CN104211244B - Renewable and the gaseous state embrane method process of by-product strong aqua of a kind of absorption agent is containing the method for ammonia feed liquid or waste water - Google Patents
Renewable and the gaseous state embrane method process of by-product strong aqua of a kind of absorption agent is containing the method for ammonia feed liquid or waste water Download PDFInfo
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Abstract
The present invention relates to a kind of renewable and method of the gaseous state embrane method Ammonia-Containing Wastewater Treatment of by-product strong aqua or feed liquid of absorption agent, comprise gaseous state embrane method deamination step, absorbed liquid rectifying regeneration step and regenerable absorbent liquid enrichment step.Ammonia nitrogen concentration in waste water is reduced to 50mg/L or 15mg/L even below 5mg/L by the present invention, the ammonia nitrogen reclaimed in waste water obtains high-purity strong aqua as byproduct simultaneously, absorption agent is renewable to be recycled, non-secondary pollution, energy consumption is low, current consumption is less than 1 KWh/ton of waste water, and steam consumption quantity is less than 0.04 ton of/ton of waste water and is even low to moderate 0.02 ton of steam/ton waste water.And as a comparison, be generally 0.12 ~ 0.18 ton of steam/ton waste water with the thermal energy consumption of the same waste water of rectifying process merely.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment, specifically, relate to a kind of absorption agent renewable and the gaseous state embrane method process ammonia nitrogen waste water of by-product strong aqua or feed liquid method.
Background technology
Many industries comprise petrochemical industry, fine chemistry industry, chemical fertilizer, Coal Chemical Industry, pharmacy, agricultural chemicals, coloured and rare metal are smelted, electronics and treatment of urban garbage etc. produce containing ammonia feed liquid or discharge ammonia-containing water, estimate that whole nation day quantity discharged is at millions of ton, its ammonia density is at tens to several ten thousand mg/litre (mg/L).Ammonia nitrogen in waste water is the important substance of body eutrophication and environmental pollution, easily causes Measures of Algae in Water Body and some microorganisms amount reproduction at short notice, consumes the dissolved oxygen in water simultaneously, has a strong impact on water quality, and cause the hydrobiont hypoxia deaths such as fish; Ammonia is oxidable under the effect of nitrobacteria is the virose nitrite of tool and nitrate, directly threatens the health of the mankind.Along with country is to the pay attention to day by day of environmental protection, the ammonia nitrogen removed in waste water is more and more indispensable.
At present, modal ammonia nitrogen removal technology has biological process, stripping and vaporizing extract process etc.Biochemical method effect stability, does not produce secondary pollution, and both economical, but has that floor space is large, low temperature aging rate is low, is subject to toxic substance impact and the shortcoming such as operational management is cumbersome.
In traditional ammonia nitrogen removal technology, the most applicablely ammonia nitrogen concentration in waste water is reduced by 90% by 1000 ~ 10000mg/L even more than 99% there is stripping (or being referred to as air lift or desorb) with qualified discharge or the technology of carrying out biochemical treatment further and distill (or being referred to as rectifying or stripping).These two processes first require the pH value of waste water from neutrality even acidity be increased to alkalescence (general requirement pH value is greater than 12), need to consume a certain amount of caustic soda or white lime.Stripping process generally needs directly to pass into the waste water in rectifying tower reactor steam to be heated to waste water water working pressure boiling point from room temperature, and waste water is concentrate tens times even ammoniacal liquor of hundreds of times through rectifying at the product that tower top obtains.But, even if having employed the conservation measuress such as heat exchanger network, generally still need consumption 0.12 ~ 0.18 ton of steam/ton waste water with vaporizing extract process process waste water.Air lift process need air and ammonia-containing water counter current contact, thus volatile ammonia is transferred to gas phase from aqueous phase reach waste water deaminizing object.In order to avoid the secondary pollution of air, the air being loaded with ammonia must by ammonia absorber, obtains ammonium salt as byproduct with acid solution absorbing ammonia.According to the difference that the temperature of waste water, ammonia content and ammonia removal rate require, air-extraction process one ton of ammonia-containing water needs 2000 ~ 6000m
3the inlet amount of air or internal circulating load, this generally needs consumption 20 ~ 40 degree of electricity/ton waste water.As can be seen here, remove/reclaim the ammonia nitrogen in waste water with stripping or air-extraction, only the expense of steam or electric consumption is just up to 15 ~ 40 yuan/ton of waste water.In addition, air lift or vaporizing extract process deamination process all need to run at a high ph, the traces of carbon dioxide of calcium ion in waste water in air lift process easily and in air reacts and produces precipitation of calcium carbonate, and in stripping process calcium hydroxide solubility with temperature rise and decline also cause produce calcium hydroxide precipitation, above two kinds of precipitations all make the easy fouling and clogging of equipment, need often to stop work, dismantle and clean.
Gaseous film (or be referred to as to support air film, liquid-liquid film absorbs) method removes ammonia nitrogen process in waste water and utilizes dewatering microporous film to separate water containing ammonia (feed liquid or waste water) and acid absorption liquid, volatile ammonia molecule in feed liquid or waste water diffuses to feed liquid-membrane interface from bulk water phase, gasification diffuses through micropore and enters absorption liquid to film-acid solution interface dissolving, and there is quick irreversible reaction with hydrogen ion, generate non-volatility ammonium radical ion and removed.This process operates at normal temperatures and pressures, without the need to heat rejection, without the need to driving the electric power of air, only needing consume low amounts of power to make feed liquid or waste water flow through membrane module, thus greatly reducing process operation expense.Because this gaseous film process directly does impellent with the chemical potential of spontaneous neutralization reaction, and due to the concentration of the free ammonia of absorption liquid side be zero, this provides maximum impetus for deamination process; This also makes this process more easily the ammonia nitrogen concentration in waste water can be down to national secondary discharge standard even below first discharge standard, can obtain certain density ammonium salt byproduct simultaneously.
