CN1718784A - Method of recovery copper, nickel and noble metal in waste water and slag by combined technology of wet method and fire method - Google Patents
Method of recovery copper, nickel and noble metal in waste water and slag by combined technology of wet method and fire method Download PDFInfo
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Abstract
A process for recovering the copper, Ni and noble metals from the sewage and dregs by the combination of wet method and fire method includes the wet process including extracting, Cu-Ni separation, removing Fe, extracting, and refining nickel carbonate, and the fire process including sintering and smelting to produce nickel matte and black copper. Its advantages are high recovery rate of Ni, Cu, Au, Ag and Pd, and no secondary pollution.
Description
Technical field
The present invention relates to a kind ofly from waste water and in the slag, reclaim the method for copper, nickel and noble metal, relate in particular to a kind of wet method---the pyrogenic process process integration is from the waste water of the processing industries such as electronics, plating, PCB surface processing and reclaim the method for copper, nickel and noble metal in the slag.
Background technology
In the waste water and slag, it also is heavy metal sewage sludge. It is the waste water of the processing industries such as electronics, plating, PCB surface processing through the solid waste of neutralisation treatment, contain various heavy, classified as hazardous waste by country. Because level of comprehensive utilization is low, not only cause certain pollution to environment, and a large amount of metals resources is wasted. Resource recycling and environmentally friendly processing with slag in the realization waste water are the significant problems that needs to be resolved hurrily at present.
The processing method of commonly using with slag in the waste water at present is to store up landfill, burning curing etc., some direct air storage. Owing to there is Leaching, easily surface water or underground water polluted. Purpose with the slag utilization in the waste water is to reclaim wherein valuable metal, but the general technical level is not high: (1) small scale; (2) treatment process is simple, and is poor to adaptability to raw material; (3) make a low multiple use; (4) exist the secondary pollution problem. High with the slag water content in the waste water, greater than 60%; Particle is thinner, is thin mud shape; Complicated contains detection device for multi metallic elements such as copper, zinc, nickel, chromium, cadmium etc. and a small amount of noble metal such as gold, silver, palladium etc.; Metal is composed mainly with states such as hydroxide, oxide, carbonate and is deposited, and the tenor fluctuation range is large. Therefore give in the waste water and the comprehensive utilization of slag brings sizable difficulty.
According to understanding, present most producers all adopt pyrometallurgical smelting in the cupric nickel waste water and slag (cupric nickel heavy metal sewage sludge) process to reclaim copper nickel, its major product is for containing corronil, low nickel matte, matte etc. Namely then carry out retailoring of blast furnace by sintering or briquetting. The one, be limited to technological level, can only intermittently produce. The 2nd, larger to cupric, raw material intractability that nickel is lower, generally this part raw material is not dealt with, the 3rd, the large coal a large amount of such as sintering process consumption of energy consumption, the coke that fusion process consumption is a large amount of. The 4th, if flue gas is dealt with improperly and can be caused secondary pollution to environment in the sintering, fusion process. The 5th, metal recovery rate is not high, is lower than 90%. The 6th, copper, nickel etc. enters in the product simultaneously, and price is low, and economic benefit is not high.
Also there is a small amount of producer to adopt wet processing to reclaim copper nickel, product is copper sulphate, nickelous sulfate and other salt etc., exist the problem of metal recovery rate low (less than 90%), part copper, nickel enter leached mud, in the waste residue such as iron dross removing, purification slag and cause damage, secondary residue also can't be processed can cause secondary pollution, the various acidic and alkaline waste waters of the inevitable generation of wet process, could discharge after the processing, so economic benefit is also not high, the more important thing is that wet-treating can only select cupric, high the processing of nickel, otherwise be difficult to obtain qualified products, cost significantly rises and does not calculate simultaneously.
With regard in the waste water and with regard to the character characteristics of slag, reach comparatively ideal comprehensive utilization effect and solve emphatically following problems: (1) is to the adaptability problem of raw material. Since in the waste water with slag from different producers, complicated component, major metal and impurity content fluctuation range are large, the impact that brings to PROCESS FOR TREATMENT is also larger. (2) the not high problem of the comprehensive utilization ratio of metal. Be limited to technical factor, metal recovery rate is not high must to cause the cost height and economic benefit descends along with turn of the market, in the waste water and slag (heavy metal sewage sludge) price increase, can bring adverse effect. (3) secondary pollution problem. Along with the appearance of promotion law on cleaner production, can strengthen the dynamics of pollution control, do not solve the secondary pollution problem, lost the prerequisite of the existence of these producers (enterprises).
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of wet method-pyrogenic process process integration to reclaim in the waste water and the method for copper, nickel and noble metal in the slag, the method has the strong adaptability to raw material, the comprehensive utilization ratio of metal is high, the high advantages such as not producing secondary pollution that reaches of metal recovery rate.
