CN102807296A - Process for deeply treating and recycling high-salinity industrial waste water - Google Patents
Process for deeply treating and recycling high-salinity industrial waste water Download PDFInfo
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- CN102807296A CN102807296A CN2012103157689A CN201210315768A CN102807296A CN 102807296 A CN102807296 A CN 102807296A CN 2012103157689 A CN2012103157689 A CN 2012103157689A CN 201210315768 A CN201210315768 A CN 201210315768A CN 102807296 A CN102807296 A CN 102807296A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a process for deeply treating and recycling high-salinity industrial waste water, which belongs to the technical field of environmental protection and comprehsnive resource utilization. Combined equipment is adopted, and comprises ultrafiltration equipment, ion exchange softening equipment, volume-type reverse osmosis equipment, medium-pressure flat plate reverse osmosis equipment, high-pressure flat plate reverse osmosis equipment, ultrahigh-pressure flat plate reverse osmosis equipment, high-pressure flat plate filtration equipment, secondary reverse osmosis equipment and the like. After being treated with a combined process, industrial waste water can be concentrated by 36-180 times; in combination with evaporative crystallization equipment, zero discharge of industrial waste water can be realized, and salts in industrial waste water can be recovered; and after secondary reverse osmosis treatment, produced water can be recycled by 100 percent. The process has the advantages of flexible combined process, small floor area, saving in investment, high efficiency, low running cost, stable and reliable effect, and the like.
Description
Technical field
The invention belongs to environment protection and comprehensive utilization of resources technical field, a kind of high salinity advanced treatment of industrial waste water reuse technology particularly is provided.
Background technology
China is the country of a serious water shortage, per capita Freshwater resources be merely world average level 1/4, rank 110 in the world, be one of whole world country that water resources is the poorest per capita.China is the water resources critical shortage not only, and water pollutes and remains serious, and the brainstrust warning: " China will can not find drinkable water resources after 20 years ", water resources critical shortage have seriously restricted Chinese economic development.Therefore it is vital developing new waste water treatment, recovery and utilization.
Membrane separation technique is progressively to grow up the middle and later periods in 20th century.Over nearly 30 years, various membrane separation techniques are in electronics, chemical industry, environmental protection, food, pharmacy and drink every field such as pure water and all obtained using widely.Along with updating of mould material, the continuous progress of stripping technique, the antifouling property of various films is greatly improved, and the application aspect environmental protection and WWT is also more and more widely.
Reverse osmosis technology is a kind of general water technology, its objective is water (solvent) desalination (solute).Reverse osmosis technology has become the most economical means of seawater and brackish water desalination, pure water and ultrapure water preparation.Along with the industriallization of the reverse osmosis membrane and the membrane module of excellent property, the range of application of reverse osmosis technology has been put into fields such as electronics, chemical industry, medicine, food, beverage, metallurgy and environmental protection from initial desalination.Reverse osmosis technology in frontier (like the production of process water with utilize again; Liquid waste disposal; Electroplating rinse water utilizes and metal recovery etc. again) utilisation technology constantly developed.
Nanofiltration is the new separation technology that on the r-o-basis, grows up, and aspect wastewater treatment, is mainly used in removing of divalent salts and concentrating of larger molecular organics.With nf membrane the formed waste liquid of pulping wood alkali extraction stages is decoloured, percent of decolourization can reach more than 98%.With nf membrane separating metal vitriol and nitrate salt from acidic solution, wherein the rejection to single nickel salt can reach 95%.
Mainly there is following several respects problem in application of membrane separation technology in advanced treatment of industrial waste water:
(1) scale problems of film: scale forming matter generally includes difficulty soluble salt, indissoluble alkali, silicon-dioxide etc.Usually adopt the mode of adding Scale inhibitors to prevent the film fouling, but in high-salt wastewater, ionic concn content is very high, scale inhibition effect is suppressed, thereby causes the film fouling.
(2) Organic pollutants problem: contain complicated organic-compound system in the trade effluent usually, even through physical chemistry and biological treatment, still residual certain density COD in the water.These remaining COD can make film forming organic fouling and microbial contamination.
(3) cycles of concentration and dense water treatment problems: because the existence of above two problems; Cause existing membrane technique to be used for WWT; Cycles of concentration not high (recovery is low); Usually can only be concentrated to 4-5 doubly (the corresponding recovery 75～80%), cycles of concentration is low to make the concentrated water yield big, and subsequent disposal pressure is bigger.