At present, adopt gaseous state embrane method process ammonia nitrogen waste water, general employing sulphuric acid soln does absorption liquid, and in deamination process often association have the osmotic distillation of water, the lower ammoniumsulphate soln of concentration (ammonium sulfate concentrations is less than 20% usually) can only be obtained in deamination process, if expect high dense ammonium salt solution or solid ammonium salt, also need to carry out evaporation concentration even evaporative crystallization.And evaporative crystallization adopts Multi-effect Evaporation Processes usually, facility investment is high, and energy consumption is large.Because the market value of ammonium sulfate is not high, if enterprise can not fully recovering, the market of the ammonium sulfate obtained also is a very large problem.On the other hand, some enterprise self can complete-reclaiming from waste water with the ammonia nitrogen that strong aqua form reclaims, or enterprise can export trade strong aqua even liquefied ammonia nearby.Therefore, enterprise wishes that the byproduct after processing ammonia nitrogen waste water is the ammoniacal liquor of finite concentration and purity.
Therefore, how addressing these problems, is the key of gaseous state embrane method deamination industrializing implementation.Meanwhile, enterprise is in the urgent need to less investment, and energy-saving effect is obvious, the deamination technology of new generation that working cost is low.
Summary of the invention
In order to overcome the weak point of existing waste water deaminizing technology, the invention provides that a kind of absorption agent is renewable can be recycled, in waste water, ammonia nitrogen can reclaim and obtain the gaseous state embrane method Ammonia-Containing Wastewater Treatment of strong aqua or the method for feed liquid.
Researchist of the present invention starts with from the principle of research gaseous film process ammonia nitrogen waste water, a set ofly to fully utilize, the Ammonia-Containing Wastewater Treatment of non-secondary pollution or the method for feed liquid through to research and develop for many years.
Ultimate principle
Ammonia is a kind of exemplary volatile weak base, and when lower concentration, (<6wt%) its vapor liquid equilibrium meets Henry's law, and under room temperature, the relative volatility of ammonia/water is about 21; Ammonia dissociation constant pKa=9.25 at room temperature, its aqueous solution is in alkalescence, and the pH meter calculation value of such as, pure water solution containing 10,100,1000,10000mg/L ammonia is 9.97,10.50,11.01,11.51 respectively.
Phosphoric acid is strong acid in a kind of non-volatile ternary, and at room temperature the dissociation constant of phosphoric acid is pKa
1=2.16, pKa
2=7.21, pKa
3=12.32.So depend on the pH value of solution, phosphoric acid can form primary ammonium phosphate, Secondary ammonium phosphate and triammonium phosphate three kinds of salt with ammonia.Such as, if the pH value of the mixed aqueous solution of ammonia and phosphoric acid is 9.25, then the amino molecule of half exists with the form of ammonium radical ion, and the phosphoric acid molecules of more than 99% exists with the form of phosphoric acid hydrogen radical ion, and remaining phosphoric acid mainly exists with the form of dihydrogen phosphate ions.According to charge-neutrality principle, high dense phosphoric acid solution has the very strong ability of preserving ammonia with ammonium radical ion form near this pH value.But under the high temperature conditions, Secondary ammonium phosphate is decomposed into primary ammonium phosphate and amino molecule, and amino molecule is easy to vaporization and enters gas phase, this is that ammonium dihydrogen phosphate makes ammonia obtain the theoretical basis concentrated by rectifying for absorbing ammonia again.
Gaseous film is separated: gaseous film sepn process is the process that volatile constituent is transmitted between two liquid phases of its close contact through microporous hydrophobic membrane.Gaseous film isolation technique is also referred to as and supports air film isolation technique, permeable membrane desorb-absorption techniques, liquid liquid film absorption techniques in periodical or patent documentation, be sometimes also called air film for short is separated or is simply referred to as irrelevantly film absorption or membrane desorption.Absorb (namely from expecting gas through microporous hydrophobic membrane liquid-absorbent solubilized component) and proper membrane desorption (namely through microporous hydrophobic membrane gas purging or the mode that vacuumizes, volatile constituent being transferred in gas phase from feed liquid) to be different from proper film, the present invention is referred to as gaseous film sepn process the process unification that volatile constituent is transmitted between two liquid phases of its close contact through microporous hydrophobic membrane.Gaseous film sepn process uses the membrane module (being usually referred to as membrane contactor) of microporous hydrophobic film production, and water containing ammonia (feed liquid) is flow through in the side of film, and opposite side flows through acidic aqueous solution (absorption liquid).When the aqueous solution pH > 10 even >11 time, ammonia nitrogen is mainly with molecular form NH
3exist, volatile NH
3from containing ammoniacal liquor feed liquid main diffusion to feed liquid-microporous membrane interface, overflow from aqueous phase gasification and dissolve in absorption liquid by the micro channel membranous wall to microporous membrane-acid absorption liquid interface with diffusion mode, there is the ammonium radical ion that quick irreversible reaction generates non-volatility in the hydrogen ion then in free ammonia molecule and sour absorption liquid, thus reaches the object of removal of ammonia and nitrogen from feed liquid.
If the solute concentration in acid absorption liquid is very high and very low containing solute concentration in ammonia feed liquid, then there is " osmotic distillation " phenomenon that water molecules moves from feed liquid to absorption liquid, consequently absorption liquid or absorption complete liquid and are diluted.Rectification method can be removed portion of water and form strong aqua when absorption completes liquid and reclaims ammoniacal liquor, but the absorption liquid after rectifying regeneration still fails to reach starting point concentration, in order to complete recycling of absorption liquid, the regenerable absorbent liquid being still in diluted state must be concentrated to original concentration again.The high-efficiency and energy-saving type technology that can be used for absorption liquid is concentrated comprises multiple-effect evaporation and multiple-effect membrane distillation.
