CN104609588A - Method used for processing high-salt high-ammonia-nitrogen waste water via membrane coupling - Google Patents
Method used for processing high-salt high-ammonia-nitrogen waste water via membrane coupling Download PDFInfo
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Abstract
The invention discloses a method used for processing high-salt high-ammonia-nitrogen waste water via membrane coupling. The method comprises steps of membrane absorption, reverse osmosis, and forward osmosis coupling. According to the method, an acid solution is taken as an absorption liquid, ammonia nitrogen in waste water is changed into ammonium salts via membrane absorption; obtained ammonium salt solution is concentrated further via reverse osmosis; the concentrated ammonium salt solution is taken as a driving liquid of forward osmosis, a high-salt waste water obtained after ammonia nitrogen removing via membrane absorption is taken as a feed liquid of forward osmosis, and forward osmosis concentration is carried out; the driving liquid ammonium salt solution is diluted, and a part of the ammonium salt solution is recycled to a reverse osmosis unit for recycling concentration. The method is capable of solving processing problems of high-salt high-ammonia-nitrogen waste water, water recovery yield is high, and quality of obtained water is excellent. The method is used for recycling concentration of high-salt high-ammonia-nitrogen waste water, concentrated water discharge amount is extremely low, and recovery of high-salt high-ammonia-nitrogen waste water is realized as far as possible.
Description
Technical field
The present invention relates to a kind of method utilizing membrane separation technique process height salt high ammonia-nitrogen wastewater, more particularly, relate to a kind of method adopting film absorption+reverse osmosis+just permeating coupling technique process height salt high ammonia-nitrogen wastewater, belong to field of industrial waste water treatment.
Background technology
In the catalyst production process of petrochemical industry, many places use ammonium salt and ammoniacal liquor, therefore, containing a large amount of ammonia nitrogen in the containing wastewater from catalyst of discharge, ammonia nitrogen in waste water mainly exists with ammonium ion (NH4+), be the important substance causing body eutrophication and environmental pollution, easily cause algae and other microorganism amount reproductions in water, oxygen in water time serious, can be made to decline, fish kill, even can cause the dry of lake; Ammonia nitrogen also can make to increase chlorine dosage in water disinfection and industrial circulating water sterilisation process; In addition, ammonia nitrogen has corrodibility to some metal (copper), and during reusing sewage, in reuse water, ammonia nitrogen can promote the breeding of microorganism in water pipe and watering equipment, forms biofouling, blocking pipe and watering equipment, and affects heat exchange efficiency.
The discharge beyond standards of ammonia nitrogen directly has influence on the overall up to standard of Catalyst Production enterprise wastewater and normal production, becomes the bottleneck of restriction Enterprise's Sustainable Development, the improvement of ammonia nitrogen waste water is become to the primary environmental issue of Catalyst Production enterprise.Therefore, researching and developing economic, practical, safe containing wastewater from catalyst NH_3-N treating technique becomes current study hotspot, significant to protecting the environment to benefit the people.
At present, mainly take to add the technology such as alkali stripping, electrolytic process, the MAP precipitator method, ion exchange method, break point chlorination to the improvement of high-concentration ammonia nitrogenous wastewater both at home and abroad; And the technology such as absorption method, chemical oxidization method, biochemical process are mainly contained to the improvement of Low Concentration Ammonia Containing Wastewater.
Add the primary treatment that alkali blow-off method is applicable to high-concentration ammonia nitrogenous wastewater, the method technology maturation, technique and operation are simple, but running cost is higher, and equipment corrosion is comparatively serious, and easily causes air secondary to pollute; Electrolytic process utilizes electrolysis to produce NaOH and Cl
2, then carry out stripping.Its running cost can be controlled in 3.0 yuan/m
3water, viable economically, the Cl that electrolysis produces
2can be used as product to sell or for water treatment, but Cl
2belong to hypertoxic gas, have certain danger, be unfavorable for safety and environment; The process such as the MAP precipitator method, ion exchange method, break point chlorination high-concentration ammonia nitrogenous wastewater, exists that technological operation is loaded down with trivial details, treatment cycle is short, processing cost is high, easily cause the shortcomings such as secondary pollution, is not suitable for heavy industrialization application.
Absorption method is the Na utilized in zeolite
+displacement NH
4 +be applicable to process Low Concentration Ammonia Containing Wastewater, use modified natural zeolite adsorption, there is adsorption efficiency higher, equipment volume is little, the feature that equipment one-time investment is little, and for high-concentration ammonia nitrogenous wastewater, frequent owing to regenerating, operational administrative is very complicated, current consumption is very large, and processing cost is high, uneconomical economically; Chemical oxidization method is in ammonia nitrogen waste water, add the oxygenant with Strong oxdiative character, as ozone, hydrogen peroxide/catalyzer, clorox etc., technical process is relative with equipment simple, and speed of response is very fast, but because oxygenant price is more expensive, make processing cost higher.In addition, these chemical strong oxidizers require acidic conditions usually, and general requirement pH is less than 2 ~ 4, therefore, need successively to regulate wastewater pH twice, add processing cost with chemical oxidization method; At present, the most frequently used method of industrial process Low Concentration Ammonia Containing Wastewater is biochemical process, it mainly adopts nitrated-denitrification principle, processing cost is lower, but influent ammonium concentration generally can not more than 500mg/L, otherwise normal operation will be affected, and ammonia nitrogen in high density itself there is restraining effect to the activity of microorganism and breeding.In addition, biochemical reaction speed is comparatively slow, and usually need longer hydraulic detention time, thus need larger structures, floor space is larger.
