CN102145949A - 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 recycle devices and methods therefor of the process hides advanced treatment 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, a large amount of Freshwater resources of the not only annual consumption of tanning industry, also discharged simultaneously a large amount of waste water, the Sustainable development of human health and entire society has been caused serious threat.Therefore should strengthen the treatment of Tannery Wastewater dynamics, carry out leather-making waste water processing and middle water reuse, have important practical significance and strategic importance from saving the Freshwater resources angle still is to say it all is very necessary from environmental angle.
There is organic pollution concentration height in the waste water of tanning industry discharging, problems such as suspended matter is many, the water yield is big, waste water composition complexity, wherein contains toxic substance sulphur and chromium.According to production process, leather-making industrial wastewater is made up 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.The chrome tanning process, the adhesive rate 60%～70% of chromic salts promptly has 30%～40% chromic salts to enter waste water.Chrome tanning degree water Cr3+3000-4000 (mg/L), CODCr10000 (mg/L), BOD52000mg/L.
Traditional leather-making waste water treatment technology is that each operation wastewater collection is mixed, and includes Sewage treatment systems together 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 handled and reclaimed to degreasing waste water, liming hair removal wastewater, Chrome Tanning Wastewater respectively, mix unified the processing then 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 height, oxygen-consumption is big, and the pollution condition of its waste water is very serious, mainly shows the following aspects:
(1) colourity: leather waste water colourity is bigger, 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 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 proteinic degradation production.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 earlier through neutralization precipitation, filter the back and import in the comprehensive wastewater pond;
(5) organic pollutant: organic content such as protein is higher in the leather-making waste water, contains a certain amount of reducing substances again, 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, objectionable impurities 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 that pH, colourity in unit
At present, be used for the method that leather-making waste water administers and mainly contain: coagulant sedimentation, absorption method, advanced oxidation processes, directly loop back usage, air supporting method, add sour 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, several method is used in combination according to the practical situation that will handle waste water.Huang Zhenxiong has introduced Guangdong tannery and has adopted flocculation sediment-activated sludge process-contact oxidation method combination process to handle leather-making waste water, from in December, 2003 treatment effect of going into operation so far stable, when water inlet COD is 3000～3500mg/L, the about 40mg/L of water outlet COD, every effluent index all reaches Guangdong Province's provincial standard (DB44/26-2001) primary standard.Application sequencing batch active sludges (SBR) such as Zhang Jie are handled 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 SBR method biochemical degradation dissolved organic matter again.The design day output is 800m
3, as water inlet 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 that with SBR art breading leather-making waste water, 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 concentrates discharging and the changeable characteristics of water quality relatively.And the investment of SBR treatment process economizes, and the 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 water inlet 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 sub-district 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 handled to water inlet COD.Actual motion shows that 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 technology, handles 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, precipitin reaction taking place with NaOH.Hold concurrently oxygen and aerobic process combined are adopted in biochemical treatment, and the oxygen of holding concurrently adopts contact acidication technology, can improve the biodegradability of waste water, remove portion C OD and SS simultaneously.Aerobic employing CAST technology is the SBR technology of improvement, has characteristics such as organic removal rate height, capacity of resisting impact load are strong.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%, the suspended substance removal rate 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, the energy consumption height.
In sum, the waste water that adopts existing leather-making waste water treatment method to handle 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 handle is called process hides advanced treatment waste water; its discharging is many; water resource waste is big; the cost height; bring secondary pollution easily; so 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; save Freshwater resources, the protection environment.
Summary of the invention
The objective of the invention is at existing investment in fixed assets in the existing leather-making waste water treatment method big, energy consumption is big, the regeneration cost of waste water is higher, reclamation rate is on the low side, 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 the process hides advanced treatment cycling utilization of wastewater devices and methods therefor of waste water reclamation recycle.
