CN103103354B - Production method for circularly recovering ultrafine nickel powder from shadow mask of discarded CRT (Cathode Ray Tube) screen - Google Patents
Production method for circularly recovering ultrafine nickel powder from shadow mask of discarded CRT (Cathode Ray Tube) screen Download PDFInfo
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Abstract
The invention relates to a production method for circularly recovering ultrafine nickel powder from a shadow mask of a discarded CRT (Cathode Ray Tube) screen. The production method comprises the following steps of: cutting of the CRT screen, screening by using a development process, strong acid dissolution and leaching, nickel precipitation by sulphur ions, acid dissolution of filter residues, extraction and enrichment, synthesis of nickel oxalate, high-temperature reduction and crushing, and therefore the ultrafine nickel powder which is more than 99.5 percent in content and 0.5-3.0mu m in FSSS (Furnace Safeguard Supervisory System) granularity can be obtained. The production method disclosed by the invention is especially suitable for separation and purification of nickel from nicochrome with high iron content, can be used for recovering metallic nickel from the shadow mask of the discarded CRT screen and circularly producing the ultrafine nickel powder, is relatively simple in process and operation, free of consumption of a great deal of electric energy and easy to implement and has an actual meaning in development of circular utilization of nickel resources; the ultrafine nickel powder is high in purity and small in particle size; and the secondary pollution in the production process is remarkably reduced.
Description
Technical field
The present invention relates to chemical metallurgy technical field, more particularly, the present invention relates to technology and method that metals resources production metallurgy product is reclaimed in a kind of waste electric products circulation.
Background technology
Nickel metal has the physico-chemical property of many extensive excellences, as good oxidation-resistance: in air, nickel surface forms NiO film, can stop further oxidation, experimental results show that: the nickel that purity is 99%, iron mold can not occur in 20 years.The resistance to corrosion of nickel is also very strong, especially strong to the resistance to corrosion of caustic alkali, in 50% boiling soda lye, the annual corrosion speed of nickel is no more than 25 microns, thereby nickel is used for manufacturing various types of stainless steels, non-retentive alloy and structural alloy steel in a large number; The elements such as nickel and chromium, copper, aluminium, cobalt can form refractory alloy, electrical alloy and non-corrosive metal etc.Its good magnetic of this external cause, nickel becomes the main component of many magneticsubstances; Nichrome is (as Ni-Cr
2o) there are high thermotolerance and large resistance, can be used to make the electrical heating element of electric furnace, electric iron, electric iron etc., can long term operation at 1100 ℃.The intensity of nickel and plasticity are also fine, can bear various press working, and therefore, nickel also gets more and more for field of chemical power source, for example, in nickel-cadmium, nickel-hydrogen cell, lithium ion battery; The nickel sheet of porous is a kind of catalyst of having many uses.In summary, the raw metal that nickel must be used as multiple product, the sustainable growth that is bound to of its demand.
Particularly in recent years, along with stainless steel is the applying of civilian industry field, the demand of nickel grows with each passing day, and usage quantity, up to more than 300,000 tons, accounts for the dimensions of market of nickel more than 50%, causes global nickel resources nervous.
And traditional high purity nickel production technology mainly be take nickel ores as raw material, by electrolytic process, produce.
Electrolytic process is normally made thick nickel anode with nickeliferous electrolytic slag or pyrite cinder etc. as raw material, through dissolving, purification and anode electrolysis method, at negative electrode, obtains electrolytic nickel; Or with above-mentioned raw materials, make nickelous chloride, nickel sulfate solution, through insoluble anode electrolytic process, make electrodeposition of nickel on negative electrode, obtain electrolytic nickel; Then electrolytic nickel is scraped and forms nickel sheet from negative electrode.
Traditional electrolytic process can make the nickel sheet that purity is very high, and still, the energy consumption of technique is very high, and in electrolytic process, vitriol, the hydrochloride of nickel volatilize acid mist, to production environment and living environment, all can produce quite serious pollution.So country's restriction: in densely populated, the regional technique that does not allow investment construction electrolysis legal system nickel of energy scarcity, this has just greatly limited the development of this industry, and then cause the seriously in short supply of nickel tablet raw material supply.And the ore of take is produced nickel raw material as main, causes consuming excessively of ore resource, does not meet the resources circulation pattern of conservation-minded society.
