CN106865850A - Cyanide cadmium wastewater zero emission treatment method - Google Patents
Cyanide cadmium wastewater zero emission treatment method Download PDFInfo
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- CN106865850A CN106865850A CN201510923100.6A CN201510923100A CN106865850A CN 106865850 A CN106865850 A CN 106865850A CN 201510923100 A CN201510923100 A CN 201510923100A CN 106865850 A CN106865850 A CN 106865850A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention discloses a kind of cyanide cadmium wastewater zero emission treatment method, the method includes that purification pretreatment, multi-cycle separation reuse, the pre-concentration of cyanide cadmium waste liquid, the circulation concentration of cyanide cadmium waste liquid and the concentrate of cyanide cadmium waste water are concentrated by evaporation five technique units.The invention also discloses a kind of cyanide cadmium Wastewater zero-discharge treatment system, the system includes raw water box, purification pretreatment system, ultrafiltration water tank, multi-cycle separation reclaiming system, concentration water tank, preconcentration technique, hyperconcetration water tank, circulation concentration systems and evaporation concentration system.Present system cost of investment is low, non-secondary pollution, will not produce sludge, while obtaining relative to 300 times of concentrates of concentrations above of cyanide cadmium waste water as cyanide cadmium liquid reuse, reduces operating cost.It is big that the present invention solves existing cyanide cadmium contaminated wastewater, the wasting of resources, difficult treatment and the problem such as uneconomical, had both saved precious metal resource, and environment is protected again.
Description
Technical field
The invention belongs to field of industrial waste water treatment, it is related to a kind of cyanide cadmium wastewater zero emission treatment method, and in particular to a kind of
Cadmium cyanide plating solution, the method for realizing wastewater zero discharge are reclaimed from cyanide cadmium waste water.
Background technology
Electroplating wastewater is both a kind of pollutant and a kind of valuable resource, due to plating usually using gold, silver, copper, nickel,
The metals such as chromium are raw material, and these metals are all to be worth precious metal very high, if it is useless to process these plating according to method of chemical treatment
Water, it will usually need substantial amounts of chemical agent, while can also produce the substantial amounts of sludge containing heavy metal, these sludge to environment according to
So there is certain pollution, although the waste water after traditional chemical treatment can reach discharge standard, a large amount of precious metals therein
It is disposed off accordingly, causes the waste of these precious metals, increased company's operating cost.For a huge sum of money in electroplating wastewater
Category composition recovery value is high, and deals with the characteristic serious to environmental hazard improperly.Inventor passes through to the various treatment sides of electroplating wastewater
Method repetition test and actual motion, have found it is a kind of it is more economical it is direct single precious metal ion method is reclaimed from rinse bath,
Realize rinse water and metal ion fully recovering and the method that classification processing cycle is utilized is carried out to electroplating washing water, these methods
It is effective to solve copper facing, nickel plating, chromium plating wastewater and recycle, and copper, nickel, chromium recovery problem.Cyanide cadmium waste water
There is very big difference with electroplating wastewater property recited above, cyanide cadmium is carried out under strongly alkaline conditions, therefore in film concentration
During the pH of waste water can be varied from, this can have a huge impact to the performance for concentrating film, for the selection for concentrating film
Also there is certain requirement, the technology for cyanide cadmium cycling utilization of wastewater is not yet reported that at present.Existing cyanide cadmium waste water
The method for the treatment of is exactly mainly to aoxidize the broken cyanide precipitation method, and conventional oxidant has sodium hypochlorite, chlorine dioxide etc., these oxidants
Although abolishing effect preferably to cyanide, reagent cost is high, complex process, investment and operating cost it is not low, and can produce
The substantial amounts of sludge of life, this can also form secondary pollution.Membrane technology is a kind of inexpensive, pollution-free, efficient Wastewater Treatment Technology
Art, at present its in terms of cyanide cadmium wastewater treatment also without reference to the equipment that patent of the present invention is proposed can effectively reclaim cyanogen
Change the plating solution in plating cadmium waste water.
The content of the invention
The purpose of the present invention is directed to the chemically and physically characteristic of above mentioned problem and cyanide cadmium waste water, using specific film process
Technical finesse cyanide cadmium waste water, there is provided the cyanide cadmium wastewater zero emission treatment method of a kind of economical and efficient, from cyanide cadmium
Cadmium plating liquid is reclaimed in waste water and is back to coating bath, while the fresh water that will be produced returns to production line recycle, so as to realize the zero of waste water
Discharge.
