CN102190386B - Ammonia-controllable recovery method of high ammonia nitrogen waste water based on membrane technology - Google Patents
Ammonia-controllable recovery method of high ammonia nitrogen waste water based on membrane technology Download PDFInfo
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- CN102190386B CN102190386B CN2011100842928A CN201110084292A CN102190386B CN 102190386 B CN102190386 B CN 102190386B CN 2011100842928 A CN2011100842928 A CN 2011100842928A CN 201110084292 A CN201110084292 A CN 201110084292A CN 102190386 B CN102190386 B CN 102190386B
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Abstract
The invention provides an ammonia-controllable recovery method of high ammonia nitrogen waste water based on a membrane technology. The method comprises the following steps: successively carrying out pH regulation, coagulation, flocculation and filtration on waste water containing ammonia (ammonium) of which ammonia (ammonium) content is more than or equal to 200mg/L-50000mg/L; then separating out and recovering ammonia by using an ammonia-controllable recovery membrane; controlling the concentration of effluent ammonia through pH regulation according to subsequent treatment requirements, wherein the minimum concentration of effluent ammonia can be below 10mg/L. After being absorbed with diluted acid, the free ammonia separated out by the ammonia-controllable recovery membrane can be used as fertilizer or industrial raw material; and sludge which is filtered out can be discharged after being concentrated The method belongs to a physic-chemical treatment process and can effectively remove high ammonia (ammonium) nitrogen from water when used for treating high ammonia (ammonium) waste water; and the method has the characteristics of low operation cost, high removal efficiency, small occupied area and the like.
Description
Technical field
The present invention relates to the water field of purification, specifically, relate to the controlled ammonia recovery method of a kind of high ammonia-nitrogen wastewater based on membrane technique.
Background technology
Ammonia is important industrial raw material, in multiple industries such as pharmacy, food-processing, rare-earth smelting, has obtained widespread use, but simultaneously; Too much ammonia can become the important component part of environmental pollution; Not only have ammonia pollution in the sewage, and in numerous industries such as rare earth, whipping agent, catalyzer, agricultural chemicals, monosodium glutamate, chemical fertilizer, leather, gunpowder, coking, oil refining, meat processing, also have high ammonia pollution, ammonia nitrogen concentration is by 200mg/L to 100; 000mg/L does not wait; Far above the concentration of ammonia in the sewage, even the percolate that garbage loading embeading produces, wherein the concentration of ammonia is also up to 1000mg/L～10000mg/L.These high ammonia waste waters, its saltiness are often also very high, and the saltiness that has even up to 16% is higher than the saltiness (2%～4%) of seawater far away.And existing standard is very tight to the requirement of ammonia in the water, and therefore the removal of ammonia nitrogen becomes problem demanding prompt solution in the high ammonia waste water.
The high ammonia waste water treatment technology of taking at present can be divided into three major types, and the one, biologic treating technique, the 2nd, chemical treatment method, the 3rd, materialization treatment technology.
Biological treatment mainly contains short-cut nitrification and denitrification, synchronous nitration and denitrification and biochemical oxidation method, is characterized in that energy consumption is relatively low, but long processing period; Water outlet ammonia nitrogen difficulty satisfies emission request, and especially biological oxidation process is converted into nitric nitrogen through aerobe with ammonia-state nitrogen; Because oxidation cycle is long; Make the water outlet concentration of suspension high, the mud-water separation difficulty, and also the total nitrogen difficulty satisfies demand up to standard.
The chemical treatment of ammonia nitrogen is exactly with the ammonia-state nitrogen in the waste water, through adding magnesium salts and phosphoric acid salt, and through behind the pH regulator, is converted into magnesium ammonium phosphate (being commonly called as struvite), magnesium ammonium phosphate is separated from system again.This method not only need consume a large amount of magnesium chlorides, phosphoric acid salt etc., and the clearance to ammonium has much room for improvement in the engineering, has the ammonium salt of considerable part still to stay in the system after the processing, is difficult to satisfy up to standard or emission request.