On the other hand, global and even Chinese electron wastes increases sharply, and once has statistics: within 2005,1.75 hundred million televisors are transported in the whole world, and wherein 1.45 hundred million is the product based on cathode tube; Again according to domestic statistics, from 1980 to 2007, China's colour television set is consumed 53,354 ten thousand altogether, and at present China has entered household electrical appliances and has scrapped superseded peak period, estimate 35,965 ten thousand of discarded colour television sets, wherein can reclaim approximately 30,746 ten thousand, major part is also to adopt cathode-ray tube CRT as display screen.
Cathode tube comprises four main devices: the metal shadow mask of sheet glass, three electron beam gun (each represents a kind of color), a glass funnel and a mesh-like.Wherein shadow mask device parts generally adopt nickel-ferro alloy material, to utilize the excellent physico-chemical property of nickel, fully to guarantee that cathode tube normally works for a long time.So shadow mask weight and nickel content because of the difference of manufacturer and production technique different: 25 inches of colour television sets for example, the shadow mask of Rhometal and the weight of its framework are generally at 500g～1500g, the nickeliferous 35-50% of shadow mask (wt%) wherein, the nickeliferous content of shadow mask fixing part such as framework also have 5-30%, the chromium that contains on a small quantity 10% left and right, ratio and the quantity of nickel are considerable.
If can a plurality of provinces and cities reclaim network with the regional household electrical appliances of setting up standard in the whole nation, and the supporting year electron wastes process for producing line for the upper scale of processing of setting up reclaims the nickel resources in discarded cathode tube, one can create the new way of circulation recovery nickel from waste, solve the problem of nickel resources worsening shortages, two are expected to look for another way, with compared with less energy-consumption and pollution, make nickel powder Industrial products
Summary of the invention
Above-mentioned shortcoming for prior art, the invention provides a kind of production method that is reclaimed extra-fine nickel powder by discarded CRT screen shadow mask circulation, its tool has the following advantages: be particularly suitable for Separation & Purification nickel from the nichrome of high ferro, can from discarded CRT screen shadow mask, reclaim nickel metal with high yield, extra-fine nickel powder is produced in recycle, the high particle diameter of product purity is little, technological operation is relatively simple, do not need to consume a large amount of electric energy, in production, secondary pollution significantly reduces, and implement easily, to opening up nickel resources recycle, there is practical significance.
For this reason, technical solution of the present invention is a kind of production method that is reclaimed extra-fine nickel powder by discarded CRT screen shadow mask circulation, and this production method comprises the steps:
A) nickel rapid detection is collected: development process screens, collects nickeliferous CRT shadow mask and mounting block thereof;
B) strong acid dissolves leaching nickel: adopt concentrated sulfuric acid dissolution CRT shadow mask and the mounting block thereof of chloride acid group, obtain nickeliferous first immersion liquid;
C) the heavy nickel of sulfonium ion: add solvable sulphide salt and sink nickel reactant in just immersion liquid, the nickelous sulfide filter residue being precipitated after filtering separation and containing siderochrome filtrate, sends to and make alkaline sedimentation, recovery siderochrome sediment containing siderochrome filtrate;
D) acid of nickelous sulfide filter residue is molten: adopt the concentrated sulfuric acid dissolution nickelous sulfide filter residue containing inferior sulfate radical, filter the falling solution that obtains single nickel salt, the principal reaction of this step is: 3H
2sO
4+ Na
2sO
3+ 2NiS=2NiSO
4+ 3S+Na
2sO
4+ 3H
2o;
E) extracting and enriching nickel: add organic P204 extraction liquid in falling solution, from falling solution, obtain organic phase and the rich nickel liquid inorganic phase of separated enrichment impurity, in addition, add again organic P507 extraction liquid in rich nickel liquid, from rich nickel liquid, obtain nickelic organic liquor and inorganic remaining liquid, nickelic organic liquor obtains inorganic nickelic liquid and saliferous acid solution through hydrochloric acid back extraction;
Above-mentioned organic P204 extraction liquid is the solution of two-(2-ethylhexyl) phosphoric acid and sulfonated kerosene, and organic P507 extraction liquid is the solution of 2-ethylhexyl phosphonic acid-2-ethylhexyl and sulfonated kerosene.