Waste water described in the application, except containing except the ammonia nitrogen of higher concentration, also has comparatively supersalinity, and COD
crrelatively low, be not suitable for adopting chemical oxidation and biochemical process process.At present, the domestic treatment for reuse process patent to this kind of characteristic waste water is less, and existing patent mostly concentrates on the process discharge aspect up to standard of ammonia nitrogen waste water.Chinese patent CN1123543C relates to a kind of catalyzer containing the process recovery method of ammonia/ammonium waste water, and key step is: 1) rarely concentrate through reverse osmosis membrane containing ammonia/ammonium waste water, and membrane permeation liquid is directly recycled or as the absorption liquid of steam stripped tower ammonia steam; 2) membrane concentration liquid mixes and add alkali with dense regulate pH containing ammonia/ammonium waste water; 3) ammonia-containing water after alkalization enters stripping tower, reclaims ammonia/ammonium wherein, and stripping is purified waste water qualified discharge.This method adopts the working cost of blow-off method, vaporizing extract process etc. slightly low than separately, but it still have employed vaporizing extract process, and the working cost enterprise of vaporizing extract process still cannot accept; In addition, stripping tower discharge water is still containing certain ammonia/ammonium, and can not reach emission request, and in waste water, salts contg is higher, can not carry out biochemical treatment, therefore this method is not applied; Chinese patent CN1872724A relates to the ammonia nitrogen in high density adopted in chemical reaction method removal waste water, reclaims ammonium salt, and water outlet is again by conventional sewage treatment process process qualified discharge; Chinese patent CN101337746A relates to a kind of method adopting high temperature deamination and stripping deamination process integration process high-concentration ammonia nitrogenous wastewater, is applicable to more than ammonia nitrogen 10000mg/L, COD
crthe trade effluent of about 20000 ~ 30000mg/L, ammonia nitrogen can be down to about 300mg/L after treatment, COD
crabout 8000 ~ 15000mg/L, processed waste water can qualified discharge through biochemical treatment; Chinese patent CN101293683A relates to a kind of method of the ammonia adopted in deamidization stripping high-concentration ammonia nitrogenous wastewater, because deamidization can make NH
3molecule breaks away from the effect of water molecules, exists with free ammonia form, and this makes the ammonia nitrogen in waste water can more effectively by stripping out; Chinese patent CN101264948A also relates to a kind of method adopting ammonia in stripping removal of ammonia and nitrogen waste water, compared with steam stripping deamination, the method steam consumption is lower, and waste water can meet national grade one discharge standard (<15mg/L) after treatment.In addition, Chinese patent CN1546393A relates to a kind of method adopting membrane absorption method process high-concentration ammonia nitrogenous wastewater, the method adopts hollow fiber membrane contactors, take sulphuric acid soln as the ammonia nitrogen waste water of absorption liquid process ammonia nitrogen concentration 1000 ~ 10000mg/L, waste water can meet national grade one discharge standard after treatment.Although the method has reclaimed the ammonia in waste water, the waste water after process only can qualified discharge, can not realize the reuse object of water resources.
It is a kind of novel absorbent process that film and regular absorbent are combined and occurred that film absorbs.This technology mainly adopts microporous hydrophobic membrane.In membrane absorption method, handled mixed gas does not directly contact with absorption liquid, the two flows in film both sides respectively, the microporous membrane adopted itself does not have selectivity, just play the effect of isolation mixed gas and absorption liquid, micropore on microporous membrane is enough large, the separated gas molecule in film side can be allowed in theory not need very high pressure just can pass microporous membrane to film opposite side, and this process mainly relies on the selective absorbing of film opposite side absorption liquid to reach the object of a certain component in separating mixed gas.Compared with other conventional suction processes, film absorption technique has following characteristics: the interface of (1) gas-liquid two-phase is fixing, is present in the both side surface place of fenestra respectively; (2) gas-liquid two-phase is not scattered in another phase mutually; (3) flowing of gas-liquid two-phase does not interfere with each other, and flow characteristics can adjust separately; (4) use hollow-fibre membrane to have very large specific surface area, effectively improve gas liquid interfacial area.The advantage that membrane absorption method has in mass-transfer performance, operation, energy consumption etc. due to it, makes this technology have good application prospect.