Process hides advanced treatment cycling utilization of wastewater device 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 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 dialysis water and condensed water, submerged ultrafiltration filtering separation system is provided with the 2nd stopping valve, the submerged ultrafiltration pond, gas blower, aerator, ultrafiltration membrane system, suction pump and dialyzate basin, described submerged ultrafiltration 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 submerged ultrafiltration pond purifies liquid waste, suction pump is crossed membranous wall from the ultra-filtration membrane inboard with the water negative pressure-pumping, the dialysis water 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 in submerged ultrafiltration pond successively, the 3rd stopping valve connects the dialyzate basin;
Described ultra-filtration membrane cleaning system is used to clean 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 in the submerged ultrafiltration pond of submerged ultrafiltration filtering separation system, the water-in of electrodialysis machine connects the outlet of the 5th stopping valve, the dialysis water out 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 make it satisfy the specification of quality of production technique waters different in the industrial production with being separated into dialysis water (de-salted water) and condensed water through submerged ultrafiltration filtering separation system gained dialysis water through electrodialysis.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 cycling utilization of wastewater method of the present invention adopts described process hides advanced treatment cycling utilization of wastewater device, said method comprising the steps of:
1) nano-catalytic electrolysis: will be after water pump extracts through the process hides advanced treatment waste water of second pond after the biochemical treatment, carry out the nano-catalytic electrolysis in the input nano-catalytic electrolysis machine, enter the setting tank precipitation through valve again, import filtration unit then 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 handling through nano-catalytic electrolytic system system flows into the immersion ultrafiltration system through pipeline and carries out ultrafiltration membrance filter processing, the water of must dialysing.
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), the electrolytic operating voltage of described nano-catalytic 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 electrolysis of process hides advanced treatment waste water is after in the valve inflow setting tank.
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 not enough and be supplemented to 6 ‰～30 ‰.
Described nano-catalytic electrolysis is the oxygen [O] that the electrolysis of process hides advanced treatment waste water process nano-catalytic is made it to generate chlorine [Cl], hydroxyl and the status nascendi of status nascendi, in order to 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), the working conditions of described electrodialysis system can be: 0.5～3.0kg/cm
2, operating voltage 50～250V, strength of current 1～3A.
Dialysis water is used for the 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 too high defective of its cost, it is undesirable to have overcome water treatment effect again, 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 advantage:
1, the rate of recovery of the rate of recovery height of water, the low water of cost 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 water price from the beginning;
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 handled, colourity was less than 8;
3, the traditional biochemical end of total release that reduces waste water COD significantly adds membrane filtration technique, though 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, reduces the total release of waste water COD significantly;
4, the biological pollution of eradicating film can be killed the bacterium in the waste water, and the biological pollution of eradicating film reduces the wash number of film significantly, reduces film cleaning regeneration cost, improves the service efficiency of film, prolongs the work-ing life of film, reduces the film replacement cost;
5, there is not secondary pollution to adopt the nano-catalytic electrolysis tech that the technology of second pond wastewater treatment is substituted the materialization treatment process, need not add 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, reducing mud significantly and adopt the present invention to handle waste water, adopt nano-catalytic electrolysis tech surrogate metallization processes after the second pond water outlet, need not add chemical substances such as flocculation agent, discoloring agent, mud has only 1/2nd of conventional art;
7, take up an area of few technological process of production weak point, compact equipment is taken up an area of few;
8, the high reprocessing cycle water colorless of reuse water quality, tasteless, water quality is far above GB/T19923-2005 " municipal effluent reclaimed wastewater reuse process water water quality " standard;
9, substitute reverse osmosis desalination or nanofiltration desalination with electrodialytic desalting, investment in fixed assets reduces significantly, and energy consumption descends significantly 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 the pollution of microorganism to 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) reduce the colourity of waste water significantly, the colourity of having passed through the process hides advanced treatment waste water of second pond after several different methods such as biochemistry, materialization are handled is 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 waste water between 60～200 through nano-catalytic.(4) organism in the oxygenolysis waste water, residual dye reduces COD fast
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 moves to the negative electrode of electrolysis machine electrolyzer, forms precipitation at negative electrode, thereby reduces the heavy metal ion content in the waste water.