Multiple-effect membrane distillation: the principle of work that multiple-effect membrane distillation is described for the GAP TYPE tubular fibre membrane distillation assembly with inner sensible heat recovering function.Gap field orientation assembly arranged in parallelly to form by tubular fibre microporous hydrophobic membrane, hollow fiber conduit (real wall kapillary) are spaced in the cavity of putamina.Two strands of low temperature in high temperature in hollow-fibre membrane tube side, hollow fiber conduit tube side are formed and to the feed liquid of adverse current after external high temperature, low-temperature heat exchange, volatile component (mainly water) in feed liquid, be vaporized into water vapor in the high temperature side of film, be delivered to the opposite side of film by fenestra and be condensed into liquid and fresh water; Because hollow-fibre membrane is hydrophobic or super-hydrophobic, not easily soaked by pending feed liquid, other nonvolatile element in feed liquid is then stopped by hollow-fibre membrane, thus realizes the concentrated object of the degree of depth.
The process driving force that multiple-effect membrane distillation method degree of depth concentration has absorbed liquid or regenerable absorbent liquid is the steam pressure difference of microporous hydrophobic membrane both sides, consume low amounts of power is only needed to drive feed solution flow in its specific operation process, operating pressure is close to normal pressure, and current consumption is very little, and process cost is low.
The heat utilization efficiency of multiple-effect membrane distillation process characterizes with water generation ratio usually.The heat of condensation that water generation ratio is normally defined consumption one ton of steam can evaporate isolated tons fresh water.The characteristic parameter that water generation ratio depends on film usually such as porosity, membranous wall is thick, micro-pore diameter etc., depends on membrane module performance, also depends on the operation factors such as the temperature of feed concentration, thermal source.
Multiple-effect membrane distillation method degree of depth concentration regenerable absorbent liquid, low-temperature heat exchange can use normal temperature water coolant, but high temperature heat exchange thermal source atmospheric steam used or 60 ~ 150 DEG C of hot water or hot steam, or the low-grade heat source such as waste heat, used heat, or subsequent technique two imitates the secondary steam of evaporation; And the multiple-effect membrane component based on gap field orientation assembly has efficient inner from heat exchange function, and the water generation ratio of degree of depth concentration process can reach 6 ~ 20, and energy consumption is very low.
Multiple-effect membrane distillation process based on direct contact membrane distillation or vacuum membrane distillation operation reaches the object of recovery of latent heat usually by external heat-exchanging system, thus can provide the water generation ratio of 1 ~ 6.
Multiple-effect membrane distillation system can adopt modular combination mode, in parallel or several membrane component of connecting, and according to the size of the pending amount adjustment equipment scale of feed liquid, can thus be applicable to the feed liquid process of various scale.
To achieve these goals, the invention provides a kind of renewable and method of the gaseous state embrane method Ammonia-Containing Wastewater Treatment of by-product strong aqua or feed liquid of absorption agent, it adopts gaseous state embrane method deamination step, absorption liquid rectifying regeneration step and regenerable absorbent liquid enrichment step successively.
Wherein, described handled ammonia-containing water or feed liquid include but not limited to pharmaceutical factory's ammonia-containing water, percolate, chemical plant ammonia-containing water, nitrogen fertilizer plant's ammonia-containing water, metallurgy industry ammonia-containing water, coke-oven plant's high-concentration ammonia nitrogenous wastewater etc.In waste water, ammonia density is 100 ~ 20000mg/L.
Described gaseous state embrane method deamination step comprises the ammonia nitrogen that will remove through pretreated ammonia-containing water or feed liquid employing gaseous film assembly in waste water or feed liquid, absorption liquid to be pH value be 4.0 ~ 6.0 ammonium dihydrogen phosphate and Secondary ammonium phosphate mixing solutions (depend on pH value, more or less containing Secondary ammonium phosphate in solution), from waste water or feed liquid, absorb the absorption after ammonia nitrogen complete liquid to change pH value into be that namely the Secondary ammonium phosphate of 8.0 ~ 10.0 and the mixing solutions of primary ammonium phosphate have absorbed liquid
One or more modes of selectivity decalcification that what described pre-treatment can adopt those skilled in the art to commonly use comprise, oxidation, foam separation, macroporous resin adsorption, security personnel's filtration, micro-filtration, ultrafiltration combine.
The surface tension of described pretreated ammonia-containing water or feed liquid brings up to 40 ~ 72mN/m, and preferred surface tension force is increased to 65 ~ 72mN/m, and pH heightens 11 ~ 12.5.
The described hollow-fibre membrane used by gaseous film assembly or flat sheet membrane are microporous hydrophobic membrane or micropore super hydrophobic film, material is polymer non-polar material, macromolecular material can be PP(polypropylene), PE(polyethylene), PVDF(polyvinylidene difluoride (PVDF)) or PTFE(tetrafluoroethylene) in one or more mixture (this kind of film meaning for hydrophobic membrane), or other has the macromolecular compound of excellent hydrophobic performance or mixture (this kind of film meaning be super hydrophobic film) than poly tetrafluoroethylene.
Described gaseous film assembly comprises the obtained shell-and-tube membrane module of tubular fibre microporous hydrophobic or super hydrophobic film, the sheet frame shell side cross flow type membrane module that single cover tubular fibre microporous hydrophobic or super hydrophobic film obtain, shell-and-tube membrane module containing two cover tubular fibre microporous hydrophobic or super hydrophobic film, or flat plate microporous hydrophobic or rolling that super hydrophobic film is obtained or sheet frame type assembly.The contact angle that micropore super hydrophobic film refers to those and water is herein greater than the microporous membrane of poly tetrafluoroethylene and water contact angle.
Described shell-and-tube gaseous film assembly comprises two profiles formula, and a kind of is shell-and-tube membrane module with pipe core liquid distributor in assembly; Another kind is the coventional type shell-and-tube membrane module without pipe core liquid distributor in assembly.
Described shell-and-tube membrane module or sheet frame shell side cross flow type membrane module tubular fibre microporous hydrophobic used or super hydrophobic film type of feed comprise: the film silk of filling braiding in filling film silk in bulk or housing in housing.
