CN102145949B - Tanning advanced treatment wastewater recycling device and method - Google Patents
Tanning advanced treatment wastewater recycling device and method Download PDFInfo
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Abstract
A tanning advanced treatment wastewater recycling device and method relate to the treatment of one kind of wastewater. The device is provided with a nanometer catalytic electrolysis system, an immersed ultrafiltration-membrane filtration separation system, an ultrafiltration membrane cleaning system and an electrodialysis system, wherein the nanometer catalytic electrolysis system is provided with a first stop valve, a water pump, a nanometer catalytic electrolysis machine, a setting tank and a filtering device; the immersed ultrafiltration-membrane filtration separation system is provided with a second stop valve, an immersed ultrafiltration membrane pool, a blower, an aerator, an ultrafiltration membrane system, a suction pump and a dialysis fluid storage tank; the ultrafiltration membrane cleaning system is provided with a cleaning solution tank, a backwashing pump, a fourth stop valve and a connection pipe; and the electrodialysis system is provided with a fifth stop valve, an electrodialysis machine, a dialysis fluid storage tank and a condensed water storage tank. The method comprises the following steps: performing nanometer catalytic electrolysis, performing immersed ultrafiltration and finally performing electrodialysis. The method is based on the combination of the nanometer catalytic electrolysis technology, the immersed ultrafiltration technology and the electrodialysis technology; the method has lower cost and higher efficiency; and wastewater can be recycled.
Description
Technical field
The present invention relates to a kind of wastewater treatment, especially relate to a kind of recycling device and method thereof of the process hides advanced treatment of waste water based on nano-catalytic electrolysis tech and electrodialytic technique.
Background technology
According to statistics, China's leather industry reaches more than 10,000 ten thousand t to environmental emission waste water every year, accounts for 0.3% of China's industrial wastewater discharge total amount; Ten thousand yuan of output value blowdown flow rates of leather industry occupy the 3rd at light industry, be only second to papermaking and brewing industry, as seen, tanning industry is a large amount of Freshwater resources of annual consumption not only, also discharged simultaneously a large amount of waste water, the Sustainable development of human health and entire society has been caused serious threat.The management that therefore should strengthen leather-making waste water is carried out leather-making waste water processing and middle water reuse and is sayed it all is very necessary from the fresh-water-saving resource view or from environmental angle, has important practical significance and strategic importance.
There are the problems such as organic pollution concentration is high, suspended matter is many, the water yield is large, waste water complicated in the waste water of tanning industry discharging, wherein contains toxic substance sulphur and chromium.According to production process, leather-making industrial wastewater is comprised of seven parts: the strong basicity depilation liming waste water of the raw hide washing water of high concentration chloride and acidleach water, limy and sodium sulphite, contain chromic blue look Chrome Tanning Wastewater, contain tannin and gallic acid dark brown vegetable tanning waste water, contain grease and saponified degreasing waste water, stuffing dyeing waste-water and each workshop section's flushing waste water thereof.Wherein, with degreasing waste water, depilation liming waste water, Chrome Tanning Wastewater are polluted the most serious.
(1) degreasing waste water: China's pigskin production accounts for 80% of tanning production, and in the degreasing waste water that pigskin is produced, fat content is up to 10000 (mg/L), CODCr20000 (mg/L).Oil wastewater accounts for total waste water 4%, but the oxygen consumption of oil wastewater load accounts for 30%～40% of total load.
(2) dehydration liming waste water: depilation liming waste water is the source of pollution of sulfide.Waste water COD Cr20000～40000 (mg/L), BOD54000 (mg/L), sodium sulphite 1200～1500 (mg/L), pH are 12, depilation liming waste water accounts for 10% of total waste water, and the oxygen consumption load accounts for total load 40%.
(3) Chrome Tanning Wastewater: Chrome Tanning Wastewater is chromic source of pollution.Chrome Tanning Process, the adhesive rate 60%～70% of chromic salts namely has 30%～40% chromic salts to enter waste water.Chrome tanning degree water Cr3+3000-4000 (mg/L), CODCr10000 (mg/L), BOD52000mg/L.
Traditional Tannery Wastewater Treatment Process is that each operation wastewater collection is mixed, and includes together Sewage treatment systems in, but owing to contain a large amount of sulfide and chromium ion in the waste water, very easily to the microorganisms restraining effect.So more reasonably be the operational path [8] of " stoste individual curing, the unified processing of comprehensive wastewater " at present, valuable resource is processed respectively and reclaimed to degreasing waste water, liming hair removal wastewater, Chrome Tanning Wastewater, then mix unified the processing with other waste water.
