CN101844845A - Method for treating waste water containing ammonia and nitrogen - Google Patents
Method for treating waste water containing ammonia and nitrogen Download PDFInfo
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- CN101844845A CN101844845A CN200910030241A CN200910030241A CN101844845A CN 101844845 A CN101844845 A CN 101844845A CN 200910030241 A CN200910030241 A CN 200910030241A CN 200910030241 A CN200910030241 A CN 200910030241A CN 101844845 A CN101844845 A CN 101844845A
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Abstract
The invention discloses a method for treating waste water containing ammonia and nitrogen, comprising the steps of: firstly, separating and recycling high content substances in ammonium nitrate waste water and enabling the discharged water to reach the national discharge standard through employing that electrodialysis has operation capacity under the working conditions of sparingly soluble salt and over-saturation; and secondly, deeply treating the discharged water meeting the standard by utilizing reverse osmosis to enable the discharged water to totally meet the indexes of desalted soft water used in ammonium nitrate industry, and simultaneously carrying out electrodialysis separation circulating treatment and recycling to achieve the effect of zero discharge of waste water in an entire system.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment, particularly a kind of ammonia, nitrogen wastewater treatment method of containing.
Background technology
Along with the growth that develops rapidly of industries such as chemical fertilizer, petrochemical complex, the high ammonia-nitrogen wastewater of Chan Shenging also becomes one of industry development restraining factors therefrom; It is reported that calendar year 2001 China marine site generation red tide is up to 77 times, ammonia nitrogen is the pollution that one of major reason of polluting, particularly high-concentration ammonia nitrogenous wastewater cause.Therefore, cost-effective control high-concentration ammonia nitrogenous wastewater pollutes the important topic that also becomes current efforts at environmental protection person's research, has obtained insider's great attention.At present, the routine techniquess such as physics, chemical method of handling ammonia nitrogen waste water at all can not cost-effective improvement purpose, has poor processing effect, the problem that working cost is high.In the biological treatment, the general A/O method that adopts, A2/O method, SBR preface batch method etc. have the Technology of certain effect to denitrogenation, the general ammonia nitrogen in waste water content of handling can not surpass 300mg/L, simultaneously, in order to realize the purpose of denitrogenation, must replenish corresponding carbon source and cooperate removing of realization ammonia nitrogen, working cost is had greatly increased, be that general enterprise can't bear at all.
The high-concentration ammonia nitrogenous wastewater source is many, and quantity discharged is big, adopts cost-effective technology to realize that processing requirements is extremely urgent.In recent years, along with the development of biotechnology, particularly the progress at full speed of the directed characteristic microbial engineering that separates and cultivate is challenged traditional denitrogenation theory, and is broken in the processing project of actual high ammonia-nitrogen wastewater.Biological denitrificaion has had a lot of progress in theory, new denitrogenation theory the practice on obtained good checking, as: 1. nitrous acid nitrated/denitrification process.This technology can be saved 25% nitrating aeration amount, saves 40% denitrifying carbon source, saves 50% denitrification reactor volume.2. nitrated/denitrification process (SND) simultaneously.In the simultaneous reactor of aerobic environment and anaerobic environment,, thereby realized the efficient denitrification under the low carbon source condition because many new nitrogen biological chemistry bacterium families are identified out that under the zoogloea effect, nitrated/denitrification carries out simultaneously.3. aerobic denitrification technology.Under aerobic condition, some aerobic denitrifying bacteria can form gaseous product such as nitrogen oxide and Nitrous Oxide by the biological action of ammonia nitrogen.4. anaerobic-aerobic metallization processes.Some microorganisms can be that oxygenant is a nitrogen with ammonia oxidation with nitrate, carbonic acid gas and oxygen.
But, very big lethality is arranged for the biological inoculum in the biochemical process because also there is the nitric acid composition in a large amount of nitric acid material of using in the production process of ammonium nitrate product in the water of condensation.Though in the dosing neutralisation energy and water in ammonia nitrogen, but reagent consumption is big, the working cost height, may produce secondary pollution, and can not reclaim useful matter in the waste water, multiple-effect evaporation condensation is owing to need to consume a large amount of energy, and the free ammonia in water evaporation and steam discharged in the lump, can cause topsoil.Analysis-by-synthesis, existing Technology is each has something to recommend him, but finally can not form being recycled and solving secondary pollution problems of resource, so in the technology popularization application facet, be subjected to the application limitations of industry.