Description of drawings
Fig. 1 is that the structure of process hides advanced treatment cycling utilization of wastewater device embodiment of the present invention is formed synoptic diagram.
Embodiment
The present invention be after the comparative study of composition, character and the existing processing scheme of existing process hides advanced treatment waste water being goed deep into system, finish to the purification of process hides advanced treatment waste water and the design of recycle usefulness technology, it uses by the combination of methods such as nano-catalytic electrolysis, precipitation, filtration, immersion ultrafiltration and electrodialysis, thereby forms a kind of purification and recycle method that is particularly suitable for process hides advanced treatment waste water.
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings.
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 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 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, submerged ultrafiltration 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, and the outlet of stopping valve 21 connects the import in submerged ultrafiltration pond 25, and the outlet in submerged ultrafiltration 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 to clean 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; Dialysis water is used for the 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 the purifying regeneration and the recycle method of the leather-making waste water that adopts process hides advanced treatment wastewater device embodiment shown in Figure 1.
Embodiment 1
The purifying regeneration and the recycle method of 150 ton per day process hides advanced treatment waste water.
Index is as shown in table 1 after measured for described printing and dyeing advanced treatment 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/ |
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 waste water 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, and post precipitation enters solid impurity, planktonic organism, bacterium, the colloid that the submergence ultrafiltration membrane system removes in anhydrating and must purify liquid waste.
The electrolytic operating voltage of described nano-catalytic 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.
Purify liquid waste process stopping valve, working shaft and the water-in of process nano-catalytic electrolysis cells and submerged ultrafiltration filtering separation system purification gained enter and carry out the electrodialytic desalting processing in the electrodialysis machine, be separated into dialysis water and condensed water, dialysis water enters the dialyzate basin through dialysis water out 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 dialysis water and concentrated solution is respectively 7T/h and 1.0T/h, dialysis water is used for the gentle leather and the dyeing process of tanning production, what condensed water was used for tanning production washes skin and liming operation, the Wastewater Recovery rate is 100%, the quality of reuse water is as shown in table 2, and the index that concentrates 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/ |
25 | 6 | pH | 8.5 | |
| 3 | Turbidity | NTU | 2.5 | 7 | Specific conductivity | μS/cm | 3900 |
| 4 | Colourity | 8 |
Embodiment 2
The purifying regeneration and the recycle method of 3000 ton per day process hides advanced treatment waste water.
The described process hides advanced treatment waste water index of process hides advanced treatment of dyeing wastewater after measured 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/ |
11 | 6 | pH | 7.7 | |
| 3 | Turbidity | NTU | 6 | 7 | Specific conductivity | μS/cm | 1100 |
| 4 | Colourity | 60 |
Process hides advanced treatment 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, neutralization precipitation after solid impurity, planktonic organism, bacterium, colloid that ultrafiltration membrane system is removed in anhydrating must purify liquid waste.
Described process hides advanced treatment waste water is because saltiness is lower, add industrial sodium-chlor earlier its saltiness is adjusted to 8.5 ‰, and then carry out the nano-catalytic electrolysis, the electrolytic operating voltage of nano-catalytic 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 dialysis water and condensed water, dialysis water enters the dialyzate basin through dialysis water out 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 dialysis water and condensed water is respectively 105T/h and 45T/h, dialysis water is used for the gentle leather and the dyeing process of tanning production, what condensed water was used for tanning production washes skin and liming operation, the Wastewater Recovery rate is 100%, the quality of reuse water is as shown in table 5, and the index that concentrates 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
The purifying regeneration and the recycle method of 6000 ton per day process hides advanced treatment waste water.
The purifying regeneration of described process hides advanced treatment waste water and recycle 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/ |
22 | 5 | pH | 7.7 | |
| 3 | Turbidity | NTU | 7.4 | 6 | Specific conductivity | μS/cm | 3100 |
Process hides advanced treatment 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 post precipitation must be purified liquid waste through solid impurity, planktonic organism, bacterium, colloid that the submerged ultrafiltration system removes in anhydrating.