After each road Waste Water Centralized of tannery, be called organic content and sulfide in the synthetic leather wastewater leather-making waste water, chromium compounds content is high, oxygen-consumption is large, the pollution condition of its waste water is very serious, is mainly manifested in the following aspects:
(1) colourity: leather waste water colourity is larger, is mainly caused by vegetable tanning, dyeing, chrome tanning and grey alkali wasteliquid;
(2) alkalescence: leather waste water is alkalescence generally, and comprehensive wastewater pH value is between 8～12.Its alkalescence mainly comes from lime, caustic soda and the sodium sulphite that the operations such as depilation are used;
(3) sulfide: the sulfide in the leather-making waste water mainly comes from grey alkaline process depilation waste liquor, and small part comes from sulfide and helps soft immersion waste liquid and the degradation production of protein.Sulphur-bearing waste solution is met acid and is easily produced H
2S gas, sulfur-bearing mud under anaerobic also can discharge H
2S gas;
(4) chromium ion: the chromium ion in the leather-making waste water mainly exists with the Cr3+ form, and content is generally at 100～3000mg/L.Normally pass through first neutralization precipitation, import in the comprehensive wastewater pond after filtering;
(5) organic pollutant: the organic content such as protein is higher in the leather-making waste water, contains again a certain amount of reducing substances, so BOD5 and CODCr are very high.
The waste water quality of each workshop section's discharging differs greatly in the process hides process, comprehensive wastewater pH after the waste water of each workshop section's discharging compiles is between 8～12, colourity, CODCr, SS, BOD5 concentration are all very high, the concentration of poisonous and harmful substances and salt is also very high, and leather industry comprehensive wastewater water quality (testing mean) sees table.
| pH | Colourity (doubly) | CODCr | SS | NH 3-N | S 2- | Cr | BOD5 |
| 8～12 | 500～3500 | 3000～4000 | 2000～4000 | 250～300 | 50～100 | 100～3000 | 1500～2000 |
Annotate: all the other are mg/L except pH, colourity in unit
The method of administering for leather-making waste water at present, mainly contains: coagulant sedimentation, absorption method, advanced oxidation processes, direct circulation recycle method, By Bubble-floating Method, acid adding absorption process, catalytic oxidation, biochemical process etc., every kind of method all has various relative merits.Because single treatment process is difficult to be effective, in practice, normally according to the practical situation that will process waste water, several method is combined with.Huang Zhenxiong has introduced Guangdong tannery and has adopted flocculation sediment-activated sludge process-contact oxidation method combination process to process leather-making waste water, from in December, 2003 treatment effect of going into operation so far stable, when influent COD is 3000～3500mg/L, water outlet COD is 40mg/L approximately, and every effluent index all reaches Guangdong Province's provincial standard (DB44/26-2001) primary standard.The application sequencing batch active sludges (SBR) such as Zhang Jie are processed the waste water of Henan tannery.At first adopt physico-chemical process to remove a large amount of toxic substances and partial organic substances in the waste water, pass through again SBR method biochemical degradation dissolved organic matter.The design day output is 800m
3, when influent COD during at 2500mg/L, water outlet COD is about 100mg/L, and (COD＜300mg/L), the running cost of this project is 0.8 yuan/ton far below the GB secondary standard.Operation result shows, uses SBR art breading leather-making waste water, and good to the adaptability of change of water quality, the resistance to overload shock ability is strong, especially is fit to leather-making waste water and relatively concentrates discharging and the changeable characteristics of water quality.And the investment of SBR treatment process economizes, and the more general activated sludge process of running cost is low.Jia Qiupings etc. adopt cavitation air flotation+two section contact oxidation technology, and the waste water disposal facility of Shenyang City tannery is transformed, and not only make the waste water after the processing reach emission request, have improved processing power and effect, and have reclaimed the Cr more than 80%
3+, make the waste water part reuse after the processing.When influent COD 3647mg/L, after this art breading, effluent COD concentration is 77mg/L, is lower than Liaoning Province " DB21-60-89 " new extension secondary standard (COD＜100mg/L).Yang Jianjun, Gao Zhongbai have introduced Xinji City examination big gun battalion process hides residential quarter and have adopted materialization+oxidation ditch process, and original jet-flow aeration Sewage treatment systems is transformed and increase-volume, and the improved processing water yield increases to 4800m
3/ d can be that waste water about 6100mg/L is effectively processed to influent COD.Actual motion shows, the processing efficiency of this reforming technology is higher, and effluent quality reaches country's " integrated wastewater discharge standard " secondary standard.Tao Rujun has introduced tanning industry district, Zhejiang and has adopted coagulating sedimentation+acidication+CAST technique, processes coming from preparation, tanning and other wet comprehensive wastewater of processing workshop section.Design maximum flooding velocity 6000m
3/ d, the sulfonium ion in the waste water be by preaeration, and add FeSO at reaction tank
4With coagulant aids PAC, thereby precipitation is removed Cr
3+Remove by in reaction tank, with NaOH precipitin reaction occuring.Hold concurrently oxygen and the aerobic technique that combines are adopted in biochemical treatment, and the oxygen of holding concurrently adopts contact acidication technique, can improve the biodegradability of waste water, remove simultaneously part COD and SS.Aerobic employing CAST technique has the characteristics such as organic removal rate is high, capacity of resisting impact load is strong for the SBR technique of improvement.The people such as Sun Yabing disclose a kind of method that adopts the electrolysis treatment leather-making waste water at Chinese patent CN100371268C, waste water COD clearance after the processing reaches 60%～80%, ammonia nitrogen removal frank reaches 50%～70%, the sulfide clearance reaches more than 95%, removal efficiency reaches 70%～80%, chroma removal rate reaches more than 85%, colibacillary eradicative rate is reached more than 99%, but, this method exists the anode consumption amount many, and energy consumption is high.
