DD210311A5 - METHOD FOR RECOVERING METALS FROM A SLUDGE - Google Patents

Abstract

The invention relates to a process for the recovery of high commercial value metals from a slurry containing lead, antimony, silver, arsenic, bismuth and copper. The object of the invention is to provide an improved process by which, in a simple and economical manner, metals of high commercial value can be recovered from a sludge, for example anode sludge, without causing ecological problems. According to the invention, the metals are recovered wet by attacking the lead containing antimony, silver, arsenic, bismuth and copper at least once by a wet method with hydrochloric acid in an aqueous solution, optionally accompanied by air or oxygen injection.

Description

Berlin / 15.9.1983

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L · H <J h WU y '62 239/18

Process for recovering metals from sludge Field of application of the invention

The invention relates to a method of recovering metals of high commercial value from a sludge having BTe ± _t Ah t in on; ' and contains other metals.

characteristics OeT ₁ known technical solutions

It is known to dry treat a sludge "for example an anode slag which contains lead and antimony other metals of high commercial value." The operations in the dry method are very complicated and cause both economic and ecological problems ,

Object of the invention

2b 1 of the invention is the provision of an improved process for the recovery of metals, with which. the disadvantages of the known Verfahrens.überwunden can be.

Explanation of the essence of the invention

The object of the invention is to carry out the recovery of metals mainly on ¹ wet ways.

The process according to the invention for the recovery of

iasERi9B3 * ii7i; 7

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Metals of high commercial value from a sludge containing lead, antiraone and possibly other metals, including silver arsenic, bismuth and copper, is that this sludge is injected at least once by a wet method with hydrochloric acid in aqueous solution, optionally accompanied by air. attacked or * treated *

This process has significant economic advantages, yields higher yields at a lower cost, and also has significant environmental benefits since it no longer produces exhaust fumes.

In particular, if the slurry, in addition to lead and antimony, also contains silver, arsenic, vanisate and copper in such amounts that their recovery is appropriate, the process of the invention comprises the following operations:

a) attacking or treating the sludge with hydrochloric acid in aqueous solution, accompanied by introduction of air or oxygen or injection;

b) decanting, siphoning and optionally filtering the attacked sludge according to a) to separate a thickened fraction rich in silver from a depleted solution;

c) Attack of the thickened fraction geniaS point b) with hydrochloric acid in aqueous solution ^ optionally accompanied by air or oxygen injection ;

d) decanting, siphoning and optionally filtering the attacked thickened fraction according to point c) to remove a silver-containing radical from an aqueous solution which is rich in hydrochloric acid and chloride;

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e) washing and filtering the silver-containing residue according to point d) to separate a purified silver-containing residue rich in silver chloride from an aqueous solution which is recycled to stage c);

f) cooling and filtering the solution according to item b) to separate a residue rich in lead chloride from a solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides;

(g) Cooling and filtration of the aqueous solution "rich in hydrochloric acid and hydrochloric acid referred to in point (d) for the removal of a residue rich in lead chloride from a solution" rich in hydrochloric acid "which becomes recyclable at stage (a).

The purified silver-containing residue which is taken off from stage e) can, subsequently, be reacted by reaction with zinc dust, ammonium hydroxide and water or alternatively by ^. directly e ^;:> Redü: ki: it! n irr silver * are transferred. The 'Blii chi oridrück'st-and ,. .can be the _t of the stuf f s} 'and, g) a $ i} $ ZPQ _n s .- .. w ± rd to Bleiw / iedergewinnung out as a pure salt, "or alternatively, when the treated sludge is from industrial Lead electrophorinus, it can be fed to the main lead handling cycle.