The purpose of the present invention can be reached by following measures：
A kind of cyanide cadmium wastewater zero emission treatment method, the method includes purification pretreatment, the circulation point of cyanide cadmium waste water
Five techniques are concentrated by evaporation from reuse, the pre-concentration of cyanide cadmium waste liquid, the circulation concentration of cyanide cadmium waste liquid and concentrate
Unit, specifically includes following steps：
(1) the purification pretreatment of cyanide cadmium waste water：Raw material cyanide cadmium waste water is sequentially passed through into quartz filter, activity
Carbon filter and the first accurate filter are filtered, and the waste water after filtering carries out ultrafiltration by UF ultrafiltration apparatus, complete purification
Pretreatment；
(2) multi-cycle separation reuse：Counter-infiltration is carried out by high-pressure pump injection reverse osmosis unit by purifying pretreated waste water
Separate, respectively obtain pure water and reverse osmosis concentrated water；The pure water feeding cadmium plating potcher for obtaining；Reverse osmosis concentrated water is shunted, a part
Reverse osmosis concentrated water is flowed back and mixes with by the pretreated waste water of purification, and reverse osmosis is carried out again by high-pressure pump injection reverse osmosis unit
Separate thoroughly；Another part reverse osmosis concentrated water enters the pre-concentration of next step cyanide cadmium solution；The counter-infiltration of the reverse osmosis unit
Film uses polyamide composite film；
(3) pre-concentration of cyanide cadmium solution：The part reverse osmosis concentrated water that step (2) is obtained is pumped into the by concentrating supercharging
Two accurate filters, then one section of nanofiltration concentration is carried out by concentrating high-pressure pump one section of nanofiltration device of feeding, respectively obtain one section
Nanofiltration fresh water and one section of nanofiltration concentrate；Pass through the useless of purification pretreatment in the one section of nanofiltration fresh water for wherein obtaining and step (1)
Water mixes, and reverse osmosis unit is injected by high-pressure pump, and separating and recovering treatment is circulated again；One section of nanofiltration device is received
Filter membrane uses polyamide composite film；
(4) the circulation concentration of cyanide cadmium waste liquid：One section of nanofiltration concentrate is pressurized by hyperconcetration and is pumped into the 3rd precision
Filter, then two sections of nanofiltration concentrations are carried out by hyperconcetration high-pressure pump two sections of nanofiltration devices of feeding, respectively obtain two sections of nanofiltrations
Fresh water and two sections of nanofiltration concentrates, two sections of nanofiltration fresh water of gained mix with reverse osmosis concentrated water in step (2), and cyaniding is carried out again
The pre-concentration treatment of cadmium plating waste liquid；One section processed by one section of nanofiltration device in two sections of nanofiltration concentrates and step (3)
Nanofiltration concentrate mixes, and again through the 3rd accurate filter and two sections of nanofiltration devices, the circulation for carrying out two sections of nanofiltration concentrates is dense
Contracting is processed；The NF membrane of two sections of nanofiltration devices uses polyamide composite film；
(5) concentrate is concentrated by evaporation：Concentrate in step (4) after circulating concentration carries out heating evaporation concentration, until
The concentration of cadmium ion reaches 30g/L in concentrate, obtains cyanide cadmium liquid and is back to cyanide cadmium aqueduct.
The method of cyanide cadmium wastewater zero discharge treatment of the present invention also includes cyanide cadmium wastewater collection, including：Adverse current is floated
The cyanide cadmium washings washed, transition pond is entered by collecting, then by elevator pump by the waste water in transition pond
Raw water box is pumped into, follow-up purification pretreatment is carried out.
In step (1), before pretreatment is purified, the booster pump of 0.2~0.5MPa can be used to enter cyanide cadmium waste water
Row supercharging.
In step (1), first by booster pump by waste water by quartz filter and active carbon filter, coarse filtration waste water
In suspension, impurity, organic matter, then carry out refined filtration with the first accurate filter, filter organic matter in waste water, impurity,
The harmful components such as suspension, so as not to these materials enter UF ultrafiltration apparatus, cause UF ultrafiltration apparatus blocking, pollution and
Service life shortening etc..Water by quartz filter, active carbon filter and the first accurate filter purified treatment directly enters
Enter UF ultrafiltration apparatus, carry out super-filtration purifying treatment, milipore filter is a kind of perforated membrane with super " screening " function, can be had
Particulate, colloid, bacterium and polymer organic matter in effect removal waste water, reduce the water quality such as turbidity, COD, TOC and refer to
Mark, makes reverse osmosis membrane obtain more reliable protection.
Quartz filter in step (1) as filter medium, for example, can select the quartz sand conduct of 60 mesh using quartz sand
Filter medium；Active carbon filter is using granular activated carbon as filter medium；The first secondary filter in step (1)
The filter opening of device is at 1~10 μm or so, it is preferred to use 5 μm of accurate filters；Ultrafiltration apparatus can be using the super of 1~20nm of aperture
The milipore filter of filter membrane, particularly 10nm.
In step (2), the pressure of the high-pressure pump is 1.5~2MPa, and the temperature of reverse osmosis unit treatment is 5~45 DEG C,
Reverse osmosis membrane preferably uses BW8040-400 polyamide composite films.
In step (2), mixed with raw material cyanide cadmium waste water by purifying during pretreated ultrafiltration concentrated water returns to raw water box
Close, after the fresh water (i.e. by purifying pretreated waste water) produced by ultrafiltration apparatus enters ultrafiltration water tank, by high pressure infusion
Entering reverse osmosis unit carries out reverse osmosis separation, and isolated pure water enters pure water tank, and being back to use cadmium plating by pure water booster pump floats
Washing trough, reverse osmosis concentrated water enters concentration water tank, carries out follow-up cyanide cadmium solution pre-concentration treatment.Reverse osmosis membrane is optional to be adopted
With the reverse osmosis membrane that aperture is 0.01~1nm, the especially reverse osmosis membrane of 0.1nm.Reverse osmosis membrane can be compound using polyamide
Film, such as BW8040-400 polyamide composite films；The concentration of cadmium ion is cadmium in raw material cyanide cadmium waste water in reverse osmosis concentrated water
2~4 times of the concentration of ion.Reverse osmosis concentrated water is shunted, and a part of reverse osmosis concentrated water backflow is pretreated useless with by purification
Water mixes, and reverse osmosis separation is carried out again by high-pressure pump injection reverse osmosis unit；Another part reverse osmosis concentrated water enters next step
The pre-concentration of cyanide cadmium solution；The reverse osmosis concentrated water of backflow and enter next step cyanide cadmium solution pre-concentration it is reverse osmosis concentrated
The volume ratio of water is 5~15：1~5, preferably 12：1.
