CN104291501B - A kind of Integrated Membrane Technology processes the method for ammonium nitrate wastewater - Google Patents
A kind of Integrated Membrane Technology processes the method for ammonium nitrate wastewater Download PDFInfo
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- CN104291501B CN104291501B CN201310298728.2A CN201310298728A CN104291501B CN 104291501 B CN104291501 B CN 104291501B CN 201310298728 A CN201310298728 A CN 201310298728A CN 104291501 B CN104291501 B CN 104291501B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a kind of method that Integrated Membrane Technology processes ammonium nitrate wastewater, its method is as follows: in ammonium nitrate wastewater stock solution after acid-base neutralization adjusts pH value technique and cooling PROCESS FOR TREATMENT, process via the Integrated Membrane Technology of ultrafilter membrane technique, reverse osmosis membrane technique, degassing film technique and electrodeionization membrane process composition the most again, respectively obtain the concentration liquid of ammonium nitrate close to 10%, through evaporative crystallization, reclaim ammonium nitrate solid product；Obtain the desalted water of ammonia nitrogen mass concentration≤1mg/L in water simultaneously, can reclaim as technique pure water or boiler feedwater.The present invention makes ammonium nitrate wastewater all get utilization.Integrated Membrane Technology of the present invention, technique is advanced；Save the energy；Administering waste water economic benefit of engineering good, sewage recovering system operating cost is low；Simple to operate, it is achieved that cleaning produces.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind of method that Integrated Membrane Technology processes ammonium nitrate wastewater.
Background technology
Process ammonium nitrate wastewater at present and mainly have following several: blow-off method, biochemical process, ion exchange and electroosmose process
Deng.It is too high that stripping rule needs to add after chemical agent regulation pH value, and stripping ammonium salt residual quantity in waste water, also has air
Secondary pollution problems.Biochemical process is by wastewater collection to biochemistry pool, with antibacterial by ammonium salt decomposition, eventually forms nitrogen.?
In biochemical reaction process, need to add carbon source and strain, and it is slightly higher to work as ammonium salt concentration in water, i.e. ammonia nitrogen reaches 500mg/L
Time, strain will be dead, it is impossible to carries out biochemical reaction.Ion exchange is that spent ion exchange resin adsorbs ammonium nitrate, but regenerates
Frequent operation, rinse water to be processed, the most convenient.Most of ammonium nitrate in waste water can be reclaimed by electroosmose process, but place
After reason, in water, the ammonia nitrogen concentration of residual is the highest, it is impossible to reach ammonia nitrogen 10mg/L in the water of promulgation national requirements for environmental protection in 2011
Index with total nitrogen≤30mg/L.Can not discharge also cannot reuse, cause the biggest puzzlement to manufacturing enterprise.Electrodialysis is
Employ the old technology of decades in desalination field, many researcheres find electrodialyzer in the case of water intermediate ion is few, meeting
Water decomposition reaction occurs between ion exchange membrane, and water decomposition becomes H+And OH—Ion, is used for supplementing the ion in water, and they become
The carrier of electric charge, this reaction referred to as polarizes reaction.After electrodialyzer polarization reaction occurs, substantial amounts of electric energy can be consumed, lead
The work efficiency sending a telegraph dialyser reduces, and effluent quality declines, and power consumption increases, and therefore general electrodialyzer prepares the electricity of pure water
Conductance is the highest, and therefore desalination field electroendosmosis analysis technology is the most progressively replaced by reverse osmosis technology now.But processing ammonium nitrate
In the field of waste water, electrodialytic technique still has comparative advantage compared with additive method.When electrodialytic technique processes waste water, many
Level series connection electrodialyzer latter end, due to the most of ammonium nitrate in water, i.e. conductive ion has been removed, water conducts electricity from
Seldom, the most easily there is polarization reaction in son.So make the ammonium nitrate removing in water not exclusively, it is impossible to reach national environmental protection and want
Asking, additionally the seal means of electrodialyzer film is relatively simple, mainly by the elastic packing between film and film, after work a period of time,
Different film convergent-divergents are uneven, cause electrodialyzer membrane stack to deform, and intermembranous string water, dense hydroecium solution crossfire is molten to freshwater room
