CN106319563A - Electrolytic copper and method for producing electrolytic copper from concentrated nitric acid copper-containing wastewater - Google Patents
Electrolytic copper and method for producing electrolytic copper from concentrated nitric acid copper-containing wastewater Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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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
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- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the field of industrial wastewater treatment and provides electrolytic copper and a method for producing the electrolytic copper from concentrated nitric acid copper-containing wastewater. The method comprises the steps of thoroughly mixing the concentrated nitric acid copper-containing wastewater with an alkaline solution containing carbanyl groups for a reaction, and separating mixed liquid obtained after the reaction, so that solid sediment and copper-containing waste liquid are obtained; subsequently, adsorbing copper ions in the copper-containing waste liquid with adsorbent, and after the copper ions are adsorbed to be saturated, backwashing the adsorbent with a sulfuric acid solution, so that a copper sulfate solution is obtained; and then, conducting electrolysis on the copper sulfate solution, so that the electrolytic copper is obtained. By means of the method for producing the electrolytic copper from the concentrated nitric acid copper-containing wastewater, nitric acid in the wastewater can be converted into a nitrogen fertilizer containing amide nitrogen and nitrate nitrogen, and the copper ions can be converted into an electrolytic copper product; meanwhile, the treated wastewater can reach the Comprehensive Water Pollutant Emission Standard of Beijing City; the problem of treatment of the concentrated nitric acid copper-containing wastewater is well solved; and resources are recycled, and the environment is protected.
Description
Technical field
The present invention relates to field of industrial waste water treatment, in particular to a kind of cathode copper and utilize concentrated nitric acid cupric to give up
The method of aquatic product cathode copper.
Background technology
Along with the continuous fast development of society, the living standard of people improves constantly, and people are to living environment simultaneously
Requirement more and more higher.But, along with the development of industrial society and being continuously increased of population, our living environment
Improve the most therewith, go from bad to worse on the contrary.The especially pollution of industrial wastewater is more and more serious, and composition also becomes increasingly complex,
Degrading the most more and more difficult, this brings threat greatly to water body and health.Therefore industrial wastewater is processed into
The emphasis of environmental problem.
Substantial amounts of concentrated nitric acid copper-containing wastewater, the process of this waste water can be produced at present in the production process of electronics industry
An always difficult problem of sewage disposal.In prior art, the process of concentrated nitric acid copper-containing wastewater uses alkalescence after having been used up dilution
The technique that material neutralizes processes, and needs to consume the product after substantial amounts of clear water and alkaline matter, and neutralization in processing procedure
Thing reclaims difficulty, and the production cost that process product carries out polish is too high, causes and cannot comprehensively utilize it, meanwhile,
Waste water after process is also unable to reach pollutant comprehensive discharge standard, after above-mentioned discharge of wastewater enters water body, causes water body the richest
Nutrient laden, easily causes secondary pollution to water body.The trace copper ion contained in waste water cannot be reclaimed simultaneously, cause resource wave
Take.
Therefore studying and explore the technique processing concentrated nitric acid copper-containing wastewater the most economically and reasonably, reclaiming therein has valency
Metallic copper, improves the level of comprehensive utilization of resources, and the nitric acid in concentrated nitric acid copper-containing wastewater carries out harmless treatment, meanwhile,
Discharge water after process reaches " Beijing's water pollutant comprehensive discharge standard " DB11/307-2013 table three requirement, for environment
Protection and tool of increasing economic efficiency are of great significance.
In view of this, the special proposition present invention.
Summary of the invention
The first object of the present invention is a kind of method providing concentrated nitric acid copper-containing wastewater to produce cathode copper, above-mentioned dense nitre
The method that acid copper-containing wastewater produces cathode copper, have that technological process is simple, with low cost, environment will not be produced secondary pollution with
And cathode copper organic efficiency advantages of higher.
The second object of the present invention is to provide a kind of cathode copper, the production method of above-mentioned cathode copper, solution compolision
Ask the highest, directly can produce qualified standard electrolytic copper products from copper segregation liquid, have that technique is simple, handling process
The many advantages such as short, Product processing expense output low, direct tough cathode product.