Summary of the invention
The object of the present invention is to provide a kind of high salt industry waste water advanced treatment recovery technology, adopt combination membrane technology, can the saliferous trade effluent be concentrated to more than 10～180 times.Advantage of the present invention is: take up an area of less, reduced investment, efficient is high, working cost is low, effect stability is reliable etc.
The present invention includes technologies such as processing in early stage, ultrafiltration, IX, the r-o-of one-level rolling, middle locating back r-o-, high pressure flat plate reverse osmosis, ultra-high voltage flat plate reverse osmosis, the dull and stereotyped nanofiltration of high pressure, evaporative crystallization, the r-o-of secondary rolling, the particular content of process step and the technical parameter of control are following:
(1) handles early stage
High salt industry waste water at first through conventional physical, chemistry, physical chemistry or/and the method for biological treatment is carried out various necessary processing, make and handle later water-quality COD and the BOD index reaches or near " integrated wastewater discharge standard " (GB8978-1996).Its main purpose: 1., prevent pollution and damage to film with in the trade effluent the deleterious various organic solvents of film, grease, oxygenant, larger molecular organics etc. being degraded and digestion process; 2. carry out digestion process with being difficult for the small organic molecule that tunicle holds back in the trade effluent, improve film and produce quality; 3. remove other all contaminations in the trade effluent as far as possible, reduce the load of film.
(2) ultrafiltration
Adopt ultra-filtration membrane that trade effluent is carried out pre-filtering, remove and cause reverse osmosis membrane and nf membrane dirty stifled organic colloid, mineral colloid and mikrobe easily, prolong the cleaning interval and the work-ing life of follow-up r-o-and nf membrane system.
Membrane stack that ultrafiltration system is made up of working shaft (or suction pump), security personnel strainer, hyperfiltration membrane assembly and associated conduit valve etc. are formed.Wherein hyperfiltration membrane assembly can use tubular fibre submerged membrane assembly (employing suction pump), also can use traditional pillar hollow fiber film assembly (employing working shaft).Both the external-compression type polysulfone hollow fiber ultrafiltration membrane system can be used, also the inner pressed polysulfone hollow fiber ultrafiltration membrane system can be used.Ultrafiltration can also be used other ultrafiltration form: such as ceramic membrane ultrafitration, tubular membrane ultrafiltration or rolled film ultrafiltration etc.
(3) IX
Because the film system cycles of concentration that the present invention relates to is high, must use ion exchange system that feed water by reverse osmosis is softened processing, to prevent the fouling of film.
Ion exchange system is made up of ion exchange column and associated conduit valve, wherein the inner filling of ion exchange column ion exchange resin.
Preferred ion exchange resin is the used for acrylic weak Zeo-karb.The resin trade mark comprises 112, D113, D113FC, D113SC, SQD-80, SQD-85, SQD-88, SQD-112 etc. or be equal to the trade mark, ionic forms H type, CEC 10.0～20.0 mmol/g; Volume-exchange capacity 3.5～7.0 mmol/mL, water cut 40～65%, wet volume density 0.70～0.82 g/mL; Wet true density 1.10～1.20 g/mL, size range 0.315～1.25mm, >=95%; Effective size of grain 0.35 ~ 0.70 mm, coefficient of uniformity 1.1～1.6 oozes mill rate of small round spheres 90%～100% behind the mill; Transition rate of expansion (65-105% of H → Na), light yellow or oyster white.This resin has excellent anti-oxidant, anti-physical abrasion, anti-chemosmosis and anti-organic contamination ability, and very high operating capacity is arranged, and is widely used in water softening and dealkalize and handles.During this resin work is the H type, uses regeneration of hydrochloric acid.
Further preferred ion exchange resin is imido oxalic acid type or amido phosphatic type macroporous chelate resin.The resin trade mark comprises that D401, D402, D402-II and other are equal to the trade mark, ionic forms Na type, mass exchange capacity 1.45～2.0 mmolCu
2+/ g, volume-exchange capacity 0.5～0.6 mmol Cu
2+Or Ca
2+/ mL, water cut 52～58%, wet volume density 0.72～0.78 g/mL; Wet true density 1.15～1.25 g/mL, size range 0.315～1.25mm,>=95%; Effective size of grain 0.4～0.7mm, coefficient of uniformity 1.0～1.6 oozes mill rate of small round spheres 90%～100% behind the mill; Transition rate of expansion (H → Na) 40%～100%, color oyster white or grey.This resin has good selectivity and exchange capacity to polyvalent ion, and the separation that is widely used in water softening and metal is purified.During this resin work is the Na type, at first uses regeneration of hydrochloric acid during regeneration, is converted into the H type, and then with sodium hydroxide regeneration, is converted into the Na type again.
