CN108046324A - A kind of method that copper chromium nickel is recycled from the plating wastes of cupric chromium nickel - Google Patents
A kind of method that copper chromium nickel is recycled from the plating wastes of cupric chromium nickel Download PDFInfo
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- CN108046324A CN108046324A CN201711115728.9A CN201711115728A CN108046324A CN 108046324 A CN108046324 A CN 108046324A CN 201711115728 A CN201711115728 A CN 201711115728A CN 108046324 A CN108046324 A CN 108046324A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/14—Chromates; Bichromates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/06—Carbonates
Abstract
The present invention relates to a kind of methods that copper chromium nickel is recycled from the plating wastes of cupric chromium nickel, 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, relate generally to a kind of recycle copper from the plating wastes of cupric chromium nickel
The method of chromium nickel.
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 return
Amount of liquid phase is low during receipts, industrial operation and can prepare the recovery 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 multistage impact 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), from the oxidation solution slurry that (3) middle multistage impact reactor comes out, it is anti-that oxidation is continued into multistage heat preservation curing tank
It should.
(5), from the oxidation solution slurry that (4) middle heat preservation curing tank comes out, into ten grades of slurry flash-pots, obtained steam passes through
Remove heating single pipe heat exchanger heating slurry after ten grades of steam-water separators separation water, the condensed water after single pipe heat exchanger exchanges heat,
Condensation generator is removed, the steam exhaust devaporation of formation is used by sodium dichromate prepared by sodium chromate and process after recycling cupro-nickel, hence it is evident that
Ground reduces sodium dichromate steam consumption and recycles the steam consumption of cupro-nickel.
(6) the oxidation solution slurries that ten grades of slurry flash-pots come out from (5), after dropping to normal pressure, by filter filtration washing,
Filtrate is sodium chromate, can prepare sodium dichromate, and the rate of recovery of chromium reaches 99.8%.
(7) the filter residue containing cupro-nickel come out from (6) 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, and 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
(8), from filtrate after (7) 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
(9), from the filtrate of (8) 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, impinging stream is anti-
The series for answering device is 2~20 grades.
Preferably multistage heat preservation curing tank is 2~10 grades..
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 method that copper chromium nickel is recycled in plating wastes of the present invention from the ambrose alloy containing chromium, passes through single tube and sleeve heat exchange
After device heating, into multistage impact reactor, successive reaction, sodium hydroxide are carried out at certain temperature and pressure with oxygen
As reactant, sodium source is provided for the sodium chromate of formation, mixture obtained by the reaction is evaporated under reduced pressure by multistage slurry flash-pot,
Obtained steam goes heating single pipe heat exchanger by ten grades of steam-water separators, and the condensed water after single pipe heat exchanger exchanges heat is gone
Condensation generator, steam exhaust devaporation sodium dichromate and the process after recycling cupro-nickel of formation use.The oxidation slurry after normal pressure is dropped to,
By filtration washing, filtrate is sodium chromate, can prepare sodium dichromate.Filter residue containing cupro-nickel is obtained by filtration, by sulfuric acid dissolution, after filtering
Except iron.Except the filtrate after iron, sulfide is added in, at certain temperature and reaction time, reaction generation cuprous sulfide or vulcanization
Copper precipitates, and filtration washing obtains pure cuprous sulfide or copper sulphide product.Nickeliferous filtrate adds in sodium hydroxide in certain temperature
Lower neutralization filters out chromium hydroxide and returns to oxidation operation use.Pure nickeliferous filtrate adds in sodium carbonate, certain temperature and anti-
Under between seasonable, 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 Tong Genie techniques first portion general flow chart is recycled in plating wastes of the present invention；
Fig. 2 represents plating wastes recycling copper chromium nickel technique 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, completely described in Fig. 1, Fig. 2 it is of the present invention from the plating wastes of cupric chromium nickel return