F) nickelic liquid synthesis of oxalic acid nickel: add ammonium oxalate in described nickelic liquid, the synthetic nickelous oxalate wet feed that obtains, with hot wash nickelous oxalate wet feed, then dry, broken, obtain nickelous oxalate powder;
G) nickelous oxalate powder high temperature reduction, fragmentation: obtain content more than 99.5%, FSSS granularity is at the extra-fine nickel powder of 0.5～3.0 μ m.(common D50≤12 μ m, loose density 0.5-1.8g/cm
3).
The present invention is by the production method of discarding CRT screen shadow mask circulation recovery extra-fine nickel powder, adopt simple development process, just can be from discarded CRT screen shadow mask parts (containing framework), screening is removed small part substantially not nickeliferous shadow mask and framework, is left a large amount of nickeliferous shadow mask parts up to 35-50%, thereby establishes good basis for subsequent purification; Then, the inventive method, for the feature of shadow mask parts iron-nickel-chromium, is taked hydrometallurgy, with oxidisability strong acid, dissolves parts completely, and the larger negatively charged ion of recycling salify dissolubility difference is in addition separated nickel and other metal ion, simple and direct effectively; On first pure basis, then with special extraction liquid back extraction, just extract, obtain high-purity nickelous chloride, then synthetic, reduction, makes extra-fine nickel powder, and embodiment proves, each step yield of the inventive method can reach more than 95%, and product purity reaches more than 99.5%.As can be seen here, each step of the inventive method and route reclaim the finished industrial product that makes extra-fine nickel powder efficiently, at a dass.Compare and in large capacity tank liquor, apply a large amount of electric energy and cause higher temperatures to rise and compared with the electrolytic process of large volatilization, each step solution temperature of the present invention is controlled at below 40-80 ℃, substantially by solution id reaction, is remained temperature required, in solution, is applied external energy seldom; Correspondingly, the inventive method also tool have the following advantages: solution obviously reduces to the acid aerosol total amount of volatilizing in environment; Various energy consumptions are significantly lower therebetween, the waste liquid producing in dissolve purifying or can reuse, maybe can reclaim or collect wherein metallic impurity, be purified by alkaline sedimentation, then discharged, to water pollution, substantially can eliminate, therefore, the inventive method can be relatively intensive at population, energy scarcity regional as surrounding city investment found the factory.
In a word, the inventive method is particularly suitable for separating-purifying nickel from high ferrochrome exothermic, can from discarded CRT screen shadow mask, reclaim nickel metal with high yield, extra-fine nickel powder Industrial products are produced in recycle, the high particle diameter of product purity is little, technological operation is relatively simple, implement easily, do not need to consume a large amount of electric energy, in production, secondary pollution significantly reduces, have energy-saving and cost-reducing, reduce the feature of secondary pollution in producing, to opening up nickel resources recycle, there is great practical significance, contribute to realize and " reduce and pollute, the creation of resources ", open the green economy main road of " city mineral products ".
In order to isolate more quickly and easily nickeliferous higher shadow mask parts from CRT screen, the present invention also comprises following improvement:
Before described steps A, also comprise and disassemble cutting step A0: disassemble CRT screen and adopt heater strip thermal explosion method to cut it, isolate the CRT shadow mask of metal and the mounting block of metal: in described steps A, described development process comprises ammoniacal liquor and the color reaction of nickel in the ethanol solution of dimethylglyoxime.
