CN107117755A - A kind of high ammonia-nitrogen wastewater processing and ammonia recovery system and its method - Google Patents
A kind of high ammonia-nitrogen wastewater processing and ammonia recovery system and its method Download PDFInfo
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- CN107117755A CN107117755A CN201710250719.4A CN201710250719A CN107117755A CN 107117755 A CN107117755 A CN 107117755A CN 201710250719 A CN201710250719 A CN 201710250719A CN 107117755 A CN107117755 A CN 107117755A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/043—Details
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2303/16—Regeneration of sorbents, filters
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Abstract
The present invention relates to field of waste water treatment, a kind of high ammonia-nitrogen wastewater processing and ammonia recovery system and its method, including the high ammonia-nitrogen wastewater collecting pit being sequentially connected by pipeline are disclosed（1）, waste water lifting pump（2）, the first cartridge filter（3）, steam plate changes（4）, deamination membrane module（5）With outer row pond（6）；Pipeline between the waste water lifting pump and the first cartridge filter is provided with adder-subtractor（7）, ammonia nitrogen waste water from the shell side inlet and outlet of the deamination membrane module, the import and export of the tube side of deamination membrane module respectively with means for feeding acid（8）And multi-effect evaporating device（9）Connection.The present invention can be purified to high ammonia-nitrogen wastewater and to realizing the recovery of ammonia, and not only purifying rate, the rate of recovery are high, and operating efficiency is high, and cost is low.
Description
Technical field
The present invention relates to field of waste water treatment, more particularly to a kind of processing of high ammonia-nitrogen wastewater and ammonia recovery system and its side
Method.
Background technology
With developing rapidly for the industries such as chemical industry, printing and dyeing, chemical fertilizer, the high ammonia-nitrogen wastewater thus occurred turns into industry development
Restraining factors.The red tide increased frequency that China marine site occurs, ammonia nitrogen is one of main pollution factor, particularly ammonia nitrogen in high density
The pollution that waste water is caused.Thus, cost-effective control ammonia nitrogen in high density also turns into the important class that current environmental worker studies
Topic, has obtained the great attention of professional.
Ammonia nitrogen waste water is discharged into water body, particularly flows more slow lake, bay, easily causes in water algae and other micro-
Biological amount reproduction, forms eutrophication pollution, and water treatment plants operation on the one hand can be made difficult, the peculiar smell of drinking water is caused
Outside, on the other hand it can decline oxygen in water, fish mortality results even in lake destruction.Ammonia nitrogen can also make feedwater
Chlorine dosage is increased in sterilization and industrial circulating water sterilisation process, to some metals, particularly there is corrosivity to copper.When
During reusing sewage, microorganism can promote the breeding of microorganism in water-supply-pipe and water equipment in recycled water, formed after biology and blocked up
Pipeline and water equipment are filled in, and influences heat exchange efficiency.
General ammoniacal liquor and the inorganic ammonia of being formed as of ammonia nitrogen waste water exists caused jointly, and typically upper pH is in neutrality
The main source of ammonia nitrogen in waste water above is the effect of inorganic ammonia and ammoniacal liquor jointly, ammonia nitrogens of the pH in waste water under conditions of acidity
Mainly due to caused by inorganic ammonia.The method of processing ammonia nitrogen that can be effectively to this has a many, such as physical-chemical process have stripping, from
Sub- exchange, coagulating sedimentation, counter-infiltration, electrodialysis and various high-level oxidation technologies（AOTs）Etc. a variety of methods；Biological method has nitre
The water plant cultivation such as change and algae.But have the advantages that using convenient, treatment effect stabilization, adapt to waste water quality and economical
NH3-N elimination method is still among research.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of processing of high ammonia-nitrogen wastewater and ammonia recovery system and its side
Method.The present invention can be purified to high ammonia-nitrogen wastewater and to realizing the recovery of ammonia, and not only purifying rate, the rate of recovery are high, Er Qiegong
Make efficiency high, cost low.
The present invention concrete technical scheme be：A kind of processing of high ammonia-nitrogen wastewater and ammonia recovery system, including by pipeline according to
High ammonia-nitrogen wastewater collecting pit, waste water lifting pump, the first cartridge filter, the steam plate of secondary connection are changed, deamination membrane module and outer row
Pond；Pipeline between the waste water lifting pump and the first cartridge filter is provided with adder-subtractor, and ammonia nitrogen waste water is from the deamination
The shell side inlet and outlet of membrane module, the import and export of the tube side of deamination membrane module respectively with means for feeding acid and multi-effect evaporating device
Connection.