The method flow of copper chromium nickel is received, 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% (in terms of Na2Cr2O72H2O) wherein in chromium acid sodium solution, and chromium-copper nickel is electroplated
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 ten grades of single tube heat exchangers 7 and double-pipe exchange 9 is heated, the slurry after heating enters multistage impact reactor
In 10, slurry and oxygen carry out successive reaction at certain temperature and pressure, this diaphragm pump operating pressure for 3.0~
The operating temperature 150~400 of 15Mpa, double-tube heat exchanger high-temperature molten salt or heat-conducting oil heating, high-temperature molten salt or heat-conducting oil heating
DEG C, 120~300 DEG C of oxidation liquid temperature, the series of impact reactor is 2~20 grades.In multistage impact reactor 10
Oxidation solution slurry out continues oxidation reaction into multistage heat preservation curing tank 11, and multistage heat preservation curing tank is 2~10 grades.From
The oxidation solution slurry that curing tank 11 comes out is kept the temperature, into ten grades of slurry flash-pots 12, obtained steam passes through ten grades of steam-water separations
Device 13 goes ten grades of single pipe heat exchangers 7 of heating to heat slurry after separating water, the condensed water after ten grades of single pipe heat exchangers 7 exchange heat,
Ten grades of condensation generators 8 are removed, steam exhaust devaporation sodium dichromate and the process after recycling cupro-nickel of formation use.From ten grades of slurry spontaneous evaporations
The oxidation solution slurry that device 12 comes out after dropping to normal pressure, by holding vessel 14, is pumped into 16 filtration washing of filter by pump 15, filters
Liquid is sodium chromate, can prepare sodium dichromate.Cupro-nickel slag filtration washing washs for multi-stage countercurrent, and series is 2~5 grades.From filter 16
Filter residue containing cupro-nickel out, in except iron flask 17, by sulfuric acid dissolution, solution temperature is 20~60 DEG C, solution pH value after dissolving
For 1.5~3.5, the sulfuric acid solution concentration of dissolving cupro-nickel filter residue is 0.5~20%, and copper (CuO), nickel (NiO), iron (Fe2O3) rub
Your number 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 19 filtration washing of filter
Iron is removed afterwards.Iron dross removing washing is washed for multi-stage countercurrent, and series is 2~5 grades.Except the filtrate after iron enters heavy copper tank 20, addition
Sulfide is one or two kinds of for vulcanized sodium and sodium thiosulfate, copper (Cu2+) and 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 52Ten grades of single tube heat exchangers and 300m2
Double-pipe exchange is heated, and the slurry after heating enters 5 grades of 1m3In impact reactor, slurry and 300 DEG C of oxygen and pressure
Successive reaction, double-tube heat exchanger high-temperature molten salt or heat-conducting oil heating, the operating temperature of high-temperature molten salt heating are carried out under power 10Mpa
400 DEG C, 300 DEG C of oxidation liquid temperature.5 grades of impact reactors come out oxidation solution slurry, into 2 grades of 1m3It keeps the temperature ripe
Change tank and continue oxidation reaction.The oxidation solution slurry come out from heat preservation curing tank, into ten grades of 5m3Starch flash-pot, obtained steaming
Vapour passes through ten grades of 5m3Ten grades of single pipe heat exchanger heating slurries of heating are removed after steam-water separator separation water, are exchanged heat by ten grades of single tubes
Condensed water after device heat exchange, removes ten grades of 5m3Condensation generator, the about 0.6Mpa steam exhaust devaporation sodium dichromates of formation and recycling copper
Process uses after nickel.The oxidation solution slurry come out from ten grades of slurry flash-pots, after dropping to normal pressure, by holding vessel, by pumping
Enter 50m2Filter filtration washing, filtrate are 45.0% sodium chromate, and weight 1967kg can go to prepare sodium dichromate, and chromium yield is
99.8%.The cupro-nickel slag filtration washing filtered out washs for multi-stage countercurrent, and series is 3 grades.It is filtered from what filter came out containing cupro-nickel
Slag, in 5m3Except in iron flask, by adding in 300kg98% sulfuric acid dissolutions dissolving cupro-nickel filter residue, solution temperature is 50 DEG C, after dissolving
Solution ph is about 2.5.By being pumped into 50m2Except iron, scum (iron hydroxide) butt quality are after filter filtration washing
4kg.Iron dross removing washing is washed for multi-stage countercurrent, and series is 3 grades.Copper tank is sunk except the filtrate after iron enters 5m3, the 99.5% of addition
Five water sodium thiosulfate 281kg, copper temperature of sinking are 85 DEG C, when the heavy copper reaction time is 10 small, reaction generation cuprous 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.