For more efficient low-consume is low from shadow mask parts, impurely isolate nickeliferous metal, the present invention also comprises following improvement:
In described step B, with in just immersion liquid of vitriol oil control, pH value is below 0.5, adding sodium chlorate weight is the 40-80% of weight metal, and blowing air stirs, and controls temperature of reaction 70-80 ℃, reaction times 3-5 hour.
In described step C, first with 20% sodium carbonate solution, reconcile described just immersion liquid pH value at 1-2, to adding the sodium sulphite that accounts for weight metal 0.8-1.6% in first immersion liquid, to be formulated into content be 10-20% (wt) again, sink nickel, control heavy nickel process pH value at 2.0-2.5, temperature of reaction 40-50 ℃, reaction times 1-3 hour, then filtering separation.
In described step D, first nickelous sulfide filter residue is added in its weight 8-12 pure water doubly, with the vitriol oil, maintain pH value 0.5-1.0, after add the S-WAT of 0.8-1.2 times of weight of nickelous sulfide filter residue, control temperature 70-90 ℃, maintain reaction 2-4 hour, then add the sodium chlorate of 0.1-0.2 times of weight of nickelous sulfide filter residue, until nickelous sulfide filter residue dissolves completely, obtain falling solution.
In described step e, with impurity in organic phase described in hydrochloric acid back extraction, obtain containing heteroacid liquid, containing heteroacid liquid, remake alkaline sedimentation to reclaim siderochrome sediment, or add in just immersion liquid, falling solution, in addition, described inorganic remaining liquid returns and supplements just immersion liquid, falling solution or membrane sepn reuse, and described saliferous acid solution remakes alkaline sedimentation, qualified discharge after recovery salt.The add-on of P204 extraction liquid is the 5-10% of described falling solution volume; The add-on of P507 extraction liquid is the 3-8% of described falling solution volume; Described organic phase, organic liquor after back extraction purifying as corresponding extraction liquid cyclically utilizing.
For more efficient, low consumption, low impurely synthetic organic nickel salt and reduction make high pure and ultra-fine series nickel powder finished product, the present invention also comprises following improvement:
In described step F, the concentration of ammonium oxalate solution is 12-20% (wt), controls pH value at 4.1-4.3, temperature 70 C; Control 60 ℃ of temperature of reaction, control pH value 2.5-3.0 in reaction process, reaction end pH value 2.0, obtains nickelous oxalate wet feed.
In described step G, nickelous oxalate powder is reductase 12-6 hour in 300-500 ℃ of hydrogen.
In order more to reduce wet method waste liquid to the pollution of environment, the more recycle and reuse of residual impurity in waste liquid, the present invention also comprises following improvement:
Described alkaline sedimentation be described containing siderochrome filtrate or containing adding sodium hydroxide or calcium hydroxide in heteroacid liquid to more than pH8, then reclaim the siderochrome of precipitation.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Accompanying drawing explanation
Fig. 1 is the block diagram of the inventive method embodiment.
Embodiment
As Fig. 1, be depicted as the block diagram of the inventive method embodiment, comprise as the next stage: until the molten step D of nickelous sulfide acid) wet separation stage embodiment, E thereafter) extracting and enriching nickel step embodiment, F) synthesis of oxalic acid nickel step embodiment, G) nickelous oxalate powder reduction step embodiment.Specific as follows:
The wet separation stage embodiment:
A0) disassemble cutting step:
Televisor and computer complete machine are disassembled out to CRT monitor, then cut, isolate the metal partss such as shadow mask, from every CRT separating metal parts, randomly draw a slice and carry out nickel rapid detection.
A) nickel rapid detection is collected step:
Getting 0.8g dimethylglyoxime is dissolved in 100ml dehydrated alcohol standby, the ammoniacal liquor of preparation 10% is standby, by the above-mentioned metalwork sand papering of choosing, add 2 hydrogen peroxide and carry out clean, by swab stick, be stained with one to two dimethylglyoxime solution and an ammoniacal liquor again,, there is redness, from pale pink, become dark pink in friction article surface 15 seconds, shows nickeliferous; As redfree occurs showing that metalwork is not nickeliferous.