Just permeating (FO) is a kind of membrane separating process relying on osmotic pressure to drive, and namely water is spontaneously diffused into the process of lower water chemistry gesture region (high osmotic pressure side) from higher water chemistry gesture region (Hyposmolality side) by selectivity semi-permeable membranes.The motivating force of positive process of osmosis is the permeable pressure head driving liquid and stock liquid, does not need impressed pressure as motivating force.Compare with reverse osmosis process, just permeating tool and having the following advantages: fouling membrane is comparatively light, and without the need to impressed pressure, energy consumption is low, and the rate of recovery is high, concentrated water drainage is high-volume few, pollutes little, environmental friendliness.
The key that positive process of osmosis realizes is the driving liquid needing a kind of high-throughput can be recycled, and in the present invention, the absorption liquid after film absorption process is salts solution, after being concentrated further by salts solution, can meet the needs of positive process of osmosis completely.Therefore, if film is absorbed and is just permeating and combine process high salt, high ammonia-nitrogen wastewater, second stage employ is carried out to it, the driving liquid of concentrated high-concentration absorbent liquid as positive process of osmosis is passed through again using after film absorption process, not only solve the required problem driving liquid of positive process of osmosis, also solve regeneration, the process problem of film absorption liquid simultaneously, and processed the high-salt wastewater after film absorbs by positive process of osmosis simultaneously, the coupling of two kinds of technology reduces the quantity discharged of waste water to greatest extent, has important Significance for Environment.
Summary of the invention
For the deficiencies in the prior art, the invention discloses a kind of method of film coupling processing height salt high ammonia-nitrogen wastewater, aim to provide a kind of mainly for high salt high ammonia-nitrogen wastewater, after process, concentrated water drainage is high-volume few, the farthest novel method of recycle-water resource.The method adopts the technical process of film absorption+reverse osmosis+just permeating first.First, take acid solution as absorption liquid, adopting film to absorb mineralized nitrogen in waste water is ammonium salt; Secondly, reverse osmosis is adopted to be concentrated further by ammonium salt solution; Afterwards using the ammonium salt solution after concentrated as the driving liquid just permeated, film absorbs the high-salt wastewater after removing ammonia nitrogen as the feeding liquid just permeated, and carries out positive osmosis concentration process.Like this, the water just penetrated in the high-salt wastewater of feed liquid side is constantly entered into by forward osmosis membrane and drives liquid side, as driving the ammonium salt solution of liquid constantly to be diluted, when being diluted to finite concentration, returns to reverse osmosis units circulation concentration.
The technical solution used in the present invention is:
A method for film coupling processing height salt high ammonia-nitrogen wastewater, the key step of the method is:
(1) film absorbs: the feeding liquid side high salt high ammonia-nitrogen wastewater being pumped into film absorptive unit, in the absorption liquid side of film absorptive unit, pumps into acid solution as absorption liquid, and both sides solution circulated flows.
In film absorption process, the ammonia nitrogen in high salt high ammonia-nitrogen wastewater constantly enters into absorption liquid side by microporous hydrophobic membrane, enters into the ammonia nitrogen of absorption liquid side and the acid-respons of absorption liquid, generates ammonium salt;
(2) reverse osmosis: in film absorption process, the ammonium salt solution of absorption liquid side pumps into reverse osmosis units and carries out concentration.
By reverse osmosis process, the water in ammonium salt solution forms reverse osmosis produced water through reverse osmosis membrane, and reverse osmosis units trapped fluid side is concentrated ammonium salt solution;
(3) just permeate: using the ammonium salt solution of reverse osmosis units trapped fluid side as positive osmotic drive liquid, remove the high-salt wastewater after ammonia nitrogen for just to penetrate into feed liquid to absorb laggard feed liquid side through film, enter positive permeation unit and carry out positive osmosis concentration process; Under osmotic pressure effect, water after film absorbs trapped fluid side removal ammonia nitrogen in high-salt wastewater constantly enters into the ammonium salt solution of positive osmotic drive liquid side by forward osmosis membrane, ammonium salt solution is constantly diluted, and is turned back to reverse osmosis units re-start concentration by the ammonium salt solution part after diluting.
Above-mentioned steps constantly circulates, and the reverse osmosis produced water finally obtained can be back to production technique.Just penetrating into the high-salt wastewater of feed liquid side by constantly circulation is concentrated, the minute quantity of final discharge is just being permeated dense water and is being centrally disposed.
The water quality characteristic of the high salt high ammonia-nitrogen wastewater described in the present invention is: wastewater pH 8.5 ~ 10, conductance 5 ~ 50mS/cm, COD
cr0 ~ 80mg/L, SS0 ~ 200mg/L, Na
+1000 ~ 10000mg/L, NO
3 -2000 ~ 20000mg/L, Cl
-50 ~ 500mg/L, Ca
2+0 ~ 30mg/L, NH
4-N500 ~ 10000mg/L.