To cuprous sulfide product (butt) 74.59kg, content 99.2%, copper yield is 98.59%.The filtration washing sulphur from filter
Change filtrate after cuprous or copper sulfide, into except chromium tank, feed temperature controls 85 DEG C, and sodium hydroxide neutralizes, and it is 6.5 to neutralize pH value,
By being pumped into 50m2Filter filters and washes out 0.04kg chromium hydroxides (butt) return oxidation operation use, washes out
Chromium hydroxide washing is washed for multi-stage countercurrent, and series is 3 grades.Pure nickeliferous filtrate enters 5m3Heavy nickel tank, adds in
221kg98% sodium carbonate, 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.It is formed
Nickelous carbonate precipitates, by being pumped into 50m2Filter after filter washing, is dried to obtain 240kg99.6% nickelous carbonate products, heavy nickel
Filtration washing 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 52Ten grades of single tube heat exchangers and
300m2Double pipe heater is heated, and the slurry after heating enters in impact reactor, slurry and 200 DEG C of oxygen and pressure
Successive reaction, double pipe heater high-temperature molten salt or heat-conducting oil heating, the operating temperature of high-temperature molten salt heating are carried out under 60Mpa
280 DEG C, 200 DEG C of oxidation liquid temperature.7 grades of impact reactors come out oxidation solution slurry, into 5 grades of 1m3It keeps the temperature ripe
Change tank and continue oxidation reaction.The oxidation solution slurry come out from heat preservation curing tank, into ten grades of 5m3Starch flash-pot, obtained steaming
Vapour passes through ten grades of 5m3Ten grades of single pipe heat exchanger heating slurries of heating are removed after steam-water separator separation water, are exchanged heat by ten grades of single tubes
Condensed water after device heat exchange, removes ten grades of 5m3Condensation generator, the about 0.3Mpa steam exhaust devaporation sodium dichromates of formation and recycling copper
Process uses after nickel.The oxidation solution slurry come out from ten grades of slurry flash-pots, after dropping to normal pressure, by holding vessel, by pumping
Enter 50m2Filter filtration washing, filtrate are 35.0% sodium chromate, and weight 5103kg can go to prepare sodium dichromate, and chromium yield is
99.8%.The cupro-nickel slag filtration washing filtered out washs for multi-stage countercurrent, and series is 3 grades.It is filtered from what filter came out containing cupro-nickel
Slag, in 5m3Except in iron flask, by adding in 300kg98% sulfuric acid dissolutions dissolving cupro-nickel filter residue, solution temperature is 50 DEG C, after dissolving
Solution ph is about 2.5.By being pumped into 50m2Except iron, scum (iron hydroxide) butt quality are after filter filtration washing
4kg.Iron dross removing washing is washed for multi-stage countercurrent, and series is 3 grades.Except the filtrate after iron enters 5m3Heavy copper tank, the 99.5% of addition
Five water sodium thiosulfate 281kg, copper temperature of sinking are 85 DEG C, when the heavy copper reaction time is 10 small, reaction generation cuprous 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.
To cuprous sulfide product (butt) 75.00kg, content 99.30%, copper yield is 99.15%.The filtration washing from filter
Filtrate after cuprous sulfide or copper sulfide, into except chromium tank, feed temperature controls 85 DEG C, and sodium hydroxide neutralizes, and neutralizes pH value and is
6.5, by being pumped into 50m2Filter filters and washes out 0.04kg chromium hydroxides (butt) return oxidation operation use, washes
It washs out chromium hydroxide washing to wash for multi-stage countercurrent, series is 3 grades.Pure nickeliferous filtrate enters 5m3Heavy nickel tank, adds in
221kg98% sodium carbonate, 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.It is formed
Nickelous carbonate precipitates, by being pumped into 50m2Filter after filter washing, is dried to obtain 240kg99.6% nickelous carbonate products, heavy nickel
Filtration washing 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 52Ten grades of single tube heat exchangers and 150m2
Double pipe heater is heated, and the slurry after heating enters 10 grades of 1m3In impact reactor, slurry and 250 DEG C of oxygen and pressure
Successive reaction, double pipe heater high-temperature molten salt or heat-conducting oil heating, the operating temperature of high-temperature molten salt heating are carried out under power 8Mpa
350 DEG C, 250 DEG C of oxidation liquid temperature.10 grades of impact reactors come out oxidation solution slurry, into 5 grades of 1m3It keeps the temperature ripe
Change tank and continue oxidation reaction.The oxidation solution slurry come out from heat preservation curing tank, into ten grades of 5m3Starch flash-pot, obtained steaming
Vapour passes through ten grades of 5m3Ten grades of single pipe heat exchanger heating slurries of heating are removed after steam-water separator separation water, are exchanged heat by ten grades of single tubes
Condensed water after device heat exchange, removes ten grades of 5m3Condensation generator, the about 0.4Mpa steam exhaust devaporation sodium dichromates of formation and recycling copper
Process uses after nickel.The oxidation solution slurry come out from ten grades of slurry flash-pots, after dropping to normal pressure, by holding vessel, by pumping
Enter 50m2Filter filtration washing, filtrate are 40.0% sodium chromate, and weight 2965kg can go to prepare sodium dichromate, and chromium yield is
99.8%.The cupro-nickel slag filtration washing filtered out washs for multi-stage countercurrent, and series is 5 grades.It is filtered from what filter came out containing cupro-nickel
Slag, in 5m3Except in iron flask, by adding in 300kg98% sulfuric acid dissolutions dissolving cupro-nickel filter residue, solution temperature is 50 DEG C, after dissolving
Solution ph is about 2.5.By being pumped into 50m2Except iron, scum (iron hydroxide) butt quality are after filter filtration washing
4kg.Iron dross removing washing is washed for multi-stage countercurrent, and series is 3 grades.Except the filtrate after iron enters 5m3Heavy copper tank, the 99.5% of addition
Five water sodium thiosulfate 281kg, copper temperature of sinking are 85 DEG C, when the heavy copper reaction time is 10 small, reaction generation cuprous 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.
