CN108048656A - A kind of separation method of the plating wastes of the nickel containing chromium-copper - Google Patents
A kind of separation method of the plating wastes of the nickel containing chromium-copper Download PDFInfo
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- CN108048656A CN108048656A CN201711117511.1A CN201711117511A CN108048656A CN 108048656 A CN108048656 A CN 108048656A CN 201711117511 A CN201711117511 A CN 201711117511A CN 108048656 A CN108048656 A CN 108048656A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The present invention relates to a kind of separation methods of the plating wastes of ambrose alloy containing chromium, this method includes the plating wastes of the nickel containing chromium-copper and sodium hydroxide breaks into slurry in chromium acid sodium solution, with oxygen successive reaction is carried out at certain temperature and pressure, sodium hydroxide is as reactant, by filtration washing, filtrate is sodium chromate, can prepare sodium dichromate.Filter residue containing cupro-nickel is obtained by filtration, by sulfuric acid dissolution, iron is removed after filtering.Except the filtrate after iron, sulfide, reaction generation cuprous sulfide or copper sulfide precipitation, filtration washing are added in, obtains pure cuprous sulfide or copper sulphide product.Pure nickeliferous filtrate adds in sodium carbonate, obtains nickelous carbonate product, filtrate can go to prepare anhydrous sodium sulphate product.The present invention, low energy consumption, and plating wastes are easy to get, cheap, and sodium chromate, cuprous sulfide or copper sulfide, nickelous carbonate are at low cost after recycling, has the market competitiveness, meets national industry circular economy policy requirement.
Description
Technical field
The present invention relates to the processing method of plating wastes, a kind of separation side of the plating wastes of nickel containing chromium-copper is related generally to
Method.
Background technology
The harmful heavy metal being enriched in plating wastes in waste water, have the characteristics that easily accumulation, it is unstable, be easy to run off, such as
It is not dealt carefully with, it is arbitrary to stack, serious and long-range secondary pollution will be caused to human body and ecological environment.And plating wastes
In containing the heavy metals such as substantial amounts of copper, nickel, chromium, belong to valuable regenerated resources, environmental pollution can be not only solved after recycling
Problem, moreover it is possible to obtain considerable economic benefit, while solve the problems, such as that the heavy metal resources such as cupro-nickel chromium are short to a certain extent.
In the metal recovery process of plating wastes, it is known that on Zhejiang Fujian and other places, the enterprise of production and operation is mostly used three
Cupro-nickel is separated in the state of valency chromium, since separating difficulty is big, the chromium waste residue of generation contains cupro-nickel and a large amount of calcium salts, and chromium can not be abundant
It recycles, the cupro-nickel rate of recovery is less than 50%.Since chromium waste residue can not make full use of, at the national burying method forbidden
Reason, these enterprise's almost all are closed down by National Environmental Protection Agency.Qi Meifu's " recycles copper, nickel, the technique of chromium from electroplating sludge
In a research " text, using the method for waste material plus soda roasting, due to this method, amount of liquid phase is high in roasting process, can not industrialize.
And using yellow modumite method except iron and calcium salt clean, technique is difficult to control, and product copper sulfide and nickelous carbonate impurity content are high.And
Electrolysis recycles copper, of high cost.In Guo Xueyi " research of nickel, copper and chromium from electroplating sludge " text, using sulfuric acid leaching --
The heavy copper of vulcanization -- two sections neutralize except chromium -- nickelous carbonate process of enriching, Recovering Copper, chromium and nickel from electroplating sludge, and investigate
Influence factor during each process, although using two sections except the nickel that chromium process is effectively reduced in precipitation process loses,
Trivalent chromium is recycled using two-stage method, and the chromium hydroxide formed has the pollution of calcium, chromium hydroxide is difficult to be utilized again.It is separating
During cupro-nickel, due to the pollution of trivalent chromium, recycling cupro-nickel product purity only has 94%, so limits the application of product.
It can be seen that in cost than in the case of relatively low, how to be sufficiently separated chromium-copper nickel in plating wastes, and prepare pure
The compound of higher copper, chromium and nickel is spent, and the waste generated all recycles, and is the key that the present invention.
The content of the invention
Therefore, the technical problems to be solved by the invention are to overcome technological deficiency of the prior art, provide a kind of point
It is low from amount of liquid phase in the process, industrial operation and it can prepare the separation method of purity higher copper chromium nickel.
