CN101955282B - Method for realizing zero emission of dyeing wastewater with high salinity in printing and dyeing enterprises - Google Patents
Method for realizing zero emission of dyeing wastewater with high salinity in printing and dyeing enterprises Download PDFInfo
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Abstract
The invention discloses a method for realizing zero emission of dyeing wastewater with high salinity in printing and dyeing enterprises. The method comprises the following steps that: the wastewater enters a regulating reservoir first for homogenizing, and then enters a reaction tank, ferrous sulfate is added into the reaction tank to regulate the pH value and perform a coagulation reaction, effluent enters a sedimentation basin for precipitating after the reaction, supernate of the sedimentation basin is treated by an electrochemical reactor, enters a secondary sedimentation basin so as to remove scummings and dregs and enters an aeration tank for aerating, and the supernate is filtered by a manganese sand filter for deferrization after the aerating; the filtered effluent is treated by using an ultrafiltration membrane, concentrated water of the ultrafiltration membrane returns to the regulating reservoir, and fresh water enters a nanofilter membrane for treating; the fresh water outputted by the nanofilter membrane enters a reverse osmosis membrane, the outputted concentrated water returns to the regulating reservoir or is evaporated directly; and concentrated water of the reverse osmosis membrane enters an electrodialyzer, electrodialytic fresh water is refluxed to be used as inflow of the reverse osmosis membrane, and electrodialytic concentrated water enters an evaporator for evaporating. Vapor generated by evaporating can be used for printing and dyeing production, residues generated by the evaporating are used as solid wastes, and water pollutants are not discharged in the whole process.
Description
Technical field
The invention belongs to the sewage treatment project field, relate to a kind of desalination, reuse of dyeing waste-water, and realize the method for zero release.
Background technology
Textile and dyeing industry is the conventional industries of Chinese national economy, also is China's foreign exchange earning pillar industry.But textile printing and dyeing industry also is the emphasis pollution source of China's industrial water pollution thing simultaneously, and according to State Environmental Protection Administration's statistics, the dyeing waste water total amount of dyeing discharging is positioned at the 5th of each industrial sector total emission volumn of the whole nation, and environmental hazard is very serious.
Dyeing waste water is the general name of each production link waste discharge such as destarch in the dyeing process, boiling-off, dyeing, bleaching, arrangement.The dyeing waste water complicated component, changeable, COD is high, wherein dyeing waste-water is the difficult point of handling in the dyeing waste water.According to not exclusively investigation, the inorganic salt that in dyeing course, use account for 40～70% of printing and dyeing production process, and the dyestuff of discharging accounts for more than 90%.Dyeing waste-water contains multiple organic dye (like dispersed dye, substantive dyestuff, matching stain, glacial dye, reactive dyestuffs, vat dyes etc.); Colourity is high; And heavy metal elements such as nitro and amino-complex and chromium, zinc, arsenic have bigger bio-toxicity in the dye structure, are difficult to degraded.Simultaneously, in dyeing course, need to add a large amount of soda ash, sodium-chlor or Sodium sulfate anhydrous.min(99) (sodium sulfate) as dyeing accelerant and levelling agent, cause the saltiness of waste water very high, the salts contg of general dye vat draining can reach 0.8～4%, has seriously reduced the biodegradability of waste water.Dyestuff is typical bio-refractory material in the dyeing course, and the inorganic salt of high density have not only reduced microbic activity and degradation efficiency in the biological process, and unfavorable to the settlement separate ten minutes of active sludge in the biological process.Traditional dyeing waste water technology is mixed the waste water of other production links such as dyeing waste-water and rinsing, has reduced the colourity and the saltiness of waste water through the method for indirect dilution, carries out end through routine biochemistry-materialization treatment process again and handles.Nonetheless, colourity and COD remain the difficult point of printing and dyeing wastewater to reach standard.Difficult degradation dyestuff and salt are the major reasons that influences the terminal treatment efficiency of sewage.
The source control of pollutent is the key of environmental improvement.The high density dyeing waste-water of dye vat discharging is the key source of dyeing waste water hard-degraded substance in the dyeing course.According to the cleaner production investigation, the inorganic salt of this burst high density dyeing waste-water discharging account for 50～80% of printing and dyeing production process, and the dyestuff of discharging accounts for more than 90%.And inorganic salt and dyestuff are the biochemical unmanageable major reasons of dyeing waste water difficulty.With high density dyeing waste-water individual curing, realize desalination, reuse and zero release, not only can improve the processing benefit of dyeing waste water, also help and improve the treatment efficiency that mixes dyeing waste water.
Evaporation technique is an effective technology of realizing wastewater zero discharge, but evaporative process belongs to phase transition process, and consumption quantity of steam or current consumption are very big, and working cost is high.If to dyeing waste water, perhaps only be the high-concentration waste water direct evaporation of dyeing link, its cost also is difficult to accepted by enterprise.Therefore, how employing new technology, reduce evaporated water, reduce the running cost that wastewater zero discharge is handled, is the key that the dyeing waste-water zero release can practical application.