In step (3), the pressure of the concentration booster pump is 0.2~0.5MPa, concentrate the pressure of high-pressure pump for 2~
3MPa, the temperature of one section of nanofiltration device treatment is 5~45 DEG C, and the NF membrane of one section of nanofiltration device preferably uses DK8040
Polyamide composite film；In one section of nanofiltration concentrate the concentration of cadmium ion for raw material cyanide cadmium removal of Cadmium from wastewater concentration 4~
8 times.
In step (3), collected in water tank is concentrated by the part reverse osmosis concentrated water after reverse-osmosis treated, increased by concentration
Press pump sends into the second accurate filter, then sends into one section of nanofiltration device by concentration high-pressure pump and separate, and can obtain fresh water and about 4 times
Concentrate.One section of nanofiltration fresh water mixes by the waste water of purification pretreatment with step (1) in ultrafiltration water tank, by high-pressure pump
Injection reverse osmosis unit, is circulated separating and recovering treatment again；One section of nanofiltration concentrate carries out two sections into two sections of nanofiltration devices
Nanofiltration concentration.
The filter opening of the second accurate filter in step (3) is at 1~10 μm or so, it is preferred to use 5 μm of accurate filters；One
The NF membrane of section nanofiltration device can be using the NF membrane of 1~10nm of aperture, the particularly NF membrane of 1nm.One section of nanofiltration device
NF membrane can use polyamide composite film, it is preferred to use DK8040 polyamide composite films.
In step (4), the pressure of the hyperconcetration booster pump is 0.2~0.5MPa, and the pressure of hyperconcetration high-pressure pump is
1.5~3MPa, the temperature of two sections of nanofiltration device treatment is 5~45 DEG C, and two sections of NF membranes of nanofiltration device preferably use DK8040
Polyamide composite film；The concentration of cadmium ion can reach the concentration of raw material cyanide cadmium removal of Cadmium from wastewater in two sections of nanofiltration concentrates
200 times and more than.
In step (4), after one section of nanofiltration concentrate enters hyperconcetration water tank, it is pressurized using hyperconcetration booster pump, by the
Three accurate filters are filtered, and remove issuable molecule in circulation；Feeding two is injected after filtering with hyperconcetration high-pressure pump again
Section nanofiltration device carries out two sections of nanofiltration concentrations, and two sections of nanofiltration fresh water return to concentration water tank with reverse osmosis concentrated water in step (3)
Mixing, again through the second accurate filter and one section of nanofiltration device, carries out the pre-concentration treatment of cyanide cadmium waste liquid again；Two
It is mixed by one section of nanofiltration concentrate of one section of nanofiltration device treatment with step (3) that section nanofiltration concentrate enters hyperconcetration water tank
Close, again through the 3rd accurate filter and two sections of nanofiltration devices, carry out two sections of circulation concentrations of nanofiltration concentrate.When two
The operating pressure of section nanofiltration device reaches 2.5MPa, or the water outlet of two sections of nanofiltration devices when not producing fresh water substantially, and now two
The concentration of the cadmium ion of section nanofiltration concentrate can reach 200 times of concentration of raw material cyanide cadmium removal of Cadmium from wastewater and more than, will
Two sections of nanofiltration concentrates are evaporated concentration；
The 3rd accurate filter filter opening in step (4) is at 1~10 μm or so, it is preferred to use 5 μm of accurate filters；Two sections
The NF membrane of nanofiltration device is preferably using the NF membrane of aperture 1-2nm.Two sections of NF membranes of nanofiltration device can be compound using polyamide
Film, it is preferred to use DK8040 polyamide composite films, DK8040 polyamide composite films have certain resistant to high pH performance.
In step (5), the concentrate after circulating concentration is in multi-effect evaporator, single effect evaporator or easy heating
Heating evaporation concentration is carried out in groove, by the way that after evaporation and concentration, the concentration of cadmium ion can reach raw material in 30~40g/L in solution
300 times of the concentration of cyanide cadmium removal of Cadmium from wastewater and more than.