To cuprous sulfide product (butt) 9) 74.85kg, content 98.99%, copper yield is 98.32%.Diafiltration is crossed from filter
Filtrate after cuprous sulfide or copper sulfide is washed, into except chromium tank, feed temperature controls 85 DEG C, and sodium hydroxide neutralizes, and neutralizes pH value and is
6.5, by being pumped into 50m2Filter filters and washes out 0.04kg chromium hydroxides (butt) return oxidation operation use, washes
It washs out chromium hydroxide washing to wash for multi-stage countercurrent, series is 3 grades.Pure nickeliferous filtrate enters 5m3Heavy nickel tank, adds in
221kg98% sodium carbonate, 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.It is formed
Nickelous carbonate precipitates, by being pumped into 50m2Filter after filter washing, is dried to obtain 240.5kg99.55% nickelous carbonate products,
Heavy nickel filtration washing washs for multi-stage countercurrent, and series is 3 grades.From the filtrate of filter filtration washing nickelous carbonate, can go to prepare member
Bright powder 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 is soda ash to be added to calcine chromium-copper nickel waste material, the amount of liquid phase of formation (1150 DEG C or more sodium chromates and
The amount and low melting point of excessive soda ash) will be more than 35%, when production, should not operate, and scale is smaller can not be given birth to rotary kiln
Production, 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 method that copper chromium nickel is recycled from the plating wastes of cupric chromium nickel, 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 is pumped into single tube with high-pressure diaphragm pump and double pipe heater heats, slurry after heating is into more
In grade impact reactor, slurry carries out successive reaction with oxygen at certain temperature and pressure；
(4) it is anti-into oxidation is continued into multistage heat preservation curing tank from the oxidation solution slurry that (3) middle multistage impact reactor comes out
It should；
(5), from the oxidation solution slurry that (4) middle heat preservation curing tank comes out, into ten grades of slurry flash-pots, obtained steam passes through ten grades
Heating single pipe heat exchanger heating slurry is removed after steam-water separator separation water, the condensed water after single pipe heat exchanger exchanges heat is gone cold
Condensate evaporator, steam exhaust devaporation sodium dichromate and the process after recycling cupro-nickel of formation use；
(6) the oxidation solution slurries that ten grades of slurry flash-pots come out from (5), after dropping to normal pressure, by filter filtration washing, filtrate
For sodium chromate, sodium dichromate can be prepared；
(7) the filter residue containing cupro-nickel come out from (6) 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；
(8), from filtrate after (7) 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；
(9), from the filtrate of (8) 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, the series of impact reactor is 2~20 grades.
5. (4) middle multistage heat preservation curing tank is 2~10 grades for the method according to claim 1, wherein step.
6. (6) middle filtration washing washs for multi-stage countercurrent for the method according to claim 1, wherein step, series is 2~5 grades.
7. (7) 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 are respectively 0.5~3,0.5~3 and 2~5 with the ratio between the molal quantity of sulfuric acid, molten
It is 20~60 DEG C to solve temperature, and solution pH value 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.
8. the method according to claim 1, wherein step (8) 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；Heavy nickel filtration washing washs for multi-stage countercurrent, and series is 2~5 grades.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508466A (en) * | 2008-10-24 | 2009-08-19 | 天津派森科技有限责任公司 | High-efficiency, energy-conservation and clean method for producing chromate |
| CN105271632A (en) * | 2015-10-29 | 2016-01-27 | 中国科学院过程工程研究所 | Comprehensive recovery method for electroplating sludge |
-
2017
- 2017-11-13 CN CN201711115728.9A patent/CN108046324B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508466A (en) * | 2008-10-24 | 2009-08-19 | 天津派森科技有限责任公司 | High-efficiency, energy-conservation and clean method for producing chromate |
| CN105271632A (en) * | 2015-10-29 | 2016-01-27 | 中国科学院过程工程研究所 | Comprehensive recovery method for electroplating sludge |
Non-Patent Citations (1)
| Title |
|---|
| 郭学益等: ""从电镀污泥中回收镍、铜和铬的工艺研究"", 《北京科技大学学报》 * |
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