In sum, the waste water that adopts existing leather-making waste water treatment method to process can only reach emission standard, but does not reach trade effluent recycling utilization standard.At this; the second pond waste water that reaches emission standard after adopting existing leather-making waste water treatment method to process is called the process hides advanced treatment of waste water; its discharging is many; water resource waste is large; cost is high; easily bring secondary pollution; therefore be badly in need of that a kind of raw materials consumption is few, waste water after treatment can recycling utilization; and cost is low, the easy process hides advanced treatment wastewater recycling utilization method of operation; be beneficial to reduce the unit product supplies consumption in the leather production; the fresh-water-saving resource, protection of the environment.
Summary of the invention
The object of the invention is to for existing investment in fixed assets in the existing leather-making waste water treatment method large, energy consumption is large, the regeneration cost of waste water is higher, reclamation rate is on the low side, the problems such as waste water resource provide a kind of based on the application that combines with electrodialytic technique of nano-catalytic electrolysis tech, immersion ultra-filtration technique, and cost are lower, usefulness is higher, makes it to reach device for recycling tanning advanced treatment waste water and the method thereof of waste water reclamation recycle.
Device for recycling tanning advanced treatment waste water of the present invention is provided with nano-catalytic electrolytic system, submerged ultrafiltration filtering separation system, ultra-filtration membrane cleaning system and electrodialysis system;
Described nano-catalytic electrolytic system is used for the processing such as nano-catalytic electrolysis, precipitation and filtration, and the nano-catalytic electrolytic system is provided with the 1st stopping valve, water pump, nano-catalytic electrolysis machine, setting tank and filtration unit; The second pond water port of the external leather-making waste water biochemical treatment system of the import of the 1st stopping valve, the import of water pump connects the outlet of the 1st stopping valve, the import of rice catalytic electrolysis machine is admitted in the outlet of water pump, the outlet of nano-catalytic electrolysis machine connects the import of setting tank, and the import of filtration unit connects the outlet of setting tank;
Described submerged ultrafiltration filtering separation system is used for the nano-catalytic electrolytic system gained process hides filtration of purifying liquid waste, separate to get water-dialyzing and condensed water, submerged ultrafiltration filtering separation system is provided with the 2nd stopping valve, immersed ultrafiltration membrane pond, gas blower, aerator, ultrafiltration membrane system, suction pump and dialyzate basin, described immersed ultrafiltration membrane pond is connected with the setting tank outlet of nano-catalytic electrolytic system with the 2nd stopping valve through water inlet pipe, the ultra-filtration membrane of ultrafiltration membrane system is immersed in during process hides in the immersed ultrafiltration membrane pond purifies liquid waste, suction pump is crossed membranous wall from the ultra-filtration membrane inboard with the water negative pressure-pumping, the water-dialyzing that produces is collected the dialyzate basin by suction pump and is used for further must supplying the reuse water of production cocycle utilization through electrodialytic desalting, and suction pump is passed through in the outlet of immersed ultrafiltration membrane pond successively, the 3rd stopping valve connects the dialyzate basin;
Described ultra-filtration membrane cleaning system is used for cleaning the ultrafiltration membrance filter separation system, the ultra-filtration membrane cleaning system is provided with cleaning fluid tank, backwashing pump, the 4th stopping valve and duct coupling, the outlet of cleaning fluid tank connects the import of backwashing pump, the back flushing pump outlet connects the import of the 4th stopping valve, and the outlet of the 4th stopping valve connects the ultrafiltration membrane system of submerged ultrafiltration filtering separation system;
Described electrodialysis system is provided with the 5th stopping valve, electrodialysis machine, dialyzate basin and condensed water basin, the outlet of the 5th stopping valve connects the outlet of the immersed ultrafiltration membrane pond of submerged ultrafiltration filtering separation system, the water-in of electrodialysis machine connects the outlet of the 5th stopping valve, the water-dialyzing outlet of electrodialysis machine connects the dialyzate basin, and the condensed water outlet of electrodialysis machine connects the condensed water basin.
Described filtration can be adopted sand filtration, multi-medium filtering or micro-filtration etc.
Described submerged ultrafiltration filtering system can be removed solid impurity in the waste water, planktonic organism, bacterium, colloid etc., and submerged membrane adopts the open filter design of external pressure, can directly be immersed in the waste water, so the floor space of system is little.Its working conditions is: normal temperature～45 ℃, operating pressure is 3～50kPa.
Described electrodialysis system can adopt pole-reversing electroosmosis system (EDR), liquid film electrodialysis system (EDLM), fills electrodialysis system (EDI), bipolar electrodialysis system (EDMB) or electrodeless water power dialysis system etc.; Described electrodialysis system can with being separated into water-dialyzing (de-salted water) and condensed water through submerged ultrafiltration filtering separation system gained water-dialyzing through electrodialysis, make it satisfy the specification of quality of production technique waters different in the industrial production.Electrodialytic working conditions is 0.5～3.0kg/cm
2, operating voltage 50～250V, strength of current 1～3A.Described electrodialysis system can carry out one section desalination, two sections desalinations or three sections desalinations according to the saltiness in the waste water, thereby makes the saltiness of reuse water satisfy industrial process water requirement, and its ratio of desalinization can reach 45%～80%.