In order to prevent that hardness ions from penetrating resin layer, get into follow-up r-o-and nanofiltration system, cause the film scaling fouling, use the placed in-line mode of two-stage ion exchange column to move.
If use weak acid positive resin, IX water outlet are acid, need to connect degassing tower and remove the carbonic acid gas in the IX water outlet, to reduce the consumption of sodium hydroxide in the subsequent technique.Can adopt blowing-type carbonic acid gas degassing tower, be installed in ion-exchanger after, remove the carbonic acid gas that produces in the water, after decarburization, the carbonic acid gas residual volume is no more than 5mg/L in the water.Working temperature: 5～50 ℃; Spray density 40～60 m
3/ m
2H, strength ofdraft 3000m
3/ h.
Waste water after the degassing need be regulated PH to neutral with sodium hydroxide, to improve the rejection of reverse osmosis membrane before getting into reverse osmosis system.
Although softening processing has been carried out in the front, removed hardness ionses such as nearly all calcium, magnesium, high salinity waste water gets into before the r-o-, still need add Scale inhibitors, when especially sulfate ion concentration is higher in the waste water.Traditional reverse osmosis antisludging agent is only applicable to general brackish water water source usually, and when the water intermediate ion was dense, conventional reverse osmosis antisludging agent can lose effect.Therefore the Scale inhibitors that must development of new be applicable to high level salt solution.Scale inhibitors adds to before the one-level rolling r-o-security personnel strainer.
Preferred Scale inhibitors comprises YD 30 (EDTA) and salt thereof; Two hexamethylene triamine five methylenephosphonic acids (BHMTPMPA), diethylene triamine pentamethylene phosphonic (DTPMPA), ethylenediamine tetramethylene phosphonic acid (EDTMPA) etc. contain the organic phosphine Scale inhibitors and the salt thereof of methene phosphate.The Scale inhibitors addition is 2～20ppm.
Further preferred Scale inhibitors is disodium EDTA (EDTANa
2), addition is 2～20ppm.
(4) one-level rolling r-o-
One-level rolling reverse osmosis system is made up of service pump, security personnel's strainer, HPP, one-level coiled reverse osmosis membrane heap and associated conduit valve etc.
Waste water after softening and the degassing are handled is pressurizeed by service pump, and process security personnel's strainer filters, and after the HPP supercharging, gets into one-level coiled reverse osmosis membrane heap, under 1～4MPa, one-level rolling reverse osmosis concentration is intake 3～4 times.One-level rolling reverse osmosis concentrated water collects the dense water tank of one-level respectively with product water and one-level is produced water tank.One-level rolling reverse osmosis produced water such as up to standardly can carry out reuse, up to standard as not, need proceed the processing of (10) step.
The r-o-of one-level rolling can use brackish water desalination with various coiled reverse osmosis membrane assemblies, also can use sea water desaltination to use the coiled reverse osmosis membrane assembly.
(5) locating back r-o-in
Middle locating back reverse osmosis system is made up of service pump, security personnel's strainer, HPP, middle locating back r-o-membrane stack and associated conduit valve etc.
Locating back reverse osmosis system service pump in the one-level rolling reverse osmosis concentrated water warp, security personnel's strainer, HPP, locating back r-o-membrane stack in the entering carries out 3～5 times to one-level rolling reverse osmosis concentrated water and concentrates under 4～7MPa.Softened water tank or the reverse osmosis produced water tank of one-level rolling that middle locating back reverse osmosis produced water is back to before the r-o-of one-level rolling continue to handle, and the reverse osmosis concentrated water tank of locating back was proceeded next step processing during dense water was collected;
In this technological process, use the r-o-of dish tubular plate and the dull and stereotyped nanofiltration technique of different pressures grade, be used for the high multiple concentration of trade effluent.
