CN102295378A - Treatment and recycling method of ammonia nitrogen containing high-salt catalyst wastewater - Google Patents
Treatment and recycling method of ammonia nitrogen containing high-salt catalyst wastewater Download PDFInfo
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Abstract
The invention relates to a recycling method for treating ammonia nitrogen containing high-salt catalyst wastewater by adopting a membrane separation technology. The process flow of 'acid regulation, micro-filtration, membrane distillation, cooling and crystallization' is adopted in the method. By adopting the process flow, salts, ammonia nitrogen and metal ions in the wastewater can be effectively removed, and deep treatment and recycle of the ammonia nitrogen containing high-salt catalyst wastewater are realized. The process flow makes full use of the technical advantages of membrane distillation, solves the problem that the discharge of high salts, ammonia nitrogen and metal ions of the ammonia nitrogen containing high-salt catalyst wastewater does not reach the standards, and realizes recycle of the produced water. After the ammonia nitrogen containing high-salt catalyst wastewater is treated by the process flow, the reclamation rate of the wastewater is more than 90 percent, and high recycle of the ammonia nitrogen containing high-salt catalyst wastewater is realized; and the method accords with the development strategies of energy conservation and emission reduction, and has remarkable social benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of advanced treatment and reclamation method that utilizes membrane separation technique to contain the high salt catalyst waste water of ammonia nitrogen, belong to the Industrial Wastewater Treatment field.
Background technology
Ammonium salt and ammoniacal liquor are used in many places in the Catalyst Production process of petrochemical industry, therefore, contain a large amount of ammonia nitrogens in the containing wastewater from catalyst of discharging, and the ammonia nitrogen in the waste water is mainly with ammonium ion (NH
4 +) exist, be the important substance that causes body eutrophication and environmental pollution, cause that easily algae and other microorganisms breed in a large number in the water, oxygen in water is descended, fish kill, even can cause the dry of lake; Ammonia nitrogen also can make in water disinfection and the industrial circulating water germicidal treatment process and increase chlorine dosage; In addition, ammonia nitrogen has corrodibility to some metal (copper), and during reusing sewage, ammonia nitrogen can promote the breeding of microorganism in water pipe and the watering equipment in the reuse water, forms biofouling, blocking pipe and watering equipment, and influence heat exchange efficiency.
The discharging that exceeds standard of ammonia nitrogen directly has influence on the comprehensive up to standard and ordinary production of Catalyst Production enterprise wastewater, becomes the bottleneck of restriction Enterprise's Sustainable Development, the improvement of ammonia nitrogen waste water is become the primary environmental issue of Catalyst Production enterprise.Therefore, researching and developing economic, practical, safe containing wastewater from catalyst ammonia nitrogen treatment process becomes current research focus, significant to protecting the environment to benefit the people.
At present, the improvement of high-concentration ammonia nitrogenous wastewater is mainly taked to add technology such as alkali stripping, electrolytic process, the MAP precipitator method, ion exchange method, break point chlorination both at home and abroad; And the improvement of low-concentration ammonia-nitrogen waste water is mainly contained technology such as absorption method, chemical oxidization method, biochemical process.
Add the primary treatment that the alkali blow-off method is applicable to high-concentration ammonia nitrogenous wastewater, this method and technology maturation, technology and operation are simple, but running cost is higher, and equipment corrosion is more serious, and easily cause air secondary to pollute; Electrolytic process is to utilize electrolysis to produce NaOH and Cl
2, carry out stripping then.Its running cost can be controlled in 3.0 yuan/m
3Water, viable economically, the Cl that electrolysis produces
2Can be used as the product sale or be used for water treatment, but Cl
2Belong to hypertoxic gas, certain danger is arranged, be unfavorable for safety and environment; The MAP precipitator method, ion exchange method, break point chlorination etc. are handled high-concentration ammonia nitrogenous wastewater, have that technological operation is loaded down with trivial details, the processing cycle is short, processing cost is high, easily cause shortcoming such as secondary pollution, are not suitable for heavy industrialization and use.