The technical solution adopted for the present invention to solve the technical problems: a kind of wet method-pyrogenic process process integration reclaims in the waste water and the method for copper, nickel and noble metal in the slag, and it is characterized in that: it comprises wet process and pyrogenic process process, and concrete steps are as follows:
Described wet process comprises:
A, will fill in the waste water and add leaching agent sulfuric acid in the reactor of slag, and stir, the terminal point pH value is controlled at 1.0-1.5, and extraction time is 2-4 hour, and the nickel 98% or more, copper leaching enter solution; The leachings such as the iron less than 60%, chromium, aluminium enter solution;
B, leach and not filter after complete, with the A same reactor in step in, add while stirring the sodium sulfide solution with the copper equivalent, sulfuration pH value is 1.0-1.5, the formation copper sulfide enters to contain copper ashes;
Remaining copper adds 1-3kg/m in the solution3Iron replacement, pH value is 1.0-2.0, the copper of replacing enters and contains copper ashes:
The noble metal gold, silver, palladium of trace enter through sulfuration and iron replacement and contain copper ashes in the solution;
Filter, obtain containing copper ashes and solution containing nickel, realize that copper, nickel separate;
C, be under the 3.5-4.2 condition at pH value, with adding ferroxidant in the solution containing nickel of B in the step, the oxidation of divalent iron ion in the solution become ferric ion, then make the iron precipitation with the Na2CO3 neutralization and remove; Chromium also is removed simultaneously;
When reaction PH is stabilized in 4.0-4.5, add sodium fluoride and further remove calcium, magnesium, aluminium impurity, described sodium fluoride addition is 5-10kg/m3；
The nickel that the iron tramp that this step is removed reaches less than 5% enters nickel-containing iron slag;
D, be 4.0-5.0 at pH value, employing concentration is the extractant P507 of 10%-15% (V P507/V kerosene), a small amount of iron, copper, chromium, calcium, magnesium, aluminium, the zinc impurity of extraction in the solution containing nickel of C after the step; The extracted organic phase concentrated sulfuric acid back extraction regeneration organic phase of 5N-7N, raffinate is pure nickel solution;
E, employing mass concentration are the sodium carbonate precipitation of 20-30%, and precipitation terminal point pH value is 8.0-8.5, produces prepared calcium carbonate nickel;
Described pyrogenic process process comprises:
F, the nickel-containing iron slag sintering that respectively the B sulfuration copper ashes in step, C is gone on foot get copper agglomerate, nickel agglomerate;
Quality contains Cu 15-20%, Fe 12-15%, Au 10-15g/t, Ag 200-300g/t, Pd 5-15g/t, SiO in the copper agglomerate that sintering obtains2 28-35％、CaO 8-12％、S＜1％；
Quality contains Ni 2.5-3.0%, Fe 6-8%, SiO in the nickel agglomerate that sintering obtains2 28-35％，CaO 3-5％；
G, copper agglomerate or ferronickel agglomerate that F is gone on foot obtain respectively black copper or low nickel matte through the high temperature reduction melting, and described copper and noble metal gold, silver, palladium are recovered in black copper; Nickel reclaims in low nickel matte.
When adding leaching agent sulfuric acid in the above-mentioned A stage reactor, blast compressed air.
The mass concentration of vulcanized sodium was 10-15% during above-mentioned B went on foot, and adding speed is 5-10 liter/min of clock.
Temperature when above-mentioned C becomes ferric ion with the oxidation of divalent iron ion in the solution in the step is 50-60 ℃; Described ferroxidant is hydrogen peroxide.
The extraction progression of above-mentioned D in the step is three grades of extractions.
Above-mentioned F is 50-55% at sintered mixture moisture in the step, and coal charge is than being 8-10%, and sintering temperature is 800-850 ℃, and sintering time is 6-8 hour.
The reduction melting of copper agglomerate prepared in the black copper process during above-mentioned G went on foot, and coke ratio is that 15-18%, flux ratio are K1.0-1.5 for 10-15%, slag silicate degree.
The reduction melting of ferronickel agglomerate prepared in the low nickel matte process during above-mentioned G went on foot, and coke ratio is that 18-23%, flux ratio are K1.0-1.5 for 10-20%, slag silicate degree.
Advantage of the present invention:
Adopt wet method-pyrogenic process New process combining integrated treatment to reclaim copper nickel and noble metal with slag in the waste water of the present invention, this technique wet method and pyrogenic process are had complementary advantages, and have following advantage:
(1) adaptability to raw material of the present invention is strong. Because in the waste water and slag source is wide, complicated component brings certain difficulty for pyrogenic process or wet-treating, and the invention solves the adaptability difficult problem of raw material. In different types of cupric nickel waste water and slag all available technique process flexibly, technical indicator can be because material composition changes bring to production and has a strong impact on.
(2) metal comprehensive utilization ratio of the present invention is high. The present invention since the secondary residues such as copper ashes, nickel-containing iron slag, sintering and melting cigarette ash that contain in the wet processing process all enter the pyrogenic process system and obtain recycling. The nickel comprehensive recovery of this technique＞94%, copper comprehensive recovery＞96%, golden comprehensive recovery＞95%, silver-colored comprehensive recovery＞90%, palladium comprehensive recovery＞90%. And single thermal process is processed nickel recovery less than 90%, and the copper comprehensive recovery is less than 90%; Single wet processing is processed nickel recovery 75-85%, and copper recovery is greater than 96%, but noble metal can not reclaim.
(3) production process cleaning of the present invention. The present invention in process of production secondary residue of wet-treating generation all returns the processing of pyrogenic process system such as nickeliferous, the cupric cigarette ash that contains copper ashes, nickel-containing iron slag and pyrogenic attack generation. Waste residue is water granulated slag iron content calcium silicon etc., after testing without Leaching and radioactivity, can be used for operating mine slag cement or shipyard derusting abrasive medium, so slag can be sold outward. Waste water be wet-treating produce contain the heavy nickel tail washings of alkali, can be used for the flue gas desulfurization of pyrogenic process system, recycling through the lime regenerating alkali, the cycling utilization of wastewater rate is more than 70%. The pyrogenic process factory effluent is jacket water and flushing cinder waste water, temperature 70-90 degree centigrade, and can utilize its heat that the leaching in the wet-treating, iron removal step etc. are heated, then return the pyrogenic process systemic circulation and utilize waste water. Waste gas is sinter fume, the melting flue gas that pyrogenic attack produces, and enters desulfurized dust collection column and carry out desulfurization and dedusting with alkali lye behind sedimentation, spray, bag collection, and flue gas is realized qualified discharge.
(4) economic benefit of the present invention is obvious, and product of the present invention is prepared calcium carbonate nickel, black copper, low nickel matte. Prepared calcium carbonate nickel and black copper market price are high, so remarkable in economical benefits. And single thermal process can only be produced low nickel matte, and ambrose alloy enters simultaneously in the product and is difficult to separate, and not only the nickel price is low, and the valuation of copper is lower. Single wet processing is produced nickel salt, and copper is only as byproduct, and noble metal is difficult to reclaim, thereby the value of copper, noble metal does not embody. The economic benefit of the two is all poor than this technique.
(5) calcium, iron etc. in the raw material of the present invention, alkali and pyrogenic process production waste heat is fully used in the waste water, and material consumption is controlled, and comprehensive production cost is low. Production high material consumption high with the energy consumption of single pyrogenic process, single wet method the obvious advantage of having compared.