The operating pressure of dish tubular plate reverse osmosis system is higher.This membrane element not only crushing resistance is good, the more important thing is in high-pressure system because pressure disappears or when shutting down suddenly, water hammering will be far below traditional rolled film to the influence of reverse-osmosis membrane element.In actual motion, can report to the police to the membrane element of breakage through the variation of product discharge and the reduction of pressure; And can to judge through the variation of water outlet be that problem has appearred in which root film post; And change, be one of system the most safe and reliable in the global high-pressure membrane system.
Have following characteristics on dish tubular type high pressure reverse-osmosis membrane element structure and the flow process:
1. by withstand voltage flow guiding disc, the stacked and centre gangway pull bar of diaphragm is formed, and flow guiding disc is not pressed in that the O shape circle that places on the film bag surface around the central tie rod will intake and pure water separates.
2. it is short that membrane element is gone into water flow passage, and 180 degree of generation continuously that flow turn to (each standard film post corotation is to 418 times) thereby eliminated concentration polarization.
3. the spacing between the passage between film surface and the valve plate is more than 2mm, the unique design of this open type passage, even but make former water turbidity height to 80NTU works better still, so just can simplify pre-filtering.The passage of broad also can bear film surface liquid flow velocity faster, can reduce the possibility of concentration polarization greatly up to the film surface velocity of 0.4m/s.
4. because the salient point on the valve plate causes the current on film surface to become turbulence state, make that the pollution and the fouling on film surface are few, membrane stability is high, and can reach more than 3 years normal work-ing life.Because in the film post design, other annexes are all selected the element that is of high quality, and making can life-time service 15 years, every replacing film bag that only needed at a distance from 3～5 years, and very easy, expense is extremely low.
5. the diaphragm operating temperature range in the membrane element is wide, is between 5 ℃～45 ℃.Satisfy the day normal temperature of most of sewage.
The dull and stereotyped reverse-osmosis membrane element of high pressure; On whole component construction, broken the mindset of rolled film design; On traditional rolled film element, carried out bold innovation, be current r-o-field; Except rolled film, the membrane element form of unique a kind of uniqueness in the world in the r-o-field.In addition, the unique design of dish tubular membrane element makes that the element intake pressure can be up to 20MPa.
In this combination process; Should be according to the r-o-of dish tubular plate and the dull and stereotyped nanofiltration element of the water quality and the water yield situation choose reasonable different pressures grade of trade effluent; And carrying out reasonable combination as required, various assembled scheme all should be regarded as the protection domain of this patent.
(6) high pressure flat plate reverse osmosis
The dull and stereotyped reverse osmosis system of high pressure is made up of service pump, security personnel's strainer, HPP, the dull and stereotyped reverse osmosis membrane heap of high pressure and associated conduit valve etc.
In the dense water of locating back r-o-through the dull and stereotyped reverse osmosis system service pump of high pressure, security personnel's strainer, HPP gets into the dull and stereotyped reverse osmosis membrane heap of high pressure, centering locating back reverse osmosis concentrated water carries out 2～3 times and concentrates under 7～12MPa.The softened water tank that the dull and stereotyped reverse osmosis produced water of high pressure is back to before the r-o-of one-level rolling continues to handle, and the dull and stereotyped reverse osmosis concentrated water of high pressure gets into the dull and stereotyped reverse osmosis concentrated water case of high pressure, carries out next step concentration.
(7) ultra-high voltage flat plate reverse osmosis
Ultra-high voltage flat plate reverse osmosis system is made up of service pump, security personnel's strainer, HPP, ultra-high voltage flat plate reverse osmosis membrane stack and associated conduit valve etc.
The dense water of high pressure flat plate reverse osmosis is through ultra-high voltage flat plate reverse osmosis system service pump, security personnel's strainer, and HPP gets into ultra-high voltage flat plate reverse osmosis system, under 120～200MPa, the dull and stereotyped reverse osmosis concentrated water of high pressure is carried out 2～3 times and concentrates.The softened water tank that ultra-high voltage flat plate reverse osmosis product water is back to before the r-o-of one-level rolling continues to handle, after the dense water of ultra-high voltage flat plate reverse osmosis concentrates 36～180 times to raw wastewater, and the devaporation crystallization.
(8) the dull and stereotyped nanofiltration of high pressure
If multivalent anions in the raw wastewater (like sulfate radical, phosphate radical etc.) content higher (multivalent anions concentration and univalent anion concentration ratio＞1); The dense water of high pressure flat plate reverse osmosis can replace the ultra-high voltage flat plate reverse osmosis to concentrate with the dull and stereotyped nanofiltration of high pressure; Can obviously reduce the working pressure of system, reduce running cost.