Absorption method is the N that utilizes in the zeolite
a +Displacement NH
4 +Be applicable to and handle low-concentration ammonia-nitrogen waste water, use the modified natural zeolite adsorption, it is higher to have an adsorption efficiency, equipment volume is little, the characteristics that the equipment one-time investment is little, and for high-concentration ammonia nitrogenous wastewater, because regeneration is frequent, operational administrative is very complicated, current consumption is very big, and the processing cost height is uneconomical economically; Chemical oxidization method is to add the oxygenant with strong oxidizing property matter in ammonia nitrogen waste water, as ozone, hydrogen peroxide/catalyzer, clorox etc., technical process is relative with equipment simple, and speed of response is very fast, but, make processing cost higher because the oxygenant price is more expensive.In addition, these chemical strong oxidizers require acidic conditions usually, and therefore general requirement pH, needs successively to regulate wastewater pH twice with chemical oxidization method less than 2～4, has increased processing cost; At present, the most frequently used method of industrial processing low-concentration ammonia-nitrogen waste water is a biochemical process, it mainly is to adopt a nitrated denitrification principle, processing cost is lower, but influent ammonium concentration generally can not surpass 500mg/L, otherwise will influence normal operation, and ammonia nitrogen in high density itself there is restraining effect to activity and the breeding of microorganism.In addition, biochemical reaction speed is slower, needs long hydraulic detention time usually, thereby needs bigger structures, and floor space is bigger.
The described organic catalyst waste water of this patent also has than supersalinity and a certain amount of metal ion except that containing a certain amount of ammonia nitrogen, and COD
CrLower, be not suitable for adopting chemical oxidation and biochemical process to handle.At present, domestic processing reuse method patent to this specific character containing wastewater from catalyst is less, and existing patent mostly concentrates on the processing discharging up to standard aspect of ammonia nitrogen waste water.Patent CN1123543C relates to the processing recovery method that a kind of catalyzer contains ammonia/ammonium waste water, and key step is: 1) rare ammonia/ammonium waste water of containing concentrates through reverse osmosis membrane, and membrane permeation liquid is directly recycled or as the absorption liquid of steam stripped tower ammonia steam; 2) membrane concentration liquid mixes and adds alkali adjusting pH with the dense ammonia/ammonium waste water that contains; 3) ammonia-containing water after the alkalization enters stripping tower, reclaims ammonia/ammonium wherein, the stripping qualified discharge of purifying waste water.This method is lower slightly than adopting the working cost of blow-off method, vaporizing extract process etc. separately, but it has still adopted vaporizing extract process, and the working cost enterprise of vaporizing extract process still can't accept; In addition, the stripping tower discharge water still contains certain ammonia/ammonium, can not reach emission request, and salts contg is higher in the waste water, can not carry out biochemical treatment, and therefore this method is not promoted and used; Patent CN1872724A relates to the ammonia nitrogen in high density that adopts in the chemical reaction method removal waste water, reclaims ammonium salt, and water outlet is handled qualified discharge by conventional sewage treatment process again; Patent CN101337746A relates to a kind of method that adopts high temperature deamination and stripping deamination process integration to handle high-concentration ammonia nitrogenous wastewater, is applicable to more than the ammonia nitrogen 10000mg/L COD
CrTrade effluent about 20000～30000mg/L, ammonia nitrogen can be reduced to about 300mg/L after treatment, COD
CrAbout 8000～15000mg/L, but processed waste water is through the biochemical treatment qualified discharge; Patent CN101293683A relates to a kind of method that adopts the ammonia in the deamidization stripping high-concentration ammonia nitrogenous wastewater, because deamidization can make NH
3Molecule is broken away from the effect of water molecules, exists with the free ammonia form, and this makes the ammonia nitrogen in the waste water more effectively to be come out by stripping; Patent CN101264948A also relates to a kind of method that adopts ammonia in the stripping removal of ammonia and nitrogen waste water, compares with steam stripping deamination, and this method steam consumption is lower, waste water can satisfy after treatment national grade one discharge standard (＜15mg/L).In addition, patent CN1546393A relates to a kind of method that adopts membrane absorption method to handle high-concentration ammonia nitrogenous wastewater, this method adopts hollow fiber membrane contactors, with the sulphuric acid soln is the ammonia nitrogen waste water that absorption liquid is handled ammonia nitrogen concentration 1000～10000mg/L, and waste water can satisfy national grade one discharge standard after treatment.Though this method has reclaimed the ammonia in the waste water, the waste water after handling only can qualified discharge, can not realize the reuse purpose of water resources, and for the lower waste water of ammonia nitrogen concentration, this method is not too economical and practical.