The present invention is by studying, with the following method：
(1) chromium acid sodium solution is added in hollander tub, and adds in sheet or liquid sodium hydroxide, then adds in ambrose alloy containing chromium
Plating wastes mashing.
(2) the slurry of (1) middle formation is filtered by drum sieve, fine slag removes next stage hollander tub, and thick slag return is beaten again.
Will (2) middle screened stock material with high-pressure diaphragm pump be pumped into material material heat exchanger and double pipe heater heat, after heating
Slurry enters in tower reactor, and slurry carries out successive reaction with oxygen at certain temperature and pressure.
Reaction equation is as follows：
Cr2O3+8NaOH→4Na2CrO4+4H2O ①
(4) the oxidation solution slurry come out from (3) middle tower reactor exchanges heat into pan feeding material heat exchanger and cold slurry, is down to often
Dissolution fluid storage tank is arrived after pressure again.
(5), from the oxidation solution slurry of (4) middle dissolution fluid storage tank, by filter filtration washing, filtrate is sodium chromate, can be prepared
Sodium dichromate.
(6) the filter residue containing cupro-nickel come out from (5) middle filter, by sulfuric acid dissolution, controls certain pH value, is removed after filtering
Iron.Except the filtrate after iron, sulfide is added in, at certain temperature and reaction time, reaction generation cuprous sulfide or copper sulfide
Precipitation, filtration washing obtain pure cuprous sulfide or copper sulphide product.
The rate of recovery of copper can reach 99.5%.
Reaction equation is as follows：
2CuSO4+2Na2S2O3→Cu2S↓+2Na2SO4+3SO2 ②
2CuSO4+2Na2S→2CuS↓+2Na2SO4 ③
(7), from filtrate after (6) middle filtration washing cuprous sulfide or copper sulfide, add at a certain temperature in sodium hydroxide
With, filter and wash out chromium hydroxide return oxidation operation use.Pure nickeliferous filtrate adds in sodium carbonate, certain temperature and
Under reaction time, nickelous carbonate precipitation is formed, after filter washing, obtains nickelous carbonate product.
The rate of recovery of nickel can reach 99.5%.
Reaction equation is as follows：
2NiSO4+2Na2CO3→NiCO3↓+2Na2SO4 ④
(8), from the filtrate of (7) middle filtration washing nickelous carbonate, can go to prepare anhydrous sodium sulphate product.
The content of sodium chromate is 0.5~40% (with Na in preferred chromium acid sodium solution2Cr2O7·2H2O is counted), chromium-copper nickel electricity
Plate waste material and chromium acid sodium solution weight ratio 1:0.5~100, the molal quantity of chromium (Cr) and sodium hydroxide in chromium-copper nickel plating wastes
The ratio between molal quantity is 1:1.5~8.
The maximum width of preferred rotating cylinder sieve screen apertures is 0.5~5mm.
Preferably the operating pressure of diaphragm pump is 3.0~15Mpa, and double-tube heat exchanger high-temperature molten salt or conduction oil add
150~400 DEG C of the operating temperature of heat, high-temperature molten salt or heat-conducting oil heating, 120~350 DEG C of oxidation liquid temperature.
Preferred cupro-nickel slag filtration washing washs for multi-stage countercurrent, and series is 2~5 grades.
The sulfuric acid solution concentration for preferably dissolving cupro-nickel filter residue is 0.5~20%, copper (CuO), nickel (NiO), iron
(Fe2O3) molal quantity is respectively 0.5~3,0.5~3 and 2~5 with the ratio between the molal quantity of sulfuric acid, solution temperature is 20~60 DEG C, molten
Solution pH value is 1.5~3.5 after solution.Iron dross removing washing is washed for multi-stage countercurrent, and series is 2~5 grades.
The sulfide being preferably added is one or two kinds of for vulcanized sodium and sodium thiosulfate, copper (Cu2+) rub with sulfide
The ratio between you is 1:1~2, copper temperature of sinking is 60~100 DEG C, and when the heavy copper reaction time is 0.1~48 small, the copper filtration washing that sinks is more
Stage countercurrent washs, and series is 2~5 grades.