Liquid, makes water outlet water degradation, and these are all its shortcomings being difficult to overcome.Reverse osmosis is the membrance separation grown up in recent decades
Technology, is used widely in terms of sea water and brackish water desalination, large-sized boiler make up water treatment, is also used for milk and fruit
Juice and the biological and separation of biochemical preparation and concentration aspect, and the preparation aspect of drinking water and high purity water.Reverse osmosis in recent years
Technology is also applied in field of waste water treatment, but when having tried to be applied to reverse osmosis technology ammonium nitrate wastewater process,
Find that reverse osmosis membrane is the highest to the transmitance of ammonium nitrate.According to document introduction, reverse osmosis membrane is to NH4 +The clearance of ion be 70～
90%, to NO3 —The clearance of ion is 50～75%.That is reverse osmosis membrane is to NH4 +The transmitance 10～30% of ion is right
NO3 —The transmitance of ion is 25～50%.This is compared with in the of 99% with reverse osmosis membrane to the clearance of NaCl, and this gives and to realize all
The engineering that the waste water of removing ammonium nitrate processes brings the biggest difficulty so that China does not has reverse osmosis applications so far in processing nitre
The precedent of acid ammonium waste water.China's patent of invention ZL200910177557.1 discloses a kind of electrodeionization reclaiming ammonia nitrogen waste water
Method and device, the case history reclaiming ammonium nitrate wastewater shows, electric deionizer is more suitable for the ammonium nitrate of low concentration
Waste water processes, and in terms of high concentration ammonium nitrate wastewater concentration, in terms of concentrated effect, reverse osmosis technology is more applicable.The most current
When electrodialytic technique processes ammonium nitrate wastewater, its pretreating process filters and uses fiber rod to filter, can remove more than 5 μm
Particulate matter, its filtering accuracy awaits improving further.Ultrafilter membrane technique was not yet used in administering ammonium nitrate wastewater field
Process.Pretreating process use acid-base neutralization regulation solution ph to 6.5～about 7.Acid-base neutralization technique also has regulation behaviour
Make complicated and increase the defect of ammonium nitrate concn in waste water.
Summary of the invention
In order to solve prior art and process that the concentrated effect of ammonium nitrate wastewater is the best, filtering accuracy is the highest, operation complicated with
And the high deficiency of ammonium nitrate concn in processed waste water, the invention provides one Integrated Membrane Technology and process ammonium nitrate wastewater
Method, this waste water stock solution is after acid-base neutralization adjusts pH value technique and cooling PROCESS FOR TREATMENT, more successively through following membrane process step
The Integrated Films of composition processes: (1) ultrafilter membrane technique, uses ultrafilter membrane process filtration, removes in waste water stock solution more than 0.1 μm
Colloid and particulate matter, reach pollution index SDI≤3；(2) reverse osmosis membrane technique, uses reverse osmosis membrane technique to pretreated
Water carries out desalination, obtains the ammonium nitrate mass concentration dense water close to 10% and the fresh water less than 0.03%, and this dense water loopback enters nitric acid
Ammonium produces in mother solution, and the degassed membrane process of obtained fresh water enters back into electrodeionization membrane process and carries out advanced desalination；(3)
Degassing film technique, in film degasser, through the NH of reverse osmosis membrane4 +Ion and ammonia, under the drive of vacuum suction, from light
Water pass degassing film, and by 0.1～5% dust technology absorb, dust technology absorb NH4 +Ion and ammonia saturated after, by generate
Ammonium nitrate solution, periodically returns to ultrafilter membrane technique front end, so that the fresh water crossed through reverse-osmosis treated is without free ammonia；(4) electricity
Deionization membrane process, uses electrodeionization membrane process to realize advanced desalination, and the fresh water after processing degassed membrane process is carried out deeply
Degree desalination, after electrodeionization membrane process advanced desalination, the ammonia nitrogen mass concentration of water outlet is less than 1mg/L, taking off obtained by recovery
Saline, the dense water that electrodeionization membrane process produces, after repeatedly circulating concentration and reaching finite concentration, return reverse osmosis membrane technique
Reclaim.The present invention reclaims the mass concentration of ammonium nitrate wastewater stock solution below 3%.The positive effect of the present invention is: (1) present invention