(6) B nickel, copper separation in the step, cupric need be removed in the nickel leachate. Method displacement copper removal commonly used, extraction copper removal, sulfuration copper removal, in and copper removal etc. Present technique is for vulcanizing-replace compound copper removal, must not filter in the waste water and after the slag leaching, under the condition of PH1.0-1.5, remove copper more than 95% with the sodium sulfide solution of equivalent first, remaining copper adds a small amount of iron powder again and replaces copper removal, copper more than 98.5% removes incorporates slag into, obtain after the filtration cupric more than 20% (mass percent) contain copper ashes. Compare with general nickel powder displacement method, cost is low, and slag is nickeliferous low; Compare with the iron displacement method, iron concentration increases not quite in the solution, and deironing is simple. Compare with the sulfuration copper removal, it is few that nickel enters the slag loss; Simple with the extraction compare operation, be easy to control, the buying of vulcanized sodium and iron powder is convenient, and cost is low, and direx process is subjected to solution suspended particulate, calcium ion effect larger. Present technique is practical, easy, is easy to grasp, and copper nickel separates thoroughly.
(7) D adopts P507 extracting production of refining nickelous carbonate technology in the step, and P507 is a kind of acidic extractant, and name is called 2-ethylhexyl phosphoric acid list (2-ethylhexyl) fat, and solubility is atomic in water. The industrial Separation of nickel and cobalt that is usually used in the solution separates. Know that according to the extraction curve of P507 at PH be between the 4-5, nickel has higher extract and separate coefficient in other foreign metal ions. The order of its extracting metals is Fe3+＞Zn
2+＞Cu
2+＝Mn
2+＝Ca
2+＞Co
2+＞Mg
2+＞Ni
2+, contain the impurity such as a small amount of iron, copper, chromium, calcium, magnesium, aluminium, zinc in the nickel solution, then can cause a large amount of losses of nickel as adopting the chemical method precipitate and separate, so P507 can reach the purification purpose, the loss of nickel is few. With the P507 organic phase of 10%-15%9 (VP507/V kerosene), through three grades of extractions, concentration impurity ion is less than 10mg/l in the raffinate, and nickel compares greater than 4000 with impurity content in the solution, therefore can obtain prepared calcium carbonate nickel product through coprecipitated nickel hydroxide.
(8) low nickel matte is produced in the nickel-containing iron slag melting in G step, and nickel-containing iron slag is nickel solution deironing product, and is nickeliferous about 3%, and directly the wet-treating difficulty is large, so adopt pyrometallurgical smelting to reclaim nickel. With the nickel-containing iron slag sintering for agglumeration, then enter shaft smelting. Deviate from moisture in the sintering process, part of sulfuric acid salt decomposes, and sulphur about 50% is removed. General sintering process must add Iron Ore Powder to be increased into the piece rate and adjusts ferrous components, and the iron content about 20% of nickel-containing iron slag own so must not add Iron Ore Powder, also can reach good sintering effect. On the other hand, low nickel matte production must add sulphide ore, and the agglomerate sulfur-bearing of nickel-containing iron slag is greater than 2%, and the sulphide ore addition is few in the melting, and production capacity increases, and the low nickel matte sulfur content is easy to control. Iron in the raw material, sulphur composition all are utilized effectively. Adopt low charge level, large coke ratio, small powder batch operation technology in the fusion process, can effectively control furnace accretion and generate, flux is lime stone, fluorite, sulphide ore etc., and the slag type is chosen as the low high white residue type of the iron (Fe12-15% of high calcium; CaO18-22%; SiO25-35%), slag is nickeliferous less than 0.2%, and slag copper separator well, nickel direct recovery rate be greater than 92%, blast furnace production capacity 30-45 ton agglomerate/day .m2 The low nickel matte composition of producing contains: nickel 10-15%, iron 45-55%, sulphur 19-25%.
Specific embodiments:
Embodiment 1
Raw material (in the nickeliferous copper waste water and slag) composition:
Ni8.20％，Cu6.33％，Fe3.50％，CaO3.0％，Cr2.25％，MgO0.2％，
Al
2O
30.10％Zn0.11％Au3.5g/tAg60.5g/tPd2.5g/t。
Be described below by processing step:
(1) leaches
Carry out leaching with slag in the above-mentioned waste water.
Leaching-out technique condition: leaching agent: 98% sulfuric acid; Be interrupted and add.
Leaching way: leaching; 80 rev/mins of mixing speeds;
Blast 55 liter/mins of clocks of air supply;
Terminal point PH:1.3;
Extraction time: 2.5 hours.
Leach carry out copper after complete, nickel separates.
(2) copper, nickel separate:
Copper nickel isolation technics condition: A vulcanizes copper removal
Vulcanized sodium concentration 15%;
Vulcanized sodium adds 8.5 liter/mins of clocks of speed;
Sulfuration copper removal pH value 1.2;
Amount of sodium sulfide: equal equivalent thickness of copper number;
The 2.0 hours copper removal time of sulfuration;
B iron replacement copper removal
Displacement copper removal pH value 1.5;
Iron powder consumption 2kg/m3；
Time swap 1.0 hours.
Namely filter after copper removal is complete, obtain containing copper ashes and solution containing nickel. This process result such as following table:
| Project | Title | Quantity | Unit | Ni | Cu | Fe | Cr | Zn | CaO | MgO | Al 2O 3 | Au | Ag | Pd |
| Drop into | In the waste water and slag* | 1000 Kg | ％ | 8.2 | 6.33 | 3.5 | 2.25 | 0.11 | 3.0 | 0.2 | 0.1 | 3.5 | 60.5 | 2.5 |
| Sulfuric acid | 420kg | |||||||||||||
| Vulcanized sodium (60%) | 129.6 Kg | |||||||||||||
| Iron powder | 7.0kg | |||||||||||||
| Output | Contain copper ashes | 250kg | ％ | 1.25 | 25.0 | 6.92 | 4.08 | 0.01 | 11.6 2 | 0.02 | 0.15 | 13.9 0 | 239. 82 | 9.94 |
| Nickel solution | 4.00 m 3 | g/l | 19.7 2 | 0.20 | 6.17 | 3.13 | 0.27 | 0.24 | 0.49 | 0.16 | / | / | / | |
| Technical indicator | The solution metal recovery rate | ％ | 96.2 | 1.25 | 58.8 | 55.7 | 97.6 | 3.20 | 97.2 | 58.7 | / | / | / | |
| Enter the slag rate | ％ | 3.8 | 98.7 5 | 41.2 | 45.3 | 2.4 | 96.8 | 2.80 | 41.3 | 99.2 9 | 99.1 0 | 99.3 5 |
(3), deironing: nickel solution carries out deironing.