The method of the present invention comprises also the selective separation of the elements in: Lösyng are present, the antimony, bismuth, silver, arsenic _f * contains copper and lead chlorides, formed in stage f), by the following operations;

i). Hydrolyzing the solution;

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ii) cooling and filtering the hydrolyzed solution to separate a residue containing antimony from a solution depleted in said antimony;

iii) washing the antimony-containing residue with hydrochloric acid in aqueous solution and then filtering to remove a residue containing antisenoxy chloride from an aqueous solution which is recycled to stage i);

iiii) neutralizing the solution depleted according to item ii) with Na ₂ GO or another neutralizing agent and then filtering to remove a residue; which is recycled to step i), from an antimony-depleted solution containing bismuth, arsenic, silver, »copper«, lead and antiracid chlorides _Λ

The process of the present invention also encompasses the treatment of the antimony-depleted solution comprising bismuth, arsenic, silver, copper, lead, and antifungals, formed in. Stage iiii) contains »by the following operations:

j) neutralizing the solution with Na ₅ CO or other neutralizing agent and then filtering to separate a residue containing bismuth * from a bismuth-depleted solution rich in copper and arsenic chlorides;

(jj) Washing of the viscous and residual residue of bismuth oxychloride consists of an aqueous solution which is recycled to the hydrolysis stage i).

The sludge is in step a) at a temperature between 50 C and 80 C for a period between 0.5 and

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Attacked 3.0 hours while the attack on the thickened fraction geraäß stage c) at a temperature, in turn, between 50 and 80 ⁰ C, but is carried out for a time between 0.5 and 2.0 hours *

The molar concentration of hydrochloric acid in aqueous solution is selected between 3 and sarolar in the anode sludge attack stage a) and between 4 and sinoiar in the attack stage c) of the thickened fraction.

In stage f) and stage g), both the silver-depleted solution and the solution, rich in hydrochloric acid and lead chloride , are cooled to 15 ° C and 25 ° C. "

The solution containing antimony ,, bismuth, silver, arsenic, copper and Bleichlo.ride, in stage i) at a temperature between 65 and 75 ⁰ C and hydrolysed _t dia, hydrorysierte "solution is to" a temperature between "15" and 25 ^{: J 0} G ¹ 'is added ♦

The neutralization with Na ₀ CQ., Is carried out in the case of the antirone-depleted solution of stage iiii) and gives a final pH selected between 1.2 and 2, and in the case of the solution of step j) for the purpose of obtaining a final pH 'selected' between 2.0 and 2.8.

The solar concentration of the hydrochloric acid in aqueous solution must be in stage iii). _r . which ^; washing the vantirone-containing residue to a value between 0 _? 5 and 0.7 πι be selected so that an End ^ pH between 1 and 1.2

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and jj results in the step) which uafaßt washing the antimony holding strength residue., ra be selected to a value between 0.01 and 0.1, so that a final pH of 2.2 to 2.5 is maintained.

The invention will be further elucidated with reference to the drawings of the accompanying drawings, which, however, are not intended to be limiting of the invention.

In the attached drawing show:

FIG. 1 is a schematic representation of the acid treatment of the styrene amine; FIG.

FIGS. 2 and 3: a schematic representation of the separation of the sludge from the solution »

Figure 1 , The mud 1 either in the wet state or vorgabrannf _t * so; organic broths are subjected to hydrochloric acid treatment 2 in aqueous solution 3 with simultaneous air or oxygen injection 4,

The attacked sludge will be subject to further treatment 5 under decanters, scrubbers and optionally filtered, whereby a silver-rich thickened fraction 5 is separated from an ointment 7,

The sd.1 berreiche thickened fraction 6 is a second hydrochloric acid treatment 8 in aqueous solution 9. ₄ optionally

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subjected to air or oxygen injection 10,

The attacked thickened fraction 5 is itself a treatment 11 under siphoning and optionally subjected to hot filtration> so that a silver-containing residue of an aqueous solution 13, which is rich in hydrochloric acid and lead chloride, is separated * *

The aqueous solution is cooled and filtered in a filtration stage 14 to separate a residue rich in lead chloride 15 from an aqueous solution 3 rich in hydrochloric acid, which is recycled to the first hydrochloric acid treatment 2. The silver-containing residue 12 "is washed with water 16 is washed in a wash step a 17 and then filtered in a filtration step 18, to separate a purified silver-containing residue 19 from an aqueous solution 20, which is felt to be the second salt clean-up.