Summary of the invention
Technical problem to be solved by this invention provides the novel method of the high saliferous dyeing waste-water of a kind of printing and dyeing enterprise zero release.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following:
The method of the high saliferous dyeing waste-water of a kind of printing and dyeing enterprise zero release is at first sent the high density dyeing waste-water into the equalizing tank homogeneous; Get into reaction tank then, add ferrous sulfate 30～5000mg/L and regulate dyeing waste water pH value to 5～9, coagulating takes place; The reaction tank water outlet gets into the settling tank deposition, and waste water scums in settling tank and sediment, and residue effluxes as sludge treatment; The settling tank supernatant is handled through electrochemical reactor, reduces organic concentration and colourity in the waste water, gets into then that second-level settling pond scums and sediment, gets into the aeration tank aeration again, behind the aeration through filtration with manganese sand device iron removal by filtration; Through ultrafiltration membrane treatment, the dense water of ultra-filtration membrane is got back to equalizing tank earlier in water outlet after the filtration, and fresh water gets into nanofiltration membrane treatment; Nf membrane output fresh water gets into reverse osmosis membrane, and output concentrate recirculation to equalizing tank or direct evaporation are handled; The dense water of reverse osmosis membrane gets into electrodialyzer, and electrodialysis fresh water refluxes as the reverse osmosis membrane water inlet, and the dense water of electrodialysis gets into vaporizer and evaporates; The steam that evaporation produces can be back to printing and dyeing and produce, and the residue that evaporation produces is as disposition of solid waste; Discharge water pollutent not in the whole process.
Wherein, described high density dyeing waste-water is the dyeing waste-water of colourity＞500 times, COD＞500mg/L and specific conductivity＞5000 μ s/cm.
Wherein, described electrochemical reactor is pole plate type or three-diemsnional electrode type electric catalysis reactor.
Wherein, described ultra-filtration membrane is hollow-fibre membrane, tubular membrane or flat sheet membrane.
Wherein, described reverse osmosis membrane is a single-stage or multistage.
Wherein, described nf membrane is a single-stage or multistage, and can be the combination of the reverse osmosis membrane of different size.
Beneficial effect: the advance of present method mainly is:
1) utilizes desalination membrane that high slat-containing wastewater is concentrated decrement, reduced evaporated water, greatly reduce the cost of zero release.Through technologies such as r-o-, nanofiltrations, can make the saltiness of density wastewater during bring up to 5～10%, the high slat-containing wastewater amount that gets into vaporizer cuts down 50～95%, thereby greatly reduces the required expense of evaporation.
2) complicated component, waste water that organic concentration is high can cause serious film to pollute, and form the film that is difficult to clean at short notice and stop up, and make film device be difficult to normal operation.Therefore the preconditioning technique of waste water is the difficult point of membrane-concentrated.It is crucial that reduction organic concentration wherein and calcium, iron etc. are prone to cause the material concentration of film fouling.Organic removal method adopts biochemical process or physico-chemical process usually.And high saliniferous dyeing waste-water, because salts contg is high, and the salt concn fluctuation range is big, conventional biochemical treatment can't normally move.General coagulating sedimentation also can't reach removal effect preferably.Present method adopts the electrochemical oxidation organism.More complete to organic oxygenizement, and can some larger molecular organicses be oxidized to the organism than small molecules, reduce the film contamination of heavy.
3) because the salts contg of waste water is high, good conductivity, electrochemical oxidation can be realized higher current density helping the raising of oxidation efficiency under lower voltage.
4) in coagulating agent and the electrochemical oxidation process,, tend to add or discharge a large amount of iron ions removing the organic while.Iron ion is one of principal element that causes the film pollution.Need avoid adding ferruginous medicament before the conventional membrane treatment process, or avoid being provided with the technology that causes iron ion to produce.Though this process using electrochemical oxidation water outlet organic concentration significantly reduces, and can cause producing higher iron ion equally.Pollute for fear of film; The present invention is provided with the filtering method of manganese addition sand behind the aeration, and electrochemical process can be coupled with membrane treatment process, in the best treatment effect of performance; Remove the iron ion in the waste water through filtration with manganese sand, guaranteed the operation life of film device.
5) adopt present method, the fresh water effluent quality of nf membrane and reverse osmosis membrane is good, can be used for dyeing process, realizes reuse completely.The reverse osmosis membrane water outlet can be used for the purposes of hyposaline waters such as agricultural irrigation, landscape water.The water yield of the dense water generates of the dense power and water dialysis of nanofiltration that saltiness is higher is little, and behind the direct evaporation, but the printing and dyeing process steam is made in the steam reuse.Waste water can be realized complete-reclaiming, does not efflux.
6) after printing and dyeing enterprise adopted present method to handle high saliferous dyeing waste-water, the saltiness of residue waste water (comprising destarch, boiling-off, rinsing, back arrangement waste water etc.) reduced by 40～70%, and colourity reduces more than 90%, and difficult degradation COD obviously descends.Therefore, the intractability of residue waste water descends greatly, adopts the simple biochemical treatment can be up to standard.Reduced the processing cost of residue waste water.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
According to following embodiment, can understand the present invention better.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used to explain the present invention, and the present invention that should also can not limit in claims to be described in detail.
