CN104609588B - The method of film coupling processing high salt high ammonia-nitrogen wastewater - Google Patents
The method of film coupling processing high salt high ammonia-nitrogen wastewater Download PDFInfo
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- CN104609588B CN104609588B CN201310535321.7A CN201310535321A CN104609588B CN 104609588 B CN104609588 B CN 104609588B CN 201310535321 A CN201310535321 A CN 201310535321A CN 104609588 B CN104609588 B CN 104609588B
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Abstract
A kind of method that the invention discloses film coupling processing high salt high ammonia-nitrogen wastewater, uses the technological process of film absorption+reverse osmosis+just permeating coupling.With acid solution as absorbing liquid, using film to absorb mineralized nitrogen in waste water is ammonium salt；Reverse osmosis is used to be concentrated further by ammonium salt solution；Ammonium salt solution after concentrating as the feeding liquid just permeated, carries out positive osmosis concentration process as the driving liquid just permeated, the high-salt wastewater after film absorbs removal ammonia nitrogen；After being diluted as the ammonium salt solution driving liquid, part returns to reverse osmosis units and recirculates concentration.The method using the present invention efficiently solves the process problem of high salt high ammonia-nitrogen wastewater, and Water Sproading rate is high, produces water water quality good.The method using the present invention is circulated concentration to high salt high ammonia-nitrogen wastewater, and concentrated water drainage is high-volume few, has farthest reclaimed the water resource in high salt high ammonia-nitrogen wastewater.
Description
Technical field
The present invention relates to a kind of method utilizing membrane separation technique to process high salt high ammonia-nitrogen wastewater, more
Specifically, relate to a kind of using film absorptions+reverse osmosis+just permeating coupling technique to process high salt height
The method of ammonia nitrogen waste water, belongs to field of industrial waste water treatment.
Background technology
In the catalyst production process of petrochemical industry, many places use ammonium salt and ammonia, therefore, discharge
Containing wastewater from catalyst in containing a large amount of ammonia nitrogens, the ammonia nitrogen in waste water is mainly with ammonium ion (NH4+)
Exist, be the important substance causing body eutrophication and environmental pollution, easily cause algae in water
And other microorganism amount reproductions, oxygen in water can be made time serious to decline, Fish are the most dead
Die, result even in the dry of lake；Ammonia nitrogen also can make water disinfection and industrial circulating water sterilization
Processing procedure increases chlorine dosage；Additionally, ammonia nitrogen has corrosivity to some metal (copper),
During reusing sewage, microorganism during ammonia nitrogen can promote aqueduct and watering equipment in recycled water
Breeding, forms biofouling, blocking pipeline and watering equipment, and affects heat exchange efficiency.
The discharge beyond standards of ammonia nitrogen directly influence Catalyst Production enterprise wastewater overall up to standard and
Normal produce, become the bottleneck of restriction Enterprise's Sustainable Development, the improvement of ammonia nitrogen waste water is become and urges
The primary environmental issue of agent manufacturing enterprise.Therefore, research and develop economic, practical, safe
Containing wastewater from catalyst NH_3-N treating technique becomes current study hotspot, to protection environment, benefits people
Class is significant.
At present, improvement to high-concentration ammonia nitrogenous wastewater both at home and abroad is mainly taked to add alkali stripping, electrolysis
The technology such as method, the MAP sedimentation method, ion exchange, break point chlorination；And to low concentration ammonia
The improvement of nitrogen waste water mainly has the technology such as absorption method, chemical oxidization method, biochemical process.
Adding alkali blow-off method and be applicable to the primary treatment of high-concentration ammonia nitrogenous wastewater, the method technology becomes
Ripe, technique and operation are simple, but operating cost is higher, and equipment corrosion is more serious, and easily makes
Air secondary is become to pollute；Electrolysis is to utilize electrolysis to produce NaOH and Cl2, then carry out stripping.
Its operating cost can be controlled in 3.0 yuan/m3Water, viable economically, the Cl of electrolysis generation2Can conduct
Product is sold or is processed for water, but Cl2Belong to severe toxicity gas, have certain danger, unfavorable
In safety and environment；The MAP sedimentation method, ion exchange, break point chlorination etc. process highly concentrated
Degree ammonia nitrogen waste water, exists that technological operation is loaded down with trivial details, the process cycle is short, processing cost is high, easily causes
The shortcomings such as secondary pollution, are not suitable for heavy industrialization application.