Present invention also offers a kind of cyanide cadmium Wastewater zero-discharge treatment system, the system includes raw water box, purification pretreatment
System, ultrafiltration water tank, multi-cycle separation reclaiming system, concentration water tank, preconcentration technique, hyperconcetration water tank, circulation hyperconcetration
System and evaporation concentration system, the purification pretreatment system include the booster pump, quartz filter, the activity that are sequentially connected
Carbon filter, the first accurate filter and UF ultrafiltration apparatus, the multi-cycle separation reclaiming system include the high-pressure pump being sequentially connected
And reverse osmosis unit, the preconcentration technique include be sequentially connected concentration booster pump, the second accurate filter, concentration high-pressure pump
With one section of nanofiltration device, it is hyperconcetration booster pump that the circulation hyperconcetration system includes being sequentially connected, the 3rd accurate filter, super
Concentration high-pressure pump and two sections of nanofiltration devices；The evaporation concentration system includes that the evaporation concentration device being sequentially connected, dope reuse increase
Press pump；The outlet of the raw water box is connected with the entrance of the purification pretreatment system, and the UF of the purification pretreatment system surpasses
The concentrated water outlet for filtering device is connected with an entrance of raw water box, and the water outlet of ultrafiltration apparatus connects with an entrance of ultrafiltration water tank
Connect；The outlet of the ultrafiltration water tank is connected with the entrance of the multi-cycle separation reclaiming system；In the multi-cycle separation reclaiming system
The water outlet of reverse osmosis unit is connected with the entrance of pure water tank, and the outlet of the pure water tank is through pure water booster pump and cadmium plating potcher
Entrance connection；An entrance of the concentrated water outlet of reverse osmosis unit through pipeline in parallel respectively with ultrafiltration water tank, concentration water tank connects
Connect；The outlet of the concentration water tank is connected with the entrance of the preconcentration technique, one section of nanofiltration device of the preconcentration technique
Water outlet be connected with another entrance of ultrafiltration water tank, one of one section of concentrated solution outlet of nanofiltration device and hyperconcetration water tank
Entrance is connected；The outlet of the hyperconcetration water tank is connected with the entrance of the circulation hyperconcetration system, the circulation hyperconcetration system
The concentrated waters outlet of two sections of nanofiltration devices is connected with another entrance of hyperconcetration water tank in system, two sections of water outlets of nanofiltration device and
Another entrance for concentrating water tank connects；Branch road is provided with the outlet of the hyperconcetration water tank to connect with the entrance of the evaporation concentration system
Connect, the outlet of the evaporation concentration system is connected with the import of cyanide cadmium coating bath.
Preferably, the cyanide cadmium Wastewater zero-discharge treatment system also includes cyanide cadmium wastewater collection system, the cyaniding
Cadmium plating wastewater collection system includes wastewater collection pipeline and elevator pump, and the entrance in the transition pond floats through collecting and cadmium plating
The outlet connection of washing trough, the boosted pump of outlet in transition pond is connected with another entrance of raw water box.
Preferably, in the concentrated water outlet for connecting the reverse osmosis unit and the pipeline of ultrafiltration water tank, be connected the reverse osmosis unit
Concentrated water is exported and is respectively equipped with valve with the pipeline for concentrating water tank.
Preferably, connect the pipeline of the hyperconcetration water tank and the 3rd accurate filter, be connected hyperconcetration water tank with evaporation and concentration system
The branch road of system constitutes parallel pipeline.Connect the hyperconcetration water tank with the pipeline of the 3rd accurate filter, be connected hyperconcetration water
Control valve is respectively equipped with for controlling the flow direction of concentrate in hyperconcetration water tank on case and the branch road of evaporation concentration system.
Preferably, the evaporation concentration device is multi-effect evaporator, single effect evaporator or easy heating tank.
Preferably, being respectively provided with the raw water box, ultrafiltration water tank, concentration water tank, pure water tank and hyperconcetration water tank carries out height
The liquid level meter of low water level control, the liquid level meter in the raw water box, ultrafiltration water tank, pure water tank is respectively used to control supercharging
Pump, high-pressure pump, the startup and stopping of pure water booster pump, the liquid level meter in the concentration water tank are used to control concentration supercharging
The startup and stopping of pump, concentration high-pressure pump, the liquid level meter in the hyperconcetration water tank are used to control hyperconcetration booster pump and surpass
Concentrate the startup and stopping of high-pressure pump.
It is of the invention comprehensive using the " circulation of wastewater collection+waste water filtering purification+multi-cycle separation reuse+Waste water concentrating treatment+solution
The technology of concentration+be concentrated by evaporation ", realizes purification, separation, the reuse to cyanide cadmium waste water, while to cyaniding therein
Cadmium plating liquid realizes concentration, reuse.The method economy of waste water recycling, cyanide cadmium liquid recovering effect is good, low cost, while solution
Cyanide cadmium cost for wastewater treatment of having determined is high, heavy-polluted shortcoming.
It is characteristic of the invention that：The rinsing of plating piece is carried out by the method for countercurrent rinsing, it is ensured that subsequent treatment facility is in preferable water
Run under the conditions of matter, then by the relatively low raw material cyanide cadmium waste water of concentration by counter-infiltration system, the pure water of generation is back to plating
Cadmium potcher, and by the certain multiple of Waste water concentrating, recycle one section of nanofiltration system further to be concentrated to waste water, reuse
Two sections of nanofiltration systems are circulated to concentrate and concentrated, and finally reuse evaporation concentration device and concentration is evaporated to concentrate, until reaching
To expected concentration (concentration of cadmium ion is in 30~40g/L in cyanide cadmium plating solution).In this process without any secondary pollution
Thing is introduced, and the equipment used in the concentration process is the conventional equipment of electroplating enterprise, is put into without extras and man-hour, is reduced
Operation cost.The present invention with the mode of the original cyanide cadmium wastewater treatment of electroplating industry compared with, with equipment it is simple, put into
Less and operation cost is low, technical process is simple, it is easy to operate, pollute small and the concentrate after concentration can be back to coating bath etc.
Feature.
Beneficial effects of the present invention：
1st, the present invention uses the isolated pure water of polyamide composite reverse osmosis membrane and reverse osmosis concentrated water, pure water to return to production line circulation
Use, then part reverse osmosis concentrated water is flowed back and is mixed with by the pretreated waste water of purification, it is compound anti-using polyamide again
Permeable membrane carries out reverse osmosis separation, and another part reverse osmosis concentrated water is concentrated using polyamide composite nanofiltration membrane, produced by nanofiltration
Concentrate further circulation concentration is carried out to it using polyamide composite nanofiltration membrane, then be evaporated by evaporation concentration system dense
Contracting, can obtain relative to 300 times of concentrates of concentrations above of raw material cyanide cadmium waste water.The backflow of reverse osmosis concentrated water is set to be increased
The pure water recovery rate of whole system, the rate of recovery can reach more than 60%~80%, or even 90%.