In contrast: choose at random 2 CRT shadow masks and a chip part and detect that to analyze its composition as follows:
CRT shadow mask composition: Fe60.2327%, Ni37.7793%, Cr0.0325%, Co0.0969%, Cu0.0191%, Mg0.0563%, Cd0.0027%, Pb0.0082%.
CRT appendicular elements: Fe75.6719%, Ni9.1575%, Cr12.9889%, Co0.1364%, Cu0.3931%, Mg0.0528%, Cd0.0029%, Pb0.0132%.
Proof shadow mask and annex thereof are all worth recycle to carry nickel.
B) strong acid dissolves and leaches step:
Above-mentioned isolated nickel-containing alloys part is cut into fragment, take 10kg, pour in the reactor of 200L, add end water 60L, add the vitriol oil to maintain reaction process pH0.5, add sodium chlorate 6.66kg, blowing air stirs, 75 ℃ of temperature of reaction, in 4 hours reaction times, obtain filter residue 0.5kg through pressure filter press filtration, its composition comprises Ni:0.42%, Fe:2.13%, Cr:0.12%, filtrate (first immersion liquid) 59L, its composition comprises Ni:53g/L, Fe:108g/L, Cr:9g/L, other elements are all less than 1g/L.Calculate known: nickel leaching yield 99.9%, removal of impurities loss is less than 5%.
C) the heavy nickel step of sulfonium ion:
By above-mentioned just for immersion liquid 20% sodium carbonate solution (sodium carbonate 2.86kg, solution 15L) adjust pH to 1.5 left and right, then add 15% (wt) solution 32L that people is made by 4.17kg sodium sulphite and water, sink nickel, control process pH value 2.0-2.5,45 ℃ of temperature of reaction, 2 hours reaction times.Then filtering separation, obtain the wet slag 6.07kg (i.e. dry nickelous sulfide filter residue 4.79kg) of water content 21%, its assembly divides and comprises Ni:50.9%, Fe:9.14%, Cr:0.26%, containing the sodium sulfate filtrate 110L of siderochrome, its composition comprises Ni:0.4g/L, Fe:39.7g/L, Cr:4.3g/L.
Siderochrome filtrate, by sodium hydroxide solution (concentration 10mol/l, consumption 270mL) readjustment pH8 left and right precipitation siderochrome, obtains filtrate 112L, dry slag 9.35kg.The impurity elements such as Fe, the Cr that 112L filtrate major ingredient is denier, Ni, remove by membrane sepn, return to sodium carbonate, oxalic acid, extraction process water, accomplish middle water reuse.Dry slag adds sodium carbonate 9.3kg according to weight ratio at 1: 1,750 ℃ of roastings, calcination 2 hours, obtain roasting material 14.6kg, with 80 ℃ of hot water 15L washing, obtain Sodium chromate filtrate 15L that chromium content is 81.4g/l and ferric oxide again and containing the precipitation slag 12.5kg of a small amount of nickel oxide, can abandon by harmless heap; Dry slag reacts with sodium carbonate for the technique of industrial production Sodium chromate, because other materials in dry slag can not react with sodium carbonate, Sodium chromate filtrate is purer, so only have Sodium chromate and a small amount of unreacted sodium carbonate, filtrate can obtain crystals of sodium chromate by condensing crystal, can further purify and obtain pure chromic salts.As for the 15L waste water producing, contain micro-chromium, after flocculation, filtration, waste water can qualified discharge.This step nickel yield is greater than 99%.
D) the molten step of nickelous sulfide acid:
Nickelous sulfide filter residue 6.07kg, adds end water 60L, adds the vitriol oil to maintain pH value 0.5-1.0, then adds S-WAT 6.3kg, controls 80 ℃ of temperature of reaction, 3 hours reaction times, then add sodium chlorate 1kg, and dissolve completely, substantially without slag.20% sodium carbonate solution 20L for nickel lysate, adjust pH to 3.5-4.0, filter, obtain filtrate (contains sodium sulfate falling solution) 80L, its composition comprises Ni:36g/L, Fe:0.97g/L, Cr:0.047g/L, filter residue 0.98kg, its composition comprises Ni:1.12%, Fe:45.11%, Cr:1.85%, this step nickel yield is greater than 99%.
The principal reaction of this step is: 3H
2sO
4+ Na
2sO
3+ 2NiS=2NiSO
4+ 3S+Na
2sO
4+ 3H
2o.
E) extracting and enriching nickel step embodiment:
After above-mentioned removal of impurities, falling solution 80L adds the extraction liquid extracting and separating impurity of 4.5L sulfonated kerosene with the P204 of 1.5L, impurity extracts composition in 6L organic phase and comprises Fe 3.04g/l, Cr 0.1g/l, Cu 0.03g/l, Ni 0.12g/l, use HCl back extraction organic phase, the impurity that makes to be entered inorganic phase by back extraction returns to strong acid and dissolves and leach step extraction and application again again, and obtains that the P204 liquid of purifying is capable of circulation to be used again.
Through the extraction of P204 extraction liquid, obtain the rich nickel liquid of inorganic phase 90L containing Ni 33.6g/l, Fe 1.2mg/l, Cr1.3mg/l, Mg29.8mg/l, Co54.2mg/l.Rich nickel liquid obtains containing the nickelic organic liquor 5L of cobalt magnesium and inorganic remaining liquid 98L by the extraction liquid extracting and separating that the P507 of 1L adds 4L sulfonated kerosene again, and inorganic remaining liquid returns to strong acid and dissolves leaching step extraction and application again; Should be containing the nickelic organic liquor of cobalt magnesium again with the back extraction of HCl substep and change into nickelous chloride from single nickel salt and obtain: the saliferous acid solution of inorganic nickelic liquid and enriched in cobalt magnesium, the former inorganic nickelic liquid 32.5L, containing Ni:93.1g/L, Fe:1.8mg/L, Cr:0.7mg/L, Mg:1.9mg/L, Co 2.2mg/l, the latter's saliferous acid solution is containing Ni 18.3mg/l, Mg 27.4mg/l, Co 48.9mg/l, the latter's saliferous acid solution is incorporated to the remaining liquid of 98L inorganic phase, returns to nickel leaching step and does end water extraction reuse; The P507 extraction liquid that the organic phase that the back extraction of HCl substep obtains is purifying, does recycle.This step nickel loss is less than 1%.
F) synthesis of oxalic acid nickel step embodiment:
The oxalic acid solution 10L of preparation 150g/l, by ammoniacal liquor (1.5L) or logical liquefied ammonia adjusting pH value to 4.1-4.3, be mixed with ammonium oxalate solution and be heated to 70 ℃ standby.
Nickelous oxalate synthetic example 1: get above-mentioned nickel chloride solution (nickelic liquid) 1L and react with ammonium oxalate solution 2.3L, 60 ℃ of temperature of reaction, control process pH value 2.5-3.0, endpoint pH 2.0, in 10 minutes reaction times, obtains nickelous oxalate wet feed, filter liquor 3L nickel content 35mg/l, nickelous oxalate hot wash, 130 ℃ of dry doing 10 hours, fragmentation, obtain nickelous oxalate powder 1 320g, Ni content 28.8%, D50 particle diameter 5.2 μ m, loose density 0.49g/cm are surveyed in sampling
3.
Nickelous oxalate synthetic example 2: get above-mentioned nickelous chloride (nickelic liquid) 1L and react with ammonium oxalate solution 2.3L, regulate ammonium oxalate and nickelous chloride flow, control process pH value is at 2.0-2.5, endpoint pH 2.0, in 14 minutes reaction times, other is identical with above-mentioned synthesis technique, obtain nickelous oxalate powder 2 310g, Ni content 30%, D50 particle diameter 17.8 μ m, loose density 0.67g/cm
3.