Absorption method is to utilize the Na in zeolite+Displacement NH4 +, it is adaptable to process low-concentration ammonia-nitrogen and give up
Water, uses modified natural zeolite adsorption, has adsorption efficiency higher, and equipment volume is little, equipment one
The feature that the investment of secondary property is little, and for high-concentration ammonia nitrogenous wastewater, due to regeneration frequently, operation pipe
Managing extremely complex, power consumption is very big, and processing cost is high, the most uneconomical；Chemical oxidization method
It is the oxidant adding in ammonia nitrogen waste water and there is Strong oxdiative character, such as ozone, hydrogen peroxide/urge
Agent, sodium hypochlorite etc., technological process and equipment are relatively easy, and response speed is very fast, but by
Expensive in oxidant so that processing cost is higher.It addition, these chemistry strong oxidizers lead to
Often require acid condition, typically require that pH is less than 2～4, therefore, need with chemical oxidization method
Successively twice regulation wastewater pH, adds processing cost；At present, industrial processing low concentration
Ammonia nitrogen waste water most common method is biochemical process, and it mainly uses nitration denitrification principle,
Processing cost is relatively low, but influent ammonium concentration the most not can exceed that 500mg/L, otherwise by shadow
Ring properly functioning, and activity and the breeding of microorganism are had suppression to make by ammonia nitrogen in high density itself
With.Additionally, biochemical reaction speed is slower, it usually needs longer hydraulic detention time, thus
Needing bigger structures, floor space is bigger.
Herein described waste water, in addition to the ammonia nitrogen containing higher concentration, also has relatively high salinity,
And CODCrRelatively low, it is not suitable for using chemical oxidation and biochemical process to process.At present, domestic
Less to the treatment for reuse process patent of this kind of characteristic waste water, existing patent mostly concentrates on ammonia nitrogen
The process discharge aspect up to standard of waste water.Chinese patent CN1123543C relates to a kind of catalyst and contains
The process recovery method of ammonia ammonium waste water, mainly comprises the following steps: 1) dilute waste water containing ammonia ammonium is through reverse osmosis
Permeable membrane concentrates, and membrane permeation liquid directly recycles or as the absorption of steam stripping tower ammonia steam
Liquid；2) membrance concentration liquid mixes with the dense waste water containing ammonia ammonium and adds alkali regulation pH；3) containing after alkalization
Ammonia waste water enters stripper, reclaims ammonia ammonium therein, and stripping purifies water qualified discharge.This
Method is more slightly lower than the operating cost individually using blow-off method, vaporizing extract process etc., but it still have employed
Vaporizing extract process, the operating cost enterprise of vaporizing extract process still cannot accept；It addition, stripper discharge water is still
Containing certain ammonia ammonium, it is impossible to reach salt content in emission request, and waste water higher, no
Biochemical treatment, the most expanded application of the most this method can be carried out；Chinese patent CN1872724A
Relating to the ammonia nitrogen in high density using chemical reaction method to remove in waste water, reclaim ammonium salt, water outlet is led to again
Cross conventional sewage and process PROCESS FOR TREATMENT qualified discharge；Chinese patent CN101337746A relates to one
Plant the method using high temperature deamination and stripping deamination process integration to process high-concentration ammonia nitrogenous wastewater, suitable
For more than ammonia nitrogen 10000mg/L, CODcrThe industrial wastewater of 20000～about 30000mg/L,
Ammonia nitrogen can be down to about 300mg/L, COD after treatmentcr8000～about 15000mg/L,
Processed waste water can qualified discharge through biochemical treatment；Chinese patent CN101293683A relates to
A kind of method of ammonia used in deamidization stripping high-concentration ammonia nitrogenous wastewater, owing to deamidization can make
NH3Molecule breaks away from the effect of hydrone, exists with free ammonia form, and this makes the ammonia in waste water
Nitrogen can more effectively by stripping out；Chinese patent CN101264948A is directed to a kind of employing
The method of ammonia in stripping removal of ammonia and nitrogen waste water, compared with steam stripping deamination, the method steam disappears
Consumption is relatively low, and waste water can meet national grade one discharge standard (< 15mg/L) after treatment.
Additionally, Chinese patent CN1546393A relates to a kind of employing membrane absorption method processes ammonia nitrogen in high density
The method of waste water, the method use hollow fiber membrane contactors, with sulfuric acid solution for absorbing liquid at
The ammonia nitrogen waste water of reason ammonia nitrogen concentration 1000～10000mg/L, waste water can meet country after treatment
First discharge standard.Although the method has reclaimed the ammonia in waste water, but the waste water after processing is only
Energy qualified discharge, it is impossible to realize the reuse purpose of water resource.