2 compare with existing chemical treatment method, the method have the advantages that：
1) cost of investment is lower, and the equipment that the present invention is used invests less for method of chemical treatment；In addition, rinsing system
The substantial amounts of pure water of system needs carries out the rinsing of plating piece, and the system can realize the circulation-supplied of pure water, save cost.
2) method of chemical treatment can produce secondary pollution, it will usually produce substantial amounts of mud, processing cost increases, and the inventive method
Secondary pollution will not be produced, sludge will not be also produced.
3) cyanide cadmium Waste water concentrating into cyanide cadmium liquid can both have been saved precious metal resource by the present invention, be protected again
Environment.
Brief description of the drawings
Fig. 1 is system of the invention and schematic flow sheet.
Specific embodiment
Specific embodiment is further illustrated below in conjunction with drawings and Examples：
As shown in figure 1, a kind of cyanide cadmium Wastewater zero-discharge treatment system, the system includes raw water box, purification pretreatment system
System, ultrafiltration water tank, multi-cycle separation reclaiming system, concentration water tank, preconcentration technique, hyperconcetration water tank, circulation hyperconcetration system
System and evaporation concentration system, the purification pretreatment system include the booster pump, quartz filter, the activated carbon that are sequentially connected
Filter, the first accurate filter and UF ultrafiltration apparatus, the multi-cycle separation reclaiming system include the high-pressure pump that is sequentially connected and
Reverse osmosis unit, the preconcentration technique include be sequentially connected concentration booster pump, the second accurate filter, concentration high-pressure pump and
One section of nanofiltration device, it is hyperconcetration booster pump that the circulation hyperconcetration system includes being sequentially connected, the 3rd accurate filter, super dense
Contracting high-pressure pump and two sections of nanofiltration devices；The evaporation concentration system includes the evaporation concentration device, the dope reuse supercharging that are sequentially connected
Pump；The outlet of the raw water box is connected with the entrance of the purification pretreatment system, the UF ultrafiltration of the purification pretreatment system
The concentrated water outlet of device is connected with an entrance of raw water box, and the water outlet of ultrafiltration apparatus connects with an entrance of ultrafiltration water tank
Connect；The outlet of the ultrafiltration water tank is connected with the entrance of the multi-cycle separation reclaiming system；In the multi-cycle separation reclaiming system
The water outlet of reverse osmosis unit is connected with the entrance of pure water tank, and the outlet of the pure water tank is through pure water booster pump and cadmium plating potcher
Entrance connection；An entrance of the concentrated water outlet of reverse osmosis unit through pipeline in parallel respectively with ultrafiltration water tank, concentration water tank connects
Connect；The outlet of the concentration water tank is connected with the entrance of the preconcentration technique, one section of nanofiltration device of the preconcentration technique
Water outlet be connected with another entrance of ultrafiltration water tank, one of one section of concentrated solution outlet of nanofiltration device and hyperconcetration water tank
Entrance is connected；The outlet of the hyperconcetration water tank is connected with the entrance of the circulation hyperconcetration system, the circulation hyperconcetration system
The concentrated waters outlet of two sections of nanofiltration devices is connected with another entrance of hyperconcetration water tank in system, two sections of water outlets of nanofiltration device and
Another entrance for concentrating water tank connects；Branch road is provided with the outlet of the hyperconcetration water tank to connect with the entrance of the evaporation concentration system
Connect, the outlet of the evaporation concentration system is connected with the import of cyanide cadmium coating bath.
The cyanide cadmium Wastewater zero-discharge treatment system also includes cyanide cadmium wastewater collection system, the cyanide cadmium waste water
Collection system includes wastewater collection pipeline and elevator pump, and the entrance in the transition pond goes out through collecting and cadmium plating potcher
Mouth connection, the boosted pump of outlet in transition pond is connected with another entrance of raw water box.
In the concentrated water outlet for connecting the reverse osmosis unit and the pipeline of ultrafiltration water tank, it is connected the concentrated water outlet of the reverse osmosis unit
Valve is respectively equipped with the pipeline of concentration water tank.
The pipeline for connecting the hyperconcetration water tank and the 3rd accurate filter is, the branch road for being connected hyperconcetration water tank and evaporation concentration system
Constitute parallel pipeline.Connect the hyperconcetration water tank with the pipeline of the 3rd accurate filter, be connected hyperconcetration water tank and evaporates
Control valve is respectively equipped with the branch road of concentration systems is used to control the flow direction of concentrate in hyperconcetration water tank.
The evaporation concentration device is easy evaporator tank, and steam-heated pipe line is housed in evaporator tank, is heated to concentration by steam
Liquid is evaporated concentration.
Being respectively provided with the raw water box, ultrafiltration water tank, concentration water tank, pure water tank and hyperconcetration water tank carries out high-low water level control
The liquid level meter of system, the liquid level meter in the raw water box, ultrafiltration water tank, pure water tank is respectively used to control booster pump, high pressure
The startup and stopping of pump, pure water booster pump, the liquid level meter in the concentration water tank are used to control concentration booster pump, concentration high
The startup and stopping of press pump, the liquid level meter in the hyperconcetration water tank are used to control hyperconcetration booster pump and hyperconcetration high-pressure pump
Startup and stopping.