Integrated Membrane Technology is advanced, and change waste water is pure water, saving water resource, non waste discharge, and environmental benefit is good.The present invention uses electrodeionization
Membrane process can make the ammonia nitrogen mass concentration≤1mg/L in the system water outlet of process ammonium nitrate wastewater, close to the quality water of pure water
Flat, can fully recovering, saved water resource.Realize zero-emission truly, ammonium nitrate wastewater no longer exhaust emission ring
Border, environmental benefit is good.(2) energy is saved.The technical process of this Integrated Membrane Technology is carried out the most at normal temperatures, without phase transformation, therefore with
The distillation and concentration method producing phase transformation is compared, and significantly reduces energy consumption.Use reverse osmosis membrane PROCESS FOR TREATMENT ammonium nitrate wastewater and adopt
Compare energy consumption with electrodialytic technique also to decrease.As a example by desalinization, use the energy consumption of reverse osmosis membrane technique to be only and use
The 10% of electrodialysis process.(3) operating cost is low, and administering ammonium nitrate wastewater engineering has economic well-being of workers and staff.It is introduced and use electroosmose process
Or the operating cost of whole water treatment facilities of ion exchange improvement ammonium nitrate wastewater is about 4.5 yuan/ton of water, it is contemplated that this
The operating cost of whole water treatment facilities that bright integrated membrane process administers ammonium nitrate wastewater about saves 20%.Due in ammonium nitrate wastewater
Contained ammonium nitrate all reclaims with solid product, and waste water becomes pure water and all reclaims.(4) simple to operate, improve production labor
Rotating ring border, it is achieved cleaning is carried out production strictly in line with rules and regulations.
Description of drawings 1 present invention process flow chart.Wherein 1 ultrafilter；2 low pressure sum up counter-osmosis device；3 is high
Press dense water counter-osmosis device；4 low pressure fresh water counter-osmosis devices；5 film degassers；6 electric deionizing devices.
Detailed description of the invention elaborates principle, apparatus structure and example below in conjunction with the accompanying drawings.
Embodiment 1 is as it is shown in figure 1, as a example by certain factory's ammonium nitrate wastewater.In water, the mass concentration of ammonium nitrate is 0.5%, should
Waste water is the condensed fluid in Process of Ammonium Nitrate Production, and water quality is simple, in addition to containing a certain amount of ammonium nitrate, is substantially free of other salt
Class.This waste water stock solution through acid-base neutralization adjust pH value technique and cooling PROCESS FOR TREATMENT after, successively carry out constitute the present embodiment as
Under every membrane process process: (1) ultrafilter membrane technique: this waste water stock solution through acid-base neutralization adjust pH value technique and cooling PROCESS FOR TREATMENT
After, its pH value is 7, and temperature is 35 DEG C, first removes bigger particulate matter through fiber rod security personnel's filter, enters back into ultrafilter 1 mistake
Filter, removes colloid and particulate matter more than 0.1 μm in waste water stock solution, reaches pollution index SDI≤3, and ultrafilter 1 is continuously behaviour
The tubular membrane component made is formed；(2) reverse osmosis membrane technique: through the ammonium nitrate wastewater of ultrafilter membrane PROCESS FOR TREATMENT, is introduced into 1 grade
2 sections of low pressure are summed up counter-osmosis device 2 and are carried out concentrating and separating, obtain dense water and fresh water.The high-pressure thick water that dense water enters back into 1 grade 2 sections is anti-
Permeator 3 concentrates further, obtains ammonium nitrate mass concentration close to 10% concentrated solution.Its loopback is entered ammonium nitrate production female
In liquid, the fresh water simultaneously obtained through high-pressure thick water counter-osmosis device 3 processes before being recycled to ultrafilter again.And sum up through low pressure
The fresh water that counter-osmosis device 2 obtains, carries out desalination separation through 1 grade of low pressure fresh water counter-osmosis device 4 again.The dense water loopback now obtained
Process to ultrafilter 1, and the fresh water obtained enters film degasser 5；(3) degassing film technique: in film degasser 5, wear
Cross the NH of reverse osmosis membrane4 +Ion and ammonia, under the drive of vacuum suction, from fresh water through degassing film, and by 0.1% dust technology