The content of invention
At the deficiencies in the prior art, the invention provides a kind of advanced treatment and reclamation method that utilizes membrane separation technique to contain the high salt catalyst waste water of ammonia nitrogen, purpose mainly is to remove high salinity, ammonia nitrogen and the little metal ion in the waste water, solve existing high salt and the ammonia nitrogen discharging problem not up to standard that contains the high salt catalyst waste water of ammonia nitrogen, and the recycle-water resource.Adopt the method for this invention, can effectively reduce and contain the high salt catalyst discharged waste water of ammonia nitrogen, produce water and can be back to after production technique water or the simple process, realize the efficient utilization of water resources as the middle low-pressure boiler moisturizing.
The removal method that is different from ammonia nitrogen in the described ammonia nitrogen waste water of above patent the present invention is directed to the high salt of this strand containing wastewater from catalyst, contains the water quality characteristics of ammonia nitrogen and metal ion, and in conjunction with the ammonia nitrogen in the ammonia nitrogen waste water under the low pH mostly with NH
+The characteristic that exists adopts acid adjustment pre-treatment ammonia nitrogen waste water first, adopts micro-filtration+membrane distillation to hold back NH in the waste water afterwards again
+With other yin, yang ions, realized that membrane distillation produces the reuse of water, the dense water of a spot of membrane distillation obtains the crystal of a large amount of ammonium salt crystal and other salt after by crystallisation by cooling, has realized the height recycling of waste water.
At the water quality characteristics that contains the high salt catalyst waste water of ammonia nitrogen, the invention provides a kind of reuse method that adopts membrane separation technique to handle high salinity organic catalyst waste water, adopt the technical process of " acid adjustment+micro-filtration+membrane distillation+crystallisation by cooling ".At first, after will containing the high salt catalyst waste water process of ammonia nitrogen acid adjustment processing, enter turbidity and SS in the microfiltration systems removal waste water, micro-filtration produces water and concentrates through entering the membrane distillation system height after heating, membrane distillation after concentrating through the membrane distillation system produces water and can be back to after production technique water or the simple process as the middle low-pressure boiler moisturizing, the a small amount of dense water of membrane distillation discharging regularly concentrates mummification to dispose, the a small amount of dense water of membrane distillation is separated out crystal after overcooling, crystal centrally disposes after separating drying.Described process flow diagram is seen accompanying drawing 1.
The main water quality characteristic of organic catalyst high salinity waste water of the present invention is: wastewater pH 5～9, electricity is led 5～50mS/cm, COD
Cr0～80mg/L, SS 0～1000mg/L, Ca
2+0～30mg/L, Cu2～200mg/L, Zn 2～50mg/L, NH
4-N 40～400mg/L.
The present invention includes following steps:
(1) acid adjustment.Described wastewater pH is adjusted in 4～6 scopes, makes ammonia nitrogen in the waste water mostly with NH
+Form exists.Described acid solution can adopt hydrochloric acid, sulfuric acid or nitric acid;
(2) micro-filtration.Waste water pump after will handling through step (1) is gone into the removal that microfiltration systems carries out turbidity and suspended substance, the regular spoil disposal of microfiltration systems.
Described microfiltration systems (comprising the immersed microfiltration system) can adopt hollow fiber film assembly, tubular fibre curtain type film assembly, rolled membrane module and tubular membrane component, and optimum is the tubular fibre curtain type film assembly;
The mould material of described micro-filtration membrane module can be polysulfones, polyethersulfone, polyacrylonitrile, polyvinylidene difluoride (PVDF), microporous teflon membran material;
The pore diameter range of described microfiltration membrane is 0.1～1 μ m, and optimum is 0.2～0.4 μ m;
The operation scheme of described micro-filtration assembly can be filtered (comprising external-compression type and inner pressed), the filtration of external-compression type immersion tubular fibre curtain type membrane, rolling and tubular membrane for hollow-fibre membrane and be filtered, and optimum is that external-compression type immersion tubular fibre curtain type membrane filters;
Aerating system is established in bottom, described micro-filtration pond, adopts air compressor to produce pressurized air, and gas-water ratio is 5: 1～15: 1, and optimum is 8: 1～12: 1;
The filtering operational condition of described optimized operation mode external-compression type immersion tubular fibre curtain type membrane is: wastewater pH 4～6, and operating pressure-0.005～-0.02MPa, 15～30 ℃ of temperature.Under this operational condition, the permeation flux of microfiltration membrane is 40～120L/m
2H produces water turbidity and is lower than 0.5NTU;
(3) membrane distillation.The micro-filtration product water that process step (2) is handled enters the membrane distillation concentration systems and carries out the advanced desalination processing, but membrane distillation produces the water reuse, the concentrated mummification disposal of a small amount of dense water of the regular discharging of membrane distillation, and a large amount of dense water of membrane distillation then enter step (3) and handle.