It is a kind of novel absorbent process that film and regular absorbent are combined and occurred that film absorbs.Should
Technology mainly uses microporous hydrophobic membrane.In membrane absorption method, handled mixed gas and absorption
Liquid is not directly contacted with, and the two flows in film both sides respectively, the microporous membrane used not choosing itself
Selecting property, simply plays isolation mixed gas and the effect of absorbing liquid, and the micropore on microporous membrane is enough
Greatly, the gas molecule that film side can be allowed to be separated in theory need not the highest pressure and just may be used
To rely primarily on the selectivity of film opposite side absorbing liquid through microporous membrane to film opposite side, this process
Absorb and reach to separate the purpose of a certain component in mixed gas.With other conventional suction process phases
Ratio, film absorption technique has following characteristics: the interface of (1) gas-liquid two-phase is fixing, deposits respectively
It is at the both side surface of fenestra；(2) gas-liquid two-phase is not the most scattered in another phase；(3) gas-liquid
Biphase flowing does not interfere with each other, and flow behavior each can be adjusted；(4) use hollow fine
Dimension film has the biggest specific surface area, is effectively improved gas liquid interfacial area.Membrane absorption method is due to it
Have the advantage that at aspects such as mass-transfer performance, operation, energy consumptions so that this technology has well
Application prospect.
Just permeating (FO) is a kind of membrane separating process relying on osmotic pressure to drive, i.e. water passes through
Selectivity semipermeable membrane is spontaneously diffused into relatively low from higher water chemistry gesture region (Hyposmolality side)
The process in water chemistry gesture region (hyperosmosis side).The driving force of positive process of osmosis is to drive liquid
Permeable pressure head with material liquid, it is not necessary to impressed pressure is as driving force.With reverse osmosis process phase
Ratio, is just permeating and is having the advantage that fouling membrane is lighter, it is not necessary to impressed pressure, and energy consumption is low, returns
Yield is high, and concentrated water drainage is high-volume few, pollutes little, environmental friendliness.
Positive process of osmosis realize it is crucial that need the driving liquid that a kind of high flux can be recycled,
In the present invention, the absorbing liquid after film absorption process is saline solution, and saline solution is the denseest
After contracting, the needs of positive process of osmosis can be met completely.Therefore, if film being absorbed and just permeating
Combine process high salt, high ammonia-nitrogen wastewater, it is carried out secondary utilization, will absorb through film
The high-concentration absorbent liquid that after process, process concentrates again, as the driving liquid of positive process of osmosis, not only solves
The required problem driving liquid of positive process of osmosis of having determined, also solve simultaneously film absorbing liquid regeneration,
Process problem, and to have processed the high salt after film absorbs by positive process of osmosis useless simultaneously
Water, the coupling of two kinds of technology reduces the discharge capacity of waste water to greatest extent, has important environment
Meaning.
Summary of the invention
For the deficiencies in the prior art, the invention discloses a kind of film coupling processing high salt height ammonia nitrogen
The method of waste water, it is desirable to provide a kind of mainly for high salt high ammonia-nitrogen wastewater, concentrated water drainage after process
High-volume few, the farthest new method of recycle-water resource.The method uses film to absorb first
The technological process of+reverse osmosis+just permeating.First, with acid solution as absorbing liquid, use film to absorb
It is ammonium salt by mineralized nitrogen in waste water；Secondly, reverse osmosis is used to be concentrated further by ammonium salt solution；
Ammonium salt solution after concentrating afterwards is as the driving liquid just permeated, and film absorbs after removing ammonia nitrogen
High-salt wastewater, as the feeding liquid just permeated, carries out positive osmosis concentration process.So, just permeate
Water in the high-salt wastewater of feeding liquid side constantly enters into driving liquid side by forward osmosis membrane, as driving
The ammonium salt solution of hydrodynamic is constantly diluted, and when being diluted to finite concentration, backs within reverse osmosis
Unit circulation concentration thoroughly.
The technical solution used in the present invention is:
A kind of method of film coupling processing high salt high ammonia-nitrogen wastewater, mainly comprising the following steps of the method:
(1) film absorbs: high salt high ammonia-nitrogen wastewater pumps into the feeding liquid side of film absorptive unit,
The absorbing liquid side of film absorptive unit, pumps into acid solution and moves as absorbing liquid, both sides solution circulation flow.
In film absorption process, the ammonia nitrogen in high salt high ammonia-nitrogen wastewater constantly passes through microporous hydrophobic membrane
Enter into absorbing liquid side, enter into the acid reaction in the ammonia nitrogen of absorbing liquid side and absorbing liquid, generate
Ammonium salt；
(2) reverse osmosis: in film absorption process, the ammonium salt solution of absorbing liquid side pumps into reverse osmosis units
Carry out concentration.