The film internal diameter of described tubular fibre microporous hydrophobic or super hydrophobic film is 100 ~ 2000 μm, wall thickness is 30 ~ 600 μm, membranous wall micropore rate is 30 ~ 85%, aperture is 0.01 ~ 3.0 μm, useful length is 20 ~ 200cm, and the hollow-fibre membrane packing density in membrane module is 0.20 ~ 0.70.
Described absorption liquid rectifying regeneration step comprises: the absorption after pH value being raised completes liquid and adopts the method for rectifying to make absorption complete most Secondary ammonium phosphate in liquid and ammonium phosphate is decomposed into primary ammonium phosphate and free ammonia, at the bottom of rectifying tower, obtain the absorption liquid based on primary ammonium phosphate of the low ph value regenerated, tower top obtains the ammoniacal liquor that concentration is 5 ~ 15%.
Described regenerable absorbent liquid enrichment step adopts multiple-effect evaporation or multiple-effect membrane distillation to carry out concentration to regenerable absorbent liquid, due to the osmotic distillation phenomenon in gaseous film deamination process, the regenerable absorbent liquid concentration ratio initial absorption liquid concentration of the low ph value obtained at the bottom of tower is low, by multiple-effect evaporation or multiple-effect membrane distillation process, regenerable absorbent liquid is concentrated into starting point concentration Posterior circle and uses.
Specifically, in gaseous film-rectifying-multiple-effect membrane distillation (or multiple-effect evaporation) method deamination process, described absorption liquid is that the ammonium dihydrogen phosphate of pH=4.0 ~ 6.0 (also can contain a small amount of sequestrant, Scale inhibitors etc., this is composition well known to those skilled in the art), this step ammonia removal efficiency is high, do not have secondary pollution, byproduct is the concentration reclaimed from waste water is the ammoniacal liquor of 5 ~ 15%.
The present invention is for absorption liquid, and described absorption liquid is 4.0 ~ 6.0 in the initial pH value of gaseous film assembly ingress, is 8.0 ~ 10.0 in the pH value at gaseous film module outlet place, and the pH value of the absorption liquid after regeneration is 4.0 ~ 6.0, reaches the object recycled.
The absorption liquid rectifying regeneration step absorption liquid being 8.0 ~ 10.0 in gaseous film module outlet pH value of the present invention is regenerated by the mode of rectifying.Grade according to heat energy, the requirement to heat energy consumption and the ammonia concn requirement of reclaiming, rectifying tower can operate under normal pressure, decompression and pressurized conditions.It is 80 ~ 180 DEG C that column bottom temperature controls, and it is 0.05 ~ 1.0MPa that tower bottom pressure controls, and reflux ratio is 0.1 ~ 5.
The tower top of the described rectifying tower for regeneration of absorption solution can reclaim and obtain the ammoniacal liquor that concentration is 5 ~ 15%, and the ammonia soln obtained also can obtain high strong aqua, ammonia or liquefied ammonia product through further rectification process.
The type of heating of the described rectifying tower for regeneration of absorption solution can be the direct steam stripped mode of steam indirect heating or steam, or adopts the mode of thermal oil indirect heating.
The steam consumption quantity of the described rectifying tower for regeneration of absorption solution is that often process 1 ton of ammonia-containing water or feed liquid only need 0.02 ton of steam, is no more than at most 0.04 ton of steam.
The described concentration obtaining the absorption liquid regenerated through rectifying tower at the bottom of tower can control to its starting point concentration by controlling the concentration of tower top ammoniacal liquor, thus can without the concentrated and direct reuse of multiple-effect membrane distillation method.If the concentration of tower top ammoniacal liquor does not reach pre-provisioning request, another rectifying tower can be used to obtain strong aqua at tower top.
Of the present invention regenerated by rectifying after absorption liquid multiple-effect evaporation or multiple-effect membrane distillation process can be adopted to concentrate.
The water generation ratio of the described multiple-effect evaporation for regeneration of absorption solution or multiple-effect membrane distillation process is 3 ~ 20, is preferably 6 ~ 20.
The described hollow-fibre membrane used by multiple-effect membrane component or flat sheet membrane, microporous hydrophobic membrane or micropore super hydrophobic film, mould material is polymer non-polar material, macromolecular material can be PP(polypropylene), PE(polyethylene), PVDF(polyvinylidene difluoride (PVDF)) or PTFE(tetrafluoroethylene) in one or more mixture, or other has macromolecular compound or the mixture of excellent hydrophobic performance.
The film internal diameter of described microporous hydrophobic membrane is 100 ~ 2000 μm, wall thickness is 30 ~ 600 μm, and membranous wall micropore rate is 30 ~ 65%, and aperture is 0.01 ~ 0.3 μm, useful length is 20 ~ 200cm, and the hollow-fibre membrane packing density in membrane module is 0.20 ~ 0.70.
Described micropore super hydrophobic film film internal diameter be 100 ~ 2000 μm, wall thickness is 30 ~ 600 μm, and membranous wall micropore rate is 30 ~ 85%, and aperture is 0.01 ~ 3.0 μm, useful length is 20 ~ 200cm, and the hollow-fibre membrane packing density in membrane module is 0.20 ~ 0.70.
Multiple-effect distillation device of the present invention is primarily of membrane component and heat-exchange system composition.Multiple-effect distillation device has or outside heat inner in membrane component and reclaims function, thus provides very high heat utilization rate, total system water generation ratio between 3 ~ 20, preferably between 6 ~ 20.
And described multiple-effect membrane component can be the membrane component with direct contact membrane distillation and vacuum membrane distillation formal operations, also can be with the membrane component of gap field orientation formal operations.
The method of Ammonia-Containing Wastewater Treatment of the present invention or feed liquid, has the following advantages and positively effect:
1, absorption liquid of the present invention reproducible gaseous film deamination step, can remove energy-efficiently and reclaim the ammonia nitrogen in waste water, easily the ammonia nitrogen concentration in waste water can be down to national secondary discharge standard even below first discharge standard, and obtain the ammoniacal liquor that concentration is 5 ~ 15%, and absorption liquid is renewable recycles, do not have secondary pollution, running cost is low.