Preferably, sink before nickel, feed temperature control, 60~100 DEG C, it is 6.0~7.0 to neutralize pH value, washes out hydrogen-oxygen
Change chromium washing to wash for multi-stage countercurrent, series is 2~5 grades.The pH value of coprecipitated nickel hydroxide is 7.2~9.5, the temperature 60 of coprecipitated nickel hydroxide~
100 DEG C, when the coprecipitated nickel hydroxide reaction time is 0.1~48 small.Heavy nickel filtration washing washs for multi-stage countercurrent, and series is 2~5 grades.
The present invention relates to a kind of separation method of the plating wastes of ambrose alloy containing chromium, the plating that this method includes the nickel containing chromium-copper is given up
Material breaks into slurry with sodium hydroxide in chromium acid sodium solution, and after expecting material heat exchanger and double pipe heater heating, entrance is tower
Reactor carries out successive reaction with oxygen at certain temperature and pressure, and sodium hydroxide is as reactant, for the chromic acid of formation
Sodium provides sodium source, and mixture obtained by the reaction with cold slurry by after material material heat exchanger heat exchange, dropping to the slurry of the oxidation after normal pressure
Material, by filtration washing, filtrate is sodium chromate, can prepare sodium dichromate.Filter residue containing cupro-nickel is obtained by filtration, by sulfuric acid dissolution, mistake
Iron is removed after filter.Except the filtrate after iron, add in sulfide, at certain temperature and reaction time, reaction generation cuprous sulfide or
Copper sulfide precipitation, filtration washing obtain pure cuprous sulfide or copper sulphide product.Nickeliferous filtrate adds in sodium hydroxide certain
At a temperature of neutralize, filter out chromium hydroxide return oxidation operation use.Pure nickeliferous filtrate adds in sodium carbonate, certain temperature
And under the reaction time, nickelous carbonate precipitation is formed, after filter washing, obtains nickelous carbonate product, filtrate can go to prepare anhydrous sodium sulphate product.
Low energy consumption in separation process by the present invention, and plating wastes are easy to get, cheap, sodium chromate, cuprous sulfide after recycling
Or copper sulfide, nickelous carbonate are at low cost, when simultaneous recovery of chromium, will not be formed with the chromium hydroxide of the pollution of calcium, and there is no chromium hydroxides
It is difficult to the problem of being utilized again；Particularly, in separation process, liquid measure is few, is suitble to industrial applications, and the present invention is competing with market
Power is striven, meets national industry circular economy policy requirement.
Description of the drawings
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with attached drawing, to the present invention into
Row is further described.
Fig. 1 shows plating wastes separating technology first portion general flow charts of the present invention；
Fig. 2 represents plating wastes separating technology second portion general flow chart of the present invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.Following embodiment is not limited to the scope of the present invention for illustrating the present invention.
As shown in Figure 1 and Figure 2, the separation of the plating wastes of cupric chromium nickel of the present invention is completely described in Fig. 1, Fig. 2
Method flow is operated with specific reference to following methods：
1 adds in chromium acid sodium solution in hollander tub, and adds in flaky sodium hydrate, and the plating for then adding in the ambrose alloy containing chromium is given up
Material mashing, the content of sodium chromate is 0.5~40% (with Na wherein in chromium acid sodium solution2Cr2O7·2H2O is counted), the plating of chromium-copper nickel
Waste material and chromium acid sodium solution weight ratio 1:0.5~100, the molal quantity of chromium (Cr) and rubbing for sodium hydroxide in chromium-copper nickel plating wastes
The ratio between your number is 1:1.5~8.Slurry is pumped to drum sieve by delivery pump 2 and filtered, the maximum widths of rotating cylinder sieve screen apertures for 0.5~
5mm, the fine slag filtered out remove next stage hollander tub 4, and thick slag return is beaten again.Screened stock material is through the high-pressure diaphragm pump 6 of delivery pump 5