Described membrane distillation concentration systems (comprising submerged membrane distillation concentration systems) can adopt hollow fiber film assembly, curtain type film assembly and plate and frame module, and optimum is a hollow fiber film assembly;
The mould material of described membrane module can be polyvinylidene difluoride (PVDF), tetrafluoroethylene or microporous polypropylene membrane material;
The membrane pore size scope of described membrane distillation is 0.1～0.5 μ m, and optimum is 0.2 μ m;
The operation scheme of described membrane distillation can be swept formula membrane distillation (SGMD) or vacuum membrane distillation (VMD comprises inner pressed or external-compression type) for direct contact type membrane distillation (DCMD), GAP TYPE membrane distillation (AGMD), gas, and optimum is a vacuum membrane distillation;
The thermal source of described membrane distillation system can adopt factory's low-temperature waste heat, exhaust steam heating or electrically heated, in order to cut down the consumption of energy, can make full use of peripheral used heat;
The operational condition of described optimized operation mode vacuum membrane distillation is: wastewater pH 4～6,50～80 ℃ of wastewater temperatures, waste water flow velocity 0.3～1.3m/s, cold side vacuum tightness 0.07～0.095MPa.Under this operational condition, the operating flux scope of membrane distillation is 4～25L/m
2H, ratio of desalinization is higher than 99%, the water rate of recovery 80～95%;
(4) crystallisation by cooling.The dense water of membrane distillation after will concentrating through step (3) enters step (4) and handles, and the salt crystalloid of separating out after handling through step (4) focuses on or reuse, and supernatant liquor then is circulated back to the membrane distillation unit to be continued to concentrate.
Described refrigerant is water or ice cube, and the type of cooling is a small amount of dense water and the tap water water of ice cube (or contain) adverse current cooling indirectly, and cooling back wastewater temperature is 5～15 ℃.
The invention has the beneficial effects as follows:
Described organic catalyst waste water saltiness is higher, and electricity is led generally at 5～50mS/cm, also has a certain amount of ammonia nitrogen and little metal ion, NH
4-N:40～400mg/L, Cu:2～200mg/L, Zn:2～50mg/L, organism is less, and hardness is lower, therefore, can make full use of the high ammonia nitrogen removal frank advantage under the high desalination rate of membrane distillation system, the high water rate of recovery and the acidic conditions, waste water is carried out the height concentration;
The present invention adopts turbidity and the SS in the immersed microfiltration removal waste water, bottom, micro-filtration pond is established aerating system waste water is carried out aeration, quickened the shake of film silk, reduced the pollution on microfiltration membrane surface, problems such as easy obstruction of effective solution film and flux rate of decay are fast have guaranteed the long-term stability operation of microfiltration systems;
Because micro-filtration and membrane distillation system all move, and make that copper, the zinc major part in the waste water exists with ionic species, have reduced the precipitation on film, have reduced the film pollution, guaranteed the long-term stability operation of system under acidic conditions;
Because the salinity in the waste water is relatively more responsive to temperature variation, therefore, remaining at last just has a large amount of salt crystal to separate out after the dense water of membrane distillation that has certain temperature on a small quantity directly cools off;
Adopt method of the present invention, solved a discharging difficult problem that contains the high salt catalyst waste water of ammonia nitrogen basically, make full use of the low grade heat energy of system's periphery, realized containing the height recycling of the high salt catalyst waste water of ammonia nitrogen.
Contain the high salt catalyst waste water of ammonia nitrogen after handling through the inventive method, produce water power and lead≤100 μ S/cm, produce water COD
Cr＜10mg/L, NH
4-N≤5mg/L, the water rate of recovery is higher than 95%, produces water and can be used as after production technique water or the simple process as the middle low-pressure boiler moisturizing.