By reverse osmosis process, the water in ammonium salt solution is formed reverse osmosis produced through reverse osmosis membrane
Water, and reverse osmosis units trapped fluid side is the ammonium salt solution concentrated；
(3) just permeate: using the ammonium salt solution of reverse osmosis units trapped fluid side as positive osmotic drive
Liquid, to absorb the high-salt wastewater after ammonia nitrogen is removed in laggard feed liquid side for just permeating charging through film
Liquid, enters positive permeation unit and carries out positive osmosis concentration process；Under osmotic pressure effect, film absorbs
After trapped fluid side removal ammonia nitrogen, the water in high-salt wastewater is constantly entered into by forward osmosis membrane and just oozes
Thoroughly driving in the ammonium salt solution of liquid side, ammonium salt solution is constantly diluted, and the ammonium salt after being diluted is molten
Liquid part returns to reverse osmosis units and re-starts concentration.
Above-mentioned steps constantly circulates, and the reverse osmosis produced water finally given can be back to produce work
Skill.The high-salt wastewater just penetrating into feed liquid side is constantly circulated concentration, the very small amount of final discharge
Just permeating dense water to centrally dispose.
The water quality characteristic of heretofore described high salt high ammonia-nitrogen wastewater is: wastewater pH 8.5～
10, conductance 5～50mS/cm, CODcr0～80mg/L, SS0～200mg/L, Na+
1000～10000mg/L, NO3 -2000～20000mg/L, Cl-50～500mg/L, Ca2+
0～30mg/L, NH4-N500～10000mg/L.
In the specific implementation, the absorbing liquid described in step (1) is sulphuric acid, hydrochloric acid or nitric acid
Solution；
In the specific implementation, the concentration mass fraction as the acid of absorbing 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, as the ammonium salt solution of positive osmotic drive liquid described in step (3)
Mix by 1:5～1:10 with the ammonium salt solution in the reverse osmosis raw water box of reverse osmosis units to be entered
Rear entrance reverse osmosis units concentrates；
In the specific implementation, the dense water of the positive permeation unit described in step (3) by with just ooze
Penetrate into the ratio discharge of water 1:50～1:100；
In the specific implementation, the operating condition of described film absorptive unit is: feeding liquid side, waste water
PH8.5～10, wastewater temperature 15～45 DEG C, both sides crossflow velocity 0.1～1.0m/s；
In the specific implementation, the operating condition of described reverse osmosis units is: feeding liquid side, waste water
PH3～5, wastewater temperature 15～45 DEG C, operate pressure 0.6～0.9MPa, feeding liquid side form
Surface current speed 0.1～1.0m/s；
In the specific implementation, the operating condition of described positive permeation unit is: feeding liquid side, waste water
PH7.5～8, wastewater temperature 15～45 DEG C, both sides crossflow velocity 0.1～1.0m/s；
In the specific implementation, the membrane material of the forward osmosis membrane assembly of described positive permeation unit includes vinegar
Acid cellulose, polyamide or polyacrylonitrile；
In the specific implementation, the forward osmosis membrane kit form of described positive permeation unit include board-like,
Rolling, hollow fiber form or tubular type；
In the specific implementation, the membrane material of the membrane module of described film absorptive unit includes polyvinylidene fluoride
Alkene, politef or polypropylene, preferably polytetrafluoroethylene, membrane aperture is 0.2 μm；
In the specific implementation, the membrane module form of described film absorptive unit is hollow-fibre membrane group
Part；
In the specific implementation, the membrane material of the reverse osmosis membrane assembly of described reverse osmosis units is polyamides
Amine, membrane aperture 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 described positive permeation unit, the membrane module of reverse osmosis units
It is one or more groups serial or parallel connection with the membrane module of film absorptive unit；
Described high salt high ammonia-nitrogen wastewater is processed by above-mentioned steps, Water Sproading rate >=98%.
Different with above-mentioned patent, present invention is generally directed to the process problem of high salt high ammonia-nitrogen wastewater,
Employing film absorption+reverse osmosis first+just permeating coupling technique process high salt high ammonia-nitrogen wastewater, first
Using film to absorb mineralized nitrogen in waste water is ammonium salt, secondly uses reverse osmosis to be entered by ammonium salt solution
One step concentrates, and the ammonium salt solution after concentrating afterwards is as the driving liquid just permeated, and film absorbs and goes
Except the high-salt wastewater after ammonia nitrogen is as the feeding liquid just permeated, carry out positive osmosis concentration process, this
Sample, the water just penetrated in the high-salt wastewater of feed liquid side constantly enters into driving liquid by forward osmosis membrane
Side, is constantly diluted as the ammonium salt solution driving liquid, and the ammonium salt solution part after being diluted is returned
Return to reverse osmosis units and recirculate concentration.