The dull and stereotyped nanofiltration system of high pressure is made up of service pump, security personnel's strainer, HPP, the dull and stereotyped nf membrane heap of high pressure and associated conduit valve etc.
The dense water of high pressure flat plate reverse osmosis is through the dull and stereotyped nanofiltration system service pump of high pressure, security personnel's strainer, and HPP gets into the dull and stereotyped nf membrane heap of high pressure, under 70～120MPa, the dull and stereotyped reverse osmosis concentrated water of high pressure is carried out 2～3 times and concentrates.The reverse osmosis concentrated water tank of middle locating back before water is back to upper level high pressure flat plate reverse osmosis is produced in the dull and stereotyped nanofiltration of high pressure, continues to handle, after dense water concentrates 36～180 times to raw wastewater, and the devaporation crystallization.
(9) evaporative crystallization
Handle through 3～10 reverse osmosis concentration, waste water is concentrated into 10～180 times, and volume dwindles greatly; Can adopt the method for evaporative crystallization to handle; Become solid to materials such as the inorganic salt in the waste water, COD, handle by solid waste, thereby reach real wastewater zero discharge.
Evaporation and crystallization system comprises that vaporizer, condensing surface, related process pipeline valve and other indispensable annex (like tubular heat exchange etc.) form.
Evaporative crystallization can adopt economic benefits and social benefits or multiple-effect evaporation crystallization, perhaps MVR evaporative crystallization.Crystalline solid collecting packing, water of condensation are collected one-level product water tank and are proceeded to handle.
(10) secondary rolling r-o-
One-level rolling reverse osmosis produced water (containing the evaporative crystallization water of condensation) can directly carry out reuse if reach reuse standard, if water quality does not reach reuse standard, then carries out secondary rolling reverse-osmosis treated.
The r-o-of secondary rolling is made up of service pump, security personnel's strainer, HPP, secondary coiled reverse osmosis membrane heap and associated conduit valve etc.
One-level rolling reverse osmosis produced water through security personnel's strainer, gets into the two-pass reverse osmosis system through the pressurization of secondary rolling reverse osmosis feedwater pump, under 1～3MPa, one-level rolling reverse osmosis produced water is carried out 5～10 times and concentrates.Softened water tank was proceeded to handle before secondary rolling reverse osmosis concentrated water was back to the r-o-of one-level rolling, produced water and collected the reverse osmosis produced water tank of secondary rolling.
Secondary rolling reverse osmosis produced water general equal can reuse up to standard, produce water and handle through two-pass reverse osmosis, can realize 100% reuse basically.Ultrapure water is still needed and will be proceeded further processing if desired.
Through above (4)～(8) step process, the high salinity trade effluent can be concentrated 36～180 times, and wastewater flow becomes 1/36～1/180 of raw wastewater flow, and volume significantly reduces.Handle through (9) step evaporative crystallization at last, realize " zero release " of trade effluent, simultaneously, the recyclable utilization of the salt that evaporative crystallization obtains.
This high salinity advanced treatment of industrial waste water reuse technology adopts assembled technological, and each technological process of more than describing can be optimized combination according to raw wastewater water quality and water yield situation.
Description of drawings
Figure one is a high salinity advanced treatment of industrial waste water recovering process flow functional diagram.
Embodiment
Below in conjunction with embodiment the present invention is done further explanation.
Embodiment:
1500 tons/day of certain company's chemical industry pharmacy waste waters, comprising 500 tons/day of high-concentration waste waters, 600 tons/day of low concentration wastewaters, 400 tons/day of other waste water.
High-concentration waste water water quality condition: COD
Cr25000 mg/L, B/C=0.2, NH
3-N1500 mg/L, SS 500 mg/L, Cl
-5000 mg/L, total salt quantity 35000 mg/L, petroleum-type 370 mg/L, PH 10.
Low concentration wastewater water quality condition: COD
Cr1000 mg/L, NH
3-N 50 mg/L, SS 200 mg/L, total salt quantity 1500mg/L, PH 7.
After adopting oil removal → coagulating sedimentation → air supporting → hydrolysis → oxidation ditch → ozone oxidation → art breading such as sand filtration, actual water quality condition: 25 ℃ of water temperatures, PH9, CODcr:150mg/L, SS≤50mg/L, NH
3-N<5mgL, Cl
-1830 mg/L, SO
4 2-3050mg/L, total hardness 5.5mmol/L, total dissolved solidss (TDS) 6500mg/L.