Embodiment 1
In the present embodiment, the concentration of the cadmium ion of raw material cyanide cadmium waste water is 100mg/L or so, reverse osmosis concentrated underwater gold
Belong to the concentration of cadmium for 200mg/L or so, the concentration of cadmium ion is about in one section of isolated nanofiltration concentrate of one section of nanofiltration device
It is 400mg/L or so, the concentration of cadmium ion reaches 20g/L in two sections of NF membrane circulation concentrates, after evaporation and concentration, obtains
The concentration of concentrate cadmium ion is 30g/L.Referring to Fig. 1, specific mode of operation is the flow of realization：
Cyanide cadmium wastewater collection：The cyanide cadmium washings of countercurrent rinsing enter transition by cadmium plating potcher through collecting
Pond, the waste water in transition pond pumps into raw water box by elevator pump again, carries out the purification pretreatment of follow-up cyanide cadmium waste water.
The purification pretreatment of cyanide cadmium waste water：Booster pump (pressure of the booster pump that this example is selected is 0.4MPa) is used by original
The fiberglass drum pot type quartz filter and active carbon filter that material cyanide cadmium waste water injection filtering water is 8T/h are made
It is the pre-filtering device of the first accurate filter (the present embodiment uses 5 μm of accurate filters), after purified treatment in waste water
Impurity, organic matter, suspension etc. be filtered out.First accurate filter is entered by the water after filtering and UF ultrafiltration is filled
Put, carry out ultra-filtration filters, milipore filter is a kind of perforated membrane with super " screening " separation function, and it can effectively remove waste water
In particulate, colloid, bacterium and polymer organic matter, reach the effect of protection reverse osmosis membrane.The concentrated water obtained by ultrafiltration
Mix with raw material cyanide cadmium waste water into raw water box, again pass by quartz filter, active carbon filter, the first accurate mistake
Filter and the circulation of UF ultrafiltration apparatus carry out purification pretreatment；
Multi-cycle separation reclaiming system：Enter ultrafiltration water tank by purifying pretreated waste water (fresh water that i.e. ultrafiltration is obtained),
According to flow of inlet water 8T/H by 1.6MPa high-pressure pump feeding reverse osmosis unit carry out reverse osmosis separation, respectively obtain pure water and
Reverse osmosis concentrated water；The reverse osmosis membrane of the reverse osmosis unit uses polyamide composite film；Reverse osmosis membrane selection is used in the present embodiment
BW8040-400 polyamide composite reverse osmosis membranes, its major parameter is：PH value range 2~12, highest operating pressure
4MPa, film permeate 1.5T/H, salt rejection rate 85% below 45 DEG C of operation temperature, produce electrical conductivity pure less than 200 μ S
Water, (specially pure water enters pure water tank to the use of pure water retrogradation producing line, and the pure water in pure water tank is pumped into plating through pure water booster pump
Cadmium potcher reuse)；Reverse osmosis concentrated water is split into two parts：A part is back to ultrafiltration water tank and is again introduced into reverse osmosis unit to be entered
Row reverse osmosis separation, setting is back to ultrafiltration water tank with flow 6T/H；It is 8T/H according to flow of inlet water, it is known that another part is anti-
Infiltration concentrated water is flowed into concentration water tank, the overall fresh-water recovery rate of the multi-cycle separation reclaiming system of the embodiment with flow 0.5T/H
It is 75%；
The pre-concentration of cyanide cadmium solution：Reverse osmosis concentrated water in concentration water tank is by pressure for the concentration supercharging of 0.4MPa is pumped into
Second accurate filter (the present embodiment uses 5 μm of accurate filters), removes issuable particulate in circulation, to ensure to divide
It is not blocked from film；One section of nanofiltration device is sent into by the concentration high-pressure pump of 2.5MPa again.The present embodiment one section of nanofiltration device is received
Using DK8040 polyamide composite nanofiltration membranes, its major parameter is for filter membrane selection：PH value range 2~12, highest operation pressure
Power 4MPa, film permeate 1.5T/H, salt rejection rate 85% is (with MgSO4Meter), below 45 DEG C of operation temperature, produce about 4
One section of nanofiltration concentrate again, one section of nanofiltration fresh water of generation enters ultrafiltration water tank, mixes with by the waste water of purification pretreatment,
Reverse osmosis unit is injected by high-pressure pump, separating and recovering treatment is circulated again；
The circulation hyperconcetration of cyanide cadmium solution：It is dense that one section of nanofiltration concentrate produced by one section of nanofiltration preconcentration technique enters the excess of imports
After shrink case, by pressure, for the hyperconcetration supercharging of 0.4MPa is pumped into the 3rd accurate filter, (the present embodiment uses 5 μm of precisions
Filter), issuable particulate in circulation is removed, to ensure that seperation film is not blocked；With the hyperconcetration of 3.0MPa after filtering
High-pressure pump injects two sections of nanofiltration devices and separates, and two sections of NF membranes of nanofiltration device of the present embodiment are received using DK8040 polyamide is compound
Filter membrane, its major parameter is：PH value range 2~12, highest operating pressure 4MPa, film permeate 1.5T/H, salt rejection rate
85% (with MgSO4Meter), below 45 DEG C of operation temperature, two sections of nanofiltration fresh water of generation return to concentration water tank, with counter-infiltration
Concentrated water mixes, and the pre-concentration treatment of cyanide cadmium waste liquid is carried out again；Two sections of nanofiltration concentrates return to hyperconcetration water tank and are received with one section
Again through accurate filter and two sections of nanofiltration devices after filter concentration liquid mixing, two sections of nanofiltration concentration cycles treatment are carried out again；When
The operating pressure of two sections of nanofiltration devices reaches 2.5MPa, or the water outlet of two sections of nanofiltration devices when not producing fresh water substantially, now
The concentration of cadmium ions of concentrate can reach 200 times of the concentration of cadmium in raw material cyanide cadmium waste water and more than, it is then two sections of nanofiltrations are dense
Contracting liquid enters and concentration is evaporated in evaporator tank；
Concentrate is concentrated by evaporation：Concentrate after circulating concentration is pumped into evaporator tank by hyperconcetration booster pump, is evaporated
Steam-heated pipe line is housed in groove, concentrate is further concentrated by evaporation, last concentrate concentration of cadmium ions reaches
30g/L, cyanide cadmium aqueduct is back to as cyanide cadmium liquid.