The present invention operation principle be：
High ammonia-nitrogen wastewater collecting pit：Liquid ammonia pollution is collected to high ammonia-nitrogen wastewater and received by one-level Water spray tower and two grades of sour spray columns
Ji Chi.One side high ammonia-nitrogen wastewater collecting pit is Seal Design, prevents ammonia leakage from triggering security incident；On the other hand water is deposited
Deamination membrane module is pumped to by waste water lifting pump, can be according to the start and stop of height of liquid level controlling pump.
The effect of first cartridge filter is that waste water is tentatively filtered, and prevents particulate contaminant in waste water to below
Deamination film results in blockage.
The effect that steam plate is changed is that waste water is heated, and waste water only reaches after certain temperature that, ammonia therein is
It can be spun off from water.
Adder-subtractor：Adder-subtractor be in order to keep wastewater pH stable more than 10, because only that under above-mentioned pH, ability
Make waste water NH4+Change into ammonia.
Means for feeding acid：Means for feeding acid is to supply acid to the tube side of deamination membrane module, for absorbing the ammonia in tube side.
Deamination membrane module：Waste water enters in the shell side of deamination membrane module, when pH rises in waste water, ammonium ion NH4+Become
Free gaseous state NH3.At this moment gaseous state NH3The micropore on the doughnut surface of deamination membrane module can be passed through, ammonia enters from shell side
Mixed into tube side, and with sour absorbing liquid, ammonia becomes the NH of ionic state again at once after being absorbed by acid solution4+。
After the ammonia in waste water in outer row pond, shell side is separated, outer row pond is drained into.
Multi-effect evaporating device：Acid solution in deamination membrane module tube side is absorbed after ammonia, leads to multi-effect evaporating device, many
Heating evaporation is carried out in effect vaporising device, as concentration increases, ammonium salt is crystallized, after crystallization is separated with liquid, realize ammonium
The recovery of salt, can directly be sold.
, it is necessary to which the pH of waste water in the shell side of deamination membrane module is maintained at into more than 10 in said apparatus, and temperature exists
More than 35 DEG C, less than 50 DEG C, NH in such waste water phase4+Will continuously become NH3Migration of liquid is absorbed to acid, so that
The ammonia nitrogen concentration of waste water side constantly declines, and acid absorbs liquid phase due to only sour and NH4+, so what is formed is very pure ammonium
Salt, can be recycled.
Preferably, sulfuric acid storage tank, acid adding measuring pump, graphite cake that the means for feeding acid includes being sequentially connected are changed；It is described
Graphite cake is changed to be connected with deamination membrane module；And acid adding measuring pump and graphite cake alternatively between pipeline provided with being connected with sulfuric acid storage tank
Sour return duct.
Inhaled preferably, the multi-effect evaporating device includes diluted acid circulating tank, acid circulating pump, the 3rd cartridge filter, acid
Receive liquid collecting pit, MVR feed pumps, preheater, evaporator, discharging pump, thickener, centrifuge, mother liquor tank, mother liquor reflux pump；Institute
The outlet that diluted acid circulating tank is stated with the tube side of deamination membrane module is connected, diluted acid circulating tank, acid circulating pump, the 3rd cartridge filter according to
It is secondary to be connected by pipeline with the import of deamination membrane module shell side；In addition, diluted acid circulating tank, sour absorbing liquid collecting pit, MVR chargings
Pump, preheater, evaporator, discharging pump, thickener, centrifuge, mother liquor tank are sequentially connected by pipeline, and the outlet of mother liquor tank passes through
Pipeline is connected with mother liquor reflux pump, discharging pump successively again；And be additionally provided with the pipeline after mother liquor reflux pump and mother liquor tank backflow company
The mother liquor reflux pipe connect.
The operation principle of above-mentioned multi-effect evaporating device is：
Diluted acid circulating tank is recycled for reclaiming by the acid solution after deamination membrane module, and carrying out acid to it.Diluted acid circulating tank
Sour absorbing liquid collecting pit can also be led to and carry out intermediate storage.Acid solution passes through the pre- of preheater under the conveying of MVR feed pumps
Ammonium salt in heat, acid solution thoroughly dissolves so that the good fluidity of acid solution, is not easily blocked pipeline.Reach
After evaporator, heating wherein evaporates solvent, and raising, the ammonium salt acid solution of high concentration are significantly increased in this ammonium salt concentration
Continue through discharging pump and be transported to thickener, crystallized in thickener, be then delivered to the acid solution for being contaminated with crystallization
Centrifuge, crystallizes in the presence of centrifuge and is separated with acid solution, crystallization is collected, and acid solution is transported to mother liquor tank, due to mother
Acid solution in flow container is also containing ammonium salt of the part for crystallization, and it is transmitted back to mix with acid solution below in evaporator again steams again
Hair, crystallization.Make full use of resource.