In order to realize the above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps: by concentrated nitric acid copper-containing wastewater
Carry out being sufficiently mixed reaction with the alkaline solution containing carbonyl, reacted mixed liquor is separated, obtains solid sediment
And contained waste liquid；Subsequently, with the copper ion in adsorbent contained waste liquid, upon adsorption saturated after, inhale with sulfuric acid solution backwash
Attached dose generates copper-bath；Then, copper-bath is carried out electrolysis and obtain cathode copper.
In the present invention, above-mentioned carry out being sufficiently mixed reaction by concentrated nitric acid copper-containing wastewater and the alkaline solution containing carbonyl be
Refer to, owing to the reaction of above-mentioned concentrated nitric acid copper-containing wastewater with the alkaline solution containing carbonyl is exothermic reaction, when exothermic heat of reaction is complete,
After mixed liquor natural cooling, it is reaction fully.
In the present invention, have employed and carry out being sufficiently mixed reaction with the alkaline solution containing carbonyl by concentrated nitric acid copper-containing wastewater
Method, utilizes the reaction mechanism of carbonyl structure and the nitrate anion nitrogen oxygen single key structure contained in the alkaline solution containing carbonyl, makes
Alkaline solution containing carbonyl and nitrate anion react generation containing amidonitrogen and the nitrogenous fertilizer of nitrate nitrogen, meanwhile, concentrated nitric acid cupric
Waste water and alkaline solution containing carbonyl react after the contained waste liquid of isolated, by can after adsorbent copper ion
Reach " Beijing's water pollutant comprehensive discharge standard " DB11/307-2013 table three and require discharge or reuse.
Additionally, have employed, the copper-bath produced after adsorbent backwash is passed through in electrolysis bath, and adds in electrolysis bath
Pressure flow at high speed, under electric field action, gradually separates out the electrolytic method of cathode copper, solves concentrated nitric acid in prior art at negative electrode
Product after copper-containing wastewater processes reclaims difficulty, and the production cost that process product carries out polish is too high, and causing cannot be to it
The problem carrying out comprehensively utilizing.
In the present invention, sulphuric acid can be substituted with nitric acid or hydrochloric acid and adsorbent is carried out backwash.
Further, the above-mentioned alkaline solution containing carbonyl is the weak base of amide-type.
In the present invention, the pH value of the weak base of above-mentioned amide-type is 5～9.
In the present invention, above-mentioned amide substance is the most weak a kind of alkali, and it can generate corresponding with strong acid generation alcoholysis reaction
Amidonitrogen and nitrate nitrogen.
Further, above-mentioned concentrated nitric acid copper-containing wastewater carries out hybrid reaction in agitator tank with the alkaline solution containing carbonyl
Carry out, specifically, in whipping process, concentrated nitric acid copper-containing wastewater is slowly added in the alkaline solution containing carbonyl.
Further, above-mentioned concentrated nitric acid copper-containing wastewater is calculated as by volume with the mixed proportion of the alkaline solution containing carbonyl
(1～2): 1.
In the present invention, above-mentioned concentrated nitric acid copper-containing wastewater is typical but non-limiting with the mixed proportion of the alkaline solution containing carbonyl
Property for 1:1,1.2:1,1.5:1,1.7:1 or 2:1.In the present invention, above-mentioned concentrated nitric acid copper-containing wastewater and the alkalescence containing carbonyl
The reaction of solution is exothermic reaction, when concentrated nitric acid copper-containing wastewater and the alkaline solution containing carbonyl are with (1～2): the volume ratio of 1 is entered
During row reaction, reaction liberated heat can maintain reaction temperature at 30～50 DEG C, is not required to heat in course of reaction.
Simultaneously as the reaction of concentrated nitric acid copper-containing wastewater and the alkaline solution containing carbonyl is liquid phase reactor, by concentrated nitric acid
Copper-containing wastewater with the alkaline solution containing carbonyl with (1～2): the volume ratio of 1 mixes, reaction more equalize and be easily controlled, also
The conversion ratio of nitrogen in course of reaction can be improved, generate more containing amidonitrogen and the nitrogenous fertilizer of nitrate nitrogen.
Further, above-mentioned concentrated nitric acid copper-containing wastewater is 30～50 with the temperature of the alkaline solution hybrid reaction containing carbonyl
℃。
In the present invention, above-mentioned concentrated nitric acid copper-containing wastewater is typical but non-with the temperature of the alkaline solution hybrid reaction containing carbonyl
Determinate it is: 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C.
Further, the above-mentioned solid sediment that reaction mixture is centrifuged isolated for containing amidonitrogen and
The nitrogenous fertilizer of nitrate nitrogen.
In the present invention, above-mentioned containing amidonitrogen with the solid sediment of the nitrogenous fertilizer of nitrate nitrogen, it is by the alkali containing carbonyl
The carbonyl structure contained in property solution forms with the reaction bonded of nitrate anion nitrogen oxygen single key structure, it is achieved that concentrated nitric acid contained waste liquid
The reuse of middle nitric acid, the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen produced cleans through simple, it is possible to directly beat
Wrap into storehouse and sell chemical fertilizer production producer.
Further, above-mentioned adsorbent is storng-acid cation exchange resin, modified zeolite, carbon modified or chelating resin.
In the present invention, being centrifuged by reaction mixture, the contained waste liquid obtained enters through storng-acid cation exchange resin
Row cation exch ange adsorption, absorption contained waste liquid in copper ion, the liquid after absorption can reach " Beijing's water pollutant combine
Close discharge standard " DB11/307-2013 table three requirement discharge.
It is the most permissible that above-mentioned liquid after adsorbent has reached " Beijing's water pollutant comprehensive discharge standard "
Discharge, it is also possible to for reuse, obtain after concentrated nitric acid copper-containing wastewater is reacted with the alkaline solution containing carbonyl containing amide
The nitrogenous fertilizer of state nitrogen and nitrate nitrogen is carried out, it is achieved thereby that Resource Recycling Utilization, makes enterprise obtain more preferable economic benefit.
In the present invention, the column capacity of above-mentioned adsorbent and the flow of contained waste liquid can be according to the contained waste liquids of actual treatment
Amount calculates.
In the present invention, after above-mentioned adsorbent is saturated, with 5～20% sulfuric acid solution by the copper ion in adsorbent
Backwash goes out, formed copper-bath, 5～20% sulfuric acid solution backwash after adsorbent can recycle.
Further, above-mentioned sulfuric acid solution is 5～20% sulfuric acid solution.
Further, above-mentioned sulfuric acid solution is 10% sulfuric acid solution.
Further, the above-mentioned method that carries out being electrolysed by copper-bath is: be passed through in electrolysis bath by copper-bath, and
Pressurization flow at high speed in electrolysis bath, under electric field action, gradually can separate out cathode copper at negative electrode.
In the present invention, above-mentioned swiftly flowing high speed of pressurizeing in electrolysis bath refer to copper-bath with 100-15000 liter/
Hour flow velocity pressurize in electrolysis bath flow at high speed.
Above-mentioned electrolysis tech, is that one utilizes solution eddy flow working method, valuable metal is carried out the new of selective electrolysis
Technology, is particularly suitable for sewage treatment industry to low concentration, the selective electrolysis separation of complicated solution and purification, and general
Heavy metal ions in wastewater is peeled off.The principle of above-mentioned electrolysis tech is based on each metal ion theory deposition potential (E￠)
Difference, as long as the metal to be i.e. extracted and other metal ions in solution system have a bigger potential difference, then current potential calibration
Metal is prone to preferentially separate out at negative electrode, and it is it is crucial that by pressurization high speed liquid stream at a high speed, eliminate the unfavorable factor to electrolysis, keep away
Exempt from traditional electrolyte mode in electrolytic process by many factors (ion concentration, ion rheobase, anode and cathode current potential, concentration difference
Polarization, pH value, overvoltage etc.) rough sledding that affects, high-quality metal can be produced by simple technical conditions and produce
Product, simultaneously this technology can complete wide concentration range that traditional electrolyte technology can not complete (from 0. more than zero grams per liter to several hectograms/
Rise), high current density (400A/m2Electrolytic etching of metal in the case of above), and different metal product (sheet material or powder can be produced
Body).The method can effectively solve other processing mode and pollute that environment, purification of waste water difficulty be big, technological process length, production cost
High, valuable metal, the problem easily causing secondary pollution etc. cannot be reclaimed.
In the present invention, the copper-bath after sulfuric acid cleaned adsorbent is passed through in electrolysis bath, in the effect of circulating pump
Under, pressurize in electrolysis bath with the flow velocity being exceedingly fast and flow up at a high speed, under the effect of electric field, hydroxide radical anion is fixed to anode
Copper ion in movement, solution obtains electronic deposition precipitating metal copper, anion to negative electrode displacement, copper ion at negative electrode
Electronics precipitated oxygen is lost at anode.Just can go out groove after scalding, pack warehouse-in when the metallic copper on negative electrode reaches constant weight.
Meanwhile, the tail washings after electrolysis is higher because of sulfuric acid content, as sulfuric acid solution, adsorbent can be carried out backwash and regeneration recycling.
Preferably, above-mentioned concentrated nitric acid copper-containing wastewater produces the method for cathode copper, comprises the following steps:
Step (1): by concentrated nitric acid copper-containing wastewater and the alkaline solution (1～2) by volume containing carbonyl: the ratio of 1 is mixed
Close, fully react at 30～50 DEG C；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with 5～20% storng-acid cation exchange resins that absorption is saturated in sulfuric acid solution backwash step (3),
Obtain copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Compared with prior art, the invention have the benefit that
(1) concentrated nitric acid copper-containing wastewater of the present invention reacts with the alkaline solution containing carbonyl, containing carbonyl in course of reaction
The reaction mechanism of the carbonyl structure in the alkaline solution of base and nitrate anion nitrogen oxygen single key structure, make alkaline solution containing carbonyl with
Nitrate anion reaction generates containing amidonitrogen and the nitrogenous fertilizer of nitrate nitrogen, meanwhile, and concentrated nitric acid copper-containing wastewater and the alkalescence containing carbonyl
Solution react after the contained waste liquid of isolated, by can reach " Beijing's water pollutant after adsorbent copper ion
Comprehensive discharge standard " DB11/307-2013 table three require discharge or reuse.Additionally, adsorbent is produced with after sulfuric acid solution backwash
Raw copper-bath is electrolysed, and obtains cathode copper, this electrolytic method clean and effective.Present invention achieves integrated artistic not produce
Tissue regeneration promoting pollutant, do not cause secondary pollution to environment, realize comprehensive utilization of resources simultaneously, the target of saving water resource.
(2) electrolysis tech that the present invention is utilized has extremely strong selectivity to the electrolysis of copper, requires solution compolision not
High feature, directly produces qualified standard electrodeposition copper products from copper segregation liquid, by impure higher, relatively low the containing of cupric
In copper solution, institute's cupric quantitative change is now standard cathode copper, compared with producing copper sulfate or curpic carbonate process technique, has technique letter
The many advantages such as list, short, Product processing expense output low, the direct tough cathode product of handling process.
(3) present invention and prior art use the place's science and engineering that will neutralize after the dilution of concentrated nitric acid contained waste liquid with alkaline matter
Skill is compared, and has that project investment is little, the construction period is short, risk is little, free from environmental pollution, Social and economic benef@outstanding feature.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described.
Fig. 1 produces the process flow diagram of cathode copper for the concentrated nitric acid copper-containing wastewater that the present invention provides.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but those skilled in the art will
Understanding, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.In embodiment unreceipted specifically
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument unreceipted production firm person, be
Can be by the commercially available conventional products bought and obtain.