Embodiment 2
In the present embodiment, the valve closed on the concentrated water outlet of connection reverse osmosis unit and the return line of ultrafiltration water tank, make through
The reverse osmosis concentrated water that the treatment of multi-cycle separation reclaiming system is obtained all one section of nanofiltration device treatment of feeding, other operating procedures and parameter
With embodiment 1, process with the raw material cyanide cadmium waste water of embodiment 1.
The valve closed in embodiment 2 in the concentrated water outlet of connection reverse osmosis unit and the return line of ultrafiltration water tank, concentrated water whole
One section of nanofiltration device treatment of feeding, understands that it is 1.5T/H to produce fresh water amount, is according to flow of inlet water by data in embodiment 1
8T/H, it is known that concentrated water flow is 6.5T/H, then the fresh-water recovery rate of the multi-cycle separation reclaiming system of the example is 18.75%,
Much smaller than the fresh-water recovery rate in embodiment 1.
It is not directed to partly same as the prior art in the present invention or can be realized using prior art.
Claims (10)
1. a kind of cyanide cadmium wastewater zero emission treatment method, it is characterised in that the method includes the purification of cyanide cadmium waste water
Pretreatment, multi-cycle separation reuse, the pre-concentration of cyanide cadmium waste liquid, the circulation hyperconcetration of cyanide cadmium waste liquid and concentrate
Five technique units are concentrated by evaporation, following steps are specifically included：
(1) the purification pretreatment of cyanide cadmium waste water：Raw material cyanide cadmium waste water is sequentially passed through into quartz filter, activity
Carbon filter and the first accurate filter are filtered, and the waste water after filtering carries out ultrafiltration by UF ultrafiltration apparatus, complete purification
Pretreatment；
(2) multi-cycle separation reuse：Counter-infiltration is carried out by high-pressure pump injection reverse osmosis unit by purifying pretreated waste water
Separate, respectively obtain pure water and reverse osmosis concentrated water；The pure water feeding cadmium plating potcher for obtaining；Reverse osmosis concentrated water is shunted, a part
Reverse osmosis concentrated water is flowed back and mixes with by the pretreated waste water of purification, and reverse osmosis is carried out again by high-pressure pump injection reverse osmosis unit
Separate thoroughly；Another part reverse osmosis concentrated water enters the pre-concentration of next step cyanide cadmium solution；The counter-infiltration of the reverse osmosis unit
Film uses polyamide composite film；
(3) pre-concentration of cyanide cadmium solution：A part of reverse osmosis concentrated water that step (2) is obtained is pumped into by concentrating supercharging
Second accurate filter, then one section of nanofiltration concentration is carried out by concentrating high-pressure pump one section of nanofiltration device of feeding, respectively obtain one
Section nanofiltration fresh water and one section of nanofiltration concentrate；Pass through purification pretreatment in the one section of nanofiltration fresh water for wherein obtaining and step (1)
Waste water mixes, and reverse osmosis unit is injected by high-pressure pump, and separating and recovering treatment is circulated again；One section of nanofiltration device
NF membrane uses polyamide composite film；
(4) the circulation hyperconcetration of cyanide cadmium waste liquid：One section of nanofiltration concentrate is pressurized by hyperconcetration and is pumped into the 3rd essence
Close filter, then two sections of nanofiltration concentrations are carried out by hyperconcetration high-pressure pump two sections of nanofiltration devices of feeding, respectively obtain two sections and receive
Filter fresh water and two sections of nanofiltration concentrates, two sections of nanofiltration fresh water of gained mix with reverse osmosis concentrated water in step (2), and cyanogen is carried out again
Change the pre-concentration treatment of cadmium plating waste liquid；One processed by one section of nanofiltration device in two sections of nanofiltration concentrates and step (3)
Section nanofiltration concentrate mixing, again through the 3rd accurate filter and two sections of nanofiltration devices, carries out two sections of circulations of nanofiltration concentrate
Concentration；The NF membrane of two sections of nanofiltration devices uses polyamide composite film；
(5) concentrate is concentrated by evaporation：Concentrate in step (4) after circulating concentration carries out heating evaporation concentration, until
The concentration of cadmium ion reaches 30g/L in concentrate, is back to cyanide cadmium aqueduct.