Need adopt following art breading to waste water advanced processing back reuse through biochemical treatment at present.
1500 tons/day of total treatment scales, year 330 days working hours, 20 hours working hours every day.
Step (1), tubular fibre membrane ultrafiltration: throughput 110 m
3/ h (water inlet) is divided into three row, design flux 40LMH, pressure 0.25MPa, service rating 11KW.Ultrafiltration goes out the SDI2.8 of water pollution index, and turbidity is less than 0.2NTU, and the ultrafiltration water outlet gets into the ultrafiltration water tank;
Step (2), ion exchange system: be equipped with 3 covers, dual-purpose one is equipped with two series connection during use.Design discharge 90 m
3/ h, design current velocity 17m/h, 48 hours regeneration periods of design.IX column diameter 2600mm, total height 5000mm, resin layer height 1850mm, separate unit resin capacity 10m3.
Adopt acrylic acid series macropore weak acid positive resin D113, ionic forms H type, CEC 10.8 mmol/g, volume-exchange capacity 4.3 mmol/mL; Water cut 50%, wet volume density 0.78 g/mL, wet true density 1.18 g/mL, size range 0.315～1.25mm; >=95%, effective size of grain 0.40～0.70 mm, coefficient of uniformity 1.5; Ooze mill rate of small round spheres 90% behind the mill, transition rate of expansion (H → Na) 65%, light yellow.This resin has excellent anti-oxidant, anti-physical abrasion, anti-chemosmosis and anti-organic contamination ability, and very high operating capacity is arranged, and is widely used in water softening and dealkalize and handles.During this resin work is the H type, uses regeneration of hydrochloric acid.
Get into blowing-type carbonic acid gas decarburization tower through the softening water outlet of weak acid positive resin, after the decarburization, the carbonic acid gas residual volume is no more than 5mg/L in the water.Working temperature: 42 ℃; Spray density 60 m
3/ m
2H, strength ofdraft 3000m
3/ h.
After the process weak acid positive resin was softening, going out water hardness detection was 0 basically.In order to ensure film system non-scaling, being in operation adds the 3.5ppm disodium EDTA as Scale inhibitors.
Step (3); One-level rolling r-o-: be divided into two row; Every row all adopt the 6+3 two-stage structure, and film model PROC-10, PROC-10 are the highest a kind of anti-pollution reverse osmosis membrane elements of ratio of desalinization; The outstanding cleaning performance of anti-highly basic makes that PROC10 still can keep stablizing, excellent performance in the desalination of complicated waste water, even serious organic contamination takes place, still can recover the initial performance of membrane element through matting to greatest extent.
The membrane element specifications and characteristics: nominal ratio of desalinization 99.75%, minimum ratio of desalinization 99.6% is given network of rivers thickness 34mil (0.86mm), effective film area 400ft
2(37m
2), water production rate 10500GPD (39.8m
3/ d).
Advance film pressure 1.8MPa, advance film flow 47 m
3/ h, concentrated stream amount 15 m
3/ h produces discharge 32 m
3/ h produces water TDS less than 320 mg/L, produces water COD 5 mg/L.
Through one-level rolling reverse osmosis system, waste water is concentrated into 3.13 times.
Step (4), middle locating back r-o-: 30+50 two-stage structure, film model DTRO70, single assembly membrane area 9.0 ㎡, salt rejection 99.5%.Advance film pressure 4.2MPa, advance film flow 30 m
3/ h, concentrated stream amount 6 m
3/ h produces discharge 24 m
3/ h produces water TDS 500 mg/L, produces water COD 10 mg/L.
Locating back reverse osmosis system in the process, waste water has been concentrated 5 times again on former spissated basis.
Step (5), high pressure flat plate reverse osmosis: 9+7 two-stage structure, film model DTRO-120, membrane area 9.0 ㎡, salt rejection 99.5%.Advance film pressure 11MPa, advance film flow 6 m
3/ h, concentrated stream amount 2.5 m
3/ h produces discharge 3.5 m
3/ h produces water TDS 820 mg/L, produces water COD 30mg/L.
Through the dull and stereotyped reverse osmosis system of high pressure, waste water is concentrated 2.4 times again on former spissated basis.