Embodiment 1
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 1:1 by volume of the alkaline solution containing carbonyl is mixed, fills
Divide reaction；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 5% sulfuric acid solution backwash step (3) is saturated, obtain
Copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Embodiment 2
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 1.5:1 by volume of the alkaline solution containing carbonyl is mixed,
Fully reaction；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 5% sulfuric acid solution backwash step (3) is saturated, obtain
Copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Embodiment 3
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 2:1 by volume of the alkaline solution containing carbonyl is mixed, fills
Divide reaction；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 5% sulfuric acid solution backwash step (3) is saturated, obtain
Copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Comparative example 1
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 0.5:1 by volume of the alkaline solution containing carbonyl is mixed,
Fully reaction；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 5% sulfuric acid solution backwash step (3) is saturated, obtain
Copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Comparative example 2
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 3:1 by volume of the alkaline solution containing carbonyl is mixed, fills
Divide reaction；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 5% sulfuric acid solution backwash step (3) is saturated, obtain
Copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Effect example 1
In order to weigh after above-mentioned concentrated nitric acid copper-containing wastewater reacts with the alkaline solution containing carbonyl concentrated nitric acid copper-containing wastewater
Actual processing effect, special embodiment 1-3, comparative example 1-2 and the alkali of being respectively adopted the waste water that the concentration containing concentrated nitric acid is identical neutralizes
Method processes, and detects the remaining nitrogen content after process, and result is as shown in table 1.
Table 1
From above-mentioned table 1, use the concentrated nitric acid copper-containing wastewater of present invention offer in embodiment 1～3 and containing carbonyl
Alkaline solution (2～1) by volume: the ratio of 1 mixes the remaining nitrogen content of contained waste liquid after the technical scheme carrying out reacting processes
All below 0.1%, far below comparative example 1～2 and alkali neutralization method process after remaining nitrogen content, illustrate that the method for the present invention has
There is the advantage that conversion rate of nitrogen is high.
Simultaneously as the reaction of concentrated nitric acid copper-containing wastewater and the alkaline solution containing carbonyl is an exothermic reaction, by body
Long-pending than (2～1): the ratio mixing of 1 is reacted, and reaction temperature can maintain 30～50 DEG C, and reaction is the most used
Time only needs 0.5-2 hour；In comparative example 1, concentrated nitric acid copper-containing wastewater is with the alkaline solution 0.5:1's by volume containing carbonyl
Ratio mixes, and does not reaches corresponding reaction temperature, and reaction only carries out 5 minutes i.e. stopping, and fully carries out completely as reacted, and needs
Additionally increase heater；Concentrated nitric acid copper-containing wastewater and the ratio of the alkaline solution 3:1 by volume containing carbonyl in comparative example 2
Mixing, does not reaches reaction temperature equally, although reaction has been carried out 100 minutes always, but reacts and insufficient, in contained waste liquid
Nitrogen content is up to 3.2%；In prior art, the response time of alkalescence neutralisation is up to 200 minutes, and the time is relatively compared with the present invention
Long, do not have technical scheme in hgher efficiency.
In summary, concentrated nitric acid copper-containing wastewater of the present invention and the alkaline solution containing carbonyl, by volume (2～1): 1
Ratio mixing carries out the technical scheme reacted, and reaction only needs 0.5-2 hour, and conversion rate of nitrogen is high, need not extra in course of reaction
Firing equipment, in copper-containing wastewater after treatment, the mass percent of contained remaining nitrogen is only 0.01-0.1%.