2, the multiple-effect membrane distillation step process cost for concentrating regenerative absorption liquid of the present invention is low, and energy-saving effect is remarkable, and water generation ratio can reach 6 ~ 20.
3, gaseous film-rectifying of the present invention-multiple-effect membrane distillation combination removes ammonia nitrogen method in waste water or feed liquid and compares with traditional stripping, stripping deamination process, and electric energy consumption and thermal energy consumption are extremely low.Specifically in table 1.
Table 1 absorption agent renewable and the gaseous film process of by-product strong aqua and conventional procedure energy consumption comparison
4, the accessible ammonia density containing ammonia feed liquid or waste water of the present invention can reach 100 ~ 20000mg/L, include but not limited to pharmaceutical factory's ammonia-containing water, percolate, metallurgical containing ammonia feed liquid or waste water, electron trade ammonia-containing water, catalyst manufacturer ammonia-containing water, insecticide factory's ammonia-containing water, Fine Chemical Works containing ammonia feed liquid or waste water, rubber ingredients factory ammonia-containing water etc.
Accompanying drawing explanation
Fig. 1 is absorption agent of the present invention reproducible gaseous state embrane method deamination schematic flow sheet.
Fig. 2 is regeneration of absorption solution system compression rectification of the present invention and multiple-effect membrane distillation concentration process schematic.
Embodiment
Below with reference to the accompanying drawings embodiments of the invention are described.The element described in an accompanying drawing of the present invention or a kind of embodiment and feature can combine with the element shown in one or more other accompanying drawings or embodiment and feature.It should be noted that for purposes of clarity, accompanying drawing and eliminate expression and the description of unrelated to the invention, parts known to persons of ordinary skill in the art or process in illustrating.
Below in conjunction with accompanying drawing, the present invention is described further.
As shown in Figure 1, 2, the renewable and method of the embrane method Ammonia-Containing Wastewater Treatment of by-product strong aqua or feed liquid of absorption agent of the present invention, detailed process is:
Through steps such as foam separation, oxidation, macroporous resin adsorption, micro-filtration, ultrafiltration, the surface tension of ammonia-containing water or feed liquid 1 is brought up to 40 ~ 72mN/m, and preferred surface tension force brings up to 65 ~ 72mN/m, regulates its pH value 11 ~ 12.Device involved in preprocessing process and step are well known to the skilled person.
First through the tube side of first step deamination membrane module a; Waste water after first step deamination membrane module or feed liquid are ammonia-containing water or feed liquid 2, and ammonia-containing water or feed liquid 2 are through the tube side of second stage deamination membrane module b; Waste water after the deamination membrane module b of the second stage or feed liquid are ammonia-containing water or feed liquid 3, and ammonia-containing water or feed liquid 3 are again through the tube side of third stage deamination membrane module c; Waste water after third stage deamination membrane module c or feed liquid are waste water or feed liquid 4, after three grades of deamination assemblies, ammonia nitrogen concentration in waste water or feed liquid 4 can reach preset value, ammonia nitrogen concentration < 100mg/L or < 15mg/L or < 5mg/L.
PH value be 4.0 ~ 6.0 absorption liquid 5 join sealing storage V1 in, absorption liquid in piece sealing reservoir V1 carries out alone cycle by pump B1 at the shell side of third stage deamination membrane module c, due to constantly adding of osmotic distillation phenomenon and absorption liquid 5, absorption liquid measure in piece sealing reservoir V1 can increase, owing to absorbing ammonia from waste water, the pH of absorption liquid also can raise, and the absorption liquid 6 being extruded out from piece sealing reservoir V1 can enter into piece sealing reservoir V2; Absorption liquid in piece sealing reservoir V2 carries out alone cycle by pump B2 at the shell side of second stage deamination membrane module b, owing to absorbing ammonia from waste water, the pH of the absorption liquid in piece sealing reservoir V2 also can raise, constantly entering equally due to osmotic distillation phenomenon and absorption liquid 6, the absorption liquid 7 being extruded out from piece sealing reservoir V2 can enter into piece sealing reservoir V3; Absorption liquid in piece sealing reservoir V3 carries out alone cycle by pump B3 at the shell side of first step deamination membrane module a, owing to absorbing ammonia from waste water, the pH of the absorption liquid in piece sealing reservoir V3 also can raise, constantly entering equally due to osmotic distillation phenomenon and absorption liquid 7, the pH value that the absorption being extruded out from piece sealing reservoir V3 completes liquid 8 reaches 8.0 ~ 10.0, needs to regenerate.
Absorption liquid 8 enters into rectifying tower d and regenerates after interchanger C1 preheating, temperature is that the steam of 100 ~ 200 DEG C or thermal oil 12 pass into tower reactor and heat, tower top can obtain the ammoniacal liquor 9 that concentration is 3 ~ 15%, can obtain the regenerable absorbent liquid 10 that pH is 4.0 ~ 6.0 at the bottom of tower.If the concentration of the absorption liquid 10 after regeneration is lower, after caning be passed through interchanger C2 preheating, concentrated by multiple-effect membrane component e after interchanger C3 heat exchange, absorption liquid 5 after concentrated joins in sealing storage tank V1 and recycles, and multiple-effect membrane component steams fresh water 13 and can be back to use in production.
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
Gaseous state embrane method deamination process: the polypropylene microporous hydrophobic Hollow Fiber Gas Membrane assembly process of employing is containing ammonia solution.Effective film area is 19m
2, the parameter of film silk is: external diameter 0.48mm, internal diameter 0.38mm, mean pore size 0.02 μm, porosity 40%.Three membrane module series connection use.
Feed liquid: certain pharmaceutical factory's ammonia nitrogen waste water, through foam separation, ultrafiltration, to add the pre-treatment rear surface tension force such as alkali be 68mN/m, pH=11.3, the ammonia nitrogen concentration C0=1918ppm of water inlet, flow Q=300L/h, temperature T=30 DEG C;
Ammonium dihydrogen phosphate absorption liquid: initial pH is 4.6, and initial density is 1.18kg/L, inlet flow rate 15L/h, temperature 30 DEG C.