Iron removal technology condition: oxidant: hydrogen peroxide;
Hydrogen peroxide addition: till not measuring ferrous ion with inspection.
Deironing terminal point PH:4.0;
The deironing time: 3.5 hours; After further iron removal by oxidation is complete, in solution, add sodium fluoride 5kg, stirred 30 minutes, deviate from calcium magnalium impurity.
This process result such as following table
| Title | Quantity | Unit | Ni | Cu | Fe | Cr | Zn | CaO | MgO | Al 2O 3 |
| Nickel-containing iron slag | 135.2kg | ％ | 4.33 | / | 17.27 | 8.82 | 0.03 | 0.48 | / | / |
| Deironing nickel liquid | 4.50m 3 | g/l | 16.23 | 0.17 | 0.30 | 0.13 | 0.23 | 0.07 | 0.064 | 0.032 |
| The solution metal recovery rate | ％ | 92.58 | 98.50 | 5.4 | 4.70 | 96.50 | 31.7 | 14.8 | 22.5 | |
| Enter the slag rate | ％ | 7.42 | 1.50 | 94.6 | 95.30 | 3.50 | 68.3 | 85.2 | 77.5 |
(4), extraction:
Deironing nickel liquid send extraction.
Technical conditions: extractant: P507.
Extractant concentration: 10% (VP507/V kerosene).
Compare 1/5.5
Extraction progression: 3 grades.
Saponification rate: 70%;
Back washing agent: 5N sulfuric acid.
Reextraction compares 1/15
Back extraction progression: 1 grade.
After extraction, raffinate is pure nickel liquid, and saponification is sent in extracted organic phase regeneration after sulfuric acid is stripped, and strip liquor send neutralisation treatment. This process the results are shown in following table.
| Title | Quantity | Unit | Ni | Cu | Fe | Cr | Zn | CaO | MgO | Al 2O 3 |
| Pure nickel liquid | 4.70m 3 | g/l | 15.37 | 0.0018 | 0.0018 | 0.0015 | 0.0012 | 0.0030 | 0.0035 | 0.0036 |
| Anti-stripping agent | 0.5m 3 | g/l | 1.20 | 1.40 | 3.20 | 1.0 | 2.0 | 0.59 | 0.40 | 0.46 |
| The regeneration organic phase | 0.80m 3 | g/l | 0.26 | 0.07 | 0.24 | 0.10 | 0.036 | 0.015 | 0.09 | 0.026 |
| Solution metal extraction rate | ％ | 1.11 | 98.89 | 99.53 | 99.14 | 99.45 | 95.52 | 94.30 | 94.12 |
(5), prepared calcium carbonate nickel
Pure nickel liquid after extraction is used the sodium carbonate coprecipitated nickel hydroxide.
Technical conditions: concentration of sodium carbonate 20%.
Precipitation terminal point pH value: 8.5.
This process the results are shown in following table.
| Title | Quantity | Unit | Ni | Cu | Fe | Cr | Zn | CaO | MgO | Al 2O 3 |
| Prepared calcium carbonate nickel | 174.8 | ％ | 41.00 | 0.0048 | 0.0048 | 0.004 | 0.0032 | 0.008 | 0.009 | 0.0096 |
| Heavy nickel tail washings | 7.50 m 3 | g/l | 0.076 | |||||||
| Nickel recovery | ％ | 99.21 |
In the wet-treating process, obtain prepared calcium carbonate nickel 174.8kg, the nickel direct recovery rate is 87.4%.
(6), nickel-containing iron slag sintering-melting
Nickel-containing iron slag, contain copper ashes and behind sintering, obtain agglomerate, then melting.
Sintering technology condition: sintered mixture moisture 53%;
Coal charge is than 10% (butt is than 25%)
850 ℃ of sintering temperatures
Sintering time 6 hours.
Technical conditions: low nickel matte is produced black copper production
Coke ratio 22% coke ratio 16.5%
Flux than 16.5% flux than 15.0%
Slag silicate degree K1.5 slag silicate degree K1.5
Sintering-melting result such as following table:
| Project | Title | Quantity | Unit | Ni | Cu | Fe | Cr | Zn | CaO | MgO | Al 2O 3 | Au | Ag | Pd |
| Sintering | Nickel-containing iron slag | 20 tons | ％ | 4.33 | / | 17.27 | 8.82 | 0.03 | 0.48 | / | ||||
| Coal | 5.0 ton | |||||||||||||
| Back powder and cigarette ash etc. | 1.50 ton | 3.50 | 16.20 | 6.38 | 0.05 | 8.52 | 0.03 | 0.12 | ||||||
| Agglomerate | 22.50 ton | ％ | 4.08 | 16.44 | 8.26 | 0.03 | 0.99 | |||||||
| Melting | The coke consumption | 7.50 | ||||||||||||
| Flux | 6.00 | |||||||||||||
| Low nickel matte | 6.14 | ％ | 13.50 | 0.12 | 51.28 | 0.01 | 0.02 | |||||||
| Water Quenching Slag | 25.80 | ％ | 0.20 | 12.38 | 21.25 | |||||||||
| Sintering | Contain copper ashes | 36.98 | ％ | 1.25 | 25.0 | 6.92 | 4.08 | 0.01 | 11.62 | 0.02 | 0.15 | 13.90 | 239.82 | 9.94 |
| Coal | 9.25 | |||||||||||||
| Back powder and cigarette ash etc. | 2.77 | ％ | 0.89 | 18.57 | 4.86 | 2.88 | 0.11 | 8.98 | ||||||
| Agglomerate | 41.50 | ％ | 1.17 | 23.51 | 6.48 | 3.82 | 0.016 | 10.95 | 12.39 | 211.0 | 8.83 | |||
| Melting | Coke | 10.38 | ||||||||||||
| Flux | 4.50 | |||||||||||||
| Black copper | 11.51 | ％ | 81.50 | 42.59 | 696.76 | 28.71 | ||||||||
| Water Quenching Slag | 34.50 | ％ | 0.53 | 8.05 | 19.88 | |||||||||
As seen from the above table, (be 90.2% in the low nickel matte, copper recovery is that 95.38% silver raising recovery rate is that 90.65% palladium recovery rate is 90.12% for (in the black copper) 96.3% gold recovery to the nickel recovery of this process
Embodiment 2
Raw material (in the nickeliferous copper waste water and slag) composition:
Ni6.20％，Cu7.33％，Fe5.50％，CaO4.0％，Cr1.25％，MgO0.18％，
Al
2O
30.11％Zn0.13％Au3.29g/tAg70.6g/tPd3.05g/t。
Be described below by processing step:
(1) leaches: will carry out leaching with slag in the above-mentioned waste water. According to raw material condition technical conditions are adjusted. For guaranteeing to obtain leaching rate and the lower ferrum-chromium-aluminum leaching rate of higher ambrose alloy, should increase the reaction time and improve the solution pH value. Be to remain in the leaching process that pH value is 1.5, leach complete rear continuation and stir that the time increases by 1.0 hours.
Leaching-out technique condition: terminal point PH:1.5;
Extraction time: 3.5 hours.
Other conditions are with embodiment 1.
Leach and carry out ambrose alloy after complete and separate.
(2) copper, nickel separate:
Condition is with embodiment 1.
Namely filter after copper removal is complete, obtain containing copper ashes and nickel solution. The rate of recovery of nickel is 96.05% in this process nickel solution, and copper enters slag rate 98.10%, and nickel enters slag rate 3.95%.
(3) deironing: nickel solution carries out iron removal by oxidation. Because the ferrous ion content in the nickel solution is than example 1 high 1.5g/l, so the iron removal time lengthening can reach preferably de-ferrous effect in 1 hour, because co-precipitation iron, chromium removes with example 1 without than big difference.
Iron removal technology condition: deironing time: 4.0 hours;
Other conditions are with embodiment 1.
After iron removal by oxidation is complete, in solution, add sodium fluoride 5kg, stirred 30 minutes, remove calcium magnalium impurity. In this process in the solution nickel recovery be 92.15%, it is 94.88% that iron enters the slag rate, nickel enters slag rate 8.85%, iron content 0.40g/l in the nickel liquid after the deironing, calcium, magnesium, aluminium content are lower than 0.05g/l, can not affect extraction process.
(4) extraction:
With embodiment 1.
(5) prepared calcium carbonate nickel
With embodiment 1.
In the wet-treating process, process acquisition prepared calcium carbonate nickel 129.78kg with slag in the waste water per ton, the nickel direct recovery rate is 86.24%. The wet-treating process the results are shown in following table:
| Project | Title | Quantity | Unit | Ni | Cu | Fe | Cr | Zn | CaO | MgO | Al 2O 3 | Au | Ag | Pd |
| Drop into | In the waste water and slag | 1.0 ton | ％ | 6.20 | 7.33 | 5.50 | 1.25 | 0.13 | 4.0 | 0.18 | 0.11 | 3.29g/t | 70.6g/t | 3.05g/t |
| Sulfuric acid | 550kg | |||||||||||||
| Vulcanized sodium | 150kg | |||||||||||||
| Iron powder | 9.0kg | |||||||||||||
| Hydrogen peroxide | 150kg | |||||||||||||
| Sodium carbonate | 100kg | |||||||||||||
| Output | Contain copper ashes | 325kg | ％ | 0.73 | 22.26 | 6.77 | 1.48 | / | 12.16 | / | 0.13 | 10.10 | 216.50 | 9.30 |
| Nickel-containing iron slag | 158.5kg | ％ | 3.46 | / | 18.22 | 4.70 | / | 0.25 | / | 0.05 | / | / | / | |
| Prepared calcium carbonate nickel | 129.78k g | ％ | 41.2 | 0.005 | 0.005 | 0.0041 | 0.0036 | 0.0091 | 0.0093 | 0.0076 | / | / | / | |
| Heavy nickel tail washings | 6.00m 3 | g/l | 0.06 | |||||||||||
| Index | Metal recovery rate (in the product) | ％ | 86.24 | 98.70 |
(6) nickel-containing iron slag, contain copper ashes sintering-melting
Nickel-containing iron slag, contain copper ashes sintering-melting with example 1. The results are shown in following table.
| Project | Title | Quantity | Unit | Ni | Cu | Fe | Cr | Zn | CaO | MgO | Al 2O 3 | Au | Ag | Pd |
| Sintering | Nickel-containing iron slag | 20 tons | ％ | 3.46 | / | 18.22 | 4.70 | / | 0.25 | / | 0.05 | / | / | / |
| Coal | 5.0 ton | |||||||||||||
| Back powder and cigarette ash etc. | 1.50 ton | 3.50 | 16.20 | 6.38 | 0.05 | 8.52 | 0.03 | 0.12 | ||||||
| Agglomerate | 22.65 ton | ％ | 3.29 | 17.16 | 4.57 | 0.03 | 0.79 | |||||||
| Melting | The coke consumption | 7.50 ton | ||||||||||||
| Flux | 6.00 ton | |||||||||||||
| Low nickel matte | 5.05 ton | ％ | 13.28 | 0.18 | 52.32 | 0.01 | 0.02 | |||||||
| Water Quenching Slag | 25.95 ton | ％ | 0.19 | 13.08 | 20.56 | |||||||||
| Sintering | Contain copper ashes | 41.0 ton | ％ | 0.73 | 22.26 | 6.77 | 1.48 | / | 12.16 | / | 0.13 | 10.10 | 216.50 | 9.30 |
| Coal | 10.28 ton | |||||||||||||
| Back powder and cigarette ash etc. | 3.07 ton | ％ | 0.89 | 18.57 | 4.86 | 2.88 | 0.11 | 8.98 | ||||||
| Agglomerate | 46.00 ton | ％ | 7.97 | 21.08 | 6.36 | 1.55 | 0.015 | 11.44 | 9.00 | 191.50 | 8.25 | |||
| Melting | Coke | 11.50 ton | ||||||||||||
| Flux | 5.50 ton | |||||||||||||
| Black copper | 11.55 ton | ％ | 81.56 | 34.23 | 694 | 30.0 | ||||||||
| Water Quenching Slag | 40.23 ton | ％ | 0.53 | 8.56 | 19.24 | |||||||||
(be 90.07% in the low nickel matte, copper recovery is that 95.47% silver raising recovery rate is that 90.30% palladium recovery rate is 90.87% for (in the black copper) 96.00% gold recovery to the nickel recovery of this process.
Embodiment 3-6
| Sequence number | The operation title | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| 1 | Material composition | Ni8.20％，Cu6.33％， Fe3.50％，CaO3.0％， Cr2.25％，MgO0.2％， Al 2O 30.10％Zn0.11％ Au3.5g/tAg60.5g/t Pd2.5g/t。 | Ni8.20％，Cu6.33％， Fe3.50％.CaO3.0％. Cr2.25％，MgO0.2％， Al 2O 30.10％Zn0.11％ Au3.5g/tAg60.5g/t Pd2.5g/t。 | Ni6.20％，Cu7.33％， Fe5.50％，CaO4.0％， Cr1.25％，MgO0.18％， Al 2O 30.11％Zn0.13％ Au3.29g/tAg70.6g/t Pd3.05g/t。 | Ni6.20％，Cu7.33％， Fe5.50％，CaO4.0％， Cr1.25％，MgO0.18％， Al 2O 30.11％Zn0.13％ Au3.29g/tAg70.6g/t Pd3.05g/t。 |
| 2 | Leaching/copper, nickel separate | Leaching-out technique condition: industrial sulphuric acid; Sulfuric acid is interrupted and adds; Terminal point PH1.5; The Leaching way leaching; Blast compressed air; Extraction time 4 hours; Vulcanized sodium concentration 10%, copper nickel isolation technics condition: vulcanized sodium adds 5 liter/mins of clocks of speed; Sulfuration pH value 1.5 iron replacement pH values 2.0; 1 kilogram/cubic metre of iron powder consumption. | Leaching-out technique condition: industrial sulphuric acid; Sulfuric acid is interrupted and adds; Terminal point PH1.0; The Leaching way leaching; Blast compressed air; Extraction time 2 hours; Vulcanized sodium concentration 15%; Copper, nickel isolation technics condition: vulcanized sodium adds 10 liter/mins of clocks of speed; Sulfuration pH value 1.0; Iron replacement pH value 1.0; 3 kilograms/cubic metre of iron powder consumptions. | Leaching-out technique condition: industrial sulphuric acid; Sulfuric acid is interrupted and adds; Terminal point PH1.5; The Leaching way leaching; Blast compressed air; 4 hours vulcanized sodium concentration 10% of extraction time; Copper, nickel isolation technics condition: vulcanized sodium adds 5 liter/mins of clocks of speed; Sulfuration pH value 1.5; Iron replacement pH value 2.0; 1 kilogram/cubic metre of iron powder consumption. | Leaching-out technique condition: industrial sulphuric acid; Sulfuric acid is interrupted and adds; Terminal point PH1.0; The Leaching way leaching; Blast compressed air; 2 hours vulcanized sodium concentration 15% of extraction time; Copper, nickel isolation technics condition: vulcanized sodium adds 10 liter/mins of speed; Sulfuration pH value 1.0; Iron replacement pH value 1.0; 3 kilograms/cubic metre of iron powder consumptions. |
| Index: copper removal efficiency 98.60%; Nickel enters slag rate 3.78%, and gold, silver, palladium enter slag rate 99.53%. Impurity leaching rate: Fe66.75%, Cr66.56%, Al68.87% | Index copper removal efficiency 98.2%; Nickel enters slag rate 3.74%, and gold, silver, palladium enter slag rate 99.27%. Impurity leaching rate: Fe69.01%, Cr64.2%, Al65.0% | Index copper removal efficiency 98.35%; Nickel enters slag rate 3.90%, and gold, silver, palladium enter slag rate 99.45%. Impurity leaching rate: Fe64.5%, Cr65.2%, Al67.3% | Index copper removal efficiency 98.3%; Nickel enters slag rate 3.54%, and gold, silver, palladium enter slag rate 99.32%. Impurity leaching rate: Fe68.22%, Cr64.7%, Al＜65.6% | ||
| 3 | Deironing | Iron removal technology condition: ferroxidant: hydrogen peroxide; Deironing PH:3.5; The deironing time: 3 hours; Sodium fluoride addition: 5 kilograms/cube. | Iron removal technology condition: ferroxidant: hydrogen peroxide; Deironing PH:4.2; The deironing time: 4 hours; Sodium fluoride addition: 10 kilograms/cube. | Iron removal technology condition: ferroxidant: hydrogen peroxide; Deironing PH:3.5; The deironing time: 3 hours; Sodium fluoride addition: 5 kilograms/cube. | Iron removal technology condition: ferroxidant: hydrogen peroxide; Deironing PH:4.2; The deironing time: 4 hours; Sodium fluoride addition: 10 kilograms/cube. |
| Technical indicator: iron removal efficiency 94.58% nickel enters slag rate 7.62%; Calcium, magnesium, aluminium removal efficiency＞60% slag ingredient: nickel 4.52%; Iron 16.83% | Technical indicator: iron removal efficiency 92.89% nickel enters slag rate 7.88%; Calcium, magnesium, aluminium removal efficiency＞60% slag ingredient: nickel 401%; Iron 18.22% | Technical indicator: iron removal efficiency 93.9% nickel enters slag rate 8.72%; Calcium, magnesium, aluminium removal efficiency＞60% slag ingredient: nickel 3.76%; Iron 17.52% | Technical indicator: iron removal efficiency 93.32% nickel enters slag rate 8.24%; Calcium, magnesium, aluminium removal efficiency＞60% slag ingredient: nickel 3.62%; Iron 16.2% |
| 4 | Extraction | Technical conditions: extractant: P507. Extractant concentration: 10% (VP507/V kerosene). Extraction progression: 3 grades. Back washing agent: 5N sulfuric acid. Back extraction progression: 1 grade. | Technical conditions: extractant: P507. Extractant concentration: 15% (VP507/V kerosene). Extraction progression: 3 grades. Back washing agent: 7N sulfuric acid. Back extraction progression: 1 grade. | Technical conditions: extractant: P507. Extractant concentration: 12% (VP507/V kerosene). Extraction progression: 3 grades. Back washing agent: 6N sulfuric acid. Back extraction progression: 1 grade. | Technical conditions: extractant: P507. Extractant concentration: 15% (VP507/V kerosene). Extraction progression: 3 grades. Back washing agent: 7N sulfuric acid. Back extraction progression: 1 grade. |