The silver-entrained solution 7 is cooled in a cooling stage 21 and subsequently filtered in a filtration stage 22 to obtain a residue 30 rich in lead chloride from a solution 24 containing antimony. Contains bismuth, silver, "arsane", copper and lead chlorides,

If the sludge stems from industrial blister processing, the bleach chloride residue (streams 15 and 23) may be fed to the main lead handling cycle, or the lead may otherwise be recovered as a pure salt.

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The subsequent selective separation of the elements from the solution 24 is shown schematically in the FIP "2 and 3 " The solution 24, containing antimony, bismuth, silver, arsenic, copper and bleach, is led to a hydrolysis, in cooled in a cooling stage 26 and then filtered in a filtration stage 27 so that a residue 23 * containing a high percentage of antimony is separated from an antimony-depleted solution 29. The residue 2S is subjected to a saline treatment 30 in aqueous solution 31 and concentrated a filtration stage 32 is filtered _s . so that a 33 residue, which mainly contains antimony oxychloride · ,,, of an aqueous solution, is separated 34, which to that Hy-UJR; Plyßß.Btuj e, zxiruqkg.eführt 25 .. 'will "

The antifflon-depleted solution 29 is neutralized in a neutralization step 35 with Na ₂ CO or another neutralizing agent 36 and in a filtration step. 37 filt unf'e'inen rie'rt'V '' residue ''3'S'' ^ ¹ de'r'zur Hydrölys'.eätuf'e 2.5 is recirculated · ·, 39 of a solution _1, the Wisfflut-, arsenic Containing silver, copper, siliceous and antimony chlorides, in which bismuth, arsenic and optionally copper are contained in high percentage,

The antireaver verest solution 39 is neutralized in a neutralization step 40 with Na ₉ CO ₃ · or another neutralizing agent 41 and filtered in a filtration step 42 to obtain a residue 43 containing bismuth ¹ - Unfortunately it is depleted in solution 44, which is rich in copper and arsenic chlorides, to be separated *

The bismuth contains the end. Residue 43 is a hydrochloric acid

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treated 45 in aqueous solution 46 and filtered in a filtration step 47, ura a residue 48, which contains mainly Wisrachoxychlorid, separated from an aqueous solution 49, which is recycled to dsr hydrolysis step 25, *

Embodiment,. ,

The invention will now be described further, by way of example, with reference to the accompanying drawings, in which

The feed is an anode sludge derived from lead electrofinance and has a wet weight (WjW ₁ ) of 10,000 g and a solids content (s voir 793p. G

Sb 41,34: ' % 3280,7' g

Si 8.64 % 685.7 g

Ag 7.86 % 623.7 g

As 5.18 % 490.4 g

Cu 2.49% 197 6 g _ä

Pb. 8.10 % 642.8 g

74.61 % 5920.9 g

The remainder of the solid content to 100% (d _e h. 25.39%) consists of bound oxygen, sulfur bound ,. Halogens, silicon dioxide and organic substances, »

The first attack will be at 60 C for 3 hours with a

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6 m aqueous hydrochloric acid solution, accompanied by air injection, carried out "The second attack is again carried out at 60 ° C. but for 2 hours with a 7.5 m aqueous hydrochloric acid solution."

The washed, silver-containing residue 19, with a w, w, of 1793 g and a ·. s * w * of 1201 g is composed:

Sb 0, 19 ^i: % 2 _f 3 ^: g

Bi 0.042 % 0.5 g

Ag. 48.61 % 583.8 g

As 0.035 % 0.4 g

Cu 0.012 % 0.1 g

Pb 13 _{; i} 25 ^: % 159.1 g

The remainder of the solids content per 10 % by weight of bound oxygen, bound sulfur, halogens, silicon dioxide and organic substances. "The residue 23, which contains essentially lead chloride, has a value of 721 g and a s> w * