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CN85100731B - Recovery of valuable metals from industrial waste - Google Patents

Recovery of valuable metals from industrial waste Download PDF

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CN85100731B
CN85100731B CN85100731A CN85100731A CN85100731B CN 85100731 B CN85100731 B CN 85100731B CN 85100731 A CN85100731 A CN 85100731A CN 85100731 A CN85100731 A CN 85100731A CN 85100731 B CN85100731 B CN 85100731B
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ammonia
cobalt
nickel
molybdenum
tungsten
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CN85100731A (en
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张懿
陈家镛
张荣源
高文考
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Institute Of Chemical Metallurgy chinese Academy Of Sciences
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Abstract

A new process for treating the mud dregs containing Ni, Co, Cr, W and Mo features that the reducing agents such as ferrous salt or sulfite are added to the ammonia and ammonium carbonate for one-step dissolving Ni and Co in ammonia product and reducing acid to dissolve trivalent ions for alkali decomposition to separate W and Mo from Ni and Co. Compared with the prior art, the method has the advantages of higher metal extraction separation ratio, less reagent consumption in the process simplification, cost reduction and complete prevention of chromium pollution.

Description

From industrial waste, reclaim valuable metal
The invention belongs to from industrial waste the hydrometallurgy process novel process that reclaims metal, particularly be suitable for handling the entire flow of polycomponent body refuse waste materials such as nickeliferous, cobalt, chromium or nickel, cobalt, chromium, tungsten, molybdenum.
Reclaiming metal and decontamination from industrial waste is the problem of extensively gazing at both at home and abroad.The waste that produces in the electrochemical machining of high-temperature alloy part is the mixture and the chromate slurry of the multiple metal hydroxides of the nickel of sodium chloride-containing, SODIUMNITRATE, cobalt, chromium, tungsten, molybdenum, aluminium, titanium.For a long time, this chromyl mud does not have feasible solution and handles recovery, lets alone to pile up, discharge, cause a large amount of losses of valuable metal and serious environmental to pollute.In addition, such as the waste liquid that produces in high quality steel pickling, plating and the refining of metal, also at present way processing of adopting neutralization precipitation consequently cause a large amount of pulpous state waste residues to pile up and run off more.Therefore, administer this type of useless body refuse effectively, had urgency.
Handle this type of useless body refuse, generally can only adopt Wet-process metallurgy method.At present at home and abroad, Shang Weijian has the better flow process of handling this kind material.Domestic units concerned only did acidleach to nickel-base alloy electrolytic slime (not containing cobalt) and handled the test work of reclaiming nickel, because of pollution of chromium and the low processing of failing to found the factory of nickel direct yield.77 years Soviet Union non-ferrous metal No.3, Г＜`; ; AnuMOB` 〉, M. Д. propose to leach the nickel-base alloy electrolytic slime with sulfuric acid, after nickel, chromium change solution over to, two kinds of processing schemes are arranged, the first precipitates to such an extent that contain the basic nickel carbonate of chromium 0.5-3% with yellow soda ash, and sexavalent chrome still is retained in the mother liquor, needs reduction back redeposition chromium; It two reduced before coprecipitated nickel hydroxide for sexavalent chrome, then must contain the basic nickel carbonate of chromium 5-6%, and two kinds of basic nickel carbonates all need handle through the refining of complexity again, and nickel, chromium could separate.Eliminate as yet so far both at home and abroad repeatedly sour molten-traditional method of multistage fractional precipitation separating nickel, chromium, flow process is tediously long, consumes a large amount of soda acids, the metal yield is low.
Deutsches Reichs-Patent No2841271 report reclaimed chromium, copper, zinc and nickel from the non-ferrous metal hydroxide sludge in 1980, and the separation of chromium is the hot pressing Mtehod for hydrolytic precitpitation that adopts at PH0.8-3, temperature 150-260 ℃, the equipment and technology complexity.