Experimental result: the ammonia nitrogen concentration of water outlet is 45mg/L, ammonia-nitrogen removal rate 97.6%, absorption liquid outlet pH is 8.2, and flow is 21L/h.
Rectification method regeneration of absorption solution process: rectifying tower tower height is 5 meters, number of theoretical plate is 15, and adopt steam direct heating mode, vapor temperature is 130 DEG C, and reflux ratio is 0.5.
Absorption liquid feed rate is 21L/h, and pH value is 8.2;
Test-results: absorption liquid rate of discharge is 26L/h, pH is 6.0, and ammonia concn is 7%, and column bottom temperature is 130 DEG C, and tower bottom pressure is 0.35MPa, and tower top temperature is 65-99 DEG C.
Multiple-effect membrane distillation method concentration process:
Polypropylene multiple-effect membrane component is adopted to concentrate absorption liquid.The form of multiple-effect membrane component is see patent 201020638980.5, assembly is primarily of polypropylene microporous hydrophobic membrane and the real wall kapillary composition of polypropylene, and wherein the parameter of polypropylene microporous hydrophobic membrane is: internal diameter 0.33mm, external diameter 0.63mm, mean pore size 0.02 μm, porosity 60%; The parameter of the real wall kapillary of polypropylene is: internal diameter 0.4mm, external diameter 0.5mm; In assembly, the ratio of microporous polypropylene membrane and real wall kapillary is 1:1.5, and by microporous membrane film silk internal diameter, the effective film area of multiple-effect membrane component is 4.2m
2.
Multiple-effect membrane distillation process adopts hot feed mode, and low-temperature receiver adopts tap water at normal temperature.Cold-exchange is useful area 2m
2polypropylene capillary pipe cold-exchange.
Controlling absorption liquid inlet temperature is 110 DEG C, and feed rate is 26L/h, and pH value is 6.0, absorption liquid temperature out 85-93 DEG C, and cooling water inlet temperature is 15-25 DEG C.
Test-results: absorption liquid rate of discharge is 21L/h, pH value is 5.6, and room temperature lower density is 1.19kg/L, and water generation ratio is 12, and steaming light≤water yield is 5L/h.
Embodiment 2
Gaseous state embrane method deamination process: adopt the process of polypropylene gaseous film assembly containing ammonia solution.Effective film area is 19m
2, the parameter of film is: external diameter 0.48mm, internal diameter 0.38mm, mean pore size 0.02 μm, porosity 40%.Three membrane module series connection use.
Feed liquid: certain chemical plant ammonia nitrogen waste water, the ammonia nitrogen concentration C0=2480ppm of water inlet, flow Q=400L/h, pH=12.0, temperature T=30 DEG C;
Ammonium dihydrogen phosphate absorption liquid: initial pH is 5.8, and initial density is 1.18kg/L, flow 20L/h, temperature 30 DEG C.
Experimental result: the ammonia nitrogen concentration of water outlet is 86mg/L, ammonia-nitrogen removal rate 96.5%, absorption liquid outlet pH is 8.4, and flow is 24L/h.
Rectification method regeneration of absorption solution process: rectifying tower tower height is 5 meters, number of theoretical plate is 15, and adopt steam direct heating mode, vapor temperature is 130 DEG C, and reflux ratio is 0.5.
Absorption liquid feed rate is 24L/h, pH is 8.4;
Test-results: absorption liquid rate of discharge is 28L/h, pH is 5.6, and ammonia concn is 6%, and column bottom temperature is 140 DEG C, and tower bottom pressure is 0.54MPa, and tower top temperature is 65-99 DEG C.
Multiple-effect membrane distillation method concentration process:
Multiple-effect membrane component, film silk parameter and operational condition are with embodiment 1, but absorption liquid feed rate is 28L/h, and pH value is 5.6, and inlet temperature is 108 DEG C;
Test-results: absorption liquid rate of discharge is 20L/h, pH is 5.5, and room temperature lower density is 1.19kg/L, and water generation ratio is 14, steaming fresh water amount is 8L/h.
Embodiment 3
Gaseous state embrane method deamination process: adopt the process of tetrafluoroethylene gaseous film assembly containing ammonia solution.Effective film area is 10.5m
2, the parameter of film is: external diameter 1.2mm, internal diameter 0.60mm, mean pore size 0.10 μm, porosity 65%, and three membrane module series connection use.
Feed liquid: certain pharmaceutical factory's ammonia nitrogen waste water, the ammonia nitrogen concentration C0=1460ppm of water inlet, flow Q=300L/h, pH=12.5, temperature T=30 DEG C, initial surface tension is 35.0mN/m, and multistage foam separation and ultrafiltration pretreatment rear surface tension force are increased to 58mN/m;
Ammonium dihydrogen phosphate absorption liquid: initial pH is 5.6, and initial density is 1.18kg/L, flow 15L/h, temperature 30 DEG C.
Experimental result: the ammonia nitrogen concentration of water outlet is 12mg/L, ammonia-nitrogen removal rate 99.2%, and absorption liquid exit pH is 8.2, and flow is 21L/h.
Rectification method regeneration of absorption solution process: rectifying tower tower height is 5 meters, number of theoretical plate is 15, and adopt steam direct heating mode, vapor temperature is 130 DEG C.
Absorption liquid feed rate is 21L/h, and pH value is 8.0;
Test-results: absorption liquid rate of discharge is 25L/h, pH value is 5.8, and ammonia concn is 8%, and tower low temperature is 140 DEG C, and tower bottom pressure is 0.58MPa, and tower top temperature is 65-99 DEG C.