Description of drawings
Fig. 1 is a base conditioning process flow diagram of the present invention
Embodiment
Below in conjunction with description of drawings of the present invention concrete steps of the present invention.
After described waste water is at first handled by acid adjustment step 1, enter microfiltration systems 2 and carry out the removal of turbidity, suspended substance and a small amount of larger molecular organics, micro-filtration product water concentrates through entering membrane distillation unit 3 after heating afterwards, membrane distillation produce that water is back to the production technique moisturizing or after simple process as the middle low-pressure boiler moisturizing, membrane distillation regularly carries out a small amount of dense row, the a large amount of dense water of membrane distillation then enter step 4 crystallisation by cooling and separate out crystal, and crystal centrally disposes after super-dry.
Certain chemical plant contains the high salt catalyst waste water of ammonia nitrogen, and the main water quality characteristic of waste water is: wastewater pH 8.19, electricity is led 17.6mS/cm, COD
Cr61mg/L, SS 33mg/L, H
2PO
4 -116.1mg/L, Cu 5.3mg/L, Zn 2.12mg/L, Na
+3448.1mg/L, Ca
2+7.8mg/L, NO
3 -12105.7mg/L, Cl
-12.7mg/L, NH
4-N 397.2mg/L.Treatment scheme as shown in Figure 1.
Step 1: adopt hydrochloric acid that wastewater pH is adjusted to about 5 from 8.19, make ammonia nitrogen major part in the waste water with NH
+There is (under 25 ℃, during pH 5, the free ammonia in the liquid phase accounts for total ammonia ratio 0.0056%).
Step 2: waste water after the acid adjustment is pumped into the immersed microfiltration system, and the immersed microfiltration unit adopts external-compression type polyvinylidene difluoride (PVDF) tubular fibre curtain type film assembly.Operational condition is: wastewater pH 5, about 20 ℃ of wastewater temperatures are about operating pressure-0.02MPa.Under this operational condition, the permeation flux of microfiltration membrane is 60～100L/m
2H produces water turbidity and is lower than 0.2NTU;
Step 3: micro-filtration is produced water be heated to and pump into the membrane distillation system behind the specified temp and concentrate, the membrane distillation unit adopts the polyvinylidene difluoride (PVDF) hollow fiber film assembly, and the membrane distillation type adopts the inner pressed vacuum membrane distillation, and promptly the membrane module shell side is a condensation side, vacuum pumping is pending waste water in the membrane fiber hole.Operational condition is: 60 ℃ of waste water Heating temperatures, vacuum tightness-0.089MPa, waste water flow velocity 0.5m/s.Under this operational condition, the product water flux of membrane distillation remains on 5～14L/m substantially
2In the h scope, produce water pH about 5.5～6.5, the product water power is led and is lower than 100 μ S/cm, and ratio of desalinization is higher than 99%, produces water COD
Cr8mg/L, COD clearance about 87% produces water NH
4-N is less than 3mg/L, NH
4-N clearance is higher than 99%, produces water TP less than 0.02mg/L, and the water rate of recovery is higher than 90%.The membrane distillation concentration systems regularly carries out a small amount of dense row;
Step 4: a small amount of dense water of the residue of membrane distillation is carried out crystallisation by cooling handle, about 60 ℃ of inflow temperatures, tap water by the adopting lesser temps tap water of ice cube (or contain) adverse current cooling indirectly, dense water temp is reduced to about 15 ℃, a large amount of salt crystal are separated out, after it is separated drying, collect and centrally dispose, a small amount of supernatant liquor is circulated back to the membrane distillation upgrading unit and continues to handle behind the crystallisation by cooling.
After described waste water was handled through step 1～step 4, the total system water rate of recovery was higher than 90%, had realized containing the height recycling of the high salt catalyst waste water of ammonia nitrogen.
Contain the main water quality characteristic of the high salt catalyst waste water of ammonia nitrogen with embodiment 1.
Step 1: adopt hydrochloric acid that wastewater pH is adjusted to about 6 from 8.19, make ammonia nitrogen major part in the waste water with NH
+There is (under 25 ℃, during pH 6, the free ammonia in the liquid phase accounts for total ammonia ratio 0.0555%).