Embodiment 4
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 1.5:1 by volume of the alkaline solution containing carbonyl is mixed,
Fully react；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 5% sulfuric acid solution backwash step (3) is saturated, obtain
Copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Embodiment 5
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 1.5:1 by volume of the alkaline solution containing carbonyl is mixed,
Fully reaction；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 10% sulfuric acid solution backwash step (3) is saturated, obtain
To copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Embodiment 6
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 1.5:1 by volume of the alkaline solution containing carbonyl is mixed,
Fully reaction；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 20% sulfuric acid solution backwash step (3) is saturated, obtain
To copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Embodiment 7
A kind of method utilizing concentrated nitric acid copper-containing wastewater to produce cathode copper, comprises the following steps:
Step (1): the ratio of concentrated nitric acid copper-containing wastewater with the 1.5:1 by volume of the alkaline solution containing carbonyl is mixed,
Fully reaction；
Step (2): mixed liquor reaction completed is centrifuged, obtains solid sediment and contained waste liquid；Above-mentioned solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2),
Obtain adsorbing saturated storng-acid cation exchange resin；
Step (4): with the storng-acid cation exchange resin that absorption in 15% sulfuric acid solution backwash step (3) is saturated, obtain
To copper-bath；
Step (5): the copper-bath in step (4) is passed through in electrolysis bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
May be made that in the case of spirit and scope many other change and amendment.It is, therefore, intended that in the following claims
Including all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. one kind utilizes the method that concentrated nitric acid copper-containing wastewater produces cathode copper, it is characterised in that comprise the following steps: by concentrated nitric acid
Copper-containing wastewater carries out being sufficiently mixed reaction with the alkaline solution containing carbonyl, is separated by reacted mixed liquor, consolidate
Body precipitate and contained waste liquid；Subsequently, with the copper ion in adsorbent contained waste liquid, upon adsorption saturated after, molten with sulphuric acid
Liquid backwash adsorbent obtains copper-bath；Then, copper-bath is carried out electrolysis and obtain cathode copper.
Utilize the method that concentrated nitric acid copper-containing wastewater produces cathode copper the most as claimed in claim 1, it is characterised in that described contain
The alkaline solution of carbonyl is the weak base of amide-type.
Utilize the method that concentrated nitric acid copper-containing wastewater produces cathode copper the most as claimed in claim 1, it is characterised in that described dense nitre
Acid copper-containing wastewater and the mixed proportion of the alkaline solution containing carbonyl, be calculated as (1～2): 1 by volume.
4. the method utilizing concentrated nitric acid copper-containing wastewater production cathode copper as described in any one of claims 1 to 3, its feature exists
In, described concentrated nitric acid copper-containing wastewater is 30～50 DEG C with the temperature of the alkaline solution hybrid reaction containing carbonyl.
Utilize the method that concentrated nitric acid copper-containing wastewater produces cathode copper the most as claimed in claim 1, it is characterised in that described solid
Precipitate is the nitrogenous fertilizer containing amidonitrogen and nitrate nitrogen.
Utilize the method that concentrated nitric acid copper-containing wastewater produces cathode copper the most as claimed in claim 1, it is characterised in that described absorption
Agent is storng-acid cation exchange resin, modified zeolite, carbon modified or chelating resin.
Utilize the method that concentrated nitric acid copper-containing wastewater produces cathode copper the most as claimed in claim 1, it is characterised in that described sulphuric acid
Solution is 5～20% sulfuric acid solution of concentration.
Utilize the method that concentrated nitric acid copper-containing wastewater produces cathode copper the most as claimed in claim 1, it is characterised in that described by sulfur
The method that acid copper solution carries out being electrolysed is: be passed through in electrolysis bath by copper-bath, and flow at high speed of pressurizeing in electrolysis bath,
Under electric field action, gradually can separate out cathode copper at negative electrode.
Utilize the method that concentrated nitric acid copper-containing wastewater produces cathode copper the most as claimed in claim 1, it is characterised in that include following
Step:
Step (1): by concentrated nitric acid copper-containing wastewater with the alkaline solution containing carbonyl (1～2) by volume: the ratio of 1 mixes,
30～50 DEG C are fully reacted；
Step (2): the mixed liquor reacted in step (1) is centrifuged, obtains solid sediment and contained waste liquid；
Step (3): it is attached that use storng-acid cation exchange resin carries out ion-exchange absorption to contained waste liquid in step (2), obtains
Adsorb saturated storng-acid cation exchange resin；
Step (4): with 5～20% storng-acid cation exchange resins that absorption is saturated in sulfuric acid solution backwash step (3), obtain
Copper-bath；
Step (5): be passed through in electrolysis bath by the copper-bath in step (4), and flow at high speed of pressurizeing in electrolysis bath, at electricity
Under field action, gradually can separate out cathode copper at negative electrode.
10. a cathode copper, it is characterised in that described cathode copper is prepared into by method according to any one of claim 1～9
Arrive.
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