Multiple-effect membrane distillation method concentration process:
Tetrafluoroethylene multiple-effect membrane component is adopted to concentrate absorption liquid.The form of multiple-effect membrane component is see patent 201020638980.5, assembly is primarily of tetrafluoroethylene microporous hydrophobic membrane and the real wall kapillary composition of polypropylene, and wherein the parameter of tetrafluoroethylene microporous hydrophobic membrane is: internal diameter 0.6mm, external diameter 1.2mm, mean pore size 0.10 μm, porosity 65%; The parameter of the real wall kapillary of polypropylene is: internal diameter 0.4mm, external diameter 0.5mm; In assembly, the ratio of microporous polypropylene membrane and real wall kapillary is 1:2, and by microporous membrane film silk internal diameter, the effective film area of multiple-effect membrane component is 2.8m
2.
Absorption liquid feed rate is 25L/h, and pH value is 6.0, and inlet temperature is 106 DEG C;
Test-results: absorption liquid rate of discharge is 15L/h, pH value is 5.6, and room temperature lower density is 1.20kg/L, and water generation ratio is 15, and steaming fresh water amount is 10L/h.
Embodiment 4
Gaseous state embrane method deamination process: adopt polypropylene to support the process of gaseous film assembly containing ammonia solution.Effective film area is 19m
2, the parameter of film is: external diameter 0.48mm, internal diameter 0.38mm, mean pore size 0.02 μm, porosity 40%, and three membrane module series connection use.
Feed liquid: certain Fine Chemical Works ammonia nitrogen waste water, the ammonia nitrogen concentration C0=1700ppm of water inlet, wherein sodium chloride content is 190g/L, flow Q=300L/h, and pH value is adjusted to 12.5, temperature T=30 DEG C.Require that ammonia nitrogen takes off to below 5mg/L, remove the feed liquid after most ammonia nitrogen and be back to use doing of chlorine alkali workshop salt solution after hypochlorous acid oxidization is except ammonia.
Ammonium dihydrogen phosphate absorption liquid: initial pH value is 5.0, initial density is 1.18kg/L, flow 15L/h, temperature 30 DEG C.
Experimental result: the ammonia nitrogen concentration of water outlet is <4mg/L, ammonia-nitrogen removal rate 99.8%, and absorption liquid exit pH is 8.0, and flow is 17L/h.
Rectification method regeneration of absorption solution process: rectifying tower tower height is 5 meters, number of theoretical plate is 15, and adopt steam direct heating mode, vapor temperature is 140 DEG C, and reflux ratio is 0.8.
Absorption liquid feed rate is 17L/h, and pH value is 8.0;
Test-results: absorption liquid rate of discharge at the bottom of tower is 15L/h, pH value is 5.0, and room temperature lower density is 1.20kg/L; Tower top discharging ammonia concn is 12.5%, and flow is 2L/h; Column bottom temperature is 140 DEG C, and tower bottom pressure is 0.57Mpa, and tower top temperature is 65-99 DEG C.Because in former ammonia-containing water, sodium chloride concentration is very high, osmotic distillation phenomenon in gaseous state embrane method deamination process is very little, therefore acid absorption liquid is very low by dilute strength, the absorption after rectifying regeneration completes liquid also can direct reuse does absorption liquid in gaseous state embrane method deamination process without multiple-effect membrane distillation process is concentrated.
Although described the present invention and advantage thereof in detail, be to be understood that and can have carried out various change when not exceeding the spirit and scope of the present invention limited by appended claim, substituting and conversion.And the scope of the application is not limited only to the specific embodiment of process, equipment, means, method and step described by specification sheets.One of ordinary skilled in the art will readily appreciate that from disclosure of the present invention, can use perform the function substantially identical with corresponding embodiment described herein or obtain and its substantially identical result, existing and that will be developed in the future process, equipment, means, method or step according to the present invention.Therefore, appended claim is intended to comprise such process, equipment, means, method or step in their scope.
Claims (14)
1. the renewable and method for the gaseous state embrane method Ammonia-Containing Wastewater Treatment of by-product strong aqua or feed liquid of absorption agent, it is characterized in that, it adopts gaseous state embrane method deamination step, absorption liquid rectifying regeneration step and regenerable absorbent liquid enrichment step successively; Described gaseous state embrane method deamination step comprises and adopts gaseous film assembly remove and reclaim the ammonia nitrogen in waste water or feed liquid by through pretreated ammonia-containing water or feed liquid, absorption liquid to be pH value be 4.0 ~ 6.0 primary ammonium phosphate and Secondary ammonium phosphate mixing solutions, from waste water or feed liquid, absorbing the absorption liquid after ammonia nitrogen, to change pH value into be that namely the Secondary ammonium phosphate of 8.0 ~ 10.0 and the mixing solutions of primary ammonium phosphate have absorbed liquid;
Described absorption liquid rectifying regeneration step comprises: the absorption after pH value being raised completes liquid and adopts the method for rectifying to make absorption complete most Secondary ammonium phosphate in liquid and ammonium phosphate is decomposed into primary ammonium phosphate and free ammonia, at the bottom of rectifying tower, obtain the absorption liquid based on primary ammonium phosphate of the low ph value regenerated, tower top obtains the ammoniacal liquor that concentration is 5 ~ 15%;
Described regenerable absorbent liquid enrichment step adopts multiple-effect evaporation or multiple-effect membrane distillation process to carry out concentration to regenerable absorbent liquid, regenerable absorbent liquid is concentrated into starting point concentration Posterior circle and uses.
2. the method for Ammonia-Containing Wastewater Treatment according to claim 1 or feed liquid, is characterized in that, the surface tension of described pretreated ammonia-containing water or feed liquid is 40 ~ 72mN/m, and pH value is 11 ~ 12.5.
3. the method for Ammonia-Containing Wastewater Treatment according to claim 2 or feed liquid, is characterized in that, the surface tension of described pretreated ammonia-containing water or feed liquid is 65 ~ 72mN/m.
4. the Ammonia-Containing Wastewater Treatment according to claim 1-3 any one or the method for feed liquid, it is characterized in that, the hollow-fibre membrane that gaseous film assembly uses or flat sheet membrane are microporous hydrophobic membrane or micropore super hydrophobic film, its material is polymer non-polar material, macromolecular material is one or more the mixture in polypropylene, polyethylene, polyvinylidene difluoride (PVDF) or tetrafluoroethylene, or other has macromolecular compound or the mixture of excellent hydrophobic performance.