Described electrodialysis system can adopt one section electrodialysis system, two sections electrodialysis systems, three sections electrodialysis systems and four sections electrodialysis systems.
Process hides advanced treatment of waste water circulation utilization method of the present invention adopts described device for recycling tanning advanced treatment waste water, said method comprising the steps of:
1) nano-catalytic electrolysis: will be through the process hides advanced treatment of waste water of second pond after the biochemical treatment after water pump extracts, carry out the nano-catalytic electrolysis in the input nano-catalytic electrolysis machine, enter the setting tank precipitation through valve again, then input filtration unit and filter, remove the solid impurity, planktonic organism, bacterium, the colloid that produce because of the nano-catalytic electrolysis in the waste water and must purify liquid waste.
2) immersion ultra-filtration filters: the purification leather-making waste water after will processing through nano-catalytic electrolytic system system flows into the immersion ultrafiltration system through pipeline and carries out the ultrafiltration membrance filter processing, gets water-dialyzing.
3) electrodialysis: will send into electrodialysis system through water pump through the purification leather-making waste water of immersion ultrafiltration system processing gained, and carry out electrodialytic desalting, and get de-salted water and condensed water.
In step 1) in, the operating voltage of described nano-catalytic electrolysis can be 2～250V, and adjacent two interelectrode voltages can be 2～18V, and adjacent two interelectrode optimum voltages are 3～8V, and current density can be 10～280mA/cm
2, current density the best is 50～230mA/cm
2, the process hides advanced treatment of waste water flows in the setting tank by valve through electrolysis.
The sodium chloride content of described leather-making waste water can be 6 ‰～30 ‰, is preferably 0.6 ‰～1.3 ‰, can add industrial sodium-chlor when sodium chloride content is inadequate and be supplemented to 6 ‰～30 ‰.
Described nano-catalytic electrolysis is the oxygen [O] that the electrolysis of process hides advanced treatment of waste water process nano-catalytic is made it to generate chlorine [Cl], hydroxyl and the status nascendi of status nascendi, in order to the organism in the oxygenolysis waste water and ammonia nitrogen, and kill microorganism in the waste water, simultaneously, under electric field action, make suspended substance, colloid, charged corpuscle cohesion in the waste water form larger particles.
In step 2) in, the working conditions of described ultrafiltration membrance filter can be: normal temperature～45 ℃, operating pressure 3～50kPa.
In step 3) in, the working conditions of described electrodialysis system can be: 0.5～3.0kg/cm
2, operating voltage 50～250V, strength of current 1～3A.
Water-dialyzing is used for gentle leather and the dyeing process of tanning production, and what condensed water was used for tanning production washes skin and liming operation.Therefore, the whole recycling utilization of waste water.
The present invention compares with two embrane method (ultrafiltration+reverse osmosis or ultrafiltration+nanofiltration) treatment processs, both overcome the defective of its high cost, overcome again water treatment effect undesirable, the discharging the contaminated wastewater environment and defective, and can change the rotten manner that is, the change refuse is resource, with existing process hides advanced treatment wastewater and reclaiming recycle, has following outstanding advantages:
1, the rate of recovery that the rate of recovery of water is high, cost hangs down water is up to 85%～100%, and waste discharge is few, and energy consumption is low, and working cost is lower than the cost of the biochemical terminal two membrane filtration treatment technologies of tradition, and ton water (reuse water) cost is far below existing tap water price;
2, the coloring matter in the rapid oxygenolysis waste water of good decolorizing effect, good decolorizing effect.As: the second pond chroma in waste water is 200 o'clock, and after the nano-catalytic electrolysis machine was processed, colourity was less than 8;
3, the biochemical end that the total release of decrease waste water COD is traditional adds membrane filtration technique, although can realize water reuse in the part, but can not reduce the total release of waste water COD, the present invention is the organism in the oxygenolysis waste water rapidly, the total release of decrease waste water COD;
4, the biological pollution of elimination film can be killed the bacterium in the waste water, and the biological pollution of eradicating film significantly reduces the membrane washing number of times, reduces film cleaning regeneration cost, improves the service efficiency of film, in the work-ing life of prolongation film, reduces the film replacement cost;
5, there is not secondary pollution to adopt the nano-catalytic electrolysis tech that the technique of second pond wastewater treatment is substituted the materialization treatment process, need not add the chemical substances such as flocculation agent, discoloring agent and gas floatation agent, not only save cost, and save material consumption and do not produce secondary pollution;
When 6, significantly reduce mud adopts the present invention to process waste water, adopt nano-catalytic electrolysis tech surrogate metallization processes after the second pond water outlet, need not add the chemical substances such as flocculation agent, discoloring agent, mud only has 1/2nd of conventional art;
7, the few technological process of production of occupation of land is short, and compact equipment is taken up an area few;
8, the high reprocessing cycle water colorless of reuse water quality, tasteless, water quality is far above GB/T19923-2005 " reclaimed urban waste water utilizes industry water standard " standard;
9, substitute reverse osmosis desalination or nanofiltration desalination with electrodialytic desalting, investment in fixed assets significantly reduces, and energy consumption significantly descends during the equipment operation.