With more approaching on the technology of the present invention be U.S. PB-271014 report in 77 years, propose to handle in the waste water of nickeliferous, chromium, copper and slag with ammonia leaching process, sexavalent chrome in and pre reduction be trivalent.But the chromium hydroxide that generates under this condition is difficult to suppress in ammonia soaks, and still has the solubleness of 1.9 grams per liters, and does not reach good chromium separating effect, and copper, nickel recovery are also lower.77 years Deutsches Reichs-Patent No.2726783, in the waste water of, chromium nickeliferous with the leaching of ammonia, volatile salt, iron, zinc, copper and slag, nickel, chromium reach 4: 1 than only in the ammonia leaching solution, and copper, zinc, the corresponding rate of recovery of nickel are 82%, 73%, 45%.77 years clear 52-152803 of Japanese Patent to containing chromic many metals waste residue mud, need through dehydrating pre-treatment, under 150 ℃, with ammonia, ammonium salt pressurization leaching, soak rate and separate chromium in the hope of raising nickel, cuprammonium.
Therefore, adopt existing hydrometallurgical processes, process is tediously long, reagent consumption is big, or the equipment complexity, the comprehensive extraction of metal and chromium to separate index low, be very unfavorable.
Another key issue is how to isolate tungsten, molybdenum from nickel, cobalt system, and this is few research in the general hydrometallurgical processes.78 years Britain mining and metallurgy magazine No5, Millsap, WA proposed to reclaim spent catalyst with ammonia leaching process, tungsten, molybdenum can be controlled in the distilled ammonia waste liquid.But for tungstenic, Ni-based system that molybdenum is lower, the causticization alkali consumption is very big during ammonia leaching solution ammonia still process, and tungsten, molybdenum are carried in a large amount of absorption in the distillation precipitation of nickel, cobalt, and are difficult to be suppressed at liquid phase.When tungsten, molybdenum, nickel, cobalt enter the ammonia still process product simultaneously, its sepn process is not more seen research.When all changing nickel, cobalt over to solution with the acid decomposition, tungsten, molybdenum be dissolving thereupon then, at this moment, except considering complicated anionresin extraction tungsten, molybdenum, then has no other way; When considering that alkali decomposes, in the stripping ammonia still process product when tungsten, molybdenum, then because the shock absorption of carbonate in severe reaction conditions and the subcarbonate, consumption alkali height and inferior separating effect.Do not reach the aftertreatment requirement.
Therefore, isolating tungsten, molybdenum from nickel, cobalt, is to handle the new problem that the senior alloyed scrap institute of complicated component must solution.
The purpose of invention is to work out a new technological flow that is suitable for handling polycomponent body refuse waste materials such as nickeliferous, cobalt, chromium, tungsten, molybdenum.Compared to the prior art, its flow process is short, the method simple and feasible, and economical rationality especially reaches higher index on polymetallic comprehensive extraction and isolation technique, and eliminates environmental pollution effectively.
The invention provides a kind of method that reclaims Valuable Metal in Industry Waste, with the leaching of ammonia, volatile salt, it is characterized in that handling nickeliferous, cobalt, chromium or nickel, cobalt, chromium, tungsten, molybdenum is organized more.Divide the body refuse waste material, form by following steps:
(1) when having ferrous salt or other reductive agent to exist, carries out reduction ammonia-leaching with ammonia, volatile salt;
(2) carry out liquid-solid separation, the gained ammonia leaching residue reclaims chromium with ordinary method, ammonia leaching solution distillation, ammonia, carbonic acid gas is returned leaching;
(3) the ammonia still process product of above-mentioned (2) are nickeliferous, cobalt, tungsten, molybdenum filters with sulfuric acid selective dissolution overwhelming majority nickel and part cobalt;
(4) the filter residue alkali dissolution that will obtain by (3), and from solution, reclaim tungsten, molybdenum with ordinary method;
(5) will when having sulphite or nickel powder to exist, also filter by the insoluble slag that (4) obtain with sulfuric acid dissolution;
(6) merge the filtrate that obtains by (3) and (5), reclaim nickel, cobalt with ordinary method.