5. the method for Ammonia-Containing Wastewater Treatment according to claim 4 or feed liquid, it is characterized in that, described gaseous film assembly comprises the obtained shell-and-tube membrane module of tubular fibre microporous hydrophobic or super hydrophobic film, the sheet frame shell side cross flow type membrane module that single cover tubular fibre microporous hydrophobic or super hydrophobic film obtain, shell-and-tube membrane module containing two cover tubular fibre microporous hydrophobic or super hydrophobic film or flat plate microporous hydrophobic or rolling that super hydrophobic film is obtained or sheet frame type assembly.
6. the method for Ammonia-Containing Wastewater Treatment according to claim 5 or feed liquid, it is characterized in that, described shell-and-tube membrane module or sheet frame shell side cross flow type membrane module tubular fibre microporous hydrophobic membrane type of feed used comprise: the film silk of filling braiding in filling film silk in bulk or housing in housing.
7. the method for Ammonia-Containing Wastewater Treatment or feed liquid according to claim 1, is characterized in that, described absorption liquid rectifying regeneration step, and it is 80 ~ 180 that column bottom temperature controls, and it is 0.05 ~ 1.0MPa that DEG C tower bottom pressure controls, and reflux ratio is 0.1 ~ 5.
8. the method for gaseous state embrane method Ammonia-Containing Wastewater Treatment or feed liquid according to claim 1 or 7, it is characterized in that, described absorption liquid rectifying regeneration step, steam consumption quantity for the rectifying tower of regeneration of absorption solution needs 0.02 ton of steam for often processing 1 ton of strong ammonia wastewater, is no more than at most 0.04 ton of steam.
9. the method for Ammonia-Containing Wastewater Treatment or feed liquid according to claim 1, it is characterized in that, the water generation ratio of described multiple-effect evaporation or multiple-effect membrane distillation process is 3 ~ 20.
10. the method for Ammonia-Containing Wastewater Treatment or feed liquid according to claim 9, it is characterized in that, the water generation ratio of described multiple-effect evaporation or multiple-effect membrane distillation process is 6 ~ 20.
The method of 11. Ammonia-Containing Wastewater Treatment or feed liquids according to claim 1, it is characterized in that, the hollow-fibre membrane that described multiple-effect membrane distillation uses or flat sheet membrane are microporous hydrophobic membrane or micropore super hydrophobic film, its material is polymer non-polar material, macromolecular material is one or more the mixture in polypropylene, polyethylene, polyvinylidene difluoride (PVDF) or tetrafluoroethylene, or other has macromolecular compound or the mixture of hydrophobic performance more excellent in tetrafluoroethylene.
12. according to the method for Ammonia-Containing Wastewater Treatment described in claim 11 or feed liquid, and it is characterized in that, the multiple-effect distillation device that described multiple-effect membrane distillation method adopts is primarily of membrane component and heat-exchange system composition.
13. according to the method for Ammonia-Containing Wastewater Treatment described in claim 12 or feed liquid, it is characterized in that, described multiple-effect distillation device adopts the membrane component with direct contact membrane distillation and vacuum membrane distillation formal operations, or with the membrane component of gap field orientation formal operations.
The method of 14. Ammonia-Containing Wastewater Treatment or feed liquids according to claim 1, it is characterized in that, handled ammonia-containing water or feed liquid include but not limited to it is pharmaceutical factory's ammonia-containing water or feed liquid, percolate, chemical plant ammonia-containing water or feed liquid, nitrogen fertilizer plant's ammonia-containing water, metallurgy industry ammonia-containing water, coke-oven plant's high-concentration ammonia nitrogenous wastewater; In waste water or feed liquid, ammonia density is 100 ~ 20000mg/L.
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| CN105621536B (en) * | 2016-01-30 | 2018-10-23 | 秦皇岛同力达环保能源股份有限公司 | Landfill leachate ammonia nitrogen removal membrane module and landfill leachate ammonia nitrogen removal method |
| CN105776715A (en) * | 2016-05-13 | 2016-07-20 | 江苏理工学院 | Cyclic utilization method of sodium hydroxide and nitric acid in aluminum powder production |
| CN106115910A (en) * | 2016-07-28 | 2016-11-16 | 南通天蓝环保能源成套设备有限公司 | A kind of anaerobic digestion reaction vessel eliminating ammonia inhibition |
| CN106430783A (en) * | 2016-11-07 | 2017-02-22 | 昆山三环保科技有限公司 | Ternary precursor waste water treatment system and treating method thereof |
| CN109205941B (en) * | 2018-10-09 | 2021-11-02 | 浙江奇彩环境科技股份有限公司 | Resourceful treatment method for high-salt high-ammonia nitrogen wastewater |
| CN109467168A (en) * | 2018-12-29 | 2019-03-15 | 苏州艾吉克膜科技有限公司 | Ammonia-containing water handles and recycles the device and technique of ammonium hydroxide |
| CN111825189B (en) * | 2019-04-15 | 2022-09-16 | 洁海瑞泉膜技术（天津）有限公司 | Absorbent for treating ammonia-containing wastewater or feed liquid by gaseous membrane method |
| CN110204126A (en) * | 2019-06-17 | 2019-09-06 | 上海亚威环保科技有限公司 | The treating method and apparatus of lithium electricity industry ternary waste water |
| TWI748547B (en) * | 2020-07-06 | 2021-12-01 | 大陸商潔海瑞泉膜技術（天津）有限公司 | A kind of novel absorbent used for supported-gas-membrane separation process to treat ammonia-containing wastewater or feed solution |
| CN113880287A (en) * | 2021-11-19 | 2022-01-04 | 西安热工研究院有限公司 | Ammonia nitrogen recovery device and method for resin regeneration wastewater of power plant fine treatment system |
| CN115215490B (en) * | 2022-09-21 | 2023-02-07 | 河北旺效环保工程有限公司 | Pretreatment method of antibiotic production wastewater |
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