Adopt the nano-catalytic electrolysis to have following outstanding effect: (1) kills microorganism in the waste water with chlorine [Cl], hydroxyl and the nascent oxygen [O] of the status nascendi that the nano-catalytic electrolysis produces, make in the waste water microorganism live body drop to 30/below the ml, eliminate microorganism to the pollution of mould material.(2) ammonia nitrogen in the oxygenolysis waste water makes the further oxidation of residual ammonia nitrogen, and the decreasing ratio of ammonia nitrogen can reach 60～90%.(3) colourity of decrease waste water, passed through the colourity of the process hides advanced treatment of waste water of second pond after the several different methods such as biochemistry, materialization are processed between 60～200, general treatment process is difficult to further decolouring degree, and electrolysis can be reduced to 1～8 with the colourity of process hides advanced treatment of waste water between 60～200 through nano-catalytic.(4) organism in the oxygenolysis waste water, residual dye fast reducing COD
Cr(5) suspended substance, colloid, charged corpuscle in the waste water condensed form larger particles under electric field action after, remove to such an extent that purify liquid waste through filtering.(6) heavy metal ion in the waste water forms precipitation to the movable cathode of electrolysis machine electrolyzer at negative electrode, thereby reduces the heavy metal ion content in the waste water.
Description of drawings
Fig. 1 is that the structure of device for recycling tanning advanced treatment waste water embodiment of the present invention forms schematic diagram.
Embodiment
The present invention be after the comparative study of composition, character and the existing processing scheme of existing process hides advanced treatment of waste water being goed deep into system, finish to the purification of process hides advanced treatment of waste water and the design of recycle usefulness technique, it uses by the combination of the methods such as nano-catalytic electrolysis, precipitation, filtration, immersion ultrafiltration and electrodialysis, thereby forms a kind of purification and circulation utilization method that is particularly suitable for the process hides advanced treatment of waste water.
The present invention is further illustrated in connection with accompanying drawing for following examples.
Referring to Fig. 1, process hides advanced treatment wastewater device embodiment of the present invention is provided with:
The nano-catalytic electrolytic system: the nano-catalytic electrolytic system is used for the treatment steps such as nano-catalytic electrolysis, precipitation.The nano-catalytic electrolytic system is provided with stopping valve 11, working shaft 12, nano-catalytic electrolysis machine 13, setting tank 14; The external dyeing waste water of the import of stopping valve 11 (second pond) relief outlet, the import of working shaft 12 connects the outlet of stopping valve 11, and the import of rice catalytic electrolysis machine 13 is admitted in the outlet of working shaft 12, and the outlet of nano-catalytic electrolytic cell 13 connects the import of setting tank 14.
Submerged ultrafiltration filtering separation system: submerged ultrafiltration filtering separation system be used for the process hides of nano-catalytic electrolytic system gained purify liquid waste filtration, separate to get dialyzate (water) and concentrated solution; Submerged ultrafiltration filtering separation system is provided with stopping valve 21, ultrafiltration membrane system 22, gas blower 23, aerator 24, immersed ultrafiltration membrane pond 25, suction pump 26, stopping valve 27 and dialyzate (water) basin 28; The outlet of rice catalytic electrolysis system setting tank 14 is admitted in the import of stopping valve 21, the outlet of stopping valve 21 connects the import of immersed ultrafiltration membrane pond 25, and the outlet of immersed ultrafiltration membrane pond 25 enters dialyzate (water) basin 28 through suction pump 26, stopping valve 27 successively.
The ultra-filtration membrane cleaning system: the ultra-filtration membrane cleaning system is used for cleaning the ultrafiltration membrance filter separation system, is provided with cleaning fluid tank 31, backwashing pump 32, stopping valve 33; The outlet of cleaning fluid tank 31 connects the import of backwashing pump 32, and the outlet of backwashing pump 32 connects the import of stopping valve 33, and the outlet of stopping valve 33 connects ultrafiltration membrane system 22.
Electrodialysis system: electrodialysis system is provided with stopping valve 41, working shaft 42, electrodialysis machine 43, dialyzate (water) basin 44, concentrated solution basin 45.The electrodialysis machine is provided with water-in, dialyzate (water) outlet, condensed water outlet.The process hides of immersion ultrafiltration system gained is purified liquid waste and is entered electrodialysis machine 43 by stopping valve 41 and working shaft 42, be separated into dialyzate (water) and concentrated solution through the electrodialysis machine, outlet is stored in dialyzate (water) basin 44 dialyzate (water) through dialyzate (water), and outlet is stored in concentrated solution basin 45 to concentrated solution through condensed water; Water-dialyzing is used for gentle leather and the dyeing process of tanning production, and what condensed water was used for tanning production washes skin and liming operation.
Below provide purifying regeneration and the circulation utilization method of the leather-making waste water that adopts process hides advanced treatment wastewater device embodiment shown in Figure 1.
Embodiment 1
Purifying regeneration and the circulation utilization method of 150 ton per day process hides advanced treatment of waste waters.
Index is as shown in table 1 after measured for described printing and dyeing advanced treatment of waste water.