It is pumped into material material heat exchanger 7 and double pipe heater 9 is heated, the slurry after heating enters in tower reactor 10, slurry and oxygen
Gas carries out successive reaction at certain temperature and pressure, is 3.0~15Mpa in the operating pressure of this diaphragm pump, casing heats
150~400 DEG C of the operating temperature of device high-temperature molten salt or heat-conducting oil heating, high-temperature molten salt or heat-conducting oil heating, oxidation liquid
120~350 DEG C of temperature.The oxidation solution slurry that tower reactor 10 comes out goes material material heat exchanger 7 to heat slurry.From material material heat exchange
The oxidation solution slurry that device comes out after dropping to normal pressure, by dissolution fluid hold-up tank 14, is pumped into filter 16 by pump 15 and crosses diafiltration
It washs, filtrate is sodium chromate, can prepare sodium dichromate.Cupro-nickel slag filtration washing washs for multi-stage countercurrent, and series is 2~5 grades.From filtering
The filter residue containing cupro-nickel that machine 16 comes out, in except iron flask 17, by sulfuric acid dissolution, solution temperature is 20~60 DEG C, solution after dissolving
PH value is 1.5~3.5, and the sulfuric acid solution concentration of dissolving cupro-nickel filter residue is 0.5~20%, copper (CuO), nickel (NiO), iron (Fe2O3)
Molal quantity is respectively 0.5~3,0.5~3 and 2~5 with the ratio between the molal quantity of sulfuric acid, by pump 18, is pumped into filter 19 and crosses diafiltration
Iron is removed after washing.Iron dross removing washing is washed for multi-stage countercurrent, and series is 2~5 grades.Except the filtrate after iron is into heavy copper tank 20, add in
Sulfide it is one or two kinds of for vulcanized sodium and sodium thiosulfate, copper (Cu2+) with sulfide mole the ratio between be 1:1~2, heavy copper
Temperature is 60~100 DEG C, and when the heavy copper reaction time is 0.1~48 small, reaction generation cuprous sulfide or copper sulfide precipitation pass through pump
21 are pumped into 22 filtration washing of filter, and the copper filtration washing that sinks washs for multi-stage countercurrent, and series is 2~5 grades.It is sub- to obtain pure vulcanization
Copper or copper sulphide product.The filtrate after filtration washing cuprous sulfide or copper sulfide from filter 22, into except chromium tank 23, feed liquid temperature
60~100 DEG C of degree control, sodium hydroxide neutralizes, and it is 6.0~7.0 to neutralize pH value, is pumped into filter 25 by pump 24, filters and wash
It washs out chromium hydroxide and returns to oxidation operation use, wash out chromium hydroxide washing and washed for multi-stage countercurrent, series is 2~5 grades.It is pure
Net nickeliferous filtrate adds in sodium carbonate into heavy nickel tank 26, and the pH value of coprecipitated nickel hydroxide is 7.2~9.5, and the temperature 60 of coprecipitated nickel hydroxide~
100 DEG C, when the coprecipitated nickel hydroxide reaction time is 0.1~48 small.Nickelous carbonate precipitation is formed, filter 28 is pumped by pump 27, is refiltered
Washing, obtains nickelous carbonate product, and the nickel filtration washing that sinks washs for multi-stage countercurrent, and series is 2~5 grades.Diafiltration is crossed from filter 28
The filtrate of nickelous carbonate is washed, can go to prepare anhydrous sodium sulphate product.
Embodiment 1
In 5m3Chromium acid sodium solution is added in hollander tub, and adds in flaky sodium hydrate, then adds in the plating of the ambrose alloy containing chromium
Waste material is beaten, and the content of sodium chromate is 30% (with Na wherein in chromium acid sodium solution2Cr2O7·2H2O is counted), wherein chromium-copper nickel is electroplated
Waste material 1000kg (Cr10%, Ni12%, Cu6%, Fe0.2%) and chromium acid sodium solution 2000kg, the sodium hydroxide of addition
385kg.Slurry is pumped by delivery pump to aperture 3mm filter areas 5m2Drum sieve filters, and the fine slag filtered out removes next stage 5m3It beats
Stock tank, thick slag return are beaten again.Screened stock material is pumped into 500m with 25kw high-pressure diaphragm pumps 52Material material heat exchanger and 300m2Casing
Heater is heated, and the slurry after heating enters in the tower reactor of 15m high, slurry and 300 DEG C of oxygen and pressure 10Mpa