In the specific implementation, the absorption liquid described in step (1) is sulfuric acid, hydrochloric acid or salpeter solution;
In the specific implementation, the concentration massfraction as the acid of absorption liquid is 5% ~ 10%;
In the specific implementation, when the ammonium salt solution pH described in step (1) reaches 3 ~ 5, enter step (2) concentration;
In the specific implementation, enter reverse osmosis units after mixing by 1:5 ~ 1:10 with the ammonium salt solution in the reverse osmosis raw water box that will enter reverse osmosis units as the ammonium salt solution of positive osmotic drive liquid described in step (3) to concentrate;
In the specific implementation, the dense water of the positive permeation unit described in step (3) discharges in the ratio of just permeating 1:50 ~ 1:100 of intaking;
In the specific implementation, the operational condition of described film absorptive unit is: feeding liquid side, wastewater pH 8.5 ~ 10, wastewater temperature 15 ~ 45 DEG C, both sides crossflow velocity 0.1 ~ 1.0m/s;
In the specific implementation, the operational condition of described reverse osmosis units is: feeding liquid side, wastewater pH 3 ~ 5, wastewater temperature 15 ~ 45 DEG C, working pressure 0.6 ~ 0.9MPa, feeding liquid side crossflow velocity 0.1 ~ 1.0m/s;
In the specific implementation, the operational condition of described positive permeation unit is: feeding liquid side, wastewater pH 7.5 ~ 8, wastewater temperature 15 ~ 45 DEG C, both sides crossflow velocity 0.1 ~ 1.0m/s;
In the specific implementation, the mould material of the forward osmosis membrane assembly of described positive permeation unit comprises cellulose acetate, polymeric amide or polyacrylonitrile;
In the specific implementation, the forward osmosis membrane kit form of described positive permeation unit comprises board-like, rolling, hollow fiber form or tubular type;
In the specific implementation, the mould material of the membrane module of described film absorptive unit comprises polyvinylidene difluoride (PVDF), tetrafluoroethylene or polypropylene, preferably polytetrafluoroethylene, and membrane pore size is 0.2 μm;
In the specific implementation, the membrane module form of described film absorptive unit is hollow fiber film assembly;
In the specific implementation, the mould material of the reverse osmosis membrane assembly of described reverse osmosis units is polymeric amide, and membrane pore size is less than 1nm;
In the specific implementation, the reverse osmosis membrane assembly form of described reverse osmosis units is rolling;
In the specific implementation, the membrane module of the described membrane module of positive permeation unit, the membrane module of reverse osmosis units and film absorptive unit is one or more groups serial or parallel connection;
Described high salt high ammonia-nitrogen wastewater by above-mentioned steps process, Water Sproading rate >=98%.
Different with above-mentioned patent, the present invention is mainly for the process problem of high salt high ammonia-nitrogen wastewater, employing film absorption+reverse osmosis first+just permeating coupling technique process height salt high ammonia-nitrogen wastewater, first adopting film to absorb mineralized nitrogen in waste water is ammonium salt, secondly reverse osmosis is adopted to be concentrated further by ammonium salt solution, afterwards using the ammonium salt solution after concentrated as the driving liquid just permeated, film absorbs the high-salt wastewater after removing ammonia nitrogen as the feeding liquid just permeated, carry out positive osmosis concentration process, like this, the water just penetrated in the high-salt wastewater of feed liquid side is constantly entered into by forward osmosis membrane and drives liquid side, constantly diluted as driving the ammonium salt solution of liquid, turned back to reverse osmosis units by the ammonium salt solution part after diluting again to circulate concentration.
The essential distinction of the present invention and prior art is, the present invention relates to a kind for the treatment of process of high salt high ammonia-nitrogen wastewater, for process and the handling problems of the high salt high ammonia-nitrogen wastewater existed in prior art, the present invention mainly adopts film absorption+reverse osmosis+just permeate coupling process, and the high salt high ammonia-nitrogen wastewater for petroleum chemical enterprise processes.Adopt method of the present invention to efficiently solve the process problem of high salt high ammonia-nitrogen wastewater, Water Sproading rate is high, and product water water quality is good.Adopt method of the present invention to carry out circulation concentration to high salt high ammonia-nitrogen wastewater, concentrated water drainage is high-volume few, has farthest reclaimed the water resources in high salt high ammonia-nitrogen wastewater.