In addition, carrying out circulating reflux to the material in mother liquor tank, material can be made to be in flow regime all the time, prevent from blocking up
Material.
Preferably, the multi-effect evaporating device also includes forced circulation pump, forced heat-exchanging device and compressor；It is described to force
The entirety that circulating pump is constituted with forced heat-exchanging device and discharging pump formation circulation loop；The import of the compressor and the steaming of discharging pump
Vapor outlet is connected, and the outlet of compressor is connected with forced heat-exchanging device.
The moisture gasified in evaporator is transported in forced heat-exchanging device after the heating again of compressor；Steam simultaneously
Device is sent out also by forced circulation pump and forced heat-exchanging device formation circulation loop, acid solution and the steam after heating in forced heat-exchanging device
Carry out heat exchange, the temperature rise of acid solution, solvent volatilization.Above-mentioned attachment structure can abundant recycling heat energy, reduce cost.
And make the acid solution forced circulation flowing containing ammonium salt in evaporator, anti-locking apparatus is blocked（After ammonium salt concentration is uprised in acid solution
Solution viscosity is greatly improved, and mobility is very poor）.
Preferably, the pipeline that the steam plate is changed between deamination membrane module is provided with cleaning device.
Run after the regular hour, the waste water side of the hollow-fibre membrane in deamination membrane module is easily contaminated, it is necessary to enter
The regular Chemical cleaning of row, it is ensured that the normal of film is used.
Preferably, the adder-subtractor includes alkali storage tank and plus alkali measuring pump；The alkali storage tank plus alkali measuring pump and the
One cartridge filter is sequentially connected；And add and be additionally provided with pipeline between alkali measuring pump and alkali stores up tank connected alkali return duct.
Preferably, the cleaning device includes purge tank, cleaning pump and the second cartridge filter；It is the purge tank, clear
Pump, the second cartridge filter and deamination membrane module is washed to be sequentially connected；And on the pipeline between cleaning pump and the second cartridge filter
Provided with cleaning tank connected cleaning fluid return duct.
Preferably, the quantity of the deamination membrane module is multiple, series connection is formed between multiple deamination membrane modules.
Preferably, the thin liquid outlet on the thickener is connected with mother liquor tank.Liquid level part ammonium salt concentration in thickener
Relatively low acid solution, is fed directly to mother liquor tank, is circulated again, without that by centrifuge, can greatly improve operating efficiency.
Preferably, the filter membrane in the deamination membrane module is polypropylene hollow fiber membrane；Described porosity is 60-
80%, pore size filter is 0.02-0.04 microns, and wall thickness is 70 microns.The filter membrane can be directly purchased in market by the progress of above-mentioned specification,
Specified scheme progress for the present invention is special.
Preferably, the preparation method of the polypropylene hollow fiber membrane is as follows：
（a）Acrylic resin is melted, squeezed by mould as hollow fiber, is then cooled down, stretched successively, thermal finalization
Afterwards, the polypropylene hollow fiber membrane that average thickness is 65 microns is made.
（b）Tetraethyl orthosilicate is mixed with the mass concentration of its 80 times of quality for 60% ethanol solution, then side is added dropwise
Acid solution, and reacted at 50 DEG C, make to generate silicon dioxide gel in solution, untill there is no the generation of new colloidal sol；By titanium
Acid butyl ester is mixed with the ethanol of its 60 times of quality, and acid solution is then added dropwise while stirring, and is reacted at 65 DEG C, makes to generate in solution
TiO 2 sol, untill there is no the generation of new colloidal sol.
（c）By silicon dioxide gel and TiO 2 sol in mass ratio 3:1 mixing, obtains mixed sols；Again to mixing
The concentration that its quality 5% is added in colloidal sol is 0.5mol/L month sodium silicate solutions, and 0.5h is stirred at 60 DEG C；Then respectively to mixed
Close iron powder, carbon dust and acrylic acid [N- methyl perfluoro butane sulfoamido] second that its quality 4%, 1%, 2%, 0.5% is added in colloidal sol
Ester and Kynoar are simultaneously uniformly dispersed, and obtain sol paint.
（d）Sol paint is coated on to the outer surface of polypropylene hollow fiber membrane, it is last complete after standing aging 1 day
The gas phase that average thickness is 5 microns is formed after baking and curing.