The present invention is with the essential distinction of prior art, the present invention relates to a kind of high salt height ammonia
The processing method of nitrogen waste water, for present in prior art high salt high ammonia-nitrogen wastewater process and
Handling problems, the present invention mainly uses film absorption+reverse osmosis+just permeating coupling process, for stone
The high salt high ammonia-nitrogen wastewater changing enterprise processes.The method using the present invention efficiently solves height
The process problem of salt high ammonia-nitrogen wastewater, Water Sproading rate is high, produces water water quality good.Use the present invention's
Method is circulated concentration to high salt high ammonia-nitrogen wastewater, and concentrated water drainage is high-volume few, maximum journey
The water resource reclaimed in high salt high ammonia-nitrogen wastewater of degree.
The invention has the beneficial effects as follows:
1, the present invention is by using film absorption+reverse osmosis+just permeating coupling process, for petrochemical industry
The high salt high ammonia-nitrogen wastewater of enterprise has carried out advanced treatment and reclamation, and concentrated water drainage is high-volume few, and water returns
Yield is high, and product water water quality is good, has reclaimed water resource to greatest extent, has improve to greatest extent
The response rate of high salt high ammonia-nitrogen wastewater；
2, the film absorption process in the present invention and positive process of osmosis all need not impressed pressure or outer
Pressure pressure is the least, and method is simple, easily operates；
3, the film in the film absorption process in the present invention, reverse osmosis process and positive process of osmosis
Pollute the lightest, extend the continuous and steady operation time of coupling process；
4, the method using the present invention processes high salt high ammonia-nitrogen wastewater, and ammonia-nitrogen removal rate is high, water
The response rate is high, and product water water quality is good, and energy consumption is low, and processing cost is low；
5, The inventive method achieves membrane separation technique for efficient coupling that petrochemical wastewater processes
Close.The method using the present invention, whole coupling process is possible not only to obtain lot of pure water, with
Time also solve high salt high ammonia-nitrogen wastewater be difficult to process problem, improve waste water to greatest extent
The response rate, 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: absorbing liquid；5: absorbing 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 permeating raw water box；
12: positive permeation unit；13: the dense water of just infiltration of discharge.
Detailed description of the invention
Below, in conjunction with the drawings and specific embodiments, invention is further described.
Seeing Fig. 1, the 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 film absorbs former
High salt high ammonia-nitrogen wastewater in water tank 2 pumps into the feeding liquid side of film absorptive unit 3 and circulates；
Secondly, absorbing liquid 4 enters absorbing liquid water tank 5, the absorbing liquid in absorbing liquid water tank 5, pumps into
The absorbing liquid side of film absorptive unit circulates.Under film Absorption, high salt high ammonia-nitrogen wastewater
In ammonia nitrogen constantly enter into absorbing liquid side by microporous hydrophobic membrane, and the acid absorption of absorbing liquid side
Liquid reaction generates ammonium salt；
(2) reverse osmosis.In film absorption process, the ammonium salt solution of absorbing liquid side pumps into reverse osmosis units
7 carry out concentration.By reverse osmosis isolation, the water in ammonium salt solution passes through reverse osmosis membrane shape
Become reverse osmosis produced water 8, and reverse osmosis units trapped fluid side be concentrate ammonium salt solution 9 enter
Drive liquid water tank 10；
(3) just permeate.Absorb the high-salt wastewater after ammonia nitrogen is removed in laggard feed liquid side through film to enter
Just permeating raw water box 11, just to permeate the high-salt wastewater in raw water box 11 for just penetrating into feed liquid,
It is positive osmotic drive liquid to drive the ammonium salt solution in liquid water tank 10, respectively enters and just permeate list
Unit 12 both sides circulate, and carry out positive osmosis concentration process.Under osmotic pressure effect, film is inhaled
The water taken in the high-salt wastewater after ammonia nitrogen is removed in feed liquid side is constantly entered into by forward osmosis membrane
In the ammonium salt solution of positive osmotic drive liquid side, ammonium salt solution is constantly diluted, the ammonium after being diluted
Saline solution part returns to reverse osmosis units and re-starts concentration.