The invention has the beneficial effects as follows:
1, the present invention is by adopting film absorption+reverse osmosis+just permeate coupling process, high salt high ammonia-nitrogen wastewater for petroleum chemical enterprise has carried out advanced treatment and reclamation, concentrated water drainage is high-volume few, Water Sproading rate is high, produce water water quality good, reclaim water resources to greatest extent, improve the rate of recovery of high salt high ammonia-nitrogen wastewater to greatest extent;
2, the film absorption process in the present invention and positive process of osmosis do not need impressed pressure or outer pressure pressure very little, method is simple, easily operates;
3, the fouling membrane in the film absorption process in the present invention, reverse osmosis process and positive process of osmosis is all comparatively light, extends the continuous and steady operation time of coupling process;
4, adopt method process height salt high ammonia-nitrogen wastewater of the present invention, ammonia-nitrogen removal rate is high, and Water Sproading rate is high, and product water water quality is good, and energy consumption is low, and processing costs is low;
5, The inventive method achieves the efficient coupling of membrane separation technique for petrochemical wastewater process.Adopt method of the present invention, whole coupling process not only can obtain lot of pure water, and what also solve high salt high ammonia-nitrogen wastewater is difficult to process problem simultaneously, improves waste water reclamation rate to greatest extent, whole coupling process concentrated water drainage is high-volume few, has important environmental benefit.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of method in the present invention
In figure: 1: high salt high ammonia-nitrogen wastewater; 2: film absorbs raw water box; 3: film absorptive unit; 4: absorption liquid; 5: absorption liquid water tank; 6: reverse osmosis raw water box; 7: reverse osmosis units; 8: reverse osmosis produced water; 9: ammonium salt solution; 10: drive liquid water tank; 11: just permeate raw water box; 12: positive permeation unit; 13: the dense water of just infiltration of discharge.
Embodiment
Below, by reference to the accompanying drawings and specific embodiment, invention is further described.
See Fig. 1, concrete technology step of the present invention is:
(1) film absorbs.High salt high ammonia-nitrogen wastewater 1 enters film and absorbs raw water box 2, and the feeding liquid side that the film high salt high ammonia-nitrogen wastewater absorbed in raw water box 2 pumps into film absorptive unit 3 circulates; Secondly, absorption liquid 4 enters absorption liquid water tank 5, the absorption liquid in absorption liquid water tank 5, and the absorption liquid side pumping into film absorptive unit circulates.Under film sorption, the ammonia nitrogen in high salt high ammonia-nitrogen wastewater constantly enters into absorption liquid side by microporous hydrophobic membrane, and the sour absorption liquid reaction of absorption liquid side generates ammonium salt;
(2) reverse osmosis.In film absorption process, the ammonium salt solution of absorption liquid side pumps into reverse osmosis units 7 and carries out concentration.By reverse osmosis isolation, the water in ammonium salt solution forms reverse osmosis produced water 8 through reverse osmosis membrane, and to be concentrated ammonium salt solution 9 enter in reverse osmosis units trapped fluid side drives liquid water tank 10;
(3) just permeate.Enter through the film high-salt wastewater absorbed after laggard feed liquid side removal ammonia nitrogen and just permeate raw water box 11, just to permeate high-salt wastewater in raw water box 11 for just to penetrate into feed liquid, be positive osmotic drive liquid to drive the ammonium salt solution in liquid water tank 10, enter positive permeation unit 12 both sides respectively to circulate, carry out positive osmosis concentration process.Under osmotic pressure effect, water in high-salt wastewater after film absorbs feeding liquid side removal ammonia nitrogen constantly enters into the ammonium salt solution of positive osmotic drive liquid side by forward osmosis membrane, ammonium salt solution is constantly diluted, and is turned back to reverse osmosis units re-start concentration by the ammonium salt solution part after diluting.
Embodiment 1
Process flow diagram is shown in Fig. 1.In figure, the water quality characteristic of high salt high ammonia-nitrogen wastewater 1 is: wastewater pH 8.5, conductance 5mS/cm, COD
cr80mg/L, SS100mg/L, Na
+1000mg/L, NO
3 -2000mg/L, Cl
-50mg/L, Ca
2+0mg/L, NH
4-N500mg/L.
Film absorbent assembly used is polytetrafluoroethylene (PTFE) tubular fibre microporous hydrophobic membrane module, and membrane pore size is 0.2 μm; Reverse osmosis membrane assembly used is polymeric amide rolled membrane module, and membrane pore size is less than 1nm; Forward osmosis membrane assembly used is cellulose acetate plate and frame module;