Step 2: waste water after the acid adjustment is pumped into the immersed microfiltration system, and the immersed microfiltration unit adopts external-compression type polyvinylidene difluoride (PVDF) tubular fibre curtain type film assembly.Operational condition is: wastewater pH 6, about 20 ℃ of wastewater temperatures are about operating pressure-0.02MPa.Under this operational condition, the permeation flux of microfiltration membrane is 60～100L/m
2H produces water turbidity and is lower than 0.2NTU;
Step 3: micro-filtration is produced water be heated to and pump into the membrane distillation system behind the specified temp and concentrate, the membrane distillation unit adopts the polyvinylidene difluoride (PVDF) hollow fiber film assembly, and the membrane distillation type adopts the inner pressed vacuum membrane distillation, and promptly the membrane module shell side is a condensation side, vacuum pumping is pending waste water in the membrane fiber hole.Operational condition is: 60 ℃ of waste water Heating temperatures, vacuum tightness-0.089MPa, waste water flow velocity 0.5m/s.Under this operational condition, the product water flux of membrane distillation remains on 6～15L/m substantially
2In the h scope, produce water pH about 6.2～7, the product water power is led and is lower than 100 μ S/cm, produces water COD
Cr10mg/L produces water NH
4-N is 5mg/L, produces water TP less than 0.02mg/L, and the water rate of recovery is higher than 90%.The membrane distillation concentration systems regularly carries out a small amount of dense row;
Step 4: a small amount of dense water of the residue of membrane distillation is carried out crystallisation by cooling handle, about 60 ℃ of inflow temperatures, tap water by the adopting lesser temps tap water of ice cube (or contain) adverse current cooling indirectly, dense water temp is reduced to about 15 ℃, a large amount of salt crystal are separated out, after it is separated drying, collect and centrally dispose, a small amount of supernatant liquor is circulated back to the membrane distillation upgrading unit and continues to handle behind the crystallisation by cooling.
After described waste water was handled through step 1～step 4, the total system water rate of recovery was higher than 90%, had realized containing the height recycling of the high salt catalyst waste water of ammonia nitrogen.
Certain chemical plant contains the high salt catalyst waste water of ammonia nitrogen, and the main water quality characteristic of waste water is: wastewater pH 8.24, electricity is led 20.9mS/cm, COD
Cr12mg/L, SS 940mg/L, Cu 185mg/L, Zn 45.6mg/L, NO
3 -12122.6mg/L, PO
4 3-(in P) 0.3mg/L, NH
4-N 252mg/L.Treatment scheme as shown in Figure 1.
Step 1: adopt hydrochloric acid that wastewater pH is adjusted to about 5.5 from 8.24, make ammonia nitrogen major part in the waste water with NH
+Exist.
Step 2: waste water after the acid adjustment is pumped into the immersed microfiltration system, and the immersed microfiltration unit adopts external-compression type polyvinylidene difluoride (PVDF) tubular fibre curtain type film assembly.Operational condition is: wastewater pH 5.5, about 20 ℃ of wastewater temperatures are about operating pressure-0.02MPa.Under this operational condition, the permeation flux of microfiltration membrane is 50～80L/m
2H produces water turbidity and is lower than 0.3NTU;
Step 3: micro-filtration is produced water be heated to and pump into the membrane distillation system behind the specified temp and concentrate, the membrane distillation unit adopts the polyvinylidene difluoride (PVDF) hollow fiber film assembly, and the membrane distillation type adopts the inner pressed vacuum membrane distillation, and promptly the membrane module shell side is a condensation side, vacuum pumping is pending waste water in the membrane fiber hole.Operational condition is: 60 ℃ of waste water Heating temperatures, vacuum tightness-0.089MPa, waste water flow velocity 0.5m/s.Under this operational condition, the product water flux of membrane distillation remains on 4～12L/m substantially
2In the h scope, produce water pH about 5.7～6.5, the product water power is led and is lower than 100 μ S/cm, and ratio of desalinization is higher than 99%, produces water COD
CrLess than 5mg/L, produce water NH
4-N is less than 4mg/L, NH
4-N clearance is higher than 98%, and the water rate of recovery is higher than 90%.The membrane distillation concentration systems regularly carries out a small amount of dense row;
Step 4: a small amount of dense water of the residue of membrane distillation is carried out crystallisation by cooling handle, about 60 ℃ of inflow temperatures, tap water by the adopting lesser temps tap water of ice cube (or contain) adverse current cooling indirectly, dense water temp is reduced to about 15 ℃, a large amount of salt crystal are separated out, after it is separated drying, collect and centrally dispose, a small amount of supernatant liquor is circulated back to the membrane distillation upgrading unit and continues to handle behind the crystallisation by cooling.