Absorb, absorb NH at dust technology4 +Ion and ammonia saturated after, the ammonium nitrate solution that will generate, before periodically returning ultrafilter membrane technique
End, so that the fresh water crossed through reverse-osmosis treated is without free ammonia；(4) electrodeionization membrane process: use 1 grade of electric deionizing device 6
Realize advanced desalination, the fresh water processed through film degasser 5 is carried out advanced desalination, after electric deionizing device 6 advanced desalination,
The ammonia nitrogen mass concentration of water outlet is less than 1mg/L, the desalted water obtained by recovery, and the dense water that electric deionizing device 6 produces, through repeatedly
After circulation concentration reaches finite concentration, return to low pressure fresh water counter-osmosis device 4 front end and reclaim.
Embodiment 2 is as a example by certain factory's ammonium nitrate wastewater.In water, the mass concentration of ammonium nitrate is 2%, and this waste water is ammonium nitrate
Condensed fluid in production process, water quality is simple, in addition to containing a certain amount of ammonium nitrate, is substantially free of other salt impurity.This waste water
Stock solution, after acid-base neutralization adjusts pH value technique and cooling PROCESS FOR TREATMENT, carries out constituting following every film of the present embodiment successively
PROCESS FOR TREATMENT: (1) ultrafilter membrane technique: this waste water stock solution through acid-base neutralization adjust pH value technique and cooling PROCESS FOR TREATMENT after, its pH value
Being 6.5, temperature is 30 DEG C, first removes bigger particulate matter through fiber rod security personnel's filter, enters back into ultrafilter 1 and filter, removes useless
More than colloid and the particulate matter of 0.1 μm in water stock solution, reaching pollution index SDI≤3, ultrafilter 1 is that the hollow of continuous operation is fine
Dimension hyperfiltration membrane assembly is formed；(2) reverse osmosis membrane technique: through the ammonium nitrate wastewater of ultrafilter membrane PROCESS FOR TREATMENT, is introduced into 1 grade 2 sections
Low pressure is summed up counter-osmosis device 2 and is carried out concentrating and separating, obtains dense water and fresh water.Dense water enters back into the high-pressure thick water reverse osmosis of 1 grade 1 section
Device 3 concentrates further thoroughly, obtains ammonium nitrate mass concentration close to 10% concentrated solution.Its loopback is entered ammonium nitrate production mother solution
In, the fresh water simultaneously obtained through high-pressure thick water counter-osmosis device 3 processes before being recycled to ultrafilter again.And it is blanket anti-through low pressure
The fresh water that permeator 2 obtains, carries out desalination separation through 1 grade of low pressure fresh water counter-osmosis device 4 again.The dense water now obtained is recycled to
Process before ultrafilter 1, and the fresh water obtained enters film degasser 5；(3) degassing film technique: in film degasser 5, pass
The NH of reverse osmosis membrane4 +Ion and ammonia, under the drive of vacuum suction, from fresh water through degassing film, and inhaled by 5% dust technology
Receive, absorb NH at dust technology4 +Ion and ammonia saturated after, the ammonium nitrate solution that will generate, before periodically returning ultrafilter membrane technique
End, so that the fresh water crossed through reverse-osmosis treated is without free ammonia；(4) electrodeionization membrane process: use 1 grade of electric deionizing device 6
Realize advanced desalination, the fresh water processed through film degasser 5 is carried out advanced desalination, after electric deionizing device 6 advanced desalination,
The ammonia nitrogen mass concentration of water outlet is less than 1mg/L, the desalted water obtained by recovery, and the dense water that electric deionizing device 6 produces, through repeatedly
After circulation concentration reaches finite concentration, return to low pressure fresh water counter-osmosis device 4 front end and reclaim.Application and popularization Integrated Membrane Technology
Process the method and device of ammonium nitrate wastewater, the zero-emission of ammonium nitrate wastewater recovery system can be realized, i.e. solve ammonium nitrate and give up
Water discharges the problem of environmental pollution that causes, has reclaimed again ammonium nitrate solid product and desalted water, and achieve economical and environmentally friendly is double
Good harvest.Integrated Films technique of the present invention, advanced technology；Save the energy；Administering waste water economic well-being of workers and staff good, sewage recovering system runs
Expense is low；Simple to operate, it is achieved cleaning is carried out production strictly in line with rules and regulations.