The polypropylene hollow fiber membrane difference of polypropylene hollow fiber membrane made from the above method and prior art exists
In its outer surface is located at coating.The coating has the effect that：1st, because the both sides decibel of polypropylene hollow fiber membrane is alkali
Liquid and acid solution, therefore polypropylene hollow fiber membrane needed with superpower corrosion resistance, and it is superpower containing corrosion resistance in coating
Silicon materials, the corrosion resistance of membrane material can be lifted.2nd, polypropylene hollow fiber membrane works long hours use, due to its outside table
For a long time and waste water, the organic matter in waste water easily results in blockage to its micropore in face, and contains iron powder, carbon dust and third in coating
Olefin(e) acid [N- methyl perfluoro butane sulfoamido] ethyl ester and titanium dioxide；First, iron powder and carbon dust can be formed in water environment
Micro cell, can carry out light electrolysis, so that micropore is unimpeded to the organic matter being embedded in film layer micropore.Secondly, acrylic acid
[N- methyl perfluoro butane sulfoamido] ethyl ester is fluorine-containing material, and it has ultralow surface energy, and organic matter dirt is not easy attached
In membrane material surface, even if there is part dirt to be attached to membrane material surface, also only membrane material need to be carried out simply to rinse
Dirt is washed out, anti-soil effect is played.Furthermore, titanium dioxide has photocatalysis effect, under light illumination, be attached in membrane material
Organic matter will degrade.Therefore, in the case where simple cleaning performance after membrane material is heavily contaminated is poor, only need more
Hollow-fibre membrane is changed, dirty hollow-fibre membrane is subjected to automatically cleaning under light illumination.3rd, in general in hollow-fibre membrane table
After the applying coating of face, the porosity of membrane material can be caused to be greatly reduced, cause ammonia percent of pass seriously to reduce, influence filtering effect
Really.The coating of the present invention is first prepared respectively obtains mixed sols after silicon dioxide gel and TiO 2 sol, mixing, then to mixed
Close colloidal sol and carry out hydrophobically modified with moon sodium silicate solution（Reduce water to infiltrate coating, so as to influence gas permeability）, then will mixing
Colloidal sol is coated on film surface, successively carries out aging, dry solidification, forms the high porosity with three-dimensional net structure, height ventilative
The low hydrophobic gas phase of rate, thickness, can't significantly affect the filter efficiency of hollow-fibre membrane.
A kind of high ammonia-nitrogen wastewater processing and ammonia recovery method, comprise the following steps：
（1）Spray is collected：Liquid ammonia pollution is collected extremely by turning into high ammonia-nitrogen wastewater after one-level Water spray tower and two grades of sour spray columns
High ammonia-nitrogen wastewater collecting pit；
（2）Plus alkali heating：Alkali lye is added into waste water, makes wastewater pH stable more than 10, to heating waste water after waste water filtering
Ammonium ion is set to become free gaseous state ammonia to 35-50 DEG C；
（3）Deamination：In the shell side that waste water is delivered to deamination membrane module, while the sulfuric acid in means for feeding acid is changed by graphite cake
In the tube side that deamination membrane module is delivered to after cooling；The filter membrane that ammonia in waste water is passed through in deamination membrane module enters from shell side
Tube side simultaneously mixes with sulfuric acid and becomes ammonium ion again；
（4）Arranged outside waste water：Waste water after deamination in deamination membrane module shell side is delivered to outer row pond；
（5）Acid cycle：Sulfuric acid in deamination membrane module tube side is delivered in means for feeding acid again and carries out reflux cycle；Simultaneously
By part of sulfuric acid in means for feeding acid after filtering, multi-effect evaporating device is delivered to；
（6）Multiple-effect evaporation：Sulfuric acid is first carried out to be preheated to 50-60 DEG C, 100-110 DEG C of evaporation is then further heated to, with
The concentration of ammonium salt increases in sulfuric acid, and ammonium salt is crystallized；
（7）Centrifuge：After the sulfuric acid proportion doped with ammonium salt crystallization reaches 0.95-1.05g/mL, it is delivered to successively
Thickener and centrifuge carry out ammonium salt crystallization separation, ammonium salt crystallization are collected, while sulfuric acid is continued on into mother liquor tank；
（8）Reflux cycle is evaporated：Sulfuric acid in mother liquor tank is transmitted back to after being mixed in multi-effect evaporating device with the sulfuric acid of rear feeding
It is evaporated again.
Preferably, the h 2 so 4 concentration in deamination membrane module is controlled 50%；The alkali lye is that mass concentration is 30%
Sodium hydroxide solution.
Preferably, when the filter membrane in deamination membrane module is blocked, being carried out by cleaning device to it chemical clear
Wash.