After described waste water was handled through step 1～step 4, the total system water rate of recovery was higher than 90%, had realized containing the height recycling of the high salt catalyst waste water of ammonia nitrogen.
Contain the main water quality characteristic of the high salt catalyst waste water of ammonia nitrogen with embodiment 3.
Step 1: adopt hydrochloric acid that wastewater pH is adjusted to about 4 from 8.24, make ammonia nitrogen major part in the waste water with NH
+Exist.
Step 2: waste water after the acid adjustment is pumped into the immersed microfiltration system, and the immersed microfiltration unit adopts external-compression type polyvinylidene difluoride (PVDF) tubular fibre curtain type film assembly.Operational condition is: wastewater pH 4, about 20 ℃ of wastewater temperatures are about operating pressure-0.02MPa.Under this operational condition, the permeation flux of microfiltration membrane is 60～90L/m
2H produces water turbidity and is lower than 0.2NTU;
Step 3: micro-filtration is produced water be heated to and pump into the membrane distillation system behind the specified temp and concentrate, the membrane distillation unit adopts the polyvinylidene difluoride (PVDF) hollow fiber film assembly, and the membrane distillation type adopts the inner pressed vacuum membrane distillation, and promptly the membrane module shell side is a condensation side, vacuum pumping is pending waste water in the membrane fiber hole.Operational condition is: 60 ℃ of waste water Heating temperatures, vacuum tightness-0.089MPa, waste water flow velocity 0.5m/s.Under this operational condition, the product water flux of membrane distillation remains on 5～13L/m substantially
2In the h scope, produce water pH about 5～6, the product water power is led and is lower than 80 μ S/cm, produces water COD
CrLess than 5mg/L, produce water NH
4-N is less than 3mg/L, and the water rate of recovery is higher than 90%.The membrane distillation concentration systems regularly carries out a small amount of dense row;
Step 4: a small amount of dense water of the residue of membrane distillation is carried out crystallisation by cooling handle, about 60 ℃ of inflow temperatures, tap water by the adopting lesser temps tap water of ice cube (or contain) adverse current cooling indirectly, dense water temp is reduced to about 15 ℃, a large amount of salt crystal are separated out, after it is separated drying, collect and centrally dispose, a small amount of supernatant liquor is circulated back to the membrane distillation upgrading unit and continues to handle behind the crystallisation by cooling.
After described waste water was handled through step 1～step 4, the total system water rate of recovery was higher than 90%, had realized containing the height recycling of the high salt catalyst waste water of ammonia nitrogen.
Claims (10)
1. reuse method that adopts membrane separation technique to handle high salinity organic catalyst waste water may further comprise the steps:
(1) acid adjustment: described wastewater pH is adjusted in 4～6 scopes;
(2) micro-filtration: the waste water pump after will handling through step (1) is gone into the removal that microfiltration systems carries out turbidity and suspended substance, the regular spoil disposal of microfiltration systems;
(3) membrane distillation: the micro-filtration product water that process step (2) is handled enters the membrane distillation concentration systems and carries out the advanced desalination processing, but membrane distillation produces the water reuse, the a small amount of dense water of membrane distillation discharging regularly concentrates mummification to dispose, and a large amount of dense water of membrane distillation then enter step (3) and handle;
(4) crystallisation by cooling: the dense water of membrane distillation after will concentrating through step (3) enters step (4) and handles, and the salt crystalloid of separating out after handling through step (4) focuses on or reuse, and supernatant liquor then is circulated back to the membrane distillation unit to be continued to concentrate.
2. method according to claim 1, wherein step (1) adopts hydrochloric acid, sulfuric acid or nitre acid for adjusting pH value.
3. method according to claim 1 and 2, wherein the described microfiltration systems of step (2) adopts hollow fiber film assembly, tubular fibre curtain type film assembly, rolled membrane module and tubular membrane component, and optimum is the tubular fibre curtain type film assembly.