Step is as follows: (1) film absorbs, and high salt high ammonia-nitrogen wastewater 1 enters film and absorbs raw water box 2, and the feeding liquid side that the film high salt high ammonia-nitrogen wastewater absorbed in raw water box 2 pumps into film absorptive unit 3 circulates; Concentration massfraction as absorption liquid be 5% sulphuric acid soln 4 enter absorption liquid water tank 5, the absorption liquid side that the sulphuric acid soln in absorption liquid water tank 5 pumps into film absorptive unit circulates.Under film sorption, the ammonia nitrogen in high salt high ammonia-nitrogen wastewater constantly enters into absorption liquid side by microporous hydrophobic membrane, and the absorption liquid sulfuric acid reaction of absorption liquid side generates ammonium sulfate.When ammoniumsulphate soln pH reaches 3, enter step (2) concentration; (2) reverse osmosis, in film absorption process, the ammoniumsulphate soln of absorption liquid side pumps into reverse osmosis units 7 and carries out concentration.By reverse osmosis isolation, the water in ammoniumsulphate soln forms reverse osmosis produced water 8 through reverse osmosis membrane, and to be concentrated ammoniumsulphate soln 9 enter in reverse osmosis trapped fluid side drives liquid water tank 10; (3) just permeate, enter through the film high-salt wastewater absorbed after laggard feed liquid side removal ammonia nitrogen and just permeate raw water box 11, just to permeate high-salt wastewater in raw water box 11 for just to penetrate into feed liquid, be positive osmotic drive liquid to drive the ammoniumsulphate soln in liquid water tank 10, enter positive permeation unit 12 both sides respectively to circulate, carry out positive osmosis concentration process.Under osmotic pressure effect, the water in the high-salt wastewater after film absorbs feeding liquid side removal ammonia nitrogen constantly enters into the ammoniumsulphate soln of positive osmotic drive liquid side by forward osmosis membrane, ammoniumsulphate soln is constantly diluted.Wherein, enter reverse osmosis units after mixing by 1:10 with the ammoniumsulphate soln in the reverse osmosis raw water box that will enter reverse osmosis units as the ammoniumsulphate soln of positive osmotic drive liquid in step (3) to concentrate; The dense water of the positive permeation unit in step (3) discharges in 1:100 ratio with water inlet;
In operational process, the operational condition of film absorptive unit is: feeding liquid side, wastewater pH 8.5, wastewater temperature 15 DEG C, both sides crossflow velocity 0.1m/s; The operational condition of reverse osmosis units is: feeding liquid side, wastewater pH 3, wastewater temperature 15 DEG C, working pressure 0.6MPa, feeding liquid side crossflow velocity 0.1m/s; The operational condition of positive permeation unit is: feeding liquid side, wastewater pH 7.5, wastewater temperature 15 DEG C, both sides crossflow velocity 0.1m/s;
Under the operational condition of above-mentioned film absorptive unit, film absorbing film flux remains on 4 ~ 7L/m
2h, the dense water NH after film absorbs
4-N content 5mg/L; Under the operational condition of above-mentioned reverse osmosis units, reverse osmosis membrane flux remains on 12 ~ 16L/m
2h, reverse osmosis produced water conductivity is less than 100 μ s/cm, produces water water quality and is better than tap water, can be back to production technique; Under the operational condition of above-mentioned positive permeation unit, forward osmosis membrane flux remains on 3 ~ 6L/m
2h.
High salt high ammonia-nitrogen wastewater by above-mentioned steps process, Water Sproading rate 99%.
Embodiment 2
Process flow diagram is shown in Fig. 1.In figure, the water quality characteristic of high salt high ammonia-nitrogen wastewater 1 is: wastewater pH 9.3, conductance 25mS/cm, COD
cr80mg/L, SS100mg/L, Na
+5000mg/L, NO
3 -10000mg/L, Cl
-270mg/L, Ca
2+20mg/L, NH
4-N6000mg/L.
Film absorbent assembly used is polytetrafluoroethylene (PTFE) tubular fibre microporous hydrophobic membrane module, and membrane pore size is 0.2 μm; Reverse osmosis membrane assembly used is polymeric amide rolled membrane module, and membrane pore size is less than 1nm; Forward osmosis membrane assembly used is cellulose acetate plate and frame module;
Be different from embodiment 1 in operation steps: absorption liquid used in step (1) to be concentration massfraction be 7% salpeter solution; When the ammonium nitrate solution pH in step (1) reaches 4, enter step (2) concentration; After mixing by 1:7 with the ammonium nitrate solution in the reverse osmosis raw water box that will enter reverse osmosis units as the ammonium nitrate solution of positive osmotic drive liquid in step (3), enter reverse osmosis units concentrate; The dense water of the positive permeation unit in step (3) discharges in 1:70 ratio with water inlet;
In operational process, the operational condition of film absorptive unit is: feeding liquid side, wastewater pH 9.3, wastewater temperature 35 DEG C, both sides crossflow velocity 0.5m/s; The operational condition of reverse osmosis units is: feeding liquid side, wastewater pH 4, wastewater temperature 35 DEG C, working pressure 0.7MPa, feeding liquid side crossflow velocity 0.5m/s; The operational condition of positive permeation unit is: feeding liquid side, wastewater pH 8, wastewater temperature 35 DEG C, both sides crossflow velocity 0.5m/s;
Under the operational condition of above-mentioned film absorptive unit, film absorbing film flux remains on 5 ~ 9L/m
2h, the dense water NH after film absorbs
4-N content about 10mg/L; Under the operational condition of above-mentioned reverse osmosis units, reverse osmosis membrane flux remains on 14 ~ 17L/m
2h, reverse osmosis produced water conductivity is less than 100 μ s/cm, produces water water quality and is better than tap water, can be back to production technique; Under the operational condition of above-mentioned positive permeation unit, forward osmosis membrane flux remains on 5 ~ 7L/m
2h.
High salt high ammonia-nitrogen wastewater is by above-mentioned steps process, and Water Sproading rate is higher than 98.57%.