Lower carry out successive reaction, double-tube heat exchanger high-temperature molten salt or heat-conducting oil heating, 400 DEG C of the operating temperature of high-temperature molten salt heating,
300 DEG C of oxidation liquid temperature.Tower reactor come out oxidation solution slurry, into after pan feeding material heat exchanger, into dissolution fluid
Hold-up tank, the oxidation solution slurry come out from hold-up tank, by being pumped into 50m2Filter filtration washing, filtrate are 45.0% chromic acid
Sodium is (with Na2Cr2O7·2H2O is counted), weight 1967kg can go to prepare sodium dichromate, and chromium yield is 99.8%.The cupro-nickel filtered out
Slag filtration washing washs for multi-stage countercurrent, and series is 3 grades.The filter residue containing cupro-nickel come out from filter, in 5m3Except in iron flask, warp
Addition 300kg98% sulfuric acid dissolutions dissolving cupro-nickel filter residue is crossed, solution temperature is 50 DEG C, and solution pH value is about 2.5 after dissolving.Pass through
It is pumped into 50m2Except iron after filter filtration washing, scum (iron hydroxide) butt quality is 4kg.Iron dross removing washing is multistage inverse
Stream washing, series are 3 grades.Except the filtrate after iron enters 5m3Heavy copper tank, 99.5% 5 water sodium thiosulfate 281kg of addition sink
Copper temperature is 85 DEG C, and when the heavy copper reaction time is 10 small, reaction generation cuprous sulfide precipitation, copper removal tank liquid is by being pumped into 50m2
Filter filtration washing, the copper filtration washing that sinks wash for multi-stage countercurrent, and series is 3 grades.Obtain cuprous sulfide product (butt)
74.59kg, content 99.2%, copper yield are 98.59%.The filtrate after filtration washing copper sulfide from filter, into except chromium
Tank, feed temperature control 85 DEG C, and sodium hydroxide neutralizes, and it is 6.5 to neutralize pH value, by being pumped into 50m2Filter is filtered and washed
It washs out 0.04kg chromium hydroxides (butt) and returns to oxidation operation use, wash out chromium hydroxide washing and washed for multi-stage countercurrent, grade
Number is 3 grades.Pure nickeliferous filtrate enters 5m3Heavy nickel tank adds in 221kg98% sodium carbonate, and the pH value of coprecipitated nickel hydroxide is 9.0, is sunk
90 DEG C of the temperature of shallow lake nickel, when the coprecipitated nickel hydroxide reaction time is 3 small.Nickelous carbonate precipitation is formed, by being pumped into 50m2Filter, after
Filter washing is dried to obtain 241kg99.5% nickelous carbonate products, and the nickel filtration washing that sinks washs for multi-stage countercurrent, and series is 3 grades.From
The filtrate of filter filtration washing nickelous carbonate can go to prepare anhydrous sodium sulphate product.
Embodiment 2
In 5m3Chromium acid sodium solution is added in hollander tub, and adds in flaky sodium hydrate, then adds in the plating of the ambrose alloy containing chromium
Waste material is beaten, and the content of sodium chromate is 30% (with Na wherein in chromium acid sodium solution2Cr2O7·2H2O is counted), wherein chromium-copper nickel is electroplated
Waste material 1000kg (Cr10%, Ni12%, Cu6%, Fe0.2%) and chromium acid sodium solution 5000kg, the sodium hydroxide of addition
450kg.Slurry is pumped by delivery pump to aperture 0.5mm filter areas 5m2Drum sieve filters, and the fine slag filtered out removes next stage 5m3
Hollander tub, thick slag return are beaten again.Screened stock material is pumped into 500m with 25kw high-pressure diaphragm pumps 52Material material exchanger and 300m2Casing
Heater is heated, and the slurry after heating enters in tower reactor, and 200 DEG C of slurry and oxygen under pressure 60Mpa with carrying out
Successive reaction, double pipe heater high-temperature molten salt or heat-conducting oil heating, 280 DEG C of the operating temperature of high-temperature molten salt heating, oxidation are anti-
Answer 200 DEG C of liquid temperature degree.In the oxidation solution slurry that tower reactor comes out, material material heat exchanger heating slurry is removed, expects heat exchanger from material
Oxidation solution slurry out, after dropping to normal pressure, by dissolution fluid holding vessel, by being pumped into 50m2Filter filtration washing, filter
Liquid is 35.0% sodium chromate, and weight 5103kg can go to prepare sodium dichromate, and chromium yield is 99.8%.The cupro-nickel slag mistake filtered out
Filter washing is washed for multi-stage countercurrent, and series is 3 grades.The filter residue containing cupro-nickel come out from filter, in 5m3Except in iron flask, by adding
Enter 300kg98% sulfuric acid dissolutions dissolving cupro-nickel filter residue, solution temperature is 50 DEG C, and solution pH value is about 2.5 after dissolving.By pumping
Enter 50m2Except iron after filter filtration washing, scum (iron hydroxide) butt quality is 4kg.Iron dross removing washing is washed for multi-stage countercurrent
It washs, series is 3 grades.Except the filtrate after iron enters 5m3Heavy copper tank, 99.5% 5 water sodium thiosulfate 281kg of addition, heavy copper temperature
It spends for 85 DEG C, when the heavy copper reaction time is 10 small, reaction generation copper sulfide precipitation, copper removal tank liquid is by being pumped into 50m2Filter
Filtration washing, the copper filtration washing that sinks wash for multi-stage countercurrent, and series is 3 grades.Copper sulphide product (butt) 75.00kg is obtained, is contained
It measures as 99.30%, copper yield is 99.15%.The filtrate after filtration washing cuprous sulfide or copper sulfide from filter, into except chromium
Tank, feed temperature control 85 DEG C, and sodium hydroxide neutralizes, and it is 6.5 to neutralize pH value, by being pumped into 50m2Filter is filtered and washed
It washs out 0.04kg chromium hydroxides (butt) and returns to oxidation operation use, wash out chromium hydroxide washing and washed for multi-stage countercurrent, grade
Number is 3 grades.Pure nickeliferous filtrate enters 5m3Heavy nickel tank adds in 221kg98% sodium carbonate, and the pH value of coprecipitated nickel hydroxide is 9.0, is sunk
90 DEG C of the temperature of shallow lake nickel, when the coprecipitated nickel hydroxide reaction time is 3 small.Nickelous carbonate precipitation is formed, by being pumped into 50m2Filter, after
Filter washing is dried to obtain 240kg99.6% nickelous carbonate products, and the nickel filtration washing that sinks washs for multi-stage countercurrent, and series is 3 grades.From
The filtrate of filter filtration washing nickelous carbonate can go to prepare anhydrous sodium sulphate product.
Embodiment 3
In 5m3Chromium acid sodium solution is added in hollander tub, and adds in flaky sodium hydrate, then adds in the plating of the ambrose alloy containing chromium
Waste material is beaten, and the content of sodium chromate is 30% (with Na wherein in chromium acid sodium solution2Cr2O7·2H2O is counted), wherein chromium-copper nickel is electroplated
Waste material 1000kg (Cr10%, Ni12%, Cu6%, Fe0.2%) and chromium acid sodium solution 3000kg, the sodium hydroxide of addition
250kg.Slurry is pumped by delivery pump to aperture 1mm filter areas 5m2Drum sieve filters, and the fine slag filtered out removes next stage 5m3It beats
Stock tank, thick slag return are beaten again.Screened stock material is pumped into 200m with 25kw high-pressure diaphragm pumps 52Material material heat exchanger and 150m2Casing
Heater is heated, and the slurry after heating enters in tower reactor, and 250 DEG C of slurry and oxygen under pressure 8Mpa with being connected
Continuous reaction, double pipe heater high-temperature molten salt or heat-conducting oil heating, 350 DEG C of the operating temperature of high-temperature molten salt heating, oxidation reaction
250 DEG C of liquid temperature degree.In the oxidation solution slurry that tower reactor comes out, material material heat exchanger heating slurry is removed, is gone out from material material heat exchanger
The oxidation solution slurry come, after dropping to normal pressure, by dissolution fluid holding vessel, by being pumped into 50m2Filter filtration washing, filtrate
For 40.0% sodium chromate, weight 2965kg can go to prepare sodium dichromate, and chromium yield is 99.8%.The cupro-nickel slag filtering filtered out
It washs and is washed for multi-stage countercurrent, series is 5 grades.The filter residue containing cupro-nickel come out from filter, in 5m3Except in iron flask, by adding in
300kg98% sulfuric acid dissolutions dissolve cupro-nickel filter residue, and solution temperature is 50 DEG C, and solution pH value is about 2.5 after dissolving.By being pumped into
50m2Except iron after filter filtration washing, scum (iron hydroxide) butt quality is 4kg.Iron dross removing washing is washed for multi-stage countercurrent