The materialization treatment technology can be divided into air stripping technology and heating distillation technology again, through pH regulator the high ammonium of the ionic state in the waste water is converted into the ammonia of free state or molecular state earlier exactly, again through air stripping or add thermal rectification the ammonia of molecular state is removed from system.Adopt the stripping technology to remove ammonia owing to need a large amount of air, it is big therefore to have a power consumption, and stripping tower is prone to fouling, easy generation of secondary pollution and go out characteristics such as shipwreck meets the demands.Adopt the heating distillation technology to remove ammonia; Have and reclaim ammonia purity advantages of higher, but since at the bottom of gaseous ammonia that ammonia still process needs to heat, steam and the still distillate all need the cold cooling, so energy consumption is higher; Use more at ammonia synthesizing industry on the engineering; But because the distillation operation difficulty is big, water outlet generally also needs advanced treatment, otherwise is difficult to satisfy emission request.
Summary of the invention
The present invention is intended to overcome the defective that prior art exists, and provides a kind of high ammonia-nitrogen wastewater based on membrane technique controlled ammonia recovery method.
In order to realize the object of the invention; The controlled ammonia recovery method of a kind of high ammonia-nitrogen wastewater based on membrane technique of the present invention, it is that high ammonia (ammonium) waste water is carried out Separation and Recovery through controlled ammonia reclamation film to ammonia successively again after slagging-off, pH regulator, coagulation, coacervation, filtration.
Aforesaid method also comprises the step to isolated free ammonia evaporation concentration after diluted acid absorbs.
Aforesaid method, grid or mesh size that slagging-off is used are 1mm～5mm.
Aforesaid method, said pH regulator are meant under whipped state and add alkaline matter that said alkaline matter is the emulsion of quicklime and/or sodium hydroxide, Pottasium Hydroxide or the sodium carbonate solution of 10g/L～500g/L.
Aforesaid method; Said coagulation is meant dosing coagulant under whipped state; And continuously stirring 0.5min～3min, said coagulating agent is the aqueous solution of Poly aluminum Chloride (PAC), polyaluminium sulfate, bodied ferric sulfate or poly-ferric chloride, adding the concentration that forms in the waste water into is 100mg/L～6000mg/L.
Aforesaid method; Said coacervation is meant under whipped state and adds flocculation agent; And continuously stirring 0.5min～3min; Said flocculation agent is a formula weight at 3,000,000～1,600 ten thousand negatively charged ion, positively charged ion or non-ionic polyacrylamide (PAM), and adding the concentration that forms in the waste water into is 0.5mg/L-20mg/L.
Aforesaid method is removed greater than the material of 30 μ m particle diameter after the filtration from waste water.
Aforesaid method, said diluted acid are 5%～20% sulfuric acid and recycle.
When aforesaid method, said evaporation concentration are meant pH when absorption liquid＞2, can discharge and carry out heating evaporation and concentrate, to obtain lenticular ammonium sulfate.
The object of the invention can also adopt following technical measures further to realize.
The controlled ammonia recovery method of a kind of high ammonia-nitrogen wastewater provided by the invention based on membrane technique; Be with high ammonia (ammonium) waste water successively after slagging-off, pH regulator, coagulation, coacervation, filtration; Through controlled ammonia reclamation film ammonia is carried out Separation and Recovery again, after ammino requires in the water outlet, just get into the hypomere treatment process or efflux; The free ammonia that is gone out by membrane sepn obtains ammonia sulfate crystal through evaporation concentration again after diluted acid absorbs, can be used as fertilizer or industrial raw material and use; Filter the mud that produces and concentrate the back outward transport.Said slagging-off is meant with thick suspended substances such as the scum silica frost in the removal waste water such as grid or screen cloth, branch leaf, plastic sheet, stones; PH regulator is meant under whipped state and adds alkaline matter, to form the mixed solution of required pH value, makes ion state ammonium fully be converted into free state ammonia; Said coagulation is meant dosing coagulant under whipped state, to form alumen ustum; Coacervation is meant under whipped state and adds flocculation agent to 0.5mg/L～20mg/L, so that with the big particulate matter of alumen ustum formation agglomerated together; Filtration is meant through device the large particulate matter in the water is separated with water; The separation of ammonia reclamation film is meant after the free ammonia in the high ammonia waste water sees through film and is absorbed by acid absorption liquid; Evaporation concentration is meant ammonia is absorbed the absorption liquid that reaches capacity, and sends into heating evaporation equipment, obtains lenticular ammonium sulfate through evaporation concentration.