Embodiment 1:
Certain printing and dyeing enterprise, workshop sections such as destarch, boiling-off, dyeing, rinsing all produce waste water, and the main dyestuff of wherein dyeing section is reactive dyestuffs, and the main auxiliary agent that adopts is sodium-chlor and sodium hydroxide.In order to reduce the salt concn of waste discharge, reach the farming matter standard (TDS＜1000mg/L), height is contained salt dyeing section waste water individual curing that pours water.The COD 2000mg/L of wherein intaking, 1200 times of colourities, specific conductivity 20000 μ s/cm.
The concrete operations flow process is seen Fig. 1.At first the high density dyeing waste-water is sent into the equalizing tank homogeneous; Get into reaction tank then, add ferrous sulfate 30～5000mg/L and regulate dyeing waste water pH value to 7, coagulating takes place; The reaction tank water outlet gets into the settling tank deposition, and waste water scums in settling tank and sediment, and residue effluxes as sludge treatment; The settling tank supernatant is handled through electrochemical reactor, control current density 50～500A/m
2, electrolysis time 2～50min reduces organic concentration and colourity in the waste water, and the back that scums gets into the aeration tank aeration with the abundant oxidation of ferrous iron in the waste water, passes through filtration with manganese sand device iron removal by filtration behind the aeration; Through ultrafiltration membrane treatment, the dense water of ultra-filtration membrane is got back to equalizing tank earlier in water outlet after the filtration, and fresh water gets into nanofiltration membrane treatment and removes organism and part divalent salts; Nf membrane output fresh water gets into reverse osmosis membrane, and output concentrate recirculation to equalizing tank or direct evaporation are handled; The dense water of reverse osmosis membrane gets into electrodialyzer, and electrodialysis fresh water refluxes as the reverse osmosis membrane water inlet, and the dense water of electrodialysis gets into vaporizer and evaporates; The steam that evaporation produces can be back to printing and dyeing and produce, and the residue that evaporation produces is as disposition of solid waste; Discharge water pollutent not in the whole process.
Wherein, ultra-filtration membrane is to be hollow-fibre membrane, also can be flat sheet membrane or tubular membrane, and mould material can be organically, also can be inorganic.Molecular weight cut-off is 6000～300000.
Wherein, the nf membrane molecular weight cut-off is 100～1000.
Wherein, reverse osmosis membrane can adopt the sea water desaltination film, also can adopt the low pressure reverse osmosis film.The dense water of reverse osmosis membrane gets into electrodialyzer and further concentrates, and the fresh water of r-o-can be used for reuse or farming is irritated.
The removal effect of principal pollutant index is seen table 1.
Table 1 removal effect
Claims (5)
1. the method for the high saliferous dyeing waste-water of printing and dyeing enterprise zero release is characterized in that at first the high density dyeing waste-water being sent into the equalizing tank homogeneous; Get into reaction tank then, add ferrous sulfate 30～5000mg/L and regulate dyeing waste water pH value to 5～9, coagulating takes place; The reaction tank water outlet gets into the settling tank deposition, and waste water scums in settling tank and sediment, and residue effluxes as sludge treatment; The settling tank supernatant is handled through electrochemical reactor, reduces organic concentration and colourity in the waste water, gets into then that second-level settling pond scums and sediment, gets into the aeration tank aeration again, behind the aeration through filtration with manganese sand device iron removal by filtration; Through ultrafiltration membrane treatment, the dense water of ultra-filtration membrane is got back to equalizing tank earlier in water outlet after the filtration, and fresh water gets into nanofiltration membrane treatment; Nf membrane output fresh water gets into reverse osmosis membrane, and output concentrate recirculation to equalizing tank or direct evaporation are handled; The dense water of reverse osmosis membrane gets into electrodialyzer, and electrodialysis fresh water refluxes as the reverse osmosis membrane water inlet, and the dense water of electrodialysis gets into vaporizer and evaporates; The steam that evaporation produces can be back to printing and dyeing and produce, and the residue that evaporation produces is as disposition of solid waste; Discharge water pollutent not in the whole process;
Wherein, described high density dyeing waste-water is the dyeing waste-water of colourity＞500 times, COD＞500mg/L and specific conductivity＞5000 μ s/cm.
2. the method for the high saliferous dyeing waste-water of printing and dyeing enterprise according to claim 1 zero release is characterized in that described electrochemical reactor is pole plate type or three-diemsnional electrode type electric catalysis reactor.
3. the method for the high saliferous dyeing waste-water of printing and dyeing enterprise according to claim 1 zero release is characterized in that described ultra-filtration membrane is hollow-fibre membrane, tubular membrane or flat sheet membrane.
4. the method for the high saliferous dyeing waste-water of printing and dyeing enterprise according to claim 1 zero release is characterized in that described nf membrane is a single-stage or multistage.
5. the method for the high saliferous dyeing waste-water of printing and dyeing enterprise according to claim 1 zero release is characterized in that described reverse osmosis membrane is a single-stage or multistage.
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