2. cyanide cadmium wastewater zero emission treatment method according to claim 1, it is characterised in that the cyanide cadmium gives up
The method of water zero discharge treatment also includes cyanide cadmium wastewater collection, including：The cyanide cadmium washings of countercurrent rinsing are by receiving
Collection pipeline enters transition pond, and the waste water in transition pond then is pumped into raw water box by elevator pump, carries out follow-up purification
Pretreatment.
3. cyanide cadmium wastewater zero emission treatment method according to claim 1, it is characterised in that in step (1)
In, before pretreatment is purified, cyanide cadmium waste water is pressurized using the booster pump of 0.2~0.5MPa.
4. cyanide cadmium wastewater zero emission treatment method according to claim 1, it is characterised in that in step (2)
In, the pressure of the high-pressure pump is 1.5~2MPa；The temperature of reverse osmosis unit treatment is 5~45 DEG C；Reverse osmosis membrane is used
BW8040-400 polyamide composite films.
5. cyanide cadmium wastewater zero emission treatment method according to claim 1, it is characterised in that in step (2),
The volume ratio of the reverse osmosis concentrated water of backflow and the reverse osmosis concentrated water into the pre-concentration of next step cyanide cadmium solution is 5~15：
1~5.
6. cyanide cadmium wastewater zero emission treatment method according to claim 1, it is characterised in that in step (3)
In, the pressure of the concentration booster pump is 0.2~0.5MPa；The pressure for concentrating high-pressure pump is 2~3MPa；One section of nanofiltration device
The temperature for the treatment of is 5~45 DEG C；The NF membrane of one section of nanofiltration device uses DK8040 polyamide composite films.
7. cyanide cadmium wastewater zero emission treatment method according to claim 1, it is characterised in that in step (4)
In, the pressure of the hyperconcetration booster pump is 0.2~0.5MPa；The pressure of hyperconcetration high-pressure pump is 1.5~3MPa；Two sections are received
The temperature of filter device treatment is 5~45 DEG C；Two sections of NF membranes of nanofiltration device use DK8040 polyamide composite films.
8. cyanide cadmium wastewater zero emission treatment method according to claim 1, it is characterised in that cadmium in reverse osmosis concentrated water
The concentration of ion is 2~4 times of the concentration of raw material cyanide cadmium removal of Cadmium from wastewater；
The concentration of cadmium ion is 4~8 times of the concentration of raw material cyanide cadmium removal of Cadmium from wastewater in one section of nanofiltration concentrate.
9. a kind of cyanide cadmium Wastewater zero-discharge treatment system, it is characterised in that the system includes raw water box, purification pretreatment
System, ultrafiltration water tank, multi-cycle separation reclaiming system, concentration water tank, preconcentration technique, hyperconcetration water tank, circulation hyperconcetration
System and evaporation concentration system, the purification pretreatment system include the booster pump, quartz filter, the activity that are sequentially connected
Carbon filter, the first accurate filter and UF ultrafiltration apparatus, the multi-cycle separation reclaiming system include the high-pressure pump being sequentially connected
And reverse osmosis unit, the preconcentration technique include be sequentially connected concentration booster pump, the second accurate filter, concentration high-pressure pump
With one section of nanofiltration device, it is hyperconcetration booster pump that the circulation hyperconcetration system includes being sequentially connected, the 3rd accurate filter, super
Concentration high-pressure pump and two sections of nanofiltration devices；The evaporation concentration system includes that the evaporation concentration device being sequentially connected, dope reuse increase
Press pump；The outlet of the raw water box is connected with the entrance of the purification pretreatment system, and the UF of the purification pretreatment system surpasses
The concentrated water outlet for filtering device is connected with an entrance of raw water box, and the water outlet of ultrafiltration apparatus connects with an entrance of ultrafiltration water tank
Connect；The outlet of the ultrafiltration water tank is connected with the entrance of the multi-cycle separation reclaiming system；In the multi-cycle separation reclaiming system
The water outlet of reverse osmosis unit is connected with the entrance of pure water tank, and the outlet of the pure water tank is through pure water booster pump and cadmium plating potcher
Entrance connection；An entrance of the concentrated water outlet of reverse osmosis unit through pipeline in parallel respectively with ultrafiltration water tank, concentration water tank connects
Connect；The outlet of the concentration water tank is connected with the entrance of the preconcentration technique, one section of nanofiltration device of the preconcentration technique
Water outlet be connected with another entrance of ultrafiltration water tank, one of one section of concentrated solution outlet of nanofiltration device and hyperconcetration water tank
Entrance is connected；The outlet of the hyperconcetration water tank is connected with the entrance of the circulation hyperconcetration system, the circulation hyperconcetration system
The concentrated waters outlet of two sections of nanofiltration devices is connected with another entrance of hyperconcetration water tank in system, two sections of water outlets of nanofiltration device and
Another entrance for concentrating water tank connects；Branch road is provided with the outlet of the hyperconcetration water tank to connect with the entrance of the evaporation concentration system
Connect, the outlet of the evaporation concentration system is connected with the import of cyanide cadmium coating bath.
10. cyanide cadmium Wastewater zero-discharge treatment system according to claim 9, it is characterised in that the cyanide cadmium
Wastewater zero-discharge treatment system also includes cyanide cadmium wastewater collection system, and the cyanide cadmium wastewater collection system includes waste water
Collecting and elevator pump, the entrance in the transition pond are connected through collecting with the outlet of cadmium plating potcher, transition pond
The boosted pump of outlet be connected with another entrance of raw water box.
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