Wherein, Said pH regulator is meant to satisfying ammonia clearance x (0≤x＜1), needs with alkaline matter pH to be adjusted to the represented pH value of formula
.
Said filtration is meant through devices such as strainers particle diameter in the water is separated from contain ammoniacal liquor greater than particulate matter or the alumen ustum of 30 μ m.
Said controlled ammonia reclamation film separation is meant the high ammoniacal liquor of transferring the pH value; Through the special ammonia separatory membrane; Separated the going out of most free ammonias wherein, and remaining total ammonia in the water outlet (small portion free ammonia and ion ammonium with) can be adjusted through pH according to subsequent request.
By technique scheme, the present invention has advantage and beneficial effect at least:
(1) the controlled ammonia recovery method of a kind of high ammonia-nitrogen wastewater of the present invention based on membrane technique, processing technological flow is short, and installations and facilities can compactly be laid, and therefore take up an area of and economize convenient management.
(2) the controlled ammonia recovery method of a kind of high ammonia-nitrogen wastewater based on membrane technique of the present invention disposablely can be removed 60%～99.5% ammonia, the inorganic phosphorus more than 70%, and suspended substance more than 75% and part COD, so processing efficiency is high.
(3) the controlled ammonia recovery method of a kind of high ammonia-nitrogen wastewater based on membrane technique of the present invention belongs to the materialization treatment process, and start and stop are convenient, can be continuously or intermittent operation, so adaptive faculty is strong.
(4) the controlled ammonia recovery method of a kind of high ammonia-nitrogen wastewater of the present invention based on membrane technique, main consumed power, a spot of flocculation agent, flocculation agent and sulfuric acid, so working cost is low.
(5) the controlled ammonia recovery method of a kind of high ammonia-nitrogen wastewater of the present invention based on membrane technique; Film water outlet ammonia nitrogen concentration can be controlled according to the pH value that formula
is calculated through clearance x; Therefore the water outlet ammonia nitrogen is controlled, for follow-up requirement to ammonia provides reliable guarantee.
Description of drawings
Fig. 1 is that preferred embodiment of the present invention is based on the controlled ammonia recovery method schema of the high ammonia-nitrogen wastewater of membrane technique.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.The various medicaments that present embodiment adopts are commercial; The controlled ammonia reclamation film that adopts is to be produced by the clean source of Tianjin Lan Hai Environmental Protection Technology Co., Ltd, and marque is LH-4040.
Embodiment 1
The high ammonia waste water purifying treatment of certain chemical industry group, treatment scale is 240m
3/ d, water quality ammonia nitrogen are 3000mg/L～9000mg/L, and average out to 4200mg/L, COD are 2000mg/L～3000mg/L, average 2520mg/L; Require the water outlet ammonia nitrogen less than 50mg/L, COD is less than 100mg/L.Waste water under the whipped state, adds the emulsion of quicklime and the sodium hydroxide of 10g/L earlier after grid (aperture is 1mm) slagging-off; After the pH value transferred to 11.6, add poly-ferric chloride by the concentration of 100mg/L and carry out coagulation, add 1.5mg/L anionic polyacrylamide (formula weight 1,000 ten thousand) again and carry out coacervation; Form flco, after the filtration particle diameter is removed from waste water greater than the material of 30 μ m, after controlled ammonia reclamation film separates; The water outlet ammonia nitrogen is 40.0mg/L, and COD is 90mg/L, and the pH value is 9.35.Absorption liquid adopts 12% sulfuric acid to recycle, and when pH＞2, upgrades.The average removal rate of ammonia reaches more than 98.6% in the waste water.