Step (6), the dull and stereotyped nanofiltration of high pressure: 4+3 two-stage structure, film model PTNF-120, membrane area 9.0 ㎡.Advance film pressure 9.5MPa, advance film flow 2.5 m
3/ h, concentrated stream amount 1 m
3/ h produces discharge 1.5 m
3/ h produces water TDS 20000 mg/L, produces water COD 1000mg/L, produces water and is back to the reverse osmosis concentrated water tank of one-level rolling, continues to handle.
Through the dull and stereotyped nanofiltration system of high pressure, waste water is concentrated 2.5 times again on former spissated basis.
The final dense water of nanofiltration is used to ash-flushing water and uses.Basically realized wastewater zero discharge.
Through above processing, waste water is by 94 m
3/ h is concentrated to 1 m
3/ h, cycles of concentration reach 94 times.The product water of one-level rolling r-o-, the dull and stereotyped reverse osmosis produced water of middle locating back r-o-one-level high pressure merge, and are used for the recirculated cooling water make up water.
Province, 800 square metres of the total floor spaces of factory building are taken up an area of in above system; Easy and simple to handle, be equipped with the PLC system, can realize unattended operation; Running cost is cheap, comprises power charge, chemical agent expense, personnel's wage, changes film expense, equipment amortization, and overall running cost is no more than 5.20 yuan of/ton water.
Claims (7)
1. high salinity advanced treatment of industrial waste water reuse technology, it is characterized in that: the technical parameter of process step and control is following:
(1) handles early stage
High salt industry waste water at first through conventional physical, chemistry, physical chemistry or/and the method for biological treatment is carried out various necessary processing, make and handle later water-quality COD and the BOD index reaches or near " integrated wastewater discharge standard " (GB8978-1996);
(2) ultrafiltration
Adopt ultra-filtration membrane that trade effluent is carried out pre-filtering, remove and cause reverse osmosis membrane and nf membrane dirty stifled organic colloid, mineral colloid and mikrobe easily, prolong the cleaning interval and the work-ing life of follow-up r-o-and nf membrane system; Tubular fibre submerged membrane assembly is used in ultrafiltration, or uses the pillar hollow fiber film assembly;
(3) IX
Use ion exchange system that feed water by reverse osmosis is softened processing, to prevent the fouling of film;
Ion exchange system is made up of ion exchange column and associated conduit valve, loads ion exchange resin in the ion exchange column.
Said ion exchange resin is used for acrylic weak Zeo-karb or imido oxalic acid type macroporous chelate resin or amido phosphatic type macroporous chelate resin;
(4) one-level rolling r-o-
Waste water after softening and the degassing are handled is pressurizeed by service pump, through security personnel's strainer, gets into one-level rolling reverse osmosis system, under 1～4MPa, the waste water after handling through (1) to (3) step is carried out 3～4 times and concentrates; One-level rolling reverse osmosis concentrated water collects the dense water tank of one-level respectively with product water and one-level is produced water tank; One-level rolling reverse osmosis produced water is up to standard, promptly carries out reuse, and is not up to standard, need proceed the processing of (10) step.
