CN105461131A - Electroplating rinse water concentrate treatment method - Google Patents
Electroplating rinse water concentrate treatment method Download PDFInfo
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- CN105461131A CN105461131A CN201410820383.7A CN201410820383A CN105461131A CN 105461131 A CN105461131 A CN 105461131A CN 201410820383 A CN201410820383 A CN 201410820383A CN 105461131 A CN105461131 A CN 105461131A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses an electroplating rinse water concentrate treatment method. The method comprises the following steps: carrying out membrane treatment on electroplating rinse water to obtain electroplating rinse water concentrate; adjusting the pH value of the electroplating rinse water concentrate to 3-5; allowing the electroplating rinse water concentrate with the pH value of 3-5 to enter a water concentrate tank, heating the concentrate to 60-90DEG C, allowing the concentrate to enter the inner side of a hollow fiber membrane in a membrane distillation device, carrying out membrane distilling concentration, allowing steam generated by the electroplating rinse water concentrate at the inner side of the hollow fiber membrane to go through membrane holes, enter the outer side of the hollow fiber membrane and directly contact with circulating cooling water for cooling and condensing in order to obtain product water, returning the inner side water concentrate to the water concentrate tank, heating the inner side water concentrate to 60-90DEG C, allowing the heated water concentrate to enter the membrane distillation device, and stopping concentration when the membrane flux of the membrane distillation device decreases to 50-70% of an initial flux in order to obtain concentrated water. The method has the advantages of easy operation, long service life of the membrane of the membrane distillation device, low energy consumption, and high concentration ratio and desalination rate.
Description
Technical field
The invention belongs to Treatment of Industrial Water field, relate to a kind for the treatment of process of sewage, particularly a kind for the treatment of process of electroplating rinse water condensed water.
Background technology
Electroplating wastewater is important source of pollution of field of industrial production.The proportion of electroplating wastewater shared by trade effluent is less, but in plating production process, chemical feedstocks utilization ratio is lower, and pollutant discharge amount is many.In addition, in electroplating wastewater, pollutant kind is many, and toxicity is large, and harm is serious: the heavy metal ion wherein contained, prussiate, sexavalent chrome etc. belong to carcinogenic, teratogenesis or mutagenic highly toxic substance, very harmful to the mankind.In addition, electroplating wastewater contains a large amount of precious metals, enters natural system if dealt with improperly, not only contaminate environment but also waste resource.If can reclaim or realize resource circulation utilization, huge environmental benefit and economic benefit will be brought undoubtedly.
Membrane treatment process is a kind of electroplate rinsing water technology of maturation application, for electroplate rinsing water treatment provides the solution of " green ", obtains and promotes widely.Adopt membrane technique to carry out separation to the heavy metal rinse water that production process produces to concentrate, the recovery of metal ion can be realized, again can reuse water resource.Conventional membrane method treating process mainly refers to the combination process of micro-filtration (MF) or ultrafiltration (UF) and reverse osmosis (RO) or nanofiltration (NF) at present, i.e. MF/UF+RO/NF, contriver adopts this technique to carry out concentration (ZL200810235197.1 to parcel plating waste water, CN103539294A), find that adopting separately embrane method to be difficult to realization is concentrated into tank liquor concentration, also need the means such as fiting chemical process, electrolysis to process further, thus cause the loaded down with trivial details and secondary pollution problems of technique.
Summary of the invention
The object of the present invention is to provide a kind for the treatment of process of electroplating rinse water condensed water, the method can break through the restriction of the osmotic pressure of reverse osmosis/nanofiltration own, the dense water of high density after reverse osmosis/nanofiltration being concentrated concentrates further, reach the concentration of plating solution in electroplating process, thus realize the reuse of plating solution and rinse water, realize " zero release ".