Embodiment 2
The high ammonia waste water purifying treatment of certain Rare Earth Company, treatment scale 600m
3/ d, water quality ammonia nitrogen are 4000mg/L～5000mg/L, and average out to 4350mg/L, COD are greater than 250mg/L, and suspended substance is 600mg/L, require the water outlet ammonia nitrogen less than 25mg/L, and COD is less than 150mg/L.Waste water under the whipped state, adds the emulsion of quicklime and the sodium hydroxide of 250g/L earlier after grid (aperture is 3mm) slagging-off; After pH transferred to 11.8, add poly-ferric chloride by the concentration of 80mg/L and carry out coagulation, add 1.2mg/L cationic polyacrylamide (formula weight 1,200 ten thousand) again and carry out coacervation; Form flco, after the filtration particle diameter is removed from waste water greater than the material of 30 μ m, after controlled ammonia reclamation film separates; The water outlet ammonia nitrogen is 20.0mg/L, and COD is 130mg/L, and the pH value is 9.32.Absorption liquid adopts 8% sulfuric acid to recycle, and when pH＞2, upgrades.The average removal rate of ammonia reaches more than 99.5% in the waste water.
Embodiment 3
The high ammonia waste water purifying treatment of certain insecticide factory, treatment scale is 700m
3/ d, water quality ammonia nitrogen are 20000mg/L～30000mg/L, and average out to 24700mg/L, suspended substance are 200mg/L, and COD is 2000mg/L; Requiring the water outlet ammonia nitrogen is 15mg/L.Effectively carry out reflux dilution method at 2: 1 by reflux ratio for guaranteeing that subsequent disposal is up to standard, design discharge is 2100m when promptly handling
3/ d, ammonia nitrogen concentration becomes 6700mg/L～10000mg/L thus, average 8230mg/L.Former water through grid (aperture is 5mm) slagging-off, under the whipped state, is added the emulsion of quicklime and the sodium hydroxide of 500g/L earlier; After pH transferred to 12.3, add poly-ferric chloride by the concentration of 300mg/L and carry out coagulation, add 5mg/L non-ionic polyacrylamide (formula weight 1,600 ten thousand) again and carry out coacervation; Form flco, after the filtration particle diameter is removed from waste water greater than the material of 30 μ m, after controlled ammonia reclamation film separates; The water outlet ammonia nitrogen is 12.0mg/L; Suspended substance is 25mg/L, and COD is 250mg/L, and pH is 9.40.Absorption liquid adopts 20% sulfuric acid to recycle, and when pH＞2, upgrades.The average removal rate of ammonia reaches more than 99.9% in the waste water.
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or the improvement on the basis of not departing from spirit of the present invention, made all belong to the scope that requirement of the present invention is protected.
Claims (8)
1. the controlled ammonia recovery method of the high ammonia-nitrogen wastewater based on membrane technique is characterized in that, high ammonia waste water is carried out Separation and Recovery through controlled ammonia reclamation film to ammonia successively again after slagging-off, pH regulator, coagulation, coacervation, filtration;
Said pH regulator is meant to satisfying ammonia clearance x; Wherein 0≤x＜1 adds alkaline matter pH is adjusted to the represented pH value of formula
under whipped state;
Grid or mesh size that slagging-off is used are 1mm～5mm.
2. method according to claim 1 is characterized in that, also comprises the step to isolated free ammonia evaporation concentration after diluted acid absorbs.
3. method according to claim 1 and 2 is characterized in that, said alkaline matter is the emulsion of quicklime and/or sodium hydroxide, Pottasium Hydroxide, the sodium carbonate solution of 10g/L～500g/L.
4. method according to claim 1 and 2; It is characterized in that; Said coagulation is meant dosing coagulant under whipped state; Said coagulating agent is the aqueous solution of Poly aluminum Chloride (PAC), polyaluminium sulfate, bodied ferric sulfate or poly-ferric chloride, and adding the concentration that forms in the waste water into is 100mg/L～6000mg/L.
