CN101798124B - Method for treating ammonia and nitrogen in coking wastewater - Google Patents
Method for treating ammonia and nitrogen in coking wastewater Download PDFInfo
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- CN101798124B CN101798124B CN201010145704XA CN201010145704A CN101798124B CN 101798124 B CN101798124 B CN 101798124B CN 201010145704X A CN201010145704X A CN 201010145704XA CN 201010145704 A CN201010145704 A CN 201010145704A CN 101798124 B CN101798124 B CN 101798124B
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Abstract
The invention relates to a method for treating ammonia and nitrogen in coking wastewater, comprising the following steps: mixing evenly sodium hydroxide and pulverized fuel ash according to the weight ratio of 0.8-1.4:1; calcinating the mixture at 500-850 DEG C for 2h; adding water to the mixture and stirring the water to the mixture at room temperature for 3-12h; controlling the weight ratio of the water to the sodium hydroxide at 5-12:1; crystallizing the mixture at 90 DEG C for 6-14h; filtering the mixture, washing and drying to obtain zeolite synthesized by the pulverized fuel ash; directly adding the zeolite synthesized by the pulverized fuel ash to biologically-treated secondary coking wastewater, and discharging the effluent ammonia and the effluent nitrogen which reach the national primary discharging standard. The method for treating the ammonia and the nitrogen in coking wastewater needs less investment and low operation cost, is easy to operate and can turn the solid waste of pulverized fuel ash into the resource.
Description
Technical field
The present invention relates to the method that ammonia nitrogen is handled in a kind of waste water, especially a kind of flyash synthetic zeolite that utilizes is to the ammonia nitrogen processing method in the coking chemical waste water.
Background technology
Because entering in a large number of ammonia nitrogen waste water caused the eutrophication of water body, caused the excessive multiplication of algae and microorganism, finally causes the mortality of fish, even by food chain the people poisoned.The water quality eutrophication has become one of the most serious pollution of water body, and strict ammonia nitrogen discharge standard has been formulated in more and more countries and area, to improve water environment.
The complicated component of coking chemical waste water is a kind of unmanageable industrial wastewater, endangers bigger.At present, in the secondary coking chemical waste water after domestic coke-oven plant's employing general biochemical method is handled, ammonia nitrogen content does not reach national specified discharge standard as yet, need carry out the advanced treating of denitrogenation, to realize qualified discharge, reduces the purpose of environmental pollution.The deep treatment method of ammonia nitrogen mainly contains in the coking chemical waste water: biological denitrificaion method, break point chlorination method, chemical precipitation method, membrane processing method and absorption method etc.The biological denitrificaion method is removed the efficient height, but initial investment is big, the required condition harshness of growth of microorganism, and a little less than the anti-load-bearing capacity, the environmental requirement height.Break point chlorination method nitric efficiency height is not influenced by water temperature, and is easy to operate, but its break is difficult to control the easy and chlorine generation haloform of organic matter in the water.Operation is simple and reliable for chemical precipitation method, but it is higher to handle reagent cost.Film is handled nitrogenous effluent need carry out strict preliminary treatment to former water, pollute to avoid frequent film, thus the disposal cost height, operation inconvenience.
Absorption method is one of denitrification treatment technology of using always, small investment, and technology is simple, and is easy to operate, carries out having special advantages aspect the advanced treating at the ammonia nitrogen waste water of centering low concentration.Seek the cheap sorbing material of effectively removing ammonia nitrogen in the waste water and become problem demanding prompt solution in the water protection.
Flyash is the solid waste of coal-burning power plant's discharging, and its discharge capacity and day sharp increase not only take a large amount of soils, and cause serious environmental to be polluted.How according to the characteristic of flyash, recycling flyash has been subjected to researcher's common concern.Studies show that, flyash and flyash synthetic zeolite have better performance in wastewater treatment, publication number is the CN1064664 patent, with flyash is the coking chemical waste water of sorbent treatment from the biochemistry outlet, COD, volatile phenol, cyanide, sulfide, BOD, colourity all reach the coking chemical waste water discharge standard in the water of processing back, but ammonia-nitrogen content is higher, still can not realize qualified discharge; Publication number is a CN 101077815A patent, earlier use the flocculant preliminary treatment, use flyash-quick lime adsorption treatment coking chemical waste water again after, ammonia-nitrogen content is reduced to 19.8mg/L by 77.67mg/L in the water quality, but do not reach first discharge standard yet, and treatment process relative complex; Publication number is the patent of CN 1296129C, utilizes the flyash synthetic zeolite to carry out sewage synchronous denitrification dephosphorizing advanced treating, but in flyash synthetic zeolite process, has added materials such as siliceous, aluminium, has increased the cost of synthetic zeolite.
Summary of the invention
In order to solve the deficiency that prior art exists, can not qualified discharge at the ammonia nitrogen in the secondary coking chemical waste water of coke-oven plant after biochemical treatment, the invention provides a kind of method of utilizing the flyash synthetic zeolite ammonia nitrogen in the coking chemical waste water to be carried out advanced treating.
To achieve these goals, the measure that the inventive method is taked is with flyash and NaOH mixes and roasting, adds water again and at room temperature stirs, and 90 ℃ of crystallization are filtered then, washing, and oven dry makes the flyash synthetic zeolite; The flyash synthetic zeolite directly added in the secondary coking chemical waste water after the biochemical treatment adsorb, solid-liquid isolated by filtration then can realize the qualified discharge of ammonia nitrogen in the coking chemical waste water.
The inventive method is to utilize the flyash synthetic zeolite that the ammonia nitrogen in the coking chemical waste water is carried out advanced treating, and its concrete steps are as follows:
1) with flyash be raw material, in NaOH: the flyash weight ratio was that 0.8～1.4 ratio mixes two kinds of compositions, 500-850 ℃ of roasting 2 hours;
2) in above-mentioned steps 1) add water in the gained mixture, at room temperature stirred 3-12 hour, control water: the NaOH weight ratio is 5～12, again at 90 ℃ of crystallization 6-14 hours, filters then, washing, oven dry makes the flyash synthetic zeolite;
3) with above-mentioned steps 2) gained flyash synthetic zeolite directly adds in the secondary coking chemical waste water after the biochemical treatment, and dosage is a 30g/L waste water, and at normal temperature absorption 45-120 branch, the solid-liquid isolated by filtration can realize the qualified discharge to ammonia nitrogen in the coking chemical waste water then.
Compared with prior art, the inventive method is utilized in the secondary coking chemical waste water after the flyash synthetic zeolite directly adds biochemical treatment and is carried out denitrogenation processing, adopt lower operating cost and investment cost, make ammonia nitrogen qualified discharge in the coking chemical waste water, reach the purpose that reduces environmental pollution, realize the resource of solid waste coal ash simultaneously.
The inventive method is simple to operate, only needs absorption and two steps of isolated by filtration to get final product; Need not other adding set, small investment, operating cost is low; With the solid waste coal ash synthetic zeolite, need not to add materials such as siliceous, aluminium, have characteristics such as raw material is cheap and easy to get, synthesis technique is simple, cost is low; Outside the pollution problem of flyash synthetic zeolite ammonia nitrogen in solving coking chemical waste water, also find a kind of good approach, realized the resource of flyash, improved the added value of flyash simultaneously for the utilization of solid waste coal ash and disposal.Adopting the flyash synthetic zeolite that ammonia nitrogen in the coking chemical waste water is carried out adsorption treatment has good effect, and ammonia nitrogen is reduced to below the 15mg/L by 120mg/L, reaches national grade one discharge standard.
The specific embodiment
Below by embodiment the specific embodiment of the present invention is further detailed, but embodiments of the present invention are not limited to following embodiment.
Embodiment 1
The employing solid waste coal ash is a raw material, in NaOH: the flyash weight ratio is that 1.2 ratio mixes two kinds of compositions, 500 ℃ of roastings 2 hours, again in water: the NaOH weight ratio is that 7 ratio adds in the calcining matter of water after mixing, and stirring at room 6 hours, again 90 ℃ of crystallization 6 hours, filter then, washing, oven dry makes the flyash synthetic zeolite.
The flyash synthetic zeolite is directly added in the secondary coking chemical waste water after the biochemical treatment, and dosage is a 30g/L waste water, normal temperature absorption 45 minutes, handles that ammonia nitrogen is reduced to 10.63mg/L by 120mg/L in the water body of back, and clearance is 91%.
Embodiment 2
The employing solid waste coal ash is a raw material, in NaOH: the flyash weight ratio is that 1.2 ratio mixes two kinds of compositions, 850 ℃ of roastings 2 hours, again in water: the NaOH weight ratio is that 12 ratio adds in the calcining matter of water after mixing, and stirring at room 3 hours, again 90 ℃ of crystallization 6 hours, filter then, washing, oven dry makes the flyash synthetic zeolite.
The flyash synthetic zeolite is directly added in the secondary coking chemical waste water after the biochemical treatment, and dosage is a 30g/L waste water, normal temperature absorption 45 minutes, handles that ammonia nitrogen is reduced to 12.79mg/L by 120mg/L in the water body of back, and clearance is 89%.
Embodiment 3
The employing solid waste coal ash is a raw material, in NaOH: the flyash weight ratio is that 1.0 ratio mixes two kinds of compositions, 550 ℃ of roastings 2 hours, again in water: the NaOH weight ratio is that 7 ratio adds water in the roasting sample, and stirring at room 10 hours, again 90 ℃ of crystallization 8 hours, filter then, washing, oven dry makes the flyash synthetic zeolite.
The flyash synthetic zeolite is directly added in the secondary coking chemical waste water after the biochemical treatment, and dosage is a 30g/L waste water, normal temperature absorption 60 minutes, handles that ammonia nitrogen is reduced to 13.55mg/L by 120mg/L in the water body of back, and clearance is 89%.
Embodiment 4
The employing solid waste coal ash is a raw material, in NaOH: the flyash weight ratio is that 1.4 ratio mixes two kinds of compositions, 700 ℃ of roastings 2 hours, again in water: the NaOH weight ratio is that 8 ratio adds water in the roasting sample, and stirring at room 8 hours, again 90 ℃ of crystallization 12 hours, filter then, washing, oven dry makes the flyash synthetic zeolite.
The flyash synthetic zeolite is directly added in the secondary coking chemical waste water after the biochemical treatment, and dosage is a 30g/L waste water, normal temperature absorption 90 minutes, handles that ammonia nitrogen is reduced to 14.42mg/L by 120mg/L in the water body of back, and clearance is 88%.
Embodiment 5
The employing solid waste coal ash is a raw material, in NaOH: the flyash weight ratio is that 1.2 ratio mixes two kinds of compositions, 800 ℃ of roastings 2 hours, again in water: the ratio of NaOH weight ratio 10 adds water in the roasting sample, and stirring at room 4 hours, again 90 ℃ of crystallization 14 hours, filter then, washing, oven dry makes the flyash synthetic zeolite.
The flyash synthetic zeolite is directly added in the secondary coking chemical waste water after the biochemical treatment, and dosage is a 30g/L waste water, normal temperature absorption 120 minutes, handles that ammonia nitrogen is reduced to 14.17mg/L by 120mg/L in the water body of back, and clearance is 88%.
Embodiment 6
The employing solid waste coal ash is a raw material, in NaOH: the flyash weight ratio is that 0.8 ratio mixes two kinds of compositions, 650 ℃ of roastings 2 hours, again in water: the NaOH weight ratio is that 5 ratio adds water in the roasting sample, and stirring at room 12 hours, again 90 ℃ of crystallization 10 hours, filter then, washing, oven dry makes the flyash synthetic zeolite.