Table 1
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 130 | 5 | Ammonia nitrogen | mg/L | 3.8 |
| 2 | SS | mg/L | 25 | 6 | Saltiness | ‰ | 7.6 |
| 3 | Turbidity | NTU | 9 | 7 | pH | 8.1 | |
| 4 | Colourity | 80 | 8 | Specific conductivity | μS/cm | 2350 |
After 150 tons of process hides advanced treatment of waste waters are pressed the flow velocity extraction of 7.5T/h through working shaft, in the input nano-catalytic electrolysis machine, the nano-catalytic brine electrolysis directly enters setting tank, enters the immersed ultrafiltration membrane system after the precipitation and must purify liquid waste except solid impurity, planktonic organism, bacterium, colloid in anhydrating.
The operating voltage of described nano-catalytic electrolysis is 8～9V, strength of current is 500～510A, chlorine [Cl], hydroxyl and the nascent oxygen [O] of the status nascendi that the nano-catalytic electrolysis produces, kill the organism in microorganism in the waste water, the oxygenolysis waste water, and after making suspended substance, colloid, charged corpuscle in the waste water under electric field action, form larger particles, system is removed through the submerged ultrafiltration filtering separation, makes purification of waste water, and measuring SDI is 0.9.
Enter through stopping valve, working shaft and water-in through purifying liquid waste of nano-catalytic electrolysis cells and submerged ultrafiltration filtering separation system purification gained and to carry out electrodialytic desalting in the electrodialysis machine and process, be separated into water-dialyzing and condensed water, water-dialyzing enters the dialyzate basin through water-dialyzing outlet and pipeline, and condensed water enters in the condensed water basin through condensed water outlet and pipeline.
Described electrodialysis system is pole-reversing electroosmosis system (EDR), and electrodialytic working conditions is 0.5kg/cm
2, operating voltage 50～250V, strength of current 1～3A.
The flow velocity of described water-dialyzing and concentrated solution is respectively 7T/h and 1.0T/h, water-dialyzing is used for gentle leather and the dyeing process of tanning production, what condensed water was used for tanning production washes skin and liming operation, the rate of recovery of waste water is 100%, the quality of reuse water is as shown in table 2, and the index of concentrated waste water is as shown in table 3.
Table 2
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 19 | 4 | Colourity | 1 | |
| 2 | SS | mg/L | Do not detect | 5 | pH | 6.7 | |
| 3 | Turbidity | NTU | 1.1 | 6 | Specific conductivity | μS/cm | 420 |
Table 3
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 88 | 5 | Saltiness | ‰ | 1.8 |
| 2 | SS | mg/L | 25 | 6 | pH | 8.5 | |
| 3 | Turbidity | NTU | 2.5 | 7 | Specific conductivity | μS/cm | 3900 |
| 4 | Colourity | 8 |
Embodiment 2
Purifying regeneration and the circulation utilization method of 3000 ton per day process hides advanced treatment of waste waters.
The described process hides advanced treatment of waste water after measured index of process hides advanced treatment of dyeing wastewater is as shown in table 4:
Table 4
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 56 | 5 | Saltiness | ‰ | 0.6 |
| 2 | SS | mg/L | 11 | 6 | pH | 7.7 | |
| 3 | Turbidity | NTU | 6 | 7 | Specific conductivity | μS/cm | 1100 |
| 4 | Colourity | 60 |
The process hides advanced treatment of waste water is after working shaft is pressed the extraction of 150T/h flow velocity, in the input nano-catalytic electrolytic cell, the nano-catalytic brine electrolysis directly enters setting tank, and neutralization precipitation must be purified liquid waste except solid impurity, planktonic organism, bacterium, colloid in anhydrating by ultrafiltration membrane system.
Described process hides advanced treatment of waste water is because saltiness is lower, add first industrial sodium-chlor its saltiness is adjusted to 8.5 ‰, and then carry out the nano-catalytic electrolysis, the operating voltage of nano-catalytic electrolysis is 5～6V, strength of current is 1560～1580A, the nano-catalytic electrolysis produces the chlorine [Cl] of status nascendi, hydroxyl and nascent oxygen [O], to kill microorganism in the waste water, organism in the oxygenolysis waste water, and make suspended substance in the waste water, colloid, charged corpuscle forms larger particles under electric field action after, removal is purified liquid waste water through submerged ultrafiltration filtering separation system, and measuring SDI is 1.3.
Carry out the electrodialytic desalting processing through purifying liquid waste of nano-catalytic electrolysis cells and submerged ultrafiltration filtering separation purification unit gained in the electrodialysis machine through entering through stopping valve, working shaft and water-in, be separated into water-dialyzing and condensed water, water-dialyzing enters the dialyzate basin through water-dialyzing outlet and pipeline, and condensed water enters in the condensed water basin through condensed water outlet and pipeline.
Described electrodialysis system is for filling electrodialysis system (EDI), and electrodialytic working conditions is operating voltage 3.0kg/cm
2, operating voltage 150～250V, strength of current 2～3A.
The flow velocity of described water-dialyzing and condensed water is respectively 105T/h and 45T/h, water-dialyzing is used for gentle leather and the dyeing process of tanning production, what condensed water was used for tanning production washes skin and liming operation, the rate of recovery of waste water is 100%, the quality of reuse water is as shown in table 5, and the index of concentrated waste water is as shown in table 6.