| Technical indicator: nickel extraction yield: 1.87%. Impurity extraction yield:＞95%. raffinate impurity concentration:＜10mg/l. | Technical indicator: nickel extraction yield: 1.76%. Impurity extraction yield:＞95%. raffinate impurity concentration:＜10mg/l. | Technical indicator: nickel extraction yield: 1.732%. Impurity extraction yield:＞95%. raffinate impurity concentration:＜10mg/l. | Technical indicator: nickel extraction yield: 1.98%. Impurity extraction yield:＞95%. raffinate impurity concentration:＜10mg/l. | ||
| 5 | Prepared calcium carbonate nickel | Technical conditions: concentration of sodium carbonate 20%. Precipitation terminal point PH value: 8.0. Washing/drying/washing | Technical conditions: concentration of sodium carbonate 30%. Precipitation terminal point PH value: 8.5. Washing/drying/washing | Technical conditions: concentration of sodium carbonate 20%. Precipitation terminal point PH value: 8.0. Washing/drying/washing | Technical conditions: concentration of sodium carbonate 30%. Precipitation terminal point PH value: 8.5. Washing/drying/washing |
| Technical indicator: the nickeliferous 0.08/l of nickel rate of deposition 98.30%. tail washings. Prepared calcium carbonate nickel composition: Ni41.26%, Fe, 0.005%; Cu0.003%; Cr0.0041%; SO40.02%; Cl0.008% hydrochloric acid insoluble substance 0.035%; Sodium and alkaline-earth metal 0.021%. | Technical indicator: the nickeliferous 0.04g/l of nickel rate of deposition 99.02%. tail washings. Prepared calcium carbonate nickel composition: Ni42.23%, Fe, 0.005%; Cu0.004%; Cr0.0036%; SO40.04%; Cl0.004% hydrochloric acid insoluble substance 0.038%; Sodium and alkaline-earth metal 0.05%. | Technical indicator: the nickeliferous 0.06g/l of nickel rate of deposition 98.41%. tail washings. Prepared calcium carbonate nickel composition: Ni42.09%, Fe, 0.005%; Cu0.004%; Cr0.0045%; SO40.05%; Cl0.006% hydrochloric acid insoluble substance 0.042%; Sodium and alkaline-earth metal 0.01% | Technical indicator: nickel rate of deposition 98.65%. tail washings is nickeliferous＜0.08g/l. Prepared calcium carbonate nickel composition: Ni41.3%, Fe, 0.005%; Cu0.004% Cr0.0031%; SO40.06%; Cl0.004% hydrochloric acid insoluble substance＜0.032%; Sodium and alkaline-earth metal＜005%. | ||
| 6 | Sintering | Sintering technology condition: sintered mixture moisture 55%; Coal is than 8%; Sintering temperature 850 sintering times 8 hours. | Sintering technology condition: sintered mixture moisture 50%; Coal is than 10%; Sintering temperature 850 sintering times 6 hours. | Sintering technology condition: sintered mixture moisture 50%; Coal is than 8%; During sintering temperature 850 sintering 8 hours. | Sintering technology condition: sintered mixture moisture 55%; Coal is than 10%; Sintering temperature 850 sintering times 6 hours. |
| Sintering technology index: become piece rate 78.3%; Agglomerate composition: nickel agglomerate copper agglomerate Ni3.0% Cu18.6% Fe6.53% Fe13.2% SiO233.6％ SiO 229.1％ CaO4.20％ CaO10.1％ S0.73％ | Sintering technology index: become piece rate 74.6%; Agglomerate composition: nickel agglomerate copper agglomerate Ni2.89% Cu17.63% Fe5.96% Fe11.29% SiO234.5％ SiO 230.6％ CaO4.87％ CaO11.60％ S0.52％ | Sintering technology index: become piece rate 80.2%; Agglomerate composition: nickel agglomerate copper agglomerate Ni2.78% Cu18.29% Fe7.83% Fe114.30% SiO231.48％ SiO 233.96％ CaO5.00％ CaO11.96％ S0.87％ | Sintering technology index: become piece rate 75.2%; Agglomerate composition: nickel agglomerate copper agglomerate Ni2.66% Cu15-20% Fe6.87% Fe14.22% SiO231.24％ SiO 229.28％ CaO4.17％ CaO11.83％ S0.36％ |
| Au12.39g/t Ag211g/t Pd8.83g/t | Au12.66g/t Ag210.6g/t Pd8.20g/t | Au1101g/t Ag208.2g/t Pd6.98g/t | Au110.96g/t Ag205.27g/t Pd6.32g/t | ||
| 7 | Melting | Technical conditions: low nickel matte produce black copper produce coke ratio 18% coke ratio 15% flux than 10% flux than 10% silicate degree K0.8 silicate degree K0.5 | Technical conditions: low nickel matte produce black copper produce coke ratio 23% coke ratio 18% flux than 20% flux than 15% silicate degree K1 silicate degree K1 | Technical conditions: low nickel matte produce black copper produce coke ratio 18% coke ratio 15% flux than 10% flux than 10% silicate degree K0.8 silicate degree K0.5 | Technical conditions: low nickel matte produce black copper produce coke ratio 23% coke ratio 18% flux than 20% flux than 15% silicate degree K1.0 silicate degree K1.0 |
| Technical indicator metal recovery rate metal recovery rate Ni90.5% Cu96.4% Au95.2% Ag90.3% Pd90.4% low nickel matte composition black copper composition Ni13.27% Cu84.58%, Fe50.23% Pb+Zn3.21% Au42.59g/t, Ag696.6g/t, Pd28.71g/t slag ingredient slag ingredient Ni0.22% Cu0.48% FeO13.05% FeO9.33% SiO229.27％ SiO 226.38％ CaO19.21％ CaO22.64％ | Technical indicator metal recovery rate metal recovery rate Ni91.16% Cu96.23% Au95.6% Ag91.3% Pd91.4% low nickel matte composition black copper composition Ni12.58% Cu83.26%, Fe52.01% Pb+Zn4.66% Au40.87g/t, Ag683.2g/t, Pd27.21g/t slag ingredient slag ingredient Ni0.20% Cu0.47% FeO14.32% FeO9.53% SiO231.56％ SiO 228.65％ CaO18.86％ CaO22.24％ | Technical indicator metal recovery rate metal recovery rate Ni90.33% Cu96.54% Au95.21% Ag91.03% Pd90.62% low nickel matte composition black copper composition Ni13.00% Cu83.34%, Fe53.21% Pb+Zn4.60% Au41.53g/t, Ag700.5g/t Pd230.36g/t slag ingredient slag ingredient Ni0.21 %Cu0.39% FeO13.68% FeO9.13% SiO230.20％ SiO 227.96％ CaO18.50％ CaO23.27％ | Technical indicator metal recovery rate metal recovery rate Ni90.76% Cu96.87% Au96.1% Ag92.1% Pd1.35% low nickel matte composition black copper composition Ni12.86% Cu82.86%, Fe53.62% Pb+Zn4.75% Au40.76g/t Ag690.53g/t Pd224.69g/t slag ingredient slag ingredient Ni0.23% Cu0.46% FeO12.99% FeO8.96% SiO229.85％ SiO 227.32％ CaO16.53％ CaO22.58％ |