Flow process provided by the present invention comprises reduction ammonia-leaching and two essential parts of purification separation.Handled typical material sees Table 1.
Reduction ammonia-leaching workshop section comprises reductive leaching, solid-liquid separation and distills three unit operations.Can directly enter ammonia without pretreated slurries such as the desalinization of soil by flooding or leaching and drying and dehydratings and soak operation,, contain NH at the nickeliferous about 5-20 grams per liter of suspension (in main metallic nickel feeding quantity) 3The 60-120 grams per liter, CO 2The 50-110 grams per liter is in carrying out airtight leaching below 100 ℃.In leaching process, add a kind of reductive agent, being trivalent chromium with hexavalent chrome reduction, and in ammoniacal medium hydrolytic precipitation.Can adopt ferrous salt or sulphite, or other there is the reduction of hexavalent chromium ability and do not introduce the reductive agent of impurity in ammoniacal medium, as nickel powder, iron powder or the like.Consumption is 1.2-2.0 a times of theoretical amount.The three class chemical reactions that carried out in the reduction ammonia-leaching process can be expressed as:
Ni（OH） 2+4NH 3+（NH 4） 2CO 3→Ni（NH 3) ++CO 3 =+2H 2O （1）
2CrO 4 =+3SO 3 =+6NH 3+6NH 4 +→3Cr（NH 3） 6 3++3SO 4 =+4OH -+H 2O （2）
Cr（NH 3） 6 3++3H 2O
Figure 85100731_IMG1
Cr（OH） 3+6NH 4 +（3）
Reduction ammonia-leaching makes nickel, cobalt, tungsten, molybdenum change ammonia leaching solution over to, and chromium, iron, aluminium, titanium are suppressed at the slag phase.
Key of the present invention is, in leaching reaction (1) process, react (2) (3) simultaneously, not only simplified flow process, the more important thing is and caused chromium hydrolytic precipitation sufficient condition completely, quicken the process of balancing each other, when obtaining higher main metal leaching rate, reached fabulous chromium separating effect.
The reduction ammonia-leaching rear suspension liquid is through liquid-solid separation, and ammonia leaching solution enters Distallation systm and reclaims ammonia and carbonic acid gas and return leaching.After steaming residual suspension filtered, raffinate contains chromium＜0.5ppm, can directly discharge, and gained ammonia still process product contains chromium 0.08%, and typical ammonia still process product is formed as table 2.Ammonia leaching residue is for being the high chromium slag of principal constituent with the chromium hydroxide, and butt (110 ℃ of oven dry) contains chromium 13%, is easy to reclaim chromium with conventional sodium roasting method.
Above-mentioned reduction ammonia-leaching process also is applicable to handles nickeliferous, cobalt, chromium etc. and the simple material of tungstenic, molybdenum not.
The element isolation of purified of ammonia still process product is by two sections molten cobalt methods, isolates tungsten, molybdenum from nickel, cobalt.The key of invention is, found that tungsten in the ammonia still process product, the dissolving of molybdenum in sulfuric acid medium are to be subjected to cobaltic inhibition, therefore, the process that alkali dissolution can be removed tungsten, molybdenum is placed between two sections molten cobalts carries out, promptly make the transition, got rid of carbonate through sulfuric acid, enrichment the insoluble slag of tungsten, molybdenum enter alkali dissolution again, then strengthened process greatly.
Handle the ammonia still process product, adopt one section sulfuric acid selective dissolution earlier, terminal point PH is 2.5-5.0, and temperature of reaction is 60-100 ℃, makes most nickel and part cobalt change solution over to, and suppresses tungsten, molybdenum in the slag phase.Filter that tungsten, molybdenum content can be controlled in＜20ppm in one section acid dissoluting liquid of back gained, enrichment insoluble slag slag rate＜15% of tungsten, molybdenum.