Table 5
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 19 | 4 | Colourity | 1 | |
| 2 | SS | mg/L | Do not detect | 5 | pH | 7.1 | |
| 3 | Turbidity | NTU | 1.1 | 6 | Specific conductivity | μS/cm | 359 |
Table 6
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 75 | 4 | Saltiness | ‰ | 15.5 |
| 2 | SS | mg/L | 38 | 5 | pH | 7.9 | |
| 3 | Turbidity | NTU | 2.6 | 6 | Specific conductivity | μS/cm | 3200 |
Embodiment 3
Purifying regeneration and the circulation utilization method of 6000 ton per day process hides advanced treatment of waste waters.
The purifying regeneration of described process hides advanced treatment of waste water and recycling device, the index of the advanced treatment of dyeing wastewater of printing and dyeing after measured is as shown in table 7.
Table 7
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 91 | 4 | Saltiness | ‰ | 0.9 |
| 2 | SS | mg/L | 22 | 5 | pH | 7.7 | |
| 3 | Turbidity | NTU | 7.4 | 6 | Specific conductivity | μS/cm | 3100 |
The process hides advanced treatment of waste water is after working shaft is pressed the extraction of 300T/h flow velocity, in the input nano-catalytic electrolytic cell, the nano-catalytic brine electrolysis directly enters setting tank, and precipitation must be purified liquid waste except solid impurity, planktonic organism, bacterium, colloid in anhydrating by the submerged ultrafiltration system.
Described process hides advanced treatment of waste water saltiness is lower, and the operating voltage of nano-catalytic electrolysis is 12～13V, and strength of current is 3760～3800A.Chlorine [Cl], hydroxyl and the nascent oxygen [O] of the status nascendi that the nano-catalytic electrolysis produces, kill the organism in microorganism in the waste water, the oxygenolysis waste water, and after making suspended substance, colloid, charged corpuscle in the waste water under electric field action, form larger particles, removal is purified liquid waste water through submerged ultrafiltration filtering separation system, and measuring SDI is 1.3.
Carry out the electrodialytic desalting processing through purifying liquid waste of nano-catalytic electrolysis cells and submerged ultrafiltration filtering separation purification unit gained in the electrodialysis machine through entering through stopping valve, working shaft and water-in, be separated into water-dialyzing and condensed water, water-dialyzing enters the dialyzate basin through water-dialyzing outlet and pipeline, and condensed water enters in the condensed water basin through condensed water outlet and pipeline.
Described electrodialysis system is bipolar electrodialysis system (EDMB), and electrodialytic working conditions is operating voltage 2.3kg/cm
2, operating voltage 190～250V, strength of current 2～3A.
The flow velocity of described water-dialyzing and condensed water is respectively 255T/h and 45T/h, water-dialyzing is used for gentle leather and the dyeing process of tanning production, what condensed water was used for tanning production washes skin and liming operation, the rate of recovery of waste water is 100%, the quality of reuse water is as shown in table 8, and the index of concentrated waste water is as shown in table 9.
Table 8
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 21 | 4 | Colourity | 1 | |
| 2 | SS | mg/L | Do not detect | 5 | pH | 7.3 | |
| 3 | Turbidity | NTU | 1.3 | 6 | Specific conductivity | μS/cm | 480 |
Table 9
| Sequence number | Project | Unit | Measured value | Sequence number | Project | Unit | Measured value |
| 1 | COD Cr | mg/L | 96 | 5 | Saltiness | ‰ | 2.7 |
| 2 | SS | mg/L | 15 | 6 | pH | 7.9 | |
| 3 | Turbidity | NTU | 3 | 7 | Specific conductivity | μS/cm | 4500 |
| 4 | Colourity | 8 |
Claims (8)
1. a device for recycling tanning advanced treatment waste water is characterized in that being provided with nano-catalytic electrolytic system, submerged ultrafiltration filtering separation system, ultra-filtration membrane cleaning system and electrodialysis system;
Described nano-catalytic electrolytic system is used for nano-catalytic electrolysis, precipitation and filtration treatment, and the nano-catalytic electrolytic system is provided with the 1st stopping valve, water pump, nano-catalytic electrolysis machine, setting tank and filtration unit; The second pond water port of the external leather-making waste water biochemical treatment system of the import of the 1st stopping valve, the import of water pump connects the outlet of the 1st stopping valve, the import of rice catalytic electrolysis machine is admitted in the outlet of water pump, the outlet of nano-catalytic electrolysis machine connects the import of setting tank, and the import of filtration unit connects the outlet of setting tank;
Described submerged ultrafiltration filtering separation system is used for the nano-catalytic electrolytic system gained process hides filtration of purifying liquid waste, separate to get water-dialyzing and condensed water, submerged ultrafiltration filtering separation system is provided with the 2nd stopping valve, immersed ultrafiltration membrane pond, gas blower, aerator, ultrafiltration membrane system, suction pump and the 1st dialyzate basin, described immersed ultrafiltration membrane pond is connected with the filtration unit outlet of nano-catalytic electrolytic system with the 2nd stopping valve through water inlet pipe, aerator is located at the immersed ultrafiltration membrane pond inner bottom part, the outlet of gas blower is connected with aerator, the ultra-filtration membrane of ultrafiltration membrane system is immersed in during process hides in the immersed ultrafiltration membrane pond purifies liquid waste, suction pump is crossed membranous wall from the ultra-filtration membrane inboard with the water negative pressure-pumping, the water-dialyzing that produces is collected the 1st dialyzate basin by suction pump and is used for further must supplying the reuse water of production cocycle utilization through electrodialytic desalting, and suction pump is passed through in the outlet of immersed ultrafiltration membrane pond successively, the 3rd stopping valve connects the 1st dialyzate basin;
Described ultra-filtration membrane cleaning system is used for cleaning the ultrafiltration membrance filter separation system, the ultra-filtration membrane cleaning system is provided with cleaning fluid tank, backwashing pump, the 4th stopping valve and duct coupling, the outlet of cleaning fluid tank connects the import of backwashing pump, the back flushing pump outlet connects the import of the 4th stopping valve, and the outlet of the 4th stopping valve connects the ultrafiltration membrane system of submerged ultrafiltration filtering separation system;
Described electrodialysis system is provided with the 5th stopping valve, electrodialysis machine, the 2nd dialyzate basin and condensed water basin, the import of the 5th stopping valve connects the outlet of the 1st dialyzate basin, the outlet of the 5th stopping valve connects the water-in of electrodialysis machine, the water-dialyzing outlet of electrodialysis machine connects the 2nd dialyzate basin, and the condensed water outlet of electrodialysis machine connects the condensed water basin.