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, CODcr80mg/L, SS100mg/L, Na+
1000mg/L, NO3 -2000mg/L, Cl-50mg/L, Ca2+0mg/L, NH4-N500
mg/L。
Film absorbent assembly used is polytetrafluoroethylene (PTFE) doughnut microporous hydrophobic membrane group
Part, membrane aperture is 0.2 μm；Reverse osmosis membrane assembly used is polyamide rolled membrane module, fenestra
Footpath 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,
High salt high ammonia-nitrogen wastewater in film absorption raw water box 2 pumps into the feeding liquid side of film absorptive unit 3 and follows
Circulation moves；The sulfuric acid solution that concentration mass fraction is 5% 4 as absorbing liquid enters absorbing liquid
Water tank 5, the sulfuric acid solution in absorbing liquid water tank 5 pumps into the absorbing liquid side circulation of film absorptive unit
Flowing.Under film Absorption, the ammonia nitrogen in high salt high ammonia-nitrogen wastewater constantly passes through microporous hydrophobic
Film enters into absorbing liquid side, and the absorbing liquid sulfuric acid reaction of absorbing liquid side generates ammonium sulfate.Work as sulfur
When acid ammonium solution pH reaches 3, enter step (2) concentration；(2) reverse osmosis, film is inhaled
During receipts, the ammonium sulfate of absorbing liquid side pumps into reverse osmosis units 7 and carries out concentration.Logical
Crossing reverse osmosis isolation, the water in ammonium sulfate forms reverse osmosis produced water 8 through reverse osmosis membrane,
And reverse osmosis trapped fluid side is the ammonium sulfate 9 entrance driving liquid water tank 10 concentrated；(3) just
Infiltration, absorbs the high-salt wastewater entrance after ammonia nitrogen is removed in laggard feed liquid side through film and is just permeating former water
Case 11, just to permeate the high-salt wastewater in raw water box 11 for just penetrating into feed liquid, to drive liquid
Ammonium sulfate in water tank 10 is positive osmotic drive liquid, respectively enters positive permeation unit 12 liang
Side circulates, and carries out positive osmosis concentration process.Under osmotic pressure effect, film is absorbed into feed liquid
The water in high-salt wastewater after side removal ammonia nitrogen constantly enters into just to permeate by forward osmosis membrane and drives
In the ammonium sulfate of hydrodynamic side, ammonium sulfate is constantly diluted.Wherein, step (3)
The middle ammonium sulfate as positive osmotic drive liquid is former with the reverse osmosis of reverse osmosis units to be entered
Ammonium sulfate in water tank enters reverse osmosis units after mixing by 1:10 and concentrates；Step
(3) the dense water of the positive permeation unit in is discharged in 1:100 ratio with water inlet；
In running, the operating 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 operating condition of reverse osmosis units is:
Feeding liquid side, wastewater pH 3, wastewater temperature 15 DEG C, operate pressure 0.6MPa, feeding liquid side
Crossflow velocity 0.1m/s；The operating 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 operating condition of above-mentioned film absorptive unit, film absorbing film flux be maintained at 4～
7L/m2H, the dense water NH after film absorbs4-N content 5mg/L；At above-mentioned reverse osmosis list
Under the operating condition of unit, reverse osmosis membrane flux is maintained at 12～16L/m2H, reverse osmosis produced water
Electrical conductivity is less than 100 μ s/cm, produces water water quality and is better than tap water, can be back to production technology；
Under the operating condition of above-mentioned positive permeation unit, forward osmosis membrane flux is maintained at 3～6L/m2·h。
High salt high ammonia-nitrogen wastewater is processed by above-mentioned steps, 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, CODcr80mg/L, SS100mg/L, Na+
5000mg/L, NO3 -10000mg/L, Cl-270mg/L, Ca2+20mg/L, NH4-N6000
mg/L。
Film absorbent assembly used is polytetrafluoroethylene (PTFE) doughnut microporous hydrophobic membrane group
Part, membrane aperture is 0.2 μm；Reverse osmosis membrane assembly used is polyamide rolled membrane module, fenestra
Footpath is less than 1nm；Forward osmosis membrane assembly used is cellulose acetate plate and frame module；
Operating procedure is different from embodiment 1: absorbing liquid used in step (1) is
Concentration mass fraction is the salpeter solution of 7%；When the ammonium nitrate solution pH in step (1) reaches
During to 4, enter step (2) concentration；When in step (3) as positive osmotic drive liquid
Ammonium nitrate solution and the ammonium nitrate solution in the reverse osmosis raw water box of reverse osmosis units to be entered
Enter reverse osmosis units by 1:7 after mixing to concentrate；Positive permeation unit in step (3)
Dense water with water inlet by 1:70 ratio discharge；
In running, the operating 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 operating condition of reverse osmosis units is:
Feeding liquid side, wastewater pH 4, wastewater temperature 35 DEG C, operate pressure 0.7MPa, feeding liquid side
Crossflow velocity 0.5m/s；The operating 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 operating condition of above-mentioned film absorptive unit, film absorbing film flux be maintained at 5～