The object of the invention is to be achieved through the following technical solutions:
A treatment process for electroplating rinse water condensed water, comprises the following steps:
(1) electroplating rinse water condensed water, is prepared: adopt film process electroplating rinse water to obtain electroplating rinse water condensed water;
(2), the pH of electroplating rinse water condensed water is regulated to reach 3 ~ 5;
(3), direct contact membrane distillation concentrates: regulate pH be 3 ~ 5 electroplating rinse water condensed water enter concentrated water tank, be heated to 60 ~ 90 DEG C, membrane distillation concentration is carried out in the inner side entering the hollow-fibre membrane of distillation device, the steam that electroplating rinse water condensed water produces inside hollow-fibre membrane enters the outside of hollow-fibre membrane after fenestra, obtain producing water with the direct contact cooling condensation of recirculated cooling water, the dense water in inner side gets back to concentrated water tank, again enter distillation device after being heated to 60 ~ 90 DEG C and carry out membrane distillation concentration, until the flux depression of distillation device is 50 ~ 70% of initial flux, stop concentrated, obtain dense water.
Electroplating rinse water waste water of the present invention is from electronickelling poaching wastewater, cyanide cadmium rinse water, pyrophosphate copper plating rinse water, alkaline non-cyanogen galvanization rinse water, chromium plating rinsing water, the gold-plated rinse water of cyaniding etc., and electroplating rinse water is containing, for example lower heavy metal ion: at least one in nickel ion, cupric ion, chromium ion, zine ion, cadmium ion, gold ion, silver ions etc.; Containing, for example lower inorganic anion: at least one in chlorion, sulfate ion, nitrate radical, dichromate ion, borate ion, hydroxide ion etc.; If containing complexing agent, then comprise: at least one in cyanogen root, citric acid, oxalic acid, oxysuccinic acid, lactic acid, succinic acid, tartrate etc., complexing agent is the one of salinity, still adopts total salinity to describe.The total salinity < 2g/L of described electroplating rinse water.
In step (1), according to the disclosed membrane processing method of patent of invention (patent No. ZL200810235197.1), adopt ultrafiltration+reverse osmosis to concentrate electroplating rinse water, obtain electroplating rinse water condensed water, concrete steps are:
(A) pre-treatment: electroplating rinse water is sent into sand filter, activated charcoal filter and accurate filter by topping-up pump successively and filters; Pre-treatment generally uses the topping-up pump of pressure range 0.2 ~ 0.5MPa;
(B) one section of multi-cycle separation: once inject cartridge filter and ultra-filtration equipment by topping-up pump through pretreated electroplating rinse water, the rinse water after ultrafiltration inject one section of reverse osmosis membrane apparatus through high-pressure pump and are separated, and obtain pure water and one section of concentrated solution; The pressure range of topping-up pump is generally 0.2 ~ 0.5MPa, and the pressure range of high-pressure pump is generally 1 ~ 2.5MPa, and the temperature of one section of reverse osmosis isolation is 10 ~ 40 DEG C; The pure water of one section of multi-cycle separation directly can return electroplating assembly line and use; One section of reverse osmosis membrane needs to adopt antipollution complex reverse osmosis membrane, as LFCl antipollution complex reverse osmosis membrane etc.;
(C) two sections of multi-cycle separation: one section of concentrated solution is sent into after cartridge filter filters by topping-up pump, then deliver to two sections of reverse osmosis membrane apparatus through high-pressure pump and be separated, get water and two sections of concentrated solutions; The water wherein obtained with after pretreated electroplating rinse water merges, proceed one section of multi-cycle separation, proceed two sections of multi-cycle separation, until obtain electroplating rinse water condensed water after two sections of concentrated solutions and the merging of one section of concentrated solution; The pressure range of topping-up pump is generally 0.2 ~ 0.5MPa, and the pressure range of high-pressure pump is generally 1.5 ~ 4MPa, and the temperature of one section of reverse osmosis isolation is 10 ~ 40 DEG C; Two sections of reverse osmosis membranes generally adopt low-voltage load reverse osmosis membrane, as CPA3 low pressure composite membrane etc.