Nickelous oxalate synthetic example 3: get above-mentioned nickelous chloride (nickelic liquid) 2L and react with ammonium oxalate solution 5L, change 50 ℃ of temperature of reaction and pH value in reaction 3.0-3.5,10 minutes reaction times, other is identical with above-mentioned technique, obtain nickelous oxalate powder 3 648g, Ni content 28.4%, D50 particle diameter 4.5 μ m, loose density 0.42g/cm
3,
Nickelous oxalate synthetic example 4: get the 3 use airflow crash machine secondary breaking of 324g nickelous oxalate powder, obtain nickelous oxalate powder 4, D50 particle diameter is 3.1 μ m, loose density 0.29g/cm
3.
Ammonium oxalate precipitates nickelic liquid step, and raffinate nickel content is less than 50mg/l, and nickel yield is greater than 99%.
G) nickelous oxalate powder reduction step embodiment:
Above-described embodiment 1 nickelous oxalate powder 330 ℃ of hydrogen reducings 5 hours in push boat type reduction furnace, fragmentation obtains extra-fine nickel powder 1 (91.8g), nickel powder FSSS particle diameter 1.09 μ m, D50 particle diameter 5.6 μ m, loose density 0.71g/cm
3, nickel powder purity 99.91%.
Above-described embodiment 2 nickelous oxalate powder 490 ℃ of hydrogen reducings 2.5 hours in push boat type reduction furnace, fragmentation obtains extra-fine nickel powder 2 (91.1g), nickel powder FSSS particle diameter 2.88 μ m, D50 particle diameter 11.4 μ m, loose density 1.47g/cm
3, nickel powder purity 99.86%.
Above-described embodiment 3 nickelous oxalate powder in push boat type reduction furnace 400 ℃ reduction 3 hours, fragmentation obtains extra-fine nickel powder 3 (91.5g), nickel powder FSSS1.69 μ m, D50 particle diameter 9.6 μ m, loose density 0.92g/cm
3, nickel powder purity is 99.75%.
Above-described embodiment 4 nickelous oxalate powder, in push boat type reduction furnace, 320 ℃ of hydrogen reducings are 5 hours, and fragmentation obtains extra-fine nickel powder 4 (91.9g), nickel powder FSSS0.85 μ m, D50 particle diameter 4.3 μ m, loose density 0.63g/cm
3, nickel powder purity 99.78%.
This step nickel yield is greater than 99.8%, substantially lossless.
Claims (9)
1. by discarded CRT screen shadow mask circulation, reclaimed a production method for extra-fine nickel powder, this production method comprises the steps: A) collection of nickel rapid detection: development process screens, collects nickeliferous CRT shadow mask and mounting block thereof;
B) strong acid dissolves leaching nickel: adopt concentrated sulfuric acid dissolution CRT shadow mask and the mounting block thereof of chloracid sodium, obtain nickeliferous first immersion liquid;
C) the heavy nickel of sulfonium ion: add sodium sulphite and sink nickel reactant in just immersion liquid, the nickelous sulfide filter residue being precipitated after filtering separation and containing siderochrome filtrate, sends to and make alkaline sedimentation, recovery siderochrome sediment containing siderochrome filtrate;
D) acid of nickelous sulfide filter residue is molten: adopt the concentrated sulfuric acid dissolution nickelous sulfide filter residue containing S-WAT, filter the falling solution that obtains single nickel salt, the principal reaction of this step is: 3H
2sO
4+ Na
2sO
3+ 2NiS=2NiSO
4+ 3S+Na
2sO
4+ 3H
2o;
E) extracting and enriching nickel: add organic P204 extraction liquid in falling solution, from falling solution, obtain organic phase and the rich nickel liquid inorganic phase of separated enrichment impurity, in addition, add again organic P507 extraction liquid in rich nickel liquid, from rich nickel liquid, obtain nickelic organic liquor and inorganic remaining liquid, nickelic organic liquor obtains inorganic nickelic liquid and saliferous acid solution through hydrochloric acid back extraction;
F) nickelic liquid synthesis of oxalic acid nickel: add ammonium oxalate in described nickelic liquid, the synthetic nickelous oxalate wet feed that obtains, with hot wash nickelous oxalate wet feed, then dry, broken, obtain nickelous oxalate powder;
G) nickelous oxalate powder high temperature reduction, fragmentation: obtain content more than 99.5%, FSSS granularity is at the extra-fine nickel powder of 0.5～3.0 μ m.