4. method according to claim 1 and 2, wherein the mould material of the described microfiltration systems micro-filtration membrane module of step (2) is polysulfones, polyethersulfone, polyacrylonitrile, polyvinylidene difluoride (PVDF), microporous teflon membran material; The pore diameter range of described microfiltration membrane is 0.1～1 μ m, and optimum is 0.2～0.4 μ m.
5. method according to claim 1 and 2, wherein aerating system is established in bottom, micro-filtration pond in the step (2), adopts air compressor to produce pressurized air, and gas-water ratio is 5: 1～15: 1, and optimum is 8: 1～12: 1.
6. method according to claim 1 and 2, wherein step (2) operation scheme is that external-compression type immersion tubular fibre curtain type membrane filters, operational condition is: wastewater pH 4～6, operating pressure-0.005～-0.02MPa, 15～30 ℃ of temperature.
7. method according to claim 1, wherein the described membrane distillation concentration systems of step (3) adopts hollow fiber film assembly, curtain type film assembly and plate and frame module, and optimum is a hollow fiber film assembly.
8. method according to claim 1, wherein the mould material of the described membrane distillation concentration systems of step (3) membrane module is polyvinylidene difluoride (PVDF), tetrafluoroethylene or microporous polypropylene membrane material; The membrane pore size scope of described membrane distillation is 0.1～0.5 μ m, and optimum is 0.2 μ m.
9. method according to claim 1, step (3) operation scheme vacuum membrane distillation wherein, operational condition is: wastewater pH 4～6,50～80 ℃ of wastewater temperatures, waste water flow velocity 0.3～1.3m/s, cold side vacuum tightness 0.07～0.095MPa.
10. method according to claim 1, wherein the refrigerant in the step (4) is water or ice cube, and the type of cooling is a small amount of dense water and the tap water water of ice cube (or contain) adverse current cooling indirectly, and cooling back wastewater temperature is 5～15 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL323756A1 (en) * | 1997-12-11 | 1999-06-21 | Politechnika Szczecinska | Method of purifying aqueous solutions constituting the effluents from ion exchanger regeneration processes and system therefor |
| PL346481A1 (en) * | 2001-03-14 | 2002-09-23 | Politechnika Szczecinska | Method of increasing concentration of salt solutions by membrane distillation combined with crystallisation of salt and system therefor |
| US6649027B1 (en) * | 2000-03-07 | 2003-11-18 | Honeywell International Inc. | Water reclamation system |
| CN1850635A (en) * | 2006-05-24 | 2006-10-25 | 浙江大学 | High-salt epoxy resin production waste-water film integrated salt recovery and biochemical treatment method |
| CN101117258A (en) * | 2007-07-24 | 2008-02-06 | 浙江大学 | Method for treating epoxy resin waste-water with high alkalinity, high salt and high content of organics |
| CN101327407A (en) * | 2007-06-20 | 2008-12-24 | 天津工业大学 | Apparatus and method for evaporating and concentrating liquid |
-
2010
- 2010-06-28 CN CN 201010210974 patent/CN102295378B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL323756A1 (en) * | 1997-12-11 | 1999-06-21 | Politechnika Szczecinska | Method of purifying aqueous solutions constituting the effluents from ion exchanger regeneration processes and system therefor |
| US6649027B1 (en) * | 2000-03-07 | 2003-11-18 | Honeywell International Inc. | Water reclamation system |
| PL346481A1 (en) * | 2001-03-14 | 2002-09-23 | Politechnika Szczecinska | Method of increasing concentration of salt solutions by membrane distillation combined with crystallisation of salt and system therefor |
| CN1850635A (en) * | 2006-05-24 | 2006-10-25 | 浙江大学 | High-salt epoxy resin production waste-water film integrated salt recovery and biochemical treatment method |
| CN101327407A (en) * | 2007-06-20 | 2008-12-24 | 天津工业大学 | Apparatus and method for evaporating and concentrating liquid |
| CN101117258A (en) * | 2007-07-24 | 2008-02-06 | 浙江大学 | Method for treating epoxy resin waste-water with high alkalinity, high salt and high content of organics |
Non-Patent Citations (2)
| Title |
|---|
| > 20091231 张新妙等 膜蒸馏技术在石化废水处理领域的应用进展 第29卷, 第1期 * |
| 张新妙等: "膜蒸馏技术在石化废水处理领域的应用进展", <<化工环保>> * |
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