The r-o-of one-level rolling uses brackish water desalination with various coiled reverse osmosis membrane assemblies, or uses sea water desaltination to use the coiled reverse osmosis membrane assembly;
(5) locating back r-o-in
Locating back reverse osmosis system service pump pressurization in the one-level rolling reverse osmosis concentrated water warp, through security personnel's strainer, locating back reverse osmosis system in the entering carries out 3～5 times to one-level rolling reverse osmosis concentrated water and concentrates under 4～7MPa; Softened water tank or the reverse osmosis produced water tank of one-level rolling that middle locating back reverse osmosis produced water is back to before the r-o-of one-level rolling continue to handle, and the reverse osmosis concentrated water tank of locating back was proceeded next step processing during dense water was collected;
(6) high pressure flat plate reverse osmosis
In the dense water of locating back r-o-through the dull and stereotyped reverse osmosis system service pump pressurization of high pressure, through security personnel's strainer, get into the dull and stereotyped reverse osmosis system of high pressure, centering locating back reverse osmosis concentrated water carries out 2～3 times and concentrates under 7～12MPa; The softened water tank that the dull and stereotyped reverse osmosis produced water of high pressure is back to before the r-o-of one-level rolling continues to handle, and the dull and stereotyped reverse osmosis concentrated water of high pressure gets into the dull and stereotyped reverse osmosis concentrated water case of high pressure, carries out next step concentration;
(7) ultra-high voltage flat plate reverse osmosis
The dense water of high pressure flat plate reverse osmosis through security personnel's strainer, gets into ultra-high voltage flat plate reverse osmosis system through the service pump pressurization of ultra-high voltage flat plate reverse osmosis system, under 120～200MPa, the dull and stereotyped reverse osmosis concentrated water of high pressure is carried out 2～3 times and concentrates; The softened water tank that ultra-high voltage flat plate reverse osmosis product water is back to before the r-o-of one-level rolling continues to handle, after the dense water of ultra-high voltage flat plate reverse osmosis concentrates 36～180 times to raw wastewater, and the devaporation crystallization;
(8) the dull and stereotyped nanofiltration of high pressure
Multivalent anions sulfate radical, phosphate content are higher in raw wastewater; It is multivalent anions concentration and univalent anion concentration ratio＞1; The dense water of high pressure flat plate reverse osmosis replaces the ultra-high voltage flat plate reverse osmosis to concentrate with the dull and stereotyped nanofiltration of high pressure, reduces the working pressure of system, reduces running cost;
The dense water of high pressure flat plate reverse osmosis through security personnel's strainer, gets into the dull and stereotyped nanofiltration system of high pressure through the dull and stereotyped nanofiltration system service pump pressurization of high pressure, under 70～120MPa, the dull and stereotyped reverse osmosis concentrated water of high pressure is carried out 2～3 times and concentrates; The reverse osmosis concentrated water tank of middle locating back before water is back to upper level high pressure flat plate reverse osmosis is produced in the dull and stereotyped nanofiltration of high pressure, continues to handle, after dense water concentrates 36～180 times to raw wastewater, and the devaporation crystallization;
(9) evaporative crystallization
Handle through 3～10 reverse osmosis concentration; Waste water is concentrated into 10～180 times; Volume-diminished adopts the method for evaporative crystallization to handle to 1/10～1/180 of original volume, becomes solid to the inorganic salt in the waste water, COD material; Handle by solid waste, thereby reach real wastewater zero discharge;
Evaporative crystallization adopts economic benefits and social benefits or multiple-effect evaporation crystallization, perhaps MVR evaporative crystallization; Crystalline solid collecting packing, water of condensation are collected one-level product water tank and are proceeded to handle;
(10) secondary rolling r-o-
One-level rolling reverse osmosis produced water reaches reuse standard, directly carries out reuse; Water quality does not reach reuse standard, then carries out secondary rolling reverse-osmosis treated;
One-level rolling reverse osmosis produced water through security personnel's strainer, gets into the two-pass reverse osmosis system through the pressurization of secondary rolling reverse osmosis feedwater pump, under 1～3MPa, one-level rolling reverse osmosis produced water is carried out 5～10 times and concentrates; Softened water tank was proceeded to handle before secondary rolling reverse osmosis concentrated water was back to the r-o-of one-level rolling, produced water and collected the reverse osmosis produced water tank of secondary rolling.
2. technology according to claim 1 is characterized in that, the trade mark of described used for acrylic weak Zeo-karb comprises 112, D113, D113FC, D113SC, SQD-80, SQD-85, SQD-88, SQD-112 etc. or be equal to the trade mark.
3. technology according to claim 1 is characterized in that, the trade mark of described imido oxalic acid type macroporous chelate resin or amido phosphatic type macroporous chelate resin comprises D401, D402, D402-II.
4. technology according to claim 1 is characterized in that, degassing tower is set after IX, is used to remove the carbonic acid gas that produces after the IX.
5. technology according to claim 1 is characterized in that, described ion exchange column adopts two-stage series connection.
6. technology according to claim 1 is characterized in that, uses EDTA or its sodium salt Scale inhibitors as r-o-and nanofiltration system, and it is 2 ~ 20ppm that Scale inhibitors adds dose.
7. technology according to claim 1; It is characterized in that; Use two 1; 6-hexylidene triamine five methylenephosphonic acid BHMTPMPA or diethylene triamine pentamethylene phosphonic DTPMPA or ethylenediamine tetramethylene phosphonic acid EDTMPA contain organic phospho acid or its salt of methene phosphate as Scale inhibitors, and it is 2 ~ 20ppm that Scale inhibitors adds dose.
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