It is compared with the prior art, the beneficial effects of the invention are as follows：The present invention can be purified and right to high ammonia-nitrogen wastewater
The recovery of ammonia is realized, not only purifying rate, the rate of recovery are high, and operating efficiency is high, and cost is low.
Brief description of the drawings
Fig. 1 is a kind of structural representation of the present invention；
Fig. 2 is a kind of structural representation of adder-subtractor in the present invention；
Fig. 3 is a kind of structural representation of cleaning device in the present invention；
Fig. 4 is a kind of structural representation of means for feeding acid and multi-effect evaporating device in the present invention.
Reference is：High ammonia-nitrogen wastewater collecting pit 1, waste water lifting pump 2, the first cartridge filter 3, steam plate change 4, taken off
Ammonia membrane module 5, outer row pond 6, adder-subtractor 7, means for feeding acid 8, multi-effect evaporating device 9, cleaning device 10, alkali storage tank 11 plus alkali
Measuring pump 12, alkali return duct 13, purge tank 14, cleaning pump 15, the second cartridge filter 16, cleaning fluid return duct 17, sulfuric acid storage
Tank 18, acid adding measuring pump 19, graphite cake change 20, sour return duct 21, diluted acid circulating tank 22, the security personnel's filtering of acid circulating pump the 23, the 3rd
Device 24, sour absorbing liquid collecting pit 25, MVR feed pumps 26, preheater 27, evaporator 28, discharging pump 29, thickener 30, centrifuge
31st, mother liquor tank 32, mother liquor reflux pump 33, mother liquor reflux pipe 34, forced circulation pump 35, forced heat-exchanging device 36, compressor 37.
Embodiment
With reference to embodiment, the invention will be further described.Involved in the present invention device, attachment structure
And method, if being device well known in the art, connection structure and method without refering in particular to.
Embodiment 1
As shown in Figure 1：A kind of high ammonia-nitrogen wastewater processing and ammonia recovery system, including the high ammonia-nitrogen wastewater being sequentially connected by pipeline
Collecting pit 1, waste water lifting pump 2, the first cartridge filter 3, steam plate change 4, the deamination membrane module 5 of four series connection and outer row pond 6.
Pipeline between the waste water lifting pump and the first cartridge filter is provided with adder-subtractor 7, and ammonia nitrogen waste water is from the deamination film
The shell side inlet and outlet of component, the import and export of the tube side of deamination membrane module respectively with means for feeding acid 8 and multi-effect evaporating device 9
Connection.The pipeline that the steam plate is changed between deamination membrane module is provided with cleaning device 10.
Wherein, as shown in Fig. 2 the adder-subtractor includes alkali storage tank 11 and plus alkali measuring pump 12.The alkali storage tank plus alkali
Measuring pump and the first cartridge filter are sequentially connected；And add and be additionally provided with pipeline between alkali measuring pump and alkali stores up tank connected alkali
Return duct 13.
As shown in figure 3, the cleaning device includes purge tank 14, the cartridge filter 16 of cleaning pump 15 and second.It is described clear
Cleaning of evaporator, cleaning pump, the second cartridge filter and deamination membrane module are sequentially connected；And between cleaning pump and the second cartridge filter
Pipeline is provided with cleaning tank connected cleaning fluid return duct 17.
As shown in figure 4, sulfuric acid storage tank 18, acid adding measuring pump 19, graphite cake that the means for feeding acid includes being sequentially connected are changed
20.The graphite cake is changed to be connected with deamination membrane module；And acid adding measuring pump and graphite cake alternatively between pipeline be provided with and sulfuric acid
Store up tank connected sour return duct 21.
As shown in figure 4, the multi-effect evaporating device includes diluted acid circulating tank 22, acid circulating pump 23, the 3rd cartridge filter
24th, sour absorbing liquid collecting pit 25, MVR feed pumps 26, preheater 27, evaporator 28, discharging pump 29, thickener 30, centrifuge 31,
Mother liquor tank 32, mother liquor reflux pump 33, forced circulation pump 35, forced heat-exchanging device 36 and compressor 37.The diluted acid circulating tank is with taking off
The outlet connection of the tube side of ammonia membrane module, diluted acid circulating tank, acid circulating pump, the 3rd cartridge filter pass sequentially through pipeline and deamination
The import connection of membrane module shell side；In addition, diluted acid circulating tank, sour absorbing liquid collecting pit, MVR feed pumps, preheater, evaporator,
Discharging pump, thickener, centrifuge, mother liquor tank are sequentially connected by pipeline, and the thin liquid outlet on thickener is directly and mother liquor tank
Connection.The outlet of mother liquor tank is connected with mother liquor reflux pump, discharging pump successively again by pipeline；And on the pipeline after mother liquor reflux pump
It is additionally provided with the mother liquor reflux pipe 34 for flowing back and being connected with mother liquor tank.The entirety that the forced circulation pump is constituted with forced heat-exchanging device is with going out
Expect pump formation circulation loop；The import of the compressor and the steam (vapor) outlet of discharging pump are connected, and outlet and the pressure of compressor are changed
Hot device connection.