It washs, series is 3 grades.Except the filtrate after iron enters 5m3Heavy copper tank, 99.5% 5 water sodium thiosulfate 281kg of addition, heavy copper temperature
It spends for 85 DEG C, when the heavy copper reaction time is 10 small, reaction generation copper sulfide precipitation, copper removal tank liquid is by being pumped into 50m2Filter
Filtration washing, the copper filtration washing that sinks wash for multi-stage countercurrent, and series is 3 grades.Cuprous sulfide product (butt) 74.85kg is obtained,
Content is 98.99%, and copper yield is 98.32%.The filtrate after filtration washing cuprous sulfide or copper sulfide from filter, into except
Chromium tank, feed temperature control 85 DEG C, and sodium hydroxide neutralizes, and it is 6.5 to neutralize pH value, by being pumped into 50m2Filter, filtering is simultaneously
It washes out 0.04kg chromium hydroxides (butt) and returns to oxidation operation use, wash out chromium hydroxide washing and washed for multi-stage countercurrent,
Series is 3 grades.Pure nickeliferous filtrate enters 5m3Heavy nickel tank adds in 221kg98% sodium carbonate, and the pH value of coprecipitated nickel hydroxide is 9.0,
90 DEG C of the temperature of coprecipitated nickel hydroxide, when the coprecipitated nickel hydroxide reaction time is 3 small.Nickelous carbonate precipitation is formed, by being pumped into 50m2Filter, then
Filtration washing is dried to obtain 240.5kg99.55% nickelous carbonate products, and the nickel filtration washing that sinks washs for multi-stage countercurrent, series 3
Grade.From the filtrate of filter filtration washing nickelous carbonate, can go to prepare anhydrous sodium sulphate product.
Embodiment 1-3 specific experiments the results are shown in Table 1.
Table 1, the rate of recovery of the separated chromium-copper nickel of embodiment 1-3
| The rate of recovery | Chromium | Copper | Nickel |
| Embodiment 1 | 99.51 | 98.59 | 98.81 |
| Embodiment 2 | 99.83 | 99.15 | 98.50 |
| Embodiment 3 | 99.81 | 98.99 | 98.66 |
By 1 result of table as it can be seen that according to the method for the present invention, by fractional precipitation metallic element and filtration washing, obtained copper,
Chromium, nickel product recovery rate are high, and chromium recovery ratio is stably maintained at more than 99.5%, and copper recovery is more than 98.59%, nickel recovery
More than 98.5%, and amount of liquid phase is low in separation process, industrial operation and can prepare purity higher copper chromium nickel.
It is drawn from the research of Guo Xueyi et al., calcium method sinks data such as the following table 2 of chromium：
Table 2, except the chemical composition ratio (%) of residue after dechromising
| Ni | Cu | Cr | Fe | Ca | Mg |
| 0.76 | 0.01 | 10.86 | 0.63 | 13.39 | 0.04 |
It is drawn from data above, calcium content is 13.39% in the chromium of method recycling, and chromium is hardly resulted in again by calcium contamination
It utilizes.Although it, which studies article introduction, can be used as chromic salts raw material, hardly result in and be utilized again.
The research of Guo Xue benefits et al. is soda ash to be added to calcine chromium-copper nickel waste material, amount of liquid phase (1150 DEG C or more the chromic acid of formation
The amount and low melting point of sodium and excessive soda ash) will be more than 35%, when production, should not operate, and scale is smaller can not use revolution
Kiln produces, even if production, rotary kiln also easy ring formation, energy consumption is larger, and production cost is higher.
Chromium-copper nickel yield in the technology of the present inventor and the research method of Guo Xueyi and Qi Meifu et al. is compared as follows table
3：
Table 3, the chromium-copper nickel yield in each method
From data above Integrated comparative, the present invention has a clear superiority.
Obviously, the specific species used in above-described embodiment is only intended to clearly illustrate example, and is not pair
The restriction of embodiment.For those of ordinary skill in the art, it can also be made on the basis of the above description
Its various forms of variation or variation.There is no necessity and possibility to exhaust all the enbodiments.And it thus extends out
Obvious changes or variations still in the protection domain of the invention among.