9L/m2H, the dense water NH after film absorbs4-N content about 10mg/L；Above-mentioned instead
Under the operating condition of permeation unit, reverse osmosis membrane flux is maintained at 14～17L/m2H, reverse osmosis
Thoroughly produce water conductivity and be better than tap water less than 100 μ s/cm, product water water quality, can be back to produce
Technique；Under the operating condition of above-mentioned positive permeation unit, forward osmosis membrane flux be maintained at 5～
7L/m2·h。
High salt high ammonia-nitrogen wastewater is processed by above-mentioned steps, 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, CODcr80mg/L, SS200mg/L, Na+
10000mg/L, NO3 -20000mg/L, Cl-500mg/L, Ca2+30mg/L, NH4-N
10000mg/L。
Film absorbent assembly used is polytetrafluoroethylene (PTFE) doughnut microporous hydrophobic membrane group
Part, membrane aperture is 0.2 μm；Reverse osmosis membrane assembly used is polyamide rolled membrane module, fenestra
Footpath is less than 1nm；Forward osmosis membrane assembly used is cellulose acetate plate and frame module；
Operating procedure is different from embodiment 1: absorbing liquid used in step (1) is
Concentration mass fraction is10The hydrochloric acid solution of %；Ammonium chloride solution pH in step (1)
When reaching 5, enter step (2) concentration；When in step (3) as positive osmotic drive
The ammonium chloride solution of liquid is molten with the ammonium chloride in the reverse osmosis raw water box of reverse osmosis units to be entered
Liquid enters reverse osmosis units after mixing by 1:5 and concentrates；Just infiltration list in step (3)
The dense water of unit is discharged in 1:50 ratio with water inlet；
In running, the operating 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 operating condition of reverse osmosis units is:
Feeding liquid side, wastewater pH 5, wastewater temperature 45 DEG C, operate pressure 0.9MPa, feeding liquid side
Crossflow velocity 1.0m/s；The operating 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 operating condition of above-mentioned film absorptive unit, film absorbing film flux be maintained at 6～
10L/m2H, the dense water NH after film absorbs4-N content about 15mg/L；Above-mentioned instead
Under the operating condition of permeation unit, reverse osmosis membrane flux is maintained at 18～22L/m2H, reverse osmosis
Thoroughly produce water conductivity and be better than tap water less than 100 μ s/cm, product water water quality, can be back to produce
Technique；Under the operating condition of above-mentioned positive permeation unit, forward osmosis membrane flux be maintained at 6～
9L/m2·h。
High salt high ammonia-nitrogen wastewater is processed by above-mentioned steps, 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, CODcr0mg/L, SS0mg/L, Na+5000mg/L,
NO3 -10000mg/L, Cl-270mg/L, Ca2+30mg/L, NH4-N6000mg/L。
Film absorbent assembly used is polytetrafluoroethylene (PTFE) doughnut microporous hydrophobic membrane group
Part, membrane aperture is 0.2 μm；Reverse osmosis membrane assembly used is polyamide rolled membrane module, fenestra
Footpath is less than 1nm；Forward osmosis membrane assembly used is cellulose acetate plate and frame module；
Operating procedure is different from embodiment 1: absorbing liquid used in step (1) is
Concentration mass fraction is10The salpeter solution of %；Ammonium nitrate solution pH in step (1)
When reaching 4, enter step (2) concentration；When in step (3) as positive osmotic drive
The ammonium nitrate solution of liquid is molten with the ammonium nitrate in the reverse osmosis raw water box of reverse osmosis units to be entered
Liquid enters reverse osmosis units after mixing by 1:8 and concentrates；Just infiltration list in step (3)
The dense water of unit is discharged in 1:80 ratio with water inlet；
In running, the operating 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 operating condition of reverse osmosis units is:
Feeding liquid side, wastewater pH 4, wastewater temperature 45 DEG C, operate pressure 0.7MPa, feed side form
Surface current speed 0.7m/s；The operating 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 operating condition of above-mentioned film absorptive unit, film absorbing film flux be maintained at 6～
9L/m2H, the dense water NH after film absorbs4-N content about 10mg/L；Above-mentioned instead
Under the operating condition of permeation unit, reverse osmosis membrane flux is maintained at 16～20L/m2H, reverse osmosis
Thoroughly produce water conductivity and be better than tap water less than 100 μ s/cm, product water water quality, can be back to produce
Technique；Under the operating condition of above-mentioned positive permeation unit, forward osmosis membrane flux be maintained at 5～
7L/m2·h。
High salt high ammonia-nitrogen wastewater is processed by above-mentioned steps, Water Sproading rate 98.75%.
The foregoing is only the preferable possible embodiments of the present invention, not thereby limit to the present invention's
The scope of the claims, therefore the equivalence change that every utilization description of the invention and accompanying drawing content are made, all
It is contained in protection scope of the present invention.