Embodiment 3
Process flow diagram is shown in Fig. 1.In figure, the water quality characteristic of high salt high ammonia-nitrogen wastewater 1 is: wastewater pH 10, conductance 50mS/cm, COD
cr80mg/L, SS200mg/L, Na
+10000mg/L, NO
3 -20000mg/L, Cl
-500mg/L, Ca
2+30mg/L, NH
4-N10000mg/L.
Film absorbent assembly used is polytetrafluoroethylene (PTFE) tubular fibre microporous hydrophobic membrane module, and membrane pore size is 0.2 μm; Reverse osmosis membrane assembly used is polymeric amide rolled membrane module, and membrane pore size is less than 1nm; Forward osmosis membrane assembly used is cellulose acetate plate and frame module;
Embodiment 1 is different from: to be concentration massfraction be absorption liquid used in step (1) in operation steps
10the hydrochloric acid soln of %; When the ammonium chloride solution pH in step (1) reaches 5, enter step (2) concentration; After mixing by 1:5 with the ammonium chloride solution in the reverse osmosis raw water box that will enter reverse osmosis units as the ammonium chloride solution of positive osmotic drive liquid in step (3), enter reverse osmosis units concentrate; The dense water of the positive permeation unit in step (3) discharges in 1:50 ratio with water inlet;
In operational process, the operational condition of film absorptive unit is: feeding liquid side, wastewater pH 10, wastewater temperature 45 DEG C, both sides crossflow velocity 1.0m/s; The operational condition of reverse osmosis units is: feeding liquid side, wastewater pH 5, wastewater temperature 45 DEG C, working pressure 0.9MPa, feeding liquid side crossflow velocity 1.0m/s; The operational condition of positive permeation unit is: feeding liquid side, wastewater pH 8, wastewater temperature 45 DEG C, both sides crossflow velocity 1.0m/s;
Under the operational condition of above-mentioned film absorptive unit, film absorbing film flux remains on 6 ~ 10L/m
2h, the dense water NH after film absorbs
4-N content about 15mg/L; Under the operational condition of above-mentioned reverse osmosis units, reverse osmosis membrane flux remains on 18 ~ 22L/m
2h, reverse osmosis produced water conductivity is less than 100 μ s/cm, produces water water quality and is better than tap water, can be back to production technique; Under the operational condition of above-mentioned positive permeation unit, forward osmosis membrane flux remains on 6 ~ 9L/m
2h.
High salt high ammonia-nitrogen wastewater by above-mentioned steps process, Water Sproading rate 98%.
Embodiment 4
Process flow diagram is shown in Fig. 1.In figure, the water quality characteristic of high salt high ammonia-nitrogen wastewater 1 is: wastewater pH 9.3, conductance 25mS/cm, COD
cr0mg/L, SS0mg/L, Na
+5000mg/L, NO
3 -10000mg/L, Cl-270mg/L, Ca
2+30mg/L, NH
4-N6000mg/L.
Film absorbent assembly used is polytetrafluoroethylene (PTFE) tubular fibre microporous hydrophobic membrane module, and membrane pore size is 0.2 μm; Reverse osmosis membrane assembly used is polymeric amide rolled membrane module, and membrane pore size is less than 1nm; Forward osmosis membrane assembly used is cellulose acetate plate and frame module;
Embodiment 1 is different from: to be concentration massfraction be absorption liquid used in step (1) in operation steps
10the salpeter solution of %; When the ammonium nitrate solution pH in step (1) reaches 4, enter step (2) concentration; After mixing by 1:8 with the ammonium nitrate solution in the reverse osmosis raw water box that will enter reverse osmosis units as the ammonium nitrate solution of positive osmotic drive liquid in step (3), enter reverse osmosis units concentrate; The dense water of the positive permeation unit in step (3) discharges in 1:80 ratio with water inlet;
In operational process, the operational condition of film absorptive unit is: feeding liquid side, wastewater pH 9.3, wastewater temperature 45 DEG C, both sides crossflow velocity 0.7m/s; The operational condition of reverse osmosis units is: feeding liquid side, wastewater pH 4, wastewater temperature 45 DEG C, working pressure 0.7MPa, feeding side crossflow velocity 0.7m/s; The operational condition of positive permeation unit is: feeding liquid side, wastewater pH 8, wastewater temperature 45 DEG C, both sides crossflow velocity 0.7m/s;
Under the operational condition of above-mentioned film absorptive unit, film absorbing film flux remains on 6 ~ 9L/m
2h, the dense water NH after film absorbs
4-N content about 10mg/L; Under the operational condition of above-mentioned reverse osmosis units, reverse osmosis membrane flux remains on 16 ~ 20L/m
2h, reverse osmosis produced water conductivity is less than 100 μ s/cm, produces water water quality and is better than tap water, can be back to production technique; Under the operational condition of above-mentioned positive permeation unit, forward osmosis membrane flux remains on 5 ~ 7L/m
2h.
High salt high ammonia-nitrogen wastewater by above-mentioned steps process, Water Sproading rate 98.75%.