Claims (8)
1, a kind of wet method-pyrogenic process process integration reclaims in the waste water and the method for copper, nickel and noble metal in the slag, and it is characterized in that: it comprises wet process and pyrogenic process process, and concrete steps are as follows:
Described wet process comprises:
A, will fill in the waste water and add leaching agent sulfuric acid in the reactor of slag, and stir, the terminal point pH value is controlled at 1.0-1.5, and extraction time is 2-4 hour; Nickel more than 98%, copper leach and enter solution; The leachings such as the iron less than 60%, chromium, aluminium enter solution;
B, leach and not filter after complete, with the A same reactor in step in, add while stirring the sodium sulfide solution with the copper equivalent, sulfuration pH value is 1.0-1.5, the formation copper sulfide enters to contain copper ashes;
Remaining copper adds 1-3kg/m in the solution3Iron replacement, pH value is 1.0-2.0, the copper of replacing enters and contains copper ashes;
The noble metal gold, silver, palladium of trace enter through sulfuration and iron replacement and contain copper ashes in the solution;
Filter, obtain containing copper ashes and solution containing nickel, realize that copper, nickel separate;
C, be under the 3.5-4.2 condition at pH value, with adding ferroxidant in the solution containing nickel of B in the step, the oxidation of divalent iron ion in the solution become ferric ion, then use Na2CO
3Neutralization makes the iron precipitation and removes; Chromium also is removed simultaneously;
When reaction PH is stabilized in 4.0-4.5, add sodium fluoride and further remove calcium, magnesium, aluminium impurity, described sodium fluoride addition is 5-10kg/m3；
The nickel that the iron tramp that this step is removed reaches less than 5% enters nickel-containing iron slag;
D, be 4.0-5.0 at pH value, employing concentration is the extractant P507 of 10%-15% (V P507/V kerosene), a small amount of iron, copper, chromium, calcium, magnesium, aluminium, the zinc impurity of extraction in the solution containing nickel of C after the step; The extracted organic phase concentrated sulfuric acid back extraction regeneration organic phase of 5N-7N, raffinate is pure nickel solution;
E, employing mass concentration are the sodium carbonate precipitation of 20-30%, and precipitation terminal point pH value is 8.0-8.5, produces prepared calcium carbonate nickel;
Described pyrogenic process process comprises:
F, the nickel-containing iron slag sintering that respectively the B sulfuration copper ashes in step, C is gone on foot get copper agglomerate, nickel agglomerate;
Quality contains Cu 15-20%, Fe 12-15%, Au 10-15g/t, Ag200-300g/t, Pd 5-15g/t, SiO in the described copper agglomerate2 28-35％、CaO 8-12％、S＜1％；
Quality contains Ni2.5-3.0%, Fe6-8%, SiO in the described nickel agglomerate228-35％、CaO 3-5％；
G, copper agglomerate or ferronickel agglomerate that F is gone on foot obtain respectively black copper or low nickel matte through the high temperature reduction melting, and described copper and noble metal gold, silver, palladium are recovered in black copper; Nickel reclaims in low nickel matte.
2, method according to claim 1 is characterized in that: when adding leaching agent sulfuric acid in the A stage reactor, blast compressed air.
3, method according to claim 1 is characterized in that: the mass concentration of vulcanized sodium was 10-15% during B went on foot, and adding speed is 5-10 liter/min of clock.
4, method according to claim 1 is characterized in that: the temperature when in C step the oxidation of divalent iron ion in the solution being become ferric ion is 50-60 ℃; Described ferroxidant is hydrogen peroxide.
5, method according to claim 1 is characterized in that: the extraction progression of D in the step is three grades of extractions.
6, method according to claim 1 is characterized in that: it is 50-55% that the F step reaches at sintered mixture moisture, and coal charge is than being 8-10%, and sintering temperature is 800-850 ℃, and sintering time is 6-8 hour.
7, method according to claim 1 is characterized in that: the reduction melting of copper agglomerate prepared in the black copper process during G went on foot, and coke ratio is that 15-18%, flux ratio are K1.0-1.5 for 10-15%, slag silicate degree.
8, method according to claim 1 is characterized in that: the reduction melting of ferronickel agglomerate prepared in the low nickel matte process during G went on foot, and coke ratio is that 18-23%, flux ratio are K1.0-1.5 for 10-20%, slag silicate degree.
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