Membrane processing method also can adopt ultrafiltration+nanofiltration process, concentrates electroplating rinse water, obtains electroplating rinse water condensed water, and concrete steps are:
(A) pre-treatment: electroplating rinse water is sent into sand filter, activated charcoal filter and accurate filter by topping-up pump successively and filters; Pre-treatment generally uses the topping-up pump of pressure range 0.2 ~ 0.5MPa;
(B) one section of multi-cycle separation: inject cartridge filter and ultra-filtration equipment successively by topping-up pump through pretreated electroplating rinse water, rinse water after ultrafiltration inject one section of nano filter membrance device through high-pressure pump and are separated, and obtain one section of fresh water and one section of concentrated solution; The pressure range of topping-up pump is generally 0.2 ~ 0.5MPa, and the pressure range of high-pressure pump is generally 1 ~ 3MPa, and the temperature of one section of nanofiltration separation is 5 ~ 45 DEG C; One section of fresh water of one section of multi-cycle separation and merge through pretreated electroplating rinse water and proceed one section of multi-cycle separation; One section of nanofiltration membrane adopts DK8040 polyamide composite film;
(C) two sections of multi-cycle separation: one section of concentrated solution is sent into after cartridge filter filters by topping-up pump, then deliver to two sections of nano filter membrance devices through high-pressure pump and be separated, get two sections of fresh water and two sections of concentrated solutions; The two sections of fresh water wherein obtained with after pretreated electroplating rinse water merges, proceed one section of multi-cycle separation, proceed two sections of multi-cycle separation, until obtain electroplating rinse water condensed water after two sections of concentrated solutions and the merging of one section of concentrated solution; The pressure range of topping-up pump is generally 0.2 ~ 0.5MPa, and the pressure range of high-pressure pump is generally 1 ~ 3MPa, and the temperature of two sections of nanofiltration membrane treatment is 5 ~ 45 DEG C; Two sections of nanofiltration membrane adopt DK8040 polyamide composite film.
The total salinity of described electroplating rinse water condensed water is 40 ~ 100g/L, and pH value is 4 ~ 13.The total salinity of described electroplating rinse water condensed water is 35 ~ 120 times of the total salinity of electroplating rinse water.Electroplating rinse water condensed water contains heavy metal ion: at least one in nickel ion, cupric ion, chromium ion, zine ion, cadmium ion, gold ion, silver ions etc.; Containing, for example lower inorganic anion: at least one in chlorion, sulfate ion, nitrate radical, dichromate ion, borate ion, hydroxide ion etc.; If containing complexing agent, then comprise: at least one in cyanogen root, citric acid, oxalic acid, oxysuccinic acid, lactic acid, succinic acid, tartrate etc.
In step (2), liquid acid or acidic ion exchange resin in the inventive method, is adopted to regulate the pH of electroplating rinse water condensed water;
Whether step is distinguished containing prussiate according in electroplating rinse water condensed water, electroplating rinse water condensed water containing prussiate adopts the mode adding liquid acid to adjust pH to reach 3 ~ 5, and the electroplating rinse water condensed water not containing prussiate adopts acidic ion exchange resin post adjustment pH to reach 3 ~ 5.
Described liquid acid is one or more mixing in sulfuric acid, nitric acid, hydrochloric acid, thionamic acid and methylsulphonic acid, preferred dilute sulphuric acid or dilute hydrochloric acid, the dilute sulphuric acid of such as massfraction 5%, the dilute hydrochloric acid of massfraction 5%.
Described acidic ion exchange resin is the one of carboxylic acid fundamental mode, phosphoric acid fundamental mode or phenolic group type weakly acidic cation-exchange resin, and optimization acid's fundamental mode weakly acidic cation-exchange resin, specifically can adopt D113 weakly acidic cation-exchange resin.
Electroplating rinse water condensed water pH is regulated to reach 3 ~ 5, avoid the contingent precipitin reaction of heavy metal ion when high density concentrates in condensed water, thus the fouling membrane alleviated distillation device, reduce the trend that solid is separated out on film surface, guarantee that membrane distillation process is run under can maintaining high-throughput.
In step (3), the temperature of the inner side of the hollow-fibre membrane of described distillation device is 60 ~ 90 DEG C, and the temperature in outside is 10 ~ 30 DEG C, makes temperature outside maintain 10 ~ 30 DEG C by the recirculated cooling water passing into 10 ~ 30 DEG C.
The material of described hollow-fibre membrane is tetrafluoroethylene, polyvinylidene difluoride (PVDF) or polypropylene, preferably polytetrafluoroethylene.
The aperture of described hollow-fibre membrane is 0.1 ~ 0.2 μm, and porosity is 70 ~ 90%.
The total salinity of described dense water is 150 ~ 300g/L, described product electrical conductivity of water 5 ~ 10 μ s/cm.The total salinity of described dense water is more than 100 times of the total salinity of electroplating rinse water, is preferably 100 ~ 310 times of the total salinity of electroplating rinse water.Described dense water directly returns electroplating assembly line and uses as plating solution.
Well heater is provided with in described concentrated water tank.Described recirculated cooling water is sent into the outside of hollow-fibre membrane again at 10 ~ 30 DEG C by condenser.
Compared with prior art, the present invention has the following advantages:
1, whether contain the feature of prussiate according to electroplating rinse water condensed water, adopt liquid acid and ion exchange resin to carry out pH regulator, avoid the release of hypertoxic gas cyaniding hydrogen;
2, pH adjustment is carried out to the electroplating rinse water condensed water that pre-treatment obtains, avoid further concentration process and produce the stifled problem of film dirt; Adopt membrane distillation process, can concentrate electroplating rinse water condensed water further, simultaneously owing to have adjusted the pH value of dense water, reduce the trend that solid is separated out on film surface, therefore membrane distillation process is run under can maintaining high-throughput;
3, the total salinity of dense water that the present invention obtains can reach more than 150g/L, reaches the concentration of plating tank plating solution, thus directly return-enclosure uses.
4, the inventive method equipment is simple, the film long service life of processing ease, distillation device, energy consumption are low, has concentration ratio and the ratio of desalinization of height.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the process flow sheet that the present invention adopts ultrafiltration+reverse osmosis.
Fig. 3 is the process flow sheet that the present invention adopts ultrafiltration+nanofiltration process.
Embodiment
Concrete technical scheme of the present invention is further described by specific embodiment.
Embodiment 1
Electroplating rinse water is electronickelling poaching wastewater, and its main component has nickel ion, sulfate ion, chlorion and boric acid, and total salinity is 6.5 at 1.5g/L, pH.
(1), adopt ultrafiltration+reverse osmosis to concentrate electroplating rinse water, obtain electroplating rinse water condensed water, concrete steps are:
(A) pre-treatment: electroplating rinse water is sent into quartz filter, activated charcoal filter and 5 μ accurate filters by topping-up pump successively and filters; Pre-treatment generally uses the topping-up pump of pressure range 0.2 ~ 0.5MPa, and the present embodiment adopts the topping-up pump of 0.5MPa;
(B) one section of multi-cycle separation: enter one section of circulating filtration water tank through pretreated electroplating rinse water, by topping-up pump, (pressure range of topping-up pump is generally 0.2 ~ 0.5MPa, the present embodiment adopts the topping-up pump of 0.5MPa) inject cartridge filter and ultra-filtration equipment successively, through high-pressure pump, (pressure range of high-pressure pump is generally 1 ~ 2.5MPa to rinse water after ultrafiltration, the present embodiment adopts the high-pressure pump of 1.0MPa) inject one section of reverse osmosis membrane apparatus and be separated, obtain pure water and one section of concentrated solution; One section of reverse osmosis membrane adopts LFCl antipollution complex reverse osmosis membrane, pH scope 3-10, the highest working pressure 4MPa, and service temperature is less than 45 DEG C; The pure water of one section of multi-cycle separation directly can return electroplating assembly line and use;
(C) two sections of multi-cycle separation: one section of concentrated solution enters two sections of circulating filtration water tanks, by topping-up pump, (pressure range of topping-up pump is generally 0.2 ~ 0.5MPa, the pressure of the present embodiment topping-up pump is 0.3MPa) send into cartridge filter filter after, through high-pressure pump, (pressure range of high-pressure pump is generally 1.5 ~ 4MPa again, the present embodiment adopts the high-pressure pump of 2.0MPa) deliver to two sections of reverse osmosis membrane apparatus and be separated, two sections of reverse osmosis membranes adopt CPA3 low pressure composite membrane, pH scope 3-10, the highest working pressure 4MPa, service temperature is less than 45 DEG C; Get water and two sections of concentrated solutions, the water obtained is got back to one section of circulating filtration water tank and after pretreated electroplating rinse water merges, is proceeded one section of multi-cycle separation, two sections of concentrated solutions proceed two sections of multi-cycle separation, until obtain electroplating rinse water condensed water after entering two sections of circulating filtration water tanks and one section of concentrated solution merging after dense water collection tank again; The condensed water total salinity obtained is 80 grams per liters, and pH is 5.0;
(2), electroplating rinse water condensed water enters pH regulator pond, under agitation adds the dilution heat of sulfuric acid of massfraction 5%, regulates pH to be 3 by automatic pH Controlling System;
(3) condensed water, after pH adjustment enters concentrated water tank, and by heater heats to 80 DEG C, pump into inside distillation device hollow-fibre membrane, hollow-fibre membrane material selection tetrafluoroethylene, porosity is 80% porosity, and aperture is 0.15 μm; Simultaneously, it is the outside of the circulating condensing water feeding hollow-fibre membrane of 25 DEG C by temperature, condensed water through membrane distillation gets back to concentrated water tank, again enter distillation device after being heated to 80 DEG C and carry out membrane distillation concentration, owing to there is the temperature difference inside and outside hollow-fibre membrane, the steam that the condensed water of inner side produces enters outside by the fenestra of hollow-fibre membrane, directly contact and condensation with outside cold water, become product water, outside water of condensation is constantly circulated by recycle pump, by condenser low temperature (25 DEG C); The dense water in inner side gets back to concentrated water tank, and again pump into distillation device by recycle pump after being heated to 80 DEG C and carry out membrane distillation concentration, until when the flux depression of distillation device is 50% of initial flux, stopper film still-process, obtains dense water; The total salinity measuring dense water is 150 grams per liters; Measuring and producing electrical conductivity of water is 10 μ s/cm.
Embodiment 2
Electroplating rinse water is cyanide cadmium rinse water, and its main component is for having cadmium cyanide complexing ion, cyanide ion, sodium ion, sulfate ion, and total salinity is 1.9g/L, and pH value is 10.2.
(1), adopt ultrafiltration+nanofiltration process to concentrate electroplating rinse water, obtain electroplating rinse water condensed water, concrete steps are:
(A) pre-treatment: pre-treatment: electroplating rinse water is sent into quartz filter, activated charcoal filter and 5 μ accurate filters by topping-up pump successively and filters; Pre-treatment generally uses the topping-up pump of pressure range 0.2 ~ 0.5MPa, and the present embodiment adopts the topping-up pump of 0.5MPa;
(B) one section of multi-cycle separation: enter one section of circulating filtration water tank through pretreated electroplating rinse water, by topping-up pump, (pressure range of topping-up pump is generally 0.2 ~ 0.5MPa, the present embodiment adopts pressure 0.2MPa topping-up pump) inject cartridge filter and ultra-filtration equipment successively, through high-pressure pump, (pressure range of high-pressure pump is generally 1 ~ 3MPa to rinse water after ultrafiltration, the present embodiment adopts pressure 2MPa high-pressure pump) inject one section of nano filter membrance device and be separated, one section of nanofiltration membrane adopts DK8040 polyamide composite film, the temperature of one section of nanofiltration separation is 5 ~ 45 DEG C, obtain one section of fresh water and one section of concentrated solution, one section of fresh water of one section of multi-cycle separation enters one section of circulating filtration water tank and merges through pretreated electroplating rinse water and proceeds one section of multi-cycle separation,
(C) two sections of multi-cycle separation: one section of concentrated solution enters two sections of circulating filtration water tanks, by topping-up pump, (pressure range of topping-up pump is generally 0.2 ~ 0.5MPa, the pressure of the present embodiment topping-up pump is 0.3MPa) send into cartridge filter filter after, through high-pressure pump, (pressure range of high-pressure pump is generally 1 ~ 3MPa again, the present embodiment adopts the high-pressure pump of 1.5MPa) deliver to two sections of nano filter membrance devices and be separated, two sections of nanofiltration membrane adopt DK8040 polyamide composite film, and the temperature of two sections of nanofiltration membrane treatment is 5 ~ 45 DEG C; Get two sections of fresh water and two sections of concentrated solutions; The two sections of fresh water wherein obtained enter one section of circulating filtration water tank and after pretreated electroplating rinse water merges, proceed one section of multi-cycle separation, two sections of multi-cycle separation are proceeded, until obtain electroplating rinse water condensed water after two sections of concentrated solutions enter two sections of circulating filtration water tanks and one section of concentrated solution merging again by dense water collection tank; After ultrafiltration+nanofiltration process, obtain electroplating rinse water condensed water, its total salinity reaches 100 grams per liters, and pH is 11.4;
(2), electroplating rinse water condensed water enters the ion exchange column loading carboxylic acid type weakly acidic cation-exchange resin (model is D113), adjust ph to 10;
(3) condensed water, after pH adjustment enters concentrated water tank, and by heater heats to 70, DEG C pump into inside distillation device hollow-fibre membrane, hollow-fibre membrane material selection polyvinylidene difluoride (PVDF), porosity is 88%, and aperture is 0.20 μm; Meanwhile, be that the circulating condensing water of 15 DEG C sends into the outside of hollow-fibre membrane by temperature; Owing to there is the temperature difference inside and outside hollow-fibre membrane, the steam that the condensed water of inner side produces can enter outside by the fenestra of hollow-fibre membrane, directly contacts and condensation, become product water with outside cold water, outside water of condensation is constantly circulated by recycle pump, by condenser low temperature (15 DEG C); The dense water in inner side gets back to concentrated water tank, and again pump into distillation device by recycle pump after being heated to 70 DEG C and carry out membrane distillation concentration, until when the flux depression of distillation device is 70% of initial flux, stopper film still-process, obtains dense water; The total salinity measuring dense water is 200 grams per liters; Measuring and producing electrical conductivity of water is 8 μ s/cm.
Embodiment 3
Electroplating rinse water is cyanide cadmium rinse water, pyrophosphate copper plating rinse water, and its main component is cupric ion, pyrophosphate, citrate, tartrate anion, sodium ion, ammonium ion, potassium ion; Total salt content is 0.9g/L, and pH value is 7.5.
(1) the employing ultrafiltration+reverse osmosis, according to embodiment 1 provided concentrates electroplating rinse water, and obtain electroplating rinse water condensed water, total salinity is 75 grams per liters, and pH is 9.2;
(2), electroplating rinse water condensed water enters pH regulator pond, under agitation adds the dilute hydrochloric acid of massfraction 5%, regulates pH to be 3 ~ 4 by automatic pH Controlling System;
(3), with reference to the method for embodiment 1, carry out membrane distillation concentration to the electroplating rinse water condensed water after pH adjustment, controlling condensed water temperature is 75 DEG C, and controlled circulation condensate temperature is 18 DEG C; Hollow-fibre membrane selects polypropylene, and porosity is 70%, and aperture is 0.10 μm; When the flux depression of distillation device is 70% of initial flux, stopper film still-process, obtains dense water; The total salt content measuring dense water is 185 grams per liters; Measuring and producing electrical conductivity of water is 5 μ s/cm.