Claims (13)
1. a method for film coupling processing high salt high ammonia-nitrogen wastewater, mainly comprises the following steps:
(1) film absorbs: high salt high ammonia-nitrogen wastewater pumps into the feeding liquid side of film absorptive unit,
The absorbing liquid of film absorptive unit is surveyed, and pumps into acid solution and moves as absorbing liquid, both sides solution circulation flow；
Enter into the acid reaction in the ammonia nitrogen of absorbing liquid side and absorbing liquid, generate ammonium salt；
(2) reverse osmosis: the ammonium salt solution of film absorption process absorbing liquid side pumps into reverse osmosis units and enters
Row concentration；Water in ammonium salt solution forms reverse osmosis produced water, reverse osmosis through reverse osmosis membrane
Unit trapped fluid side is the ammonium salt solution concentrated；
(3) just permeate: be positive osmotic drive liquid with the ammonium salt solution of reverse osmosis units trapped fluid side,
With the high-salt wastewater after film absorbs laggard feed liquid side removal ammonia nitrogen for just penetrating into feed liquid, enter
Enter positive permeation unit and carry out positive osmosis concentration process；Ammonium salt solution part after being diluted returns to
Reverse osmosis units re-starts concentration；
The water quality characteristic of described high salt high ammonia-nitrogen wastewater is: wastewater pH 8.5～10, conductance 5～
50mS/cm, CODcr0～80mg/L, SS 0～200mg/L, Na+1000～10000
Mg/L, NO3 -2000～20000mg/L, Cl-50～500mg/L, Ca2+0～30mg/L,
NH4-N 500～10000mg/L.
The most according to claim 1, the method for film coupling processing high salt high ammonia-nitrogen wastewater, it is special
Levying and be, the absorbing liquid described in step (1) is sulphuric acid, hydrochloric acid or salpeter solution；As suction
The concentration of the acid receiving liquid is 5%～10%.
The most according to claim 1, the method for film coupling processing high salt high ammonia-nitrogen wastewater, it is special
Levy and be, when the ammonium salt solution pH described in step (1) reaches 3～5, enter step (2)
Concentration.
The most according to claim 1, the method for film coupling processing high salt high ammonia-nitrogen wastewater, it is special
Levy and be, described in step (3) as positive osmotic drive liquid ammonium salt solution with to enter anti-
Ammonium salt solution in the reverse osmosis raw water box of permeation unit enters reverse osmosis after pressing 1:5～1:10 mixing
Unit concentrates thoroughly.
The most according to claim 1, the method for film coupling processing high salt high ammonia-nitrogen wastewater, it is special
Levying and be, the dense water of positive permeation unit described in step (3) is by with water inlet 1:50's～1:100
Ratio is discharged.
The most according to claim 1, the method for film coupling processing high salt high ammonia-nitrogen wastewater, it is special
Levying and be, the operating 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.
The most according to claim 1, the method for film coupling processing high salt high ammonia-nitrogen wastewater, it is special
Levying and be, the operating condition of described reverse osmosis units is: feeding liquid side, wastewater pH 3～5,
Wastewater temperature 15～45 DEG C, operate pressure 0.6～0.9MPa, feeding liquid side crossflow velocity 0.1～
1.0m/s。
The most according to claim 1, the method for film coupling processing high salt high ammonia-nitrogen wastewater, it is special
Levying and be, the operating 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.
The most according to claim 1, the method for film coupling processing high salt high ammonia-nitrogen wastewater, it is special
Levy and be, the membrane material of the forward osmosis membrane assembly of described positive permeation unit include cellulose acetate,
Polyamide or polyacrylonitrile, the forward osmosis membrane kit form of described positive permeation unit include board-like,
Rolling, hollow fiber form or tubular type.
The method of film coupling processing high salt high ammonia-nitrogen wastewater the most according to claim 1, its
Being characterised by, the membrane material of the membrane module of described film absorptive unit includes Kynoar, poly-four
Fluorothene or polypropylene, membrane aperture is 0.2 μm；The membrane module form of described film absorptive unit is
Hollow fiber film assembly.
The method of 11. film coupling processing high salt high ammonia-nitrogen wastewaters according to claim 10, its
Being characterised by, the membrane material of the membrane module of described film absorptive unit is politef.
The method of 12. film coupling processing high salt high ammonia-nitrogen wastewaters according to claim 1, its
Being characterised by, the membrane material of the reverse osmosis membrane assembly of described reverse osmosis units is polyamide, fenestra
Footpath is less than 1nm；The reverse osmosis membrane assembly form of described reverse osmosis units is rolling.
The method of 13. film coupling processing high salt high ammonia-nitrogen wastewaters according to claim 1, its
Being characterised by, the described membrane module of positive permeation unit, the membrane module of reverse osmosis units and film absorb
The membrane module of unit is one or more groups serial or parallel connection.
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