Above-mentioned insoluble slag changes alkali dissolution over to, removing tungsten, molybdenum sodium hydroxide solution with about 5% concentration, its amount for the 0.2-0.4 of the total nickel content of raw material doubly, decompose tungsten at-100 ℃ of following alkali, molybdenums enter solution with sodium-salt form, nickel, cobalt are insoluble.Get high cobalt slag and alkali dissolution liquid behind the filtration washing, the latter can reclaim tungsten, molybdenum with ordinary method.
High cobalt slag enters two sections reductinic acid dissolvings, and in sulfuric acid medium, with reduction trivalent cobalts such as sulphite or nickel powders, consumption is 1.2-2.0 a times of theoretical amount, at PH3-4, and temperature 60-100 ℃, the almost whole cobalts of stripping, nickel.Get the quadratic acid lysate after the filtration, the minute quantity insoluble slag is abandoned it.
Close two sections acid dissoluting liquids of And, carry out taking off chromium with the degree of depth in the conventional sulfide copper removal, impurity such as gained nickel, cobalt scavenging solution tungstenic, molybdenum, chromium, copper are all reduced to trace.Through quaternary amine thiocyanate-extraction cobalt, nickel, cobalt are separated, obtain pure nickel, cobalt compound.
The present invention compares with the modern technique index of handling similar material both at home and abroad, and the reduction ammonia-leaching method is in metal recovery, and aspects such as single-stage nickel, chromium separating effect and elimination pollution of chromium all are better than other method.Compare as table 3 with the result of U.S. PB-271014 report in 77 years and 77 years Deutsches Reichs-Patent № .2726783.
Two sections molten cobalt methods that the present invention proposes adopt simple chemical treatment, have successfully solved the difficulty of isolating tungsten, molybdenum in the specific system from nickel, cobalt, have obtained the inaccessible good result of general method, and its result relatively sees Table 4.
By table 3,4 as seen, the every technical indicator advanced person of novel process of the present invention's proposition; Because the new process material handling of reduction ammonia-leaching do not need pre-treatment, and soaks a step at ammonia and finished the extraction of main metal and separating of chromium, two sections molten cobalt rules have been strengthened the effect that alkali dissolution is isolated tungsten, molybdenum greatly, thereby technical process is short, simple and feasible, reagent consumption is few, and process cost is low; Harmful chromium ion just is cemented in the slag phase effectively in first unit operation leaching section of process, thereby has stopped the pollution of technological operation itself fully.
Accompanying drawing is used to describe main flow process proposed by the invention.
Enumerate below and implement object lesson of the present invention, the present invention is described, but is not a kind of restriction of the present invention.
Example 1
This routine flow process is referring to accompanying drawing.Be the only concrete enforcement of the present invention.Superalloy electrolytic slime slurry 1 is added ammonia soak in the reactor 2, add the water slurry dilution, making suspension contain the material amount is that 10 grams per liter Ni(are in main metal feeding quantity), feed NH 3CO 2Gas 3 contains NH to suspension 3About 100 grams per liters, CO 2About 90 grams per liters are warming up to 60-80 ℃.Add reductive agent S-WAT 4 in leaching process, consumption is 1.5 times of required theoretical amount, and leaching time is about 2 hours, and nickel ammonia soaks rate 98% during reaction end, and cobalt ammonia soaks rate 96%, and ammonia leaching solution contains chromium 0.020 grams per liter, and Ni/Cr is than～500.Small test carries out in the 100L reactor in 2L reactor, expansion experiment.
Ammonia soaks rear suspension liquid 5 through solid-liquid separation 6, and washing gets ammonia leaching solution 7 and ammonia leaching residue 8.
Feed steam 9 in the ammonia leaching solution 7, distill 10, the NH that steams 3, CO 2Gas promptly returns leaching system 2, steams residual suspension 11 after filtration 12, and it is 0.5ppm that gained vinasse 13 contains chromium, and allow compliance with emission standards can directly be discharged.