Embodiment 4
Electroplating rinse water is alkaline non-cyanogen galvanization rinse water, and its main component is zine ion, sodium ion, hydroxide ion, and total salinity is 0.5g/L, pH is 11.2.
(1) the employing ultrafiltration+nanofiltration process, according to embodiment 2 provided concentrates electroplating rinse water, and the electroplating rinse water condensed water total salinity obtained is 60 grams per liters, and pH is 13;
(2), electroplating rinse water condensed water enters pH regulator pond, under agitation adds the dilute hydrochloric acid of massfraction 5%, regulates pH to be 4 by automatic pH Controlling System;
(3), with reference to the method for embodiment 1, carry out membrane distillation concentration to the electroplating rinse water condensed water after pH adjustment, controlling dense water temp is 65 DEG C, and controlled circulation condensate temperature is 18 DEG C; Hollow-fibre membrane selects tetrafluoroethylene, and porosity is 72%, and aperture is 0.15 μm; When the flux depression of distillation device is 66% of initial flux, stopper film still-process, obtains dense water; The total salt content measuring dense water is 155 grams per liters.Measuring and producing electrical conductivity of water is 5 μ s/cm.
Embodiment 5
Electroplating rinse water is chromium plating rinsing water, and its main component is chromium ion, sulfate ion, sodium ion, borate ion, hydrogen ion, and total salinity is 0.88g/L, pH is 4.
(1) the employing ultrafiltration+nanofiltration process, according to embodiment 2 provided concentrates electroplating rinse water, and the electroplating rinse water condensed water total salinity obtained is 90 grams per liters, and pH is 3;
(2), electroplating rinse water condensed water enters pH regulator pond, under agitation adds the hydrochloric acid of massfraction 5%, regulates pH to be 4 by automatic pH Controlling System;
(3) with reference to the method for embodiment 1, carry out membrane distillation concentration to the electroplating rinse water condensed water after pH adjustment, controlling dense water temp is 75 DEG C, and controlled circulation condensate temperature is 27 DEG C; Hollow-fibre membrane selects tetrafluoroethylene, and porosity is 88%, and aperture is 0.12 μm; When the flux depression of distillation device is 50% of initial flux, stopper film still-process, obtains dense water; The total salt content measuring dense water is 235 grams per liters; Measuring and producing electrical conductivity of water is 8 μ s/cm.
Embodiment 6
Electroplating rinse water is chromium plating rinsing water, the gold-plated rinse water of cyaniding, and its main component is gold tricyanide complexing ion, cyanide ion, sodium ion, potassium ion, hydroxide ion, and total salinity is 1.78g/L, pH is 9.8.
(1) the employing ultrafiltration+reverse osmosis, according to embodiment 1 provided concentrates electroplating rinse water, and obtain electroplating rinse water condensed water, its total salinity is 65 grams per liters, and pH is 12;
(2), electroplating rinse water condensed water enters the ion exchange column loading carboxylic acid type weakly acidic cation-exchange resin (model is D113), adjust ph to 5;
(3) with reference to the method for embodiment 1, carry out membrane distillation concentration to the electroplating rinse water condensed water after pH adjustment, controlling dense water temp is 77 DEG C, and controlled circulation condensate temperature is 26 DEG C; Hollow-fibre membrane selects tetrafluoroethylene, and porosity is 78%, and aperture is 0.13 μm; When the flux depression of distillation device is 62% of initial flux, stopper film still-process, obtains dense water; The total salinity measuring dense water is 187 grams per liters; Measuring and producing electrical conductivity of water is 8 μ s/cm.
Comparative example 1
Electroplating rinse water is electronickelling poaching wastewater, and its main component has nickel ion, sulfate ion, chlorion and boric acid, and total salinity is 6.5 at 1.5g/L, pH.Except the pH of adjustment electroplating rinse water condensed water is 6 in step (2), other operations are identical with embodiment 1, when membrane distillation system water production rate decline 50% time, dense water concentration is 100 grams per liters.