Claims (8)
1. a kind of separation method of the plating wastes of nickel containing chromium-copper, comprises the following steps：
(1) chromium acid sodium solution is added in hollander tub, and adds in sheet or liquid sodium hydroxide, then adds in the electricity of the ambrose alloy containing chromium
Plate waste material mashing；
(2) the slurry of (1) middle formation is filtered by drum sieve, fine slag removes next stage hollander tub, and thick slag return is beaten again；
Will (2) middle screened stock material with high-pressure diaphragm pump be pumped into material material heat exchanger and double pipe heater heat, the slurry after heating
Into in tower reactor, slurry carries out successive reaction with oxygen at certain temperature and pressure；
(4) the oxidation solution slurry come out from (3) middle tower reactor exchanges heat into pan feeding material heat exchanger and cold slurry, after being down to normal pressure
Dissolution fluid storage tank is arrived again；
(5), from the oxidation solution slurry of (4) middle dissolution fluid storage tank, by filter filtration washing, filtrate is sodium chromate, can prepare arsenic
Sodium；
(6) the filter residue containing cupro-nickel come out from (5) middle filter, by sulfuric acid dissolution, controls certain pH value, and iron is removed after filtering；It removes
Filtrate after iron adds in sulfide, at certain temperature and reaction time, reaction generation cuprous sulfide or copper sulfide precipitation,
Filtration washing obtains pure cuprous sulfide or copper sulphide product；
(7), from filtrate after (6) middle filtration washing cuprous sulfide or copper sulfide, sodium hydroxide is added at a certain temperature and is neutralized, mistake
It filters and washes out chromium hydroxide and return to oxidation operation use；Pure nickeliferous filtrate adds in sodium carbonate, certain temperature and reaction
Under time, nickelous carbonate precipitation is formed, after filter washing, obtains nickelous carbonate product；
(8), from the filtrate of (7) middle filtration washing nickelous carbonate, can go to prepare anhydrous sodium sulphate product.
2. the method according to claim 1, wherein step (1) in middle chromium acid sodium solution the content of sodium chromate for 0.5~40% (with
Na2Cr2O7·2H2O is counted), chromium-copper nickel plating wastes and chromium acid sodium solution weight ratio 1:0.5~100, in chromium-copper nickel plating wastes
The ratio between the molal quantity of chromium (Cr) and the molal quantity of sodium hydroxide are 1:1.5~8.
3. the method according to claim 1, wherein step (2) middle drum sieve mesh maximum width be 0.5~5mm.
4. the operating pressure of the method according to claim 1, wherein step (3) interval membrane pump is 3.0~15Mpa, double pipe heater
With high-temperature molten salt or heat-conducting oil heating, 150~400 DEG C of the operating temperature of high-temperature molten salt or heat-conducting oil heating, oxidation reaction liquid temperature
120~350 DEG C of degree.
5. (5) middle filtration washing washs for multi-stage countercurrent for the method according to claim 1, wherein step, series is 2~5 grades.
6. (6) the middle sulfuric acid solution concentration for dissolving cupro-nickel filter residue is 0.5~20% for the method according to claim 1, wherein step,
Copper (CuO), nickel (NiO), iron (Fe2O3) molal quantity is respectively 0.5~3,0.5~3 and 2~5 with the ratio between the molal quantity of sulfuric acid, it is molten
It is 20~60 DEG C to solve temperature, and solution ph is 1.5~3.5 after dissolving；Iron dross removing washing is washed for multi-stage countercurrent, and series is 2~5
Grade.The sulfide of addition is a kind of for vulcanized sodium and sodium thiosulfate, copper (Cu2+) with sulfide mole the ratio between be 1:1~2, it sinks
Copper temperature is 60~100 DEG C, and when the heavy copper reaction time is 0.1~48 small, the copper filtration washing that sinks is that multi-stage countercurrent washs, and series is
2~5 grades.
7. the method according to claim 1, wherein step (7) in, neutralize pH value be 6.0~7.0, wash out chromium hydroxide washing
It is washed for multi-stage countercurrent, series is 2~5 grades；The pH value of coprecipitated nickel hydroxide is 7.2~9.5,60~100 DEG C of the temperature of coprecipitated nickel hydroxide, precipitation
When the nickel reactant time is 0.1~48 small.
8. the method according to claim 1, wherein step (8) in sink nickel filtration washing for multi-stage countercurrent wash, series be 2~5
Grade.
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| CN111617779A (en) * | 2020-07-19 | 2020-09-04 | 河南科技大学 | Cu prepared by decomposing copper in cobalt electrolyte through ultraviolet radiation2Method of S photocatalyst |
| CN113862482A (en) * | 2021-10-08 | 2021-12-31 | 上海良仁化工有限公司 | Process for recovering chromium, copper, nickel and cobalt from electroplating sludge |
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