5. method according to claim 1 and 2; It is characterized in that; Said coacervation is meant under whipped state and adds flocculation agent; Said flocculation agent is a formula weight at 3,000,000～1,600 ten thousand negatively charged ion, positively charged ion or non-ionic polyacrylamide, and adding the concentration that forms in the waste water into is 0.5mg/L-20mg/L.
6. method according to claim 1 and 2 is characterized in that, after the filtration particle diameter is removed from waste water greater than the material of 30 μ m.
7. method according to claim 2 is characterized in that, said diluted acid is 5%～20% sulfuric acid.
8. method according to claim 2 is characterized in that, the pH of absorption liquid＞2 during evaporation concentration.
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| CN102491562A (en) * | 2011-12-20 | 2012-06-13 | 重庆锐致环保科技有限公司 | High-ammonia-nitrogen waste water resource recovery technology |
| CN103553264B (en) * | 2013-09-06 | 2015-04-08 | 苏州苏净环保工程有限公司 | Multistage-membrane-extraction biological integrated treatment system for processing high ammonia nitrogen in wastewater, and method thereof |
| CN104229937B (en) * | 2014-08-25 | 2016-04-27 | 浙江净源膜科技股份有限公司 | A kind for the treatment of process of high density free ammonia |
| CN104649515B (en) * | 2015-01-16 | 2016-11-30 | 北京交通大学 | The process process of a kind of high salinity height ammonia nitrogen Rare Earth Production waste water and device |
| CN105130051A (en) * | 2015-08-27 | 2015-12-09 | 上海晶宇环境工程股份有限公司 | Process for treating landfill leachate by using ammonia nitrogen separating membrane and special equipment for process |
| CN106007087B (en) * | 2016-07-06 | 2018-10-16 | 扬州奇创环保科技有限公司 | A kind of high-concentration ammonia nitrogenous wastewater treatment process and ammonia recovery system |
| CN108117190B (en) * | 2017-12-14 | 2021-04-02 | 瓮福（集团）有限责任公司 | Process for treating low-concentration ammonia nitrogen wastewater of phosphate fertilizer plant |
| CN110092521B (en) * | 2019-06-06 | 2020-10-16 | 盛隆资源再生（无锡）有限公司 | Water treatment method for fully utilizing resources in high-fluorine high-ammonia nitrogen wastewater |
| CN111499069A (en) * | 2020-04-28 | 2020-08-07 | 江苏永葆环保科技有限公司 | Comprehensive treatment system and treatment method for waste cutting fluid |
| CN111635086A (en) * | 2020-07-14 | 2020-09-08 | 常州时升环境工程科技有限公司 | Zero discharge system for producing ammonium salt from ammonia nitrogen-containing wastewater and treatment process thereof |
| CN113636684B (en) * | 2021-08-23 | 2023-04-18 | 江苏贞一环保科技股份有限公司 | Iron phosphate wastewater treatment system and treatment method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544436A (en) * | 2009-05-08 | 2009-09-30 | 清华大学 | Method for removing and recovering sulfate in acrylonitrile wastewater by utilizing freezing crystallization |
| CN101723523A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Treatment method for dry acrylic fiber production wastewater |
| CN101987767A (en) * | 2010-12-03 | 2011-03-23 | 沈阳工业大学 | Method for producing wastewater with high ammonia nitrogen and high salinity by treating rare earth with membrane integration |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723523A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Treatment method for dry acrylic fiber production wastewater |
| CN101544436A (en) * | 2009-05-08 | 2009-09-30 | 清华大学 | Method for removing and recovering sulfate in acrylonitrile wastewater by utilizing freezing crystallization |
| CN101987767A (en) * | 2010-12-03 | 2011-03-23 | 沈阳工业大学 | Method for producing wastewater with high ammonia nitrogen and high salinity by treating rare earth with membrane integration |
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