Wherein, the filter membrane in the deamination membrane module is polypropylene hollow fiber membrane；Its preparation method is as follows：
（a）Acrylic resin is melted, squeezed by mould as hollow fiber, is then cooled down, stretched successively, thermal finalization
Afterwards, the polypropylene hollow fiber membrane that average thickness is 65 microns is made.
（b）Tetraethyl orthosilicate is mixed with the mass concentration of its 80 times of quality for 60% ethanol solution, then side is added dropwise
Acid solution, and reacted at 50 DEG C, make to generate silicon dioxide gel in solution, untill there is no the generation of new colloidal sol；By titanium
Acid butyl ester is mixed with the ethanol of its 60 times of quality, and acid solution is then added dropwise while stirring, and is reacted at 65 DEG C, makes to generate in solution
TiO 2 sol, untill there is no the generation of new colloidal sol.
（c）By silicon dioxide gel and TiO 2 sol in mass ratio 3:1 mixing, obtains mixed sols；Again to mixing
The concentration that its quality 5% is added in colloidal sol is 0.5mol/L month sodium silicate solutions, and 0.5h is stirred at 60 DEG C；Then respectively to mixed
Close iron powder, carbon dust and acrylic acid [N- methyl perfluoro butane sulfoamido] second that its quality 4%, 1%, 2%, 0.5% is added in colloidal sol
Ester and Kynoar are simultaneously uniformly dispersed, and obtain sol paint.
（d）Sol paint is coated on to the outer surface of polypropylene hollow fiber membrane, it is last complete after standing aging 1 day
The gas phase that average thickness is 5 microns is formed after baking and curing.
After testing, polypropylene hollow fiber membrane made from the above method, its overall porosity（Containing coating）In 80 or so %,
Pore size filter is between 0.02-0.04 microns, and wall thickness is 70 microns（Containing coating）, its floating coat specific surface area is up to 500-
700cm2/ g, coating porosity is more than 90%.
High ammonia-nitrogen wastewater is handled using present system, deamination rate can reach 98% in waste water, and recovery ammonia reaches
99%。
Embodiment 2
A kind of high ammonia-nitrogen wastewater processing and ammonia recovery method, comprise the following steps：
（1）Spray is collected：Liquid ammonia pollution is collected extremely by turning into high ammonia-nitrogen wastewater after one-level Water spray tower and two grades of sour spray columns
High ammonia-nitrogen wastewater collecting pit；
（2）Plus alkali heating：Alkali lye is added into waste water（Mass concentration is 30% sodium hydroxide solution）, wastewater pH stabilization is existed
More than 10, ammonium ion is become free gaseous state ammonia to waste water is heated into 45 DEG C after waste water filtering；
（3）Deamination：In the shell side that waste water is delivered to deamination membrane module, while the sulfuric acid in means for feeding acid is changed by graphite cake
In the tube side that deamination membrane module is delivered to after cooling（H 2 so 4 concentration in deamination membrane module is controlled 50%）；In waste water
The filter membrane that ammonia is passed through in deamination membrane module enters tube side and mixed with sulfuric acid from shell side becomes ammonium ion again；
（4）Arranged outside waste water：Waste water after deamination in deamination membrane module shell side is delivered to outer row pond；
（5）Acid cycle：Sulfuric acid in deamination membrane module tube side is delivered in means for feeding acid again and carries out reflux cycle；Simultaneously
By part of sulfuric acid in means for feeding acid after filtering, multi-effect evaporating device is delivered to；
（6）Multiple-effect evaporation：Sulfuric acid is first carried out to be preheated to 55 DEG C, then further 105 DEG C of evaporations of heating, with ammonium salt in sulfuric acid
Concentration increase, ammonium salt is crystallized；
（7）Centrifuge：After the sulfuric acid proportion doped with ammonium salt crystallization reaches 1g/mL, it is delivered to successively thickener and
Centrifuge carries out ammonium salt crystallization separation, ammonium salt crystallization is collected, while sulfuric acid is continued on into mother liquor tank；
（8）Reflux cycle is evaporated：Sulfuric acid in mother liquor tank is transmitted back to after being mixed in multi-effect evaporating device with the sulfuric acid of rear feeding
It is evaporated again.