2. by discarded CRT screen shadow mask circulation, reclaimed as claimed in claim 1 the production method of extra-fine nickel powder, it is characterized in that: before described steps A, also comprise and disassemble cutting step A0: disassemble CRT screen and adopt heater strip thermal explosion method to cut it, isolate the CRT shadow mask of metal and the mounting block of metal: in described steps A, described development process comprises ammoniacal liquor and the color reaction of nickel in the ethanol solution of dimethylglyoxime.
3. by discarded CRT screen shadow mask circulation, reclaimed as claimed in claim 1 the production method of extra-fine nickel powder, it is characterized in that: in described step B, with the vitriol oil, control in just immersion liquid pH value below 0.5, adding sodium chlorate weight is the 40-80% of weight metal, blowing air stirs, control temperature of reaction 70-80 ℃, reaction times 3-5 hour.
4. by discarded CRT screen shadow mask circulation, reclaimed as claimed in claim 1 the production method of extra-fine nickel powder, it is characterized in that: in described step D, first nickelous sulfide filter residue is added in its weight 8-12 pure water doubly, with the vitriol oil, maintain pH value 0.5-1.0, after add the S-WAT of 0.8-1.2 times of weight of nickelous sulfide filter residue, control temperature 70-90 ℃, maintain reaction 2-4 hour, then the sodium chlorate that adds 0.1-0.2 times of weight of nickelous sulfide filter residue, until nickelous sulfide filter residue dissolves completely, obtains falling solution.
5. by discarded CRT screen shadow mask circulation, reclaimed as claimed in claim 1 the production method of extra-fine nickel powder, it is characterized in that: in described step e, with impurity in organic phase described in hydrochloric acid back extraction, obtain containing heteroacid liquid, containing heteroacid liquid, remake alkaline sedimentation to reclaim siderochrome sediment, or add in just immersion liquid, falling solution, in addition, described inorganic remaining liquid returns and supplements just immersion liquid, falling solution or membrane sepn reuse, described saliferous acid solution remakes alkaline sedimentation, qualified discharge after recovery salt.
6. by discarded CRT screen shadow mask circulation, reclaimed as claimed in claim 1 the production method of extra-fine nickel powder, it is characterized in that: in described step e, the add-on of P204 extraction liquid is the 5-10% of described falling solution volume; The add-on of P507 extraction liquid is the 3-8% of described falling solution volume; Described organic phase, organic liquor after back extraction purifying as corresponding extraction liquid cyclically utilizing.
7. by discarded CRT screen shadow mask circulation, reclaimed as claimed in claim 1 the production method of extra-fine nickel powder, it is characterized in that: in described step F, the concentration of ammonium oxalate solution is 12-20% (wt), control pH value at 4.1-4.3, temperature 70 C; Control 60 ℃ of temperature of reaction, control pH value 2.5-3.0 in reaction process, reaction end pH value 2.0, obtains nickelous oxalate wet feed.
8. by discarded CRT screen shadow mask circulation, reclaimed as claimed in claim 1 the production method of extra-fine nickel powder, it is characterized in that: in described step G, nickelous oxalate powder is reductase 12-6 hour in 300-500 ℃ of hydrogen.
9. by discarded CRT screen shadow mask circulation, reclaimed as claimed in claim 1 the production method of extra-fine nickel powder, it is characterized in that: described alkaline sedimentation be described containing siderochrome filtrate or containing adding sodium hydroxide or calcium hydroxide in heteroacid liquid to more than pH8, then reclaim the siderochrome of precipitation.
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| CN111088431B (en) * | 2020-01-07 | 2021-10-01 | 江苏金泰科精密科技有限公司 | Method for recycling pure nickel metal strip waste in electronic industry |
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