Claims (1)
1. the method processing ammonium nitrate wastewater with Integrated Membrane Technology, it is characterised in that: waste water stock solution adjusts pH through acid-base neutralization
After value technique and cooling PROCESS FOR TREATMENT, more successively through the Integrated Films process of following membrane process step composition: (1) ultrafilter membrane work
Skill, uses ultrafilter membrane process filtration, removes colloid and particulate matter more than 0.1 μm in waste water stock solution so that pollution index SDI
≤3；(2) reverse osmosis membrane technique, uses reverse osmosis membrane technique that pretreated water is carried out desalination, obtains ammonium nitrate quality dense
Spending the dense water close to 10% and the fresh water less than 0.03%, this dense water loopback enters in ammonium nitrate production mother solution, and obtained fresh water
Degassed membrane process enters back into electrodeionization membrane process and carries out advanced desalination；(3) degassing film technique, through reverse osmosis membrane
NH4+ ion and ammonia, under the drive of vacuum suction, from fresh water through degassing film, and by 0.1～5% dust technology absorb,
Dust technology absorb NH4+ ion and ammonia saturated after, the ammonium nitrate solution that will generate, periodically return to ultrafilter membrane technique front end, from
And make the fresh water crossed through reverse-osmosis treated not contain free ammonia；(4) electrodeionization membrane process, uses electrodeionization membrane process to realize
Advanced desalination, the fresh water after processing degassed membrane process carries out advanced desalination, goes out after electrodeionization membrane process advanced desalination
The ammonia nitrogen mass concentration of water is less than 1mg/L, the desalted water obtained by recovery, and the dense water that electrodeionization membrane process produces, through repeatedly
After circulation concentration reaches finite concentration, return reverse osmosis membrane technique and reclaim.
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| CN104944443B (en) * | 2015-06-17 | 2017-05-17 | 安徽淮化股份有限公司 | Device for recycling gaseous condensate waste water produced in ammonium nitrate production by using neutralizer |
| CN105366832A (en) * | 2015-12-15 | 2016-03-02 | 秦皇岛华恒生物工程有限公司 | Processing method of L-alanine extraction evaporation condensed water |
| CN105565567B (en) * | 2015-12-25 | 2018-08-31 | 石家庄杰克化工有限公司 | Method for processing organic wastewater with high salt in a kind of production of EDTA sodium cyanide methods |
| CN112777813A (en) * | 2021-01-21 | 2021-05-11 | 四川思达能环保科技有限公司 | Method for treating evaporated condensate water containing ammonia nitrogen |
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| US7470366B2 (en) * | 2004-05-07 | 2008-12-30 | Ge Mobile Water, Inc. | Water purification system and method using reverse osmosis reject stream in an electrodeionization unit |
| CN201305523Y (en) * | 2008-11-12 | 2009-09-09 | 恩那社(上海)水处理系统有限公司 | Processing system for transforming normal water to ultrapure water |
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