In addition, when the filter membrane in deamination membrane module is blocked, Chemical cleaning is carried out to it by cleaning device.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and equivalent structure transformation that technical spirit is made to above example, still fall within skill of the present invention
The protection domain of art scheme.
Claims (10)
1. a kind of high ammonia-nitrogen wastewater processing and ammonia recovery system, it is characterised in that：Including the high ammonia nitrogen being sequentially connected by pipeline
Wastewater collection pond（1）, waste water lifting pump（2）, the first cartridge filter（3）, steam plate changes（4）, deamination membrane module（5）With outer row
Pond（6）；Pipeline between the waste water lifting pump and the first cartridge filter is provided with adder-subtractor（7）, ammonia nitrogen waste water is from institute
State the shell side inlet and outlet of deamination membrane module, the import and export of the tube side of deamination membrane module respectively with means for feeding acid（8）And multiple-effect
Vaporising device（9）Connection；The means for feeding acid includes the sulfuric acid storage tank being sequentially connected（18）, acid adding measuring pump（19）, graphite cake
Change（20）；The graphite cake is changed to be connected with deamination membrane module；And acid adding measuring pump and graphite cake alternatively between pipeline be provided with
The sour return duct of sulfuric acid storage tank connection（21）；The multi-effect evaporating device includes diluted acid circulating tank（22）, acid circulating pump（23）,
Three cartridge filters（24）, sour absorbing liquid collecting pit（25）, MVR feed pumps（26）, preheater（27）, evaporator（28）, discharging
Pump（29）, thickener（30）, centrifuge（31）, mother liquor tank（32）, mother liquor reflux pump（33）；The diluted acid circulating tank and deamination film
The outlet connection of the tube side of component, diluted acid circulating tank, acid circulating pump, the 3rd cartridge filter pass sequentially through pipeline and deamination film group
The import connection of part shell side；In addition, diluted acid circulating tank, sour absorbing liquid collecting pit, MVR feed pumps, preheater, evaporator, discharging
Pump, thickener, centrifuge, mother liquor tank are sequentially connected by pipeline, the outlet of mother liquor tank by pipeline again successively with mother liquor reflux
Pump, discharging pump connection；And the mother liquor reflux pipe for flowing back and being connected with mother liquor tank is additionally provided with the pipeline after mother liquor reflux pump（34）；Institute
Stating multi-effect evaporating device also includes forced circulation pump（35）, forced heat-exchanging device（36）And compressor（37）；The forced circulation pump
The entirety constituted with forced heat-exchanging device and discharging pump formation circulation loop；The import of the compressor and the steam (vapor) outlet of discharging pump
Connection, the outlet of compressor is connected with forced heat-exchanging device.
2. a kind of high ammonia-nitrogen wastewater processing as claimed in claim 1 and ammonia recovery system, it is characterised in that the steam plate is changed
Pipeline between deamination membrane module is provided with cleaning device（10）.
3. a kind of high ammonia-nitrogen wastewater processing as claimed in claim 1 and ammonia recovery system, it is characterised in that the adder-subtractor
Including alkali storage tank（11）With add alkali measuring pump（12）；The alkali storage tank plus alkali measuring pump and the first cartridge filter are sequentially connected；
And add and be additionally provided with pipeline between alkali measuring pump and alkali stores up tank connected alkali return duct（13）.
4. a kind of high ammonia-nitrogen wastewater processing as claimed in claim 2 and ammonia recovery system, it is characterised in that the cleaning device
Including purge tank（14）, cleaning pump（15）With the second cartridge filter（16）；The purge tank, cleaning pump, second security personnel's filtering
Device and deamination membrane module are sequentially connected；And the pipeline between cleaning pump and the second cartridge filter is provided with cleaning tank connected
Cleaning fluid return duct（17）.
5. a kind of high ammonia-nitrogen wastewater processing as claimed in claim 1 and ammonia recovery system, it is characterised in that the deamination film group
The quantity of part is multiple, and series connection is formed between multiple deamination membrane modules.
6. a kind of high ammonia-nitrogen wastewater processing as claimed in claim 1 and ammonia recovery system, it is characterised in that on the thickener
Thin liquid outlet be connected with mother liquor tank.
7. a kind of high ammonia-nitrogen wastewater processing as claimed in claim 1 and ammonia recovery system, it is characterised in that the deamination film group
Filter membrane in part is polypropylene hollow fiber membrane；Described porosity is 60-80%, and pore size filter is 0.02-0.04 microns,
Wall thickness is 60-80 microns.