Ammonia still process product 14 enters one section sulfuric acid selective dissolution 17, add water slurryization after, be warming up to 80 ℃, slowly add dilute sulphuric acid 18, terminal point PH is controlled at 3.0, the reaction times is about 1 hour.Suspension 19 is filtered 20, get one section acid solution and separate liquid 21 and insoluble slag 22, solution contains WO 3≤ 10ppm, insoluble slag slag rate＜10%.
Insoluble slag 22 enters alkali and decomposes workshop section 23, with 5%NaOH solution 24, tungsten, molybdenum in 90 ℃ of following stripping 22 slags, alkali consumption is 0.3 times of main metallic nickel, reacts thin up after 1.5 hours, and suspension 25 enters filtration treatment 26, add water washing, get the alkali dissolution liquid 27 and the high cobalt slag 28 of tungstenic, molybdenum.
High cobalt slag enters second section reductinic acid dissolution process 29, be warming up to 80 ℃ after the water slurryization, add sulfuric acid 30, regulate PH to 3.0, add S-WAT 31 reduction trivalent cobalts, the reductive agent consumption is 2 times of theoretical amount, 1 hour reaction times, suspension 32 enters filter 23 3, and a little insoluble slag is abandoned it, and solution contains WO 3＜10ppm, nickel, the molten rate of cobalt acid～99%.
Close the acid dissoluting liquid 21 and 35 of And secondary, carry out conventional sulfide copper removal 36, in and the degree of depth take off chromium and handle 37, impurity such as tungsten, molybdenum, chromium, copper are all reduced to trace, WO in gained nickel, the cobalt scavenging solution 3～5ppm can successfully carry out the manipulation 38 of quaternary amine thiocyanate-extracting and separating cobalt, nickel, obtains pure nickel, cobalt compound 39,40.
The high chromium slag 9 after ammonia soaks, the ordinary method 15 of available sodium roasting water logging reclaims chromic salt 16, and maturing temperature can be significantly less than the situation of handling chromite, and available ordinary method 41 reclaims tungsten from alkali dissolution liquid 27, molybdenum 42, and clump is slightly
Example 2
Adopt the reduction ammonia-leaching condition of above-mentioned example 1, handle and not contain the nickel-base alloy electrolytic slime of cobalt or not nickel, cobalt, chromium, the mixed hydroxides slurry of iron of tungstenic, molybdenum, obtain close main metal ammonia and soak rate and chromium separating effect.
Example 3
The reduction ammonia-leaching condition is same as example 1, nickeliferous, cobalt, tungsten, molybdenum, the sulfuric acid selective dissolution of ammonia still process product be at 80 ℃, carry out under the pH5.0 condition, reacted 2 hours, its effect, tungsten, molybdenum suppress good, insoluble slag slag rate exceeds 8% than example 1.
Alkali decomposes above-mentioned insoluble slag, and condition is same as example 1,90 ℃, decompose with 5%NaOH solution, then alkali consumption is 0.4 times of metallic nickel.
Comparative example 1
Comparative example is the flow process that non-the present invention advocated
Soak at ammonia and not add reductive agent in the process, the same example 1 of other condition, ammonia soaks termination back solid-liquid separation, the gained ammonia leaching solution contains the Cr(III)+the Cr(VI)～1.5 grams per liters, add the S-WAT reduction of hexavalent chromium, reductive condition is same as example 1, and to contain chromium be the 1-1.5 grams per liter to solution during reaction end, does not realize that substantially chromium separates.