The flyash synthetic zeolite is directly added in the secondary coking chemical waste water after the biochemical treatment, and dosage is a 30g/L waste water, normal temperature absorption 60 minutes, handles that ammonia nitrogen is reduced to 14.81mg/L by 120mg/L in the water body of back, and clearance is 88%.
Claims (1)
1. the processing method of ammonia nitrogen in the coking chemical waste water, its method is to utilize the flyash synthetic zeolite that the ammonia nitrogen in the coking chemical waste water is carried out advanced treating, its step is as follows:
1) with flyash be raw material, in NaOH: the flyash weight ratio was that 1.0 ratio mixes two kinds of compositions, 500 ℃ of roastings 2 hours;
2) in above-mentioned steps 1) add water in the gained mixture, at room temperature stirred 3-12 hour, control water: the NaOH weight ratio is 5～12, again at 90 ℃ of crystallization 6-14 hours, filters then, washing, oven dry makes the flyash synthetic zeolite;
3) with above-mentioned steps 2) gained flyash synthetic zeolite directly adds in the secondary coking chemical waste water after the biochemical treatment, and dosage is a 30g/L waste water, and at normal temperature absorption 45-120 branch, the solid-liquid isolated by filtration can realize the qualified discharge to ammonia nitrogen in the coking chemical waste water then.
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| CN201010145704XA CN101798124B (en) | 2010-04-10 | 2010-04-10 | Method for treating ammonia and nitrogen in coking wastewater |
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| CN201010145704XA CN101798124B (en) | 2010-04-10 | 2010-04-10 | Method for treating ammonia and nitrogen in coking wastewater |
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| CN101798124B true CN101798124B (en) | 2011-08-31 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219233B (en) * | 2010-10-19 | 2012-11-07 | 华北电力大学 | Method for removing nitrogen and phosphorus in sewage by zeolite synthesized by coal ash |
| CN102188953A (en) * | 2011-03-30 | 2011-09-21 | 山西大学 | Modified coal ash used for treating ammonia nitrogen waste water and preparation method thereof |
| CN102631890A (en) * | 2012-05-02 | 2012-08-15 | 湖北富邦科技股份有限公司 | Preparation method of modified fly ash adsorbent |
| CN103586010A (en) * | 2013-10-30 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparing molecular sieve by using fly ash and mercury removal use of prepared molecular sieve |
| CN108722345B (en) * | 2018-05-24 | 2021-04-20 | 重庆大学 | Zeolite synthesized by using fly ash and method for treating high-concentration ammonia nitrogen wastewater by using zeolite |
| CN115722193B (en) * | 2022-12-01 | 2024-04-12 | 吉林大学 | Preparation method and application of ammonia nitrogen modified adsorption material with low concentration in water |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631513A (en) * | 2004-11-18 | 2005-06-29 | 上海交通大学 | Method for synthesizing zeolite by fly ash and application thereof |
| CN101475191A (en) * | 2009-01-21 | 2009-07-08 | 西安建筑科技大学 | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-room temperature long placing |
| CN101475189A (en) * | 2009-01-21 | 2009-07-08 | 西安建筑科技大学 | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-trace amount water |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631513A (en) * | 2004-11-18 | 2005-06-29 | 上海交通大学 | Method for synthesizing zeolite by fly ash and application thereof |
| CN101475191A (en) * | 2009-01-21 | 2009-07-08 | 西安建筑科技大学 | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-room temperature long placing |
| CN101475189A (en) * | 2009-01-21 | 2009-07-08 | 西安建筑科技大学 | Method for preparing zeolite molecular sieve from fly ash by using alkali fusion-trace amount water |
Non-Patent Citations (2)
| Title |
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| 崔杏雨等.利用粉煤灰合成Na-X沸石的研究.《煤炭转化》.2009,第32卷(第4期),第85页右栏倒数第2行至第86页左栏第4行. * |
| 崔杏雨等.粉煤灰合成Na-X沸石去除废水中镍离子的研究.《燃料化学学报》.2009,第37卷(第6期),第752～756页. * |
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Granted publication date: 20110831 Termination date: 20130410 |