Summary of the invention
Technical problem to be solved by this invention is that the useful matter that how will contain in ammonia, the nitrogen waste water is recycled, and can make full use of water resources again simultaneously.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows: a kind of ammonia that contains, the nitrogen wastewater treatment method, comprise that film is handled and recovery ammonia, at first rare nitric acid of adding or gaseous ammonia carry out neutralization reaction in the water of condensation that contains ammonium nitrate and free ammonia, secondly reacted phlegma is cooled off, filtering and impurity removing, phlegma is delivered to a film processing system to be separated, the ammonium nitrate solution that will separate acquisition then is delivered to the secondary film processing system once more and carries out the secondary circulation processing, the ammonium nitrate solution that obtains is delivered to the recovery of purifying of purified solution device, the aforementioned water of separating is delivered to reverse osmosis system further handles.The electrodialytic membranes material is alternately to be arranged according to certain rules by cationic membrane and anionic membrane that PA makes, and positive and negative electrode is installed at two ends respectively, constitutes electrodialyzer.Reverse osmosis is that semi-permeable membranes, water conservancy diversion layer, filter are arranged bonding rolling having on the pipe core of round in certain sequence, makes element, and former water enters the filter layer from an end.During through the filter layer, under the effect of ambient pressure, a part of water is penetrated in the water conservancy diversion layer by the hole of semi-permeable membranes, water along the water conservancy diversion layer flows to the pipe core round again, discharges through pipe core, and remainder is an ammonium nitrate solution, discharge from the filter layer the other end, return recovery system and utilize again.Native system determines to be made up of several monolithic element according to water yield size.
A kind of preferred version that contains ammonia, nitrogen wastewater treatment method of the present invention is: described neutralization reaction step is to carry out at normal temperatures and pressures, and pH value is adjusted to 5-6, and the phlegma reaction times is 50-70 minute.
The another kind of preferred version that contains ammonia, nitrogen wastewater treatment method of the present invention is: described neutralization reaction step is to carry out in two neutralization reaction jars, by the automatic switching control system of liquid level, makes its automatic conversion, collects by turns, stirs and reaction.
The another kind of preferred version that contains ammonia, nitrogen wastewater treatment method of the present invention is: described reacted phlegma is cooled to 30-35 degree centigrade.
The another kind of preferred version that contains ammonia, nitrogen wastewater treatment method of the present invention is: described filtering and impurity removing step comprises that the accurate filter of 10 microns of employings carries out pre-treatment to reacted phlegma, with 5 microns microfilters the water after handling through the secondary film processing system is filtered, its middle filtrator is provided with the backwashing water device.
The another kind of preferred version that contains ammonia, nitrogen wastewater treatment method of the present invention is: described reverse osmosis system treatment step comprises further the aforementioned water of separating is delivered to reverse osmosis system by high-pressure pump that after Flow-rate adjustment control device and pressure control set for adjusting are regulated back-purge system acts on reverse osmosis system simultaneously.
The another kind of preferred version that contains ammonia, nitrogen wastewater treatment method of the present invention is: the ammonium nitrate solution of discharging after described reverse osmosis system is handled is back to a film processing system and carries out circular treatment.
The present invention pays the utmost attention to as being idealized as most of ammonium nitrate condensation waste water with " recycling of useful matter " with to " zero release " of environment, thoroughly solve and be rich in ammonia, nitrogen discharged pollution on the environment in the ammonium nitrate wastewater and recycling free ammonia and the ammonium nitrate in the waste water, and the precious water resource recirculation is utilized as the comprehensive capable process innovation of purpose.
Along with the normal pressure neutralisation of Ammonium Nitrate by the initial stage, progressively change into the pressurization neutralisation, the large-scale ammonium nitrate enterprise of several families on particularly new has in recent years all adopted the neutralisation explained hereafter of pressurizeing.Because the raising of raw material concentration of nitric acid and the pressurization that neutralization reaction solution is made, the discharge of wastewater in the overall process will increase, and the content of free ammonia and ammonium nitrate also will have a certain proportion of raising.It is low that the polyamide (PA) film that this technique research and development is selected for use has operating pressure, and resistance to acids and bases is strong, anti-biological pollution, water production rate height have stronger chemical stability to the waste water that contains the nitric acid composition after testing especially, and can application and water treatment and many other feed liquid process field.
Technique effect of the present invention is: this technology has service ability under difficulty soluble salt, over-saturation working condition by selecting electrodialysis for use, at first the high-content separating substances in the ammonium nitrate wastewater is recycled, and the fresh water of discharge has reached discharging standards; The water that utilizes reverse osmosis that qualified discharge water is managed, discharged through further depths then reaches the desalination softening water index that the ammonium nitrate industry production is used fully, the dope of discharging returns the utilization of electrodialysis Separation and Recovery again, carries out the zero release effect of total system waste water.
Description of drawings
The invention will be further described below in conjunction with accompanying drawing.
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the concrete process flow diagram of one embodiment of the invention.
Embodiment
A nitric acid ammonia manufacturing enterprise produces 200000 tons in ammonium nitrate per year, 25 cubic metres/hour of condensation wastewater flow rates, free ammonia content 700 mg/litre wherein, ammonium nitrate content 900 mg/litre.Fig. 1 has shown process flow sheet of the present invention.Fig. 2 is the concrete process flow diagram of one embodiment of the invention, wherein: Measuring and testing setting device 1, neutralization reaction jar 2, holding tank 3, water cooler 4, accurate filter 5, condensation water tank 6, secondary concentrates circulation tank 7, membrane treatment appts 8, membrane treatment appts 9, secondary charging stock tank 10, utmost point water pot 11, utmost point water pot 12, one-level concentrates circulation tank 13, water basin 14 up to standard, high-pressure pump 15, reverse osmosis system 16, transfer equipment 17, back-purge system 18, Flow-rate adjustment control 19, pressure is regulated control 20, reuse desalination water pot 21, secondary dope jar 22, utmost point water pot 23, purified solution device 24, microfilter 25, withdrawing can 26, back-purge system 27.
This technology realizes by following flow process: in the ammonium nitrate product production process, the water vapor of discharging is after cooling, contain the water of condensation that has ammonium nitrate and free ammonia, measurement by Measuring and testing setting device 1 can get the water outlet middle reaches from ammonium content with come the water yield, automatically add rare nitric acid or gas ammonia, mixing condensation water enters neutralization reaction jar 2, carries out neutralization reaction then at normal temperatures and pressures, pH value is adjusted to 5-6, about 1 hour of phlegma residence time in the neutralization reaction jar.Mainly be to come water to collect stirring in jar with each operation, chemical reaction is even, and according to the data that the pH value automatic tester is detected, adjusts rare nitric acid or ammonia dosage automatically, and the control pH value is all the time in the scope of 5-6.
Owing to substances content in each operation water of condensation in the Ammonium Nitrate does not wait, water yield inequality, for guaranteeing the works better of later process, this operation is provided with two neutralization reaction jars 2, by the automatic switching control system 17 of liquid level, make its conversion automatically, collection by turns, stirring, neutralization reaction.Condensate temperature with conditioned reaction in finishing is about 60 degrees centigrade, with being pumped into holding tank 3.Next the phlegma that enters holding tank 3 is transported in the water cooler 4 and cools off, its temperature is dropped to below 35 degrees centigrade, sending into accurate filter 5 then filters, remove the crystal and the impurity that contain in the water of neutralization cooling back, prevent that crystal and impurity from entering film processing system, thereby cause the stifled resistance of film.Adopt each one in 10 microns accurate filters, 5 microns ultra filtration filters in the native system.5 microns ultra filtration filters are used for the filtration of the water after the secondary film processing system is handled, and strainer is provided with backwashing water device 27, so that guarantee the optimum operation and the works better of equipment.Water by filter process enters condensation water tank 6, carries out Separation and Recovery ammonium nitrate by being pumped into film processing system 8 then.
For the nitric acid ammonia concentration that makes generation reaches the requirement that utilizes and the standard of discharge water again, need carry out that a part of ammonium nitrate solution is inputed to secondary film processing system 9 and film treatment soln purifying plant 24 is handled.Wherein be provided with secondary charging stock tank 10, utmost point water pot 11,12,23, one-level concentrates circulation tank 13, secondary concentrates circulation tank 7, secondary dope jar 22, various types of pump, valve, under meter, be provided to system's operation, the nitric acid ammonia dope that reclaims after purifying enters basin 26, enter in the factory production system then and utilize, qualified discharge water enters basin 14 dischargings.Owing to do not contain mineral substance and metal ion substantially in the qualified discharge water, contain ammonia, the nitrogen of the 20-30 mg/litre of having an appointment.Characteristics according to a large amount of de-salted waters of needs in the Ammonium Nitrate.From conserve water resource and energy-saving and cost-reducing angle, qualified discharge water is sent into the reverse osmosis system main body further handle.This system is made up of high-pressure pump 15, reverse osmosis system main body 16, back-purge system 18, Flow-rate adjustment control device 19 and pressure regulating device 20.
According to water quality characteristics, these system high pressure pump 15 main energy are supplied with scope 0.7-1.5mpa, for guaranteeing not damage membrane element, be no more than limit withstand voltage, the spy is provided with Flow-rate adjustment control device 19, with flow control in the scope of 15-20T/h, pressure regulating device 20 is set, at 0.5-1.8mpa, makes membrane element under the situation of temperature, flow, pressure equalization, carry out work pressure controlling.Membrane element design variable working flow is that 18T/h, operating pressure are that 0.8-1.2mpa, ratio of desalinization are that 95%-99.9%, pH value are that 3-10, working temperature are 30 ℃.
Wherein the film of Cai Yonging is a process structure rolling composite membrane, and material is aromatic polyamides (PA) macromolecular material.According to the size and the substances content of treatment capacity, single group membrane element quantity and high porous-film or the dense film of film transmitance are selected in decision for use.For decay and the film that slows down film pollutes, native system is provided with back-purge system (18).
The return condensed liquid basin 6 of nitric acid ammonia solution of discharging after operation is handled carries out circular treatment.Ammonia-nitrogen content has only below 5 mg/litre in the high purity water of final institute output, meets the de-salted water service requirements in the nitric acid ammonia production process fully, and ammonium nitrate has also obtained sufficient recovery simultaneously.If the electricity charge are by 0.32 yuan of every kilowatt-hour, then the annual recyclable ammonium nitrate of the said firm is worth 2,150,000 yuan, 750,000 yuan of reuse de-salted waters.About about 1,600,000 yuan of whole year operation expense, can make profits about 1,300,000 yuan the whole year, deducts the blowdown of paying with disregarding 9,000,000 yuan to 1,100 ten thousand yuan of this project gross investments.
Claims (8)
1. one kind contains ammonia, the nitrogen wastewater treatment method, comprise that film is handled and recovery ammonia, it is characterized in that: at first rare nitric acid of adding or gaseous ammonia carry out neutralization reaction in the water of condensation that contains ammonium nitrate and free ammonia, secondly reacted phlegma is cooled off, filtering and impurity removing, phlegma is delivered to a film processing system to be separated, the ammonium nitrate solution that will separate acquisition then is delivered to the secondary film processing system and carries out secondary treatment, next the ammonium nitrate solution that obtains is delivered to the recovery of purifying of purified solution device, the aforementioned water of separating is delivered to reverse osmosis system further handles.
2. ammonia, the nitrogen wastewater treatment method of containing according to claim 1, it is characterized in that: described neutralization reaction step is to carry out at normal temperatures and pressures, and pH value is adjusted to 5-6, the phlegma reaction times is 50-70 minute.
3. ammonia, the nitrogen wastewater treatment method of containing according to claim 2 is characterized in that: described neutralization reaction step is to carry out in two neutralization reaction jars, by the automatic switching control system of liquid level, makes its automatic conversion, collects by turns, stirs and reaction.
4. ammonia, the nitrogen wastewater treatment method of containing according to claim 3, it is characterized in that: described reacted phlegma is cooled to 30-35 degree centigrade.
5. ammonia, the nitrogen wastewater treatment method of containing according to claim 4, it is characterized in that: described filtering and impurity removing step comprises that the accurate filter of 10 microns of employings carries out pre-treatment to reacted phlegma, with 5 microns microfilters the water after handling through the secondary film processing system is filtered, its middle filtrator is provided with back-purge system.
6. according to described ammonia, the nitrogen wastewater treatment method of containing of arbitrary claim in the claim 1 to 5, it is characterized in that: described reverse osmosis system treatment step comprises further the aforementioned water of separating is delivered to reverse osmosis system by high-pressure pump that after Flow-rate adjustment control device and pressure control set for adjusting are regulated back-purge system acts on reverse osmosis system simultaneously.
7. ammonia, the nitrogen wastewater treatment method of containing according to claim 6 is characterized in that: the ammonium nitrate solution of discharging after described reverse osmosis system is handled is back to a film processing system and carries out circular treatment.
8. according to described ammonia, the nitrogen wastewater treatment method of containing of arbitrary claim in the claim 1 to 5, it is characterized in that: enter an ammonium nitrate solution part that the purified solution device purifies from a film processing system, another part is from the secondary film processing system.
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| CN200910030241A CN101844845A (en) | 2009-03-23 | 2009-03-23 | Method for treating waste water containing ammonia and nitrogen |
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| CN200910030241A CN101844845A (en) | 2009-03-23 | 2009-03-23 | Method for treating waste water containing ammonia and nitrogen |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103373783A (en) * | 2012-04-17 | 2013-10-30 | 上海晶宇环境工程有限公司 | Zero discharging process for nitrogenous wastewater generated by photovoltaic industry and dedicated system of zero discharging process |
| CN103663774A (en) * | 2013-02-27 | 2014-03-26 | 苏州信望膜技术有限公司 | Method for treating low-concentration ammonia-containing wastewater by use of membrane separation technology |
| CN104058525A (en) * | 2014-07-01 | 2014-09-24 | 中国天辰工程有限公司 | Method for recovering and treating production wastewater containing high ammonia nitrogen and nitrate nitrogen |
| CN105152434A (en) * | 2014-05-26 | 2015-12-16 | 中冶东方工程技术有限公司秦皇岛研究设计院 | Method and device for treating pickling waste water from stainless steel cold-rolling |
| CN107266129A (en) * | 2017-07-18 | 2017-10-20 | 深圳市深投环保科技有限公司 | Recovery method and urea ammonium nitrate liquid fertilizer preparation method containing copper nitrate waste water |
| CN108698863A (en) * | 2015-12-18 | 2018-10-23 | 亚拉国际有限公司 | The method for removing removing chloride from fertilizer waste water |
| CN110845053A (en) * | 2019-10-28 | 2020-02-28 | 宿州伊维特新材料有限公司 | Method for recycling nitrous oxide pre-washing water |
| CN111892224A (en) * | 2020-08-07 | 2020-11-06 | 重庆大学 | Ammonia nitrogen wastewater treatment system and method based on south of road dialysis and osmotic distillation coupling |
| CN114804485A (en) * | 2022-04-25 | 2022-07-29 | 厦门世达膜科技有限公司 | Ammonium nitrate-containing evaporation and condensation wastewater zero-emission treatment system |
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2009
- 2009-03-23 CN CN200910030241A patent/CN101844845A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103373783B (en) * | 2012-04-17 | 2015-07-22 | 上海晶宇环境工程有限公司 | Zero discharging process for nitrogenous wastewater generated by photovoltaic industry and dedicated system of zero discharging process |
| CN103373783A (en) * | 2012-04-17 | 2013-10-30 | 上海晶宇环境工程有限公司 | Zero discharging process for nitrogenous wastewater generated by photovoltaic industry and dedicated system of zero discharging process |
| CN103663774A (en) * | 2013-02-27 | 2014-03-26 | 苏州信望膜技术有限公司 | Method for treating low-concentration ammonia-containing wastewater by use of membrane separation technology |
| CN105152434A (en) * | 2014-05-26 | 2015-12-16 | 中冶东方工程技术有限公司秦皇岛研究设计院 | Method and device for treating pickling waste water from stainless steel cold-rolling |
| CN104058525A (en) * | 2014-07-01 | 2014-09-24 | 中国天辰工程有限公司 | Method for recovering and treating production wastewater containing high ammonia nitrogen and nitrate nitrogen |
| CN104058525B (en) * | 2014-07-01 | 2016-01-20 | 中国天辰工程有限公司 | Production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen |
| CN108698863A (en) * | 2015-12-18 | 2018-10-23 | 亚拉国际有限公司 | The method for removing removing chloride from fertilizer waste water |
| CN107266129A (en) * | 2017-07-18 | 2017-10-20 | 深圳市深投环保科技有限公司 | Recovery method and urea ammonium nitrate liquid fertilizer preparation method containing copper nitrate waste water |
| CN107266129B (en) * | 2017-07-18 | 2020-12-01 | 深圳市深投环保科技有限公司 | Method for recovering copper nitrate-containing wastewater and method for preparing urea ammonium nitrate liquid fertilizer |
| CN110845053A (en) * | 2019-10-28 | 2020-02-28 | 宿州伊维特新材料有限公司 | Method for recycling nitrous oxide pre-washing water |
| CN110845053B (en) * | 2019-10-28 | 2021-06-01 | 宿州伊维特新材料有限公司 | Method for recycling nitrous oxide pre-washing water |
| CN111892224A (en) * | 2020-08-07 | 2020-11-06 | 重庆大学 | Ammonia nitrogen wastewater treatment system and method based on south of road dialysis and osmotic distillation coupling |
| CN114804485A (en) * | 2022-04-25 | 2022-07-29 | 厦门世达膜科技有限公司 | Ammonium nitrate-containing evaporation and condensation wastewater zero-emission treatment system |
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Application publication date: 20100929 |