Element Ni Co Cr Wo 3 Mo Fe Al Ti NaCl+NaNO 3
％ 23.57 4.08 3.10 2.6 1.2 1.04 1.2 1.0 ～20
Element Ni CO Cr WO 3 MO
％ 40.0 7.0 0.08 3.6 1.6

Claims (12)

1, a kind of method that reclaims Valuable Metal in Industry Waste with the leaching of ammonia, volatile salt, is characterized in that handling nickeliferous, cobalt, chromium, or nickel, cobalt, chromium, tungsten, molybdenum polycomponent body refuse waste material, is made up of following steps:
(1) when having ferrous salt or other reductive agent to exist, carries out reduction ammonia-leaching with ammonia, volatile salt;
(2) carry out liquid-solid separation, the gained ammonia leaching residue reclaims chromium with ordinary method, and with the ammonia leaching solution distillation, ammonia, carbonic acid gas return leaching;
(3) the ammonia still process product of above-mentioned (2) are nickeliferous, cobalt, tungsten, molybdenum filters with sulfuric acid selective dissolution overwhelming majority nickel and part cobalt;
(4) alkali dissolution in the filter residue that will obtain by (3), and from solution, reclaim tungsten, molybdenum with ordinary method;
(5) will when having sulphite or nickel powder to exist, also filter by the insoluble slag that (4) obtain with sulfuric acid dissolution;
(6) merge the filtrate that obtains by (3) and (5), reclaim nickel, cobalt with ordinary method.
2, method according to claim 1 is characterized in that, the ammonia process of soaking is at the nickeliferous 5-12 grams per liter of pulp suspension, and total ammonia concentration is the 60-120 grams per liter, and carbonic acid gas is the 5-110 grams per liter, and extraction temperature is got at the airtight reduction ammonia-leaching that carries out below 100 ℃.
3, according to claim 1,2 described methods, it is characterized in that, the consumption that ammonia soaks reductive agents such as the ferrous salt that adds in the process or sulphite be the required theoretical amount of reduction of hexavalent chromium 1.2-2.0 doubly.
4, method according to claim 1 is characterized in that, is at PH2.5-5.0 with acid selectivity dissoluting ammonia steaming product, temperature 60-100 ℃, and make most nickel and part cobalt change solution over to, suppress tungsten, molybdenum is in the slag phase.
5, according to the described method of claim 1-4, it is characterized in that, the enrichment of sulfuric acid selective dissolution gained the insoluble slag of tungsten, molybdenum at≤100 ℃, sodium hydroxide solution stripping tungsten, molybdenum with about 5%.
6, method according to claim 1, it is characterized in that, alkali decompose the consumption remove reductive agents such as sulphite used when the high cobalt slag of gained enters the reductinic acid dissolving behind tungsten, the molybdenum for the 1.2-2.0 of the required theoretical amount of reduction trivalent cobalt doubly, at sulfuric acid medium PH2-4, temperature 60-100 ℃, whole cobalts of stripping and nickel.
CN85100731A 1985-04-01 1985-04-01 Recovery of valuable metals from industrial waste Expired CN85100731B (en)

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US6923328B2 (en) * 2002-02-22 2005-08-02 Wave Separation Technologies Llc Method and apparatus for separating metal values
CN101885070B (en) * 2009-07-05 2011-12-14 张雪云 Method for comprehensively utilizing tungsten, nickel and iron in tungsten heavy alloy scrap
CN103011537B (en) * 2012-12-19 2014-02-19 武汉巍川环保科技有限责任公司 A method for treating sludge containing trivalent chromium and recovering heavy metals
CN105567974B (en) * 2014-11-04 2018-03-30 格林美股份有限公司 The metal recovery and comprehensive utilization process of heavy metal-containing waste water slag
CN104928478B (en) * 2015-06-09 2018-04-27 衡阳师范学院 A kind of method of electroplating sludge comprehensively recovering valuable metal
CN106868309A (en) * 2017-03-24 2017-06-20 江苏省冶金设计院有限公司 The system and method for Treatment of Copper iron powder
CN115725843A (en) * 2022-11-03 2023-03-03 北方矿业有限责任公司 A process for the comprehensive recovery of valuable metals from cobalt-rich waste
CN115806317B (en) * 2022-11-23 2024-06-25 崇义章源钨业股份有限公司 Method for preparing ammonium paratungstate by using tungsten-containing grinding waste

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