Described process hides advanced treatment waste water saltiness is lower, and the electrolytic operating voltage of nano-catalytic 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 dialysis water and condensed water, dialysis water enters the dialyzate basin through dialysis water out 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 dialysis water and condensed water is respectively 255T/h and 45T/h, dialysis water is used for the gentle leather and the dyeing process of tanning production, what condensed water was used for tanning production washes skin and liming operation, the Wastewater Recovery rate is 100%, the quality of reuse water is as shown in table 8, and the index that concentrates 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/ |
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 (10)
1. a process hides advanced treatment cycling utilization of wastewater device 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 dialysis water and condensed water, submerged ultrafiltration filtering separation system is provided with the 2nd stopping valve, the submerged ultrafiltration pond, gas blower, aerator, ultrafiltration membrane system, suction pump and dialyzate basin, described submerged ultrafiltration 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 submerged ultrafiltration pond purifies liquid waste, suction pump is crossed membranous wall from the ultra-filtration membrane inboard with the water negative pressure-pumping, the dialysis water 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 in submerged ultrafiltration pond successively, the 3rd stopping valve connects the dialyzate basin;
Described ultra-filtration membrane cleaning system is used to clean 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 in the submerged ultrafiltration pond of submerged ultrafiltration filtering separation system, the water-in of electrodialysis machine connects the outlet of the 5th stopping valve, the dialysis water out of electrodialysis machine connects the dialyzate basin, and the condensed water outlet of electrodialysis machine connects the condensed water basin.
2. a kind of process hides advanced treatment cycling utilization of wastewater device as claimed in claim 1 is characterized in that described filtration employing sand filtration, multi-medium filtering or micro-filtration.
3. a kind of process hides advanced treatment cycling utilization of wastewater device 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.
4. a kind of process hides advanced treatment cycling utilization of wastewater device 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.
5. a kind of process hides advanced treatment cycling utilization of wastewater device 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.
6. a kind of process hides advanced treatment cycling utilization of wastewater device 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.
7. process hides advanced treatment cycling utilization of wastewater method is characterized in that,
Adopt the cycling utilization of wastewater of process hides advanced treatment according to claim 1 device, said method comprising the steps of:
1) nano-catalytic electrolysis: will be after water pump extracts through the process hides advanced treatment waste water of second pond after the biochemical treatment, carry out the nano-catalytic electrolysis in the input nano-catalytic electrolysis machine, enter the setting tank precipitation through valve again, import filtration unit then 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 handling through nano-catalytic electrolytic system system flows into the immersion ultrafiltration system through pipeline and carries out ultrafiltration membrance filter processing, the water of must dialysing;
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.
8. process hides advanced treatment cycling utilization of wastewater method as claimed in claim 7, it is characterized in that in step 1), the electrolytic operating voltage of described nano-catalytic is 2～250V, adjacent two interelectrode voltages are 2～18V, adjacent two interelectrode optimum voltages are 3～8V, and current density is 10～280mA/cm
2, current density the best is 50～230mA/cm
2, the process electrolysis of process hides advanced treatment waste water is after in the valve inflow setting tank.
9. process hides advanced treatment cycling utilization of wastewater method as claimed in claim 7 is characterized in that in step 2) in, the working conditions of described ultrafiltration membrance filter is: normal temperature～45 ℃, operating pressure 3～50kPa.
10. process hides advanced treatment cycling utilization of wastewater method as claimed in claim 7 is characterized in that in step 3) 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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| 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 |
| CN106349123A (en) * | 2016-08-25 | 2017-01-25 | 江苏德玛膜科技有限公司 | Method for separating taurine 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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| 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 |
| CN106349123A (en) * | 2016-08-25 | 2017-01-25 | 江苏德玛膜科技有限公司 | Method for separating taurine 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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