The foregoing is only better possible embodiments of the present invention, not thereby limit to the scope of the claims of the present invention, therefore the equivalence change that every utilization specification sheets of the present invention and accompanying drawing content are done, be all contained in protection scope of the present invention.
Claims (14)
1. a method for film coupling processing height salt high ammonia-nitrogen wastewater, key step is:
(1) film absorbs: the feeding liquid side high salt high ammonia-nitrogen wastewater being pumped into film absorptive unit, surveys, pump into acid solution as absorption liquid at the absorption liquid of film absorptive unit, and both sides solution circulated flows; Enter into the ammonia nitrogen of absorption liquid side and the acid-respons of absorption liquid, generate ammonium salt;
(2) reverse osmosis: the ammonium salt solution of film absorption process absorption liquid side pumps into reverse osmosis units and carries out concentration; Water in ammonium salt solution forms reverse osmosis produced water through reverse osmosis membrane, and reverse osmosis units trapped fluid side is concentrated ammonium salt solution;
(3) just permeate: be positive osmotic drive liquid with the ammonium salt solution of reverse osmosis units trapped fluid side, remove the high-salt wastewater after ammonia nitrogen for just to penetrate into feed liquid to absorb laggard feed liquid side through film, enter positive permeation unit and carry out positive osmosis concentration process; Turned back to reverse osmosis units by the ammonium salt solution part after diluting and re-start concentration.
2. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, it is characterized in that, the water quality characteristic of described high salt high ammonia-nitrogen wastewater is: wastewater pH 8.5 ~ 10, conductance 5 ~ 50mS/cm, COD
cr0 ~ 80mg/L, SS0 ~ 200mg/L, Na
+1000 ~ 10000mg/L, NO
3 -2000 ~ 20000mg/L, Cl
-50 ~ 500mg/L, Ca
2+0 ~ 30mg/L, NH
4-N500 ~ 10000mg/L.
3. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, it is characterized in that, the absorption liquid described in step (1) is sulfuric acid, hydrochloric acid or salpeter solution; Concentration as the acid of absorption liquid is 5% ~ 10%.
4. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, is characterized in that, when the ammonium salt solution pH described in step (1) reaches 3 ~ 5, enter step (2) concentration.
5. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, it is characterized in that, enter reverse osmosis units after mixing by 1:5 ~ 1:10 with the ammonium salt solution in the reverse osmosis raw water box that will enter reverse osmosis units as the ammonium salt solution of positive osmotic drive liquid described in step (3) and concentrate.
6. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, is characterized in that, the dense water of positive permeation unit described in step (3) discharges in the ratio with water inlet 1:50 ~ 1:100.
7. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, it is characterized in that, the operational condition of described film absorptive unit is: feeding liquid side, wastewater pH 8.5 ~ 10, wastewater temperature 15 ~ 45 DEG C, both sides crossflow velocity 0.1 ~ 1.0m/s.
8. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, it is characterized in that, the operational condition of described reverse osmosis units is: feeding liquid side, wastewater pH 3 ~ 5, wastewater temperature 15 ~ 45 DEG C, working pressure 0.6 ~ 0.9MPa, feeding liquid side crossflow velocity 0.1 ~ 1.0m/s.
9. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, it is characterized in that, the operational condition of described positive permeation unit is: feeding liquid side, wastewater pH 7.5 ~ 8, wastewater temperature 15 ~ 45 DEG C, both sides crossflow velocity 0.1 ~ 1.0m/s.
10. the method for film coupling processing height salt high ammonia-nitrogen wastewater according to claim 1, it is characterized in that, the mould material of the forward osmosis membrane assembly of described positive permeation unit comprises cellulose acetate, polymeric amide or polyacrylonitrile, and the forward osmosis membrane kit form of described positive permeation unit comprises board-like, rolling, hollow fiber form or tubular type.
The method of 11. film coupling processing height salt high ammonia-nitrogen wastewaters according to claim 1, it is characterized in that, the mould material of the membrane module of described film absorptive unit comprises polyvinylidene difluoride (PVDF), tetrafluoroethylene or polypropylene, and membrane pore size is 0.2 μm; The membrane module form of described film absorptive unit is hollow fiber film assembly.
12. according to the method for film coupling processing height salt high ammonia-nitrogen wastewater described in claim 11, and it is characterized in that, the mould material of the membrane module of described film absorptive unit is tetrafluoroethylene.
The method of 13. film coupling processing height salt high ammonia-nitrogen wastewaters according to claim 1, it is characterized in that, the mould material of the reverse osmosis membrane assembly of described reverse osmosis units is polymeric amide, and membrane pore size is less than 1nm; The reverse osmosis membrane assembly form of described reverse osmosis units is rolling.
The method of 14. film coupling processing height salt high ammonia-nitrogen wastewaters according to claim 1, it is characterized in that, the membrane module of the described membrane module of positive permeation unit, the membrane module of reverse osmosis units and film absorptive unit is one or more groups serial or parallel connection.
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