8. a kind of high ammonia-nitrogen wastewater processing and ammonia recovery method, it is characterised in that comprise the following steps：
（1）Spray is collected：Liquid ammonia pollution is collected extremely by turning into high ammonia-nitrogen wastewater after one-level Water spray tower and two grades of sour spray columns
High ammonia-nitrogen wastewater collecting pit；
（2）Plus alkali heating：Alkali lye is added into waste water, makes wastewater pH stable more than 10, to heating waste water after waste water filtering
Ammonium ion is set to become free gaseous state ammonia to 35-50 DEG C；
（3）Deamination：In the shell side that waste water is delivered to deamination membrane module, while the sulfuric acid in means for feeding acid is changed by graphite cake
In the tube side that deamination membrane module is delivered to after cooling；The filter membrane that ammonia in waste water is passed through in deamination membrane module enters from shell side
Tube side simultaneously mixes with sulfuric acid and becomes ammonium ion again；
（4）Arranged outside waste water：Waste water after deamination in deamination membrane module shell side is delivered to outer row pond；
（5）Acid cycle：Sulfuric acid in deamination membrane module tube side is delivered in means for feeding acid again and carries out reflux cycle；Simultaneously
By part of sulfuric acid in means for feeding acid after filtering, multi-effect evaporating device is delivered to；
（6）Multiple-effect evaporation：Sulfuric acid is first carried out to be preheated to 50-60 DEG C, 100-110 DEG C of evaporation is then further heated to, with
The concentration of ammonium salt increases in sulfuric acid, and ammonium salt is crystallized；
（7）Centrifuge：After the sulfuric acid proportion doped with ammonium salt crystallization reaches 0.95-1.05g/mL, it is delivered to successively
Thickener and centrifuge carry out ammonium salt crystallization separation, ammonium salt crystallization are collected, while sulfuric acid is continued on into mother liquor tank；
（8）Reflux cycle is evaporated：Sulfuric acid in mother liquor tank is transmitted back to after being mixed in multi-effect evaporating device with the sulfuric acid of rear feeding
It is evaporated again.
9. a kind of high ammonia-nitrogen wastewater processing as claimed in claim 8 and ammonia recovery method, it is characterised in that in deamination membrane module
H 2 so 4 concentration control 50%；The alkali lye is the sodium hydroxide solution that mass concentration is 30%.
10. a kind of high ammonia-nitrogen wastewater processing as claimed in claim 8 and ammonia recovery method, it is characterised in that when deamination film group
When filter membrane in part is blocked, Chemical cleaning is carried out to it by cleaning device.
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| CN107902793A (en) * | 2017-11-08 | 2018-04-13 | 绍兴齐英膜科技有限公司 | A kind of processing method of high ammonia-nitrogen wastewater |
| CN108275818A (en) * | 2018-01-25 | 2018-07-13 | 南昌大学 | The quick recovery system of ammonia nitrogen in a kind of high ammonia nitrogen waste water of livestock poultry |
| CN109956487A (en) * | 2017-12-23 | 2019-07-02 | 张旭 | Circulating ammonia coupling reaction is filtered, washed, drying system and method |
| CN110357303A (en) * | 2019-07-16 | 2019-10-22 | 广西博世科环保科技股份有限公司 | A kind of consumer waste infiltration liquid preprocess method and system based on deamination membrane module |
| CN111333245A (en) * | 2020-04-08 | 2020-06-26 | 华电水务工程有限公司 | Power plant's condensate water regeneration waste water embrane method deamination processing system |
| 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 |
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| CN113307412A (en) * | 2021-06-21 | 2021-08-27 | 天津绿诺环保科技有限公司 | Power plant desulfurization wastewater treatment device and treatment process and application thereof |
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| CN114134346A (en) * | 2021-11-30 | 2022-03-04 | 大连理工大学 | Continuous ionic membrane sodium removal-vanadium precipitation method |
| CN114134346B (en) * | 2021-11-30 | 2022-08-12 | 大连理工大学 | Continuous ionic membrane sodium removal-vanadium precipitation method |
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Address after: Room 1701, building 1, No.22, Xinbei Road, Oriental Century Center, Xiaoshan District, Hangzhou City, Zhejiang Province 311200 Patentee after: Kaiyuan Environmental Technology Group Co.,Ltd. Address before: Room 1701, building 1, No.22, Xinbei Road, Oriental Century Center, Xiaoshan District, Hangzhou City, Zhejiang Province 311200 Patentee before: HANGZHOU KAIYUAN ENVIRONMENTAL ENGINEERING CO.,LTD. |