Comparative example 2
Electroplating rinse water is electronickelling poaching wastewater, and its main component has nickel ion, sulfate ion, chlorion and boric acid, and total salinity is 6.5 at 1.5g/L, pH.Except in step (2), the pH of adjustment electroplating rinse water condensed water is 2, membrane distillation process is produced electrical conductivity of water and is reached 200 μ s/cm.
Claims (10)
1. a treatment process for electroplating rinse water condensed water, is characterized in that comprising the following steps:
(1) electroplating rinse water condensed water, is prepared: adopt film process electroplating rinse water to obtain electroplating rinse water condensed water;
(2), the pH of electroplating rinse water condensed water is regulated to reach 3 ~ 5;
(3), direct contact membrane distillation concentrates: regulate pH be 3 ~ 5 electroplating rinse water condensed water enter concentrated water tank, be heated to 60 ~ 90 DEG C, membrane distillation concentration is carried out in the inner side entering the hollow-fibre membrane of distillation device, the steam that electroplating rinse water condensed water produces inside hollow-fibre membrane enters the outside of hollow-fibre membrane after fenestra, obtain producing water with the direct contact cooling condensation of recirculated cooling water, the dense water in inner side gets back to concentrated water tank, again enter distillation device after being heated to 60 ~ 90 DEG C and carry out membrane distillation concentration, until the flux depression of distillation device is 50 ~ 70% of initial flux, stop concentrated, obtain dense water.
2. the treatment process of electroplating rinse water condensed water according to claim 1, is characterized in that the total salinity < 2g/L of described electroplating rinse water; The total salinity of described electroplating rinse water condensed water is 40 ~ 100g/L, and pH value is 4 ~ 13.
3. the treatment process of electroplating rinse water condensed water according to claim 1, is characterized in that in step (2), adopts liquid acid or acidic ion exchange resin to regulate the pH of electroplating rinse water condensed water to reach 3 ~ 5.
4. the treatment process of electroplating rinse water condensed water according to claim 3, is characterized in that in step (2), when electroplating rinse water condensed water contains prussiate, adopts liquid acid adjustment pH to reach 3 ~ 5; When electroplating rinse water condensed water is not containing prussiate, acidic ion exchange resin post adjustment pH is adopted to reach 3 ~ 5.
5. the treatment process of the electroplating rinse water condensed water according to claim 3 or 4, is characterized in that described liquid acid is one or more mixing in sulfuric acid, nitric acid, hydrochloric acid, thionamic acid and methylsulphonic acid;
Described acidic ion exchange resin is the one of carboxylic acid fundamental mode, phosphoric acid fundamental mode or phenolic group type weakly acidic cation-exchange resin.
6. the treatment process of electroplating rinse water condensed water according to claim 1, is characterized in that in step (3), and the temperature of the inner side of the hollow-fibre membrane of described distillation device is 60 ~ 90 DEG C, and the temperature in outside is 10 ~ 30 DEG C;
Well heater is provided with in described concentrated water tank; Described recirculated cooling water is sent into the outside of hollow-fibre membrane again at 10 ~ 30 DEG C by condenser.
7. the treatment process of electroplating rinse water condensed water according to claim 1, is characterized in that in step (3), and the material of described hollow-fibre membrane is tetrafluoroethylene, polyvinylidene difluoride (PVDF) or polypropylene;
The aperture of described hollow-fibre membrane is 0.1 ~ 0.2 μm, and porosity is 70 ~ 90%.
8. the treatment process of electroplating rinse water condensed water according to claim 1, is characterized in that in step (3), and the total salinity of described dense water is 150 ~ 300g/L, described product electrical conductivity of water 5 ~ 10 μ s/cm.
9. the treatment process of electroplating rinse water condensed water according to claim 1, is characterized in that the total salinity of described dense water is more than 100 times of the total salinity of electroplating rinse water.
10. the treatment process of electroplating rinse water condensed water according to claim 1, is characterized in that, in step (3), described dense water directly returns electroplating assembly line and uses as plating solution.
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