installed, and the gas that aeration process produces feeds rare H by blower unit
2SO
4In the solution, absorb NH wherein
3The back discharging.
3. Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant according to claim 1 is characterized in that described filtration employing upflow filtration.
4. Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant according to claim 1 is characterized in that NH in the distilled ammonia wastewater after ammonia still is handled
3The concentration of-N is 100～200ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101396326A CN101172729A (en) | 2007-10-26 | 2007-10-26 | Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101396326A CN101172729A (en) | 2007-10-26 | 2007-10-26 | Physciochemical treatment technique for remained aqueous ammonia of coke-oven plant |
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| Publication Number | Publication Date |
|---|---|
| CN101172729A true CN101172729A (en) | 2008-05-07 |
Family
ID=39421522
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618920B (en) * | 2008-07-03 | 2012-05-30 | 山东铁雄冶金科技有限公司 | High COD, high ammonia nitrogen and high salinity industrial wastewater treatment method |
| CN102942266A (en) * | 2012-11-13 | 2013-02-27 | 常州大学 | Bromo-aliphatic hydrocarbon compound production waste water treatment method |
| CN103030235A (en) * | 2012-09-17 | 2013-04-10 | 何学文 | Ammonia-nitrogen wastewater treatment method |
| CN104229991A (en) * | 2014-08-26 | 2014-12-24 | 常州大学 | Device for processing high-concentration ammonia nitrogen in chemical wastewater by using surface active catalyst |
| CN104817157A (en) * | 2015-05-14 | 2015-08-05 | 四川润雅环境工程有限公司 | Chemical wastewater pretreatment method and sequencing-batch alkaline hydrolysis reactor |
| CN106830440A (en) * | 2017-03-21 | 2017-06-13 | 西安西热水务环保有限公司 | A kind of thermal power plant's high-salt wastewater dish tubular membrane concentrating and treating system and method |
| CN109809621A (en) * | 2019-03-07 | 2019-05-28 | 北京理工水环境科学研究院有限公司 | A kind of processing method containing ammonia-nitrogen sewage |
| CN111547954A (en) * | 2020-05-23 | 2020-08-18 | 季丹萍 | Coal chemical wastewater treatment system |
| CN113666560A (en) * | 2021-08-25 | 2021-11-19 | 清创人和生态工程技术有限公司 | Method for treating high-ammonia nitrogen wastewater with high harmful organic matters |
| CN115072917A (en) * | 2022-04-25 | 2022-09-20 | 信丰华锐钨钼新材料有限公司 | Efficient treatment method for high-concentration ammonia nitrogen wastewater in tungsten smelting |
-
2007
- 2007-10-26 CN CNA2007101396326A patent/CN101172729A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618920B (en) * | 2008-07-03 | 2012-05-30 | 山东铁雄冶金科技有限公司 | High COD, high ammonia nitrogen and high salinity industrial wastewater treatment method |
| CN103030235A (en) * | 2012-09-17 | 2013-04-10 | 何学文 | Ammonia-nitrogen wastewater treatment method |
| CN102942266A (en) * | 2012-11-13 | 2013-02-27 | 常州大学 | Bromo-aliphatic hydrocarbon compound production waste water treatment method |
| CN104229991A (en) * | 2014-08-26 | 2014-12-24 | 常州大学 | Device for processing high-concentration ammonia nitrogen in chemical wastewater by using surface active catalyst |
| CN104229991B (en) * | 2014-08-26 | 2016-03-09 | 常州大学 | Surfactivity catalyst treatment wastewater from chemical industry middle and high concentration ammonia nitrogen device |
| CN104817157A (en) * | 2015-05-14 | 2015-08-05 | 四川润雅环境工程有限公司 | Chemical wastewater pretreatment method and sequencing-batch alkaline hydrolysis reactor |
| CN106830440A (en) * | 2017-03-21 | 2017-06-13 | 西安西热水务环保有限公司 | A kind of thermal power plant's high-salt wastewater dish tubular membrane concentrating and treating system and method |
| CN109809621A (en) * | 2019-03-07 | 2019-05-28 | 北京理工水环境科学研究院有限公司 | A kind of processing method containing ammonia-nitrogen sewage |
| CN109809621B (en) * | 2019-03-07 | 2022-08-16 | 北京太和洁源科技发展有限公司 | Method for treating sewage containing ammonia nitrogen |
| CN111547954A (en) * | 2020-05-23 | 2020-08-18 | 季丹萍 | Coal chemical wastewater treatment system |
| CN111547954B (en) * | 2020-05-23 | 2022-09-30 | 朱栋梁 | Coal chemical wastewater treatment system |
| CN113666560A (en) * | 2021-08-25 | 2021-11-19 | 清创人和生态工程技术有限公司 | Method for treating high-ammonia nitrogen wastewater with high harmful organic matters |
| CN115072917A (en) * | 2022-04-25 | 2022-09-20 | 信丰华锐钨钼新材料有限公司 | Efficient treatment method for high-concentration ammonia nitrogen wastewater in tungsten smelting |
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