2. a kind of device for recycling tanning advanced treatment waste water as claimed in claim 1 is characterized in that the working conditions of described submerged ultrafiltration filtering system is: normal temperature～45 ℃, operating pressure is 3～50kPa.
3. a kind of device for recycling tanning advanced treatment waste water as claimed in claim 1 is characterized in that described electrodialysis system adopts pole-reversing electroosmosis system, liquid film electrodialysis system, fills electrodialysis system, bipolar electrodialysis system or electrodeless water power dialysis system.
4. a kind of device for recycling tanning advanced treatment waste water as claimed in claim 1, the working conditions that it is characterized in that described electrodialysis system is 0.5～3.0kg/cm
2, operating voltage 50～250V, strength of current 1～3A.
5. a kind of device for recycling tanning advanced treatment waste water as claimed in claim 1 is characterized in that described electrodialysis system adopts one section electrodialysis system, two sections electrodialysis systems, three sections electrodialysis systems and four sections electrodialysis systems.
6. a process hides advanced treatment of waste water circulation utilization method is characterized in that,
Adopt as claimed in claim 1 device for recycling tanning advanced treatment waste water, said method comprising the steps of:
1) nano-catalytic electrolysis: will be through the process hides advanced treatment of waste water of second pond after the biochemical treatment after water pump extracts, carry out the nano-catalytic electrolysis in the input nano-catalytic electrolysis machine, enter the setting tank precipitation through valve again, then input filtration unit and filter, remove the solid impurity, planktonic organism, bacterium, the colloid that produce because of the nano-catalytic electrolysis in the waste water and must purify liquid waste;
2) immersion ultra-filtration filters: the purification leather-making waste water after will processing through nano-catalytic electrolytic system system flows into submerged ultrafiltration filtering separation system through pipeline and carries out the ultrafiltration membrance filter processing, gets water-dialyzing;
3) electrodialysis: will send into electrodialysis system through water pump through the purification leather-making waste water of submerged ultrafiltration filtering separation system processing gained, and carry out electrodialytic desalting, and get de-salted water and condensed water.
7. process hides advanced treatment of waste water circulation utilization method as claimed in claim 6 is characterized in that in step 2) in, the working conditions of described ultrafiltration membrance filter is: normal temperature～45 ℃, operating pressure 3～50kPa.
8. process hides advanced treatment of waste water circulation utilization method as claimed in claim 6 is characterized in that in step 3), and the working conditions of described electrodialysis system is: 0.5～3.0kg/cm
2, operating voltage 50～250V, strength of current 1～3A.
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| CN102086072B (en) * | 2011-03-11 | 2012-12-26 | 波鹰(厦门)科技有限公司 | Cyclic utilization method of dyeing and printing advanced treatment wastewater |
| CN102674628B (en) * | 2012-05-03 | 2013-08-28 | 波鹰(厦门)科技有限公司 | Sewage treatment and regeneration cyclic utilization device and sewage treatment and regeneration cyclic utilization method |
| CN103387293A (en) * | 2013-05-27 | 2013-11-13 | 三达膜科技（厦门）有限公司 | Reusing method for reclaimed water of leather wastewater |
| CN105645524A (en) * | 2016-01-12 | 2016-06-08 | 波鹰(厦门)科技有限公司 | Oil recovery wastewater biochemical treatment residual COD (chemical oxygen demand) and chroma treatment device and method |
| CN106349123B (en) * | 2016-08-25 | 2018-06-05 | 江苏德玛膜科技有限公司 | A kind of method that taurine is separated in taurine crude product mother solution |
| CN111362496A (en) * | 2020-04-17 | 2020-07-03 | 莱特莱德（北京）环境技术股份有限公司 | Low-energy-consumption membrane-method antibiotic pharmaceutical wastewater recycling system and treatment process thereof |
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| CN101704594A (en) * | 2009-11-27 | 2010-05-12 | 波鹰(厦门)科技有限公司 | Device and method for purifying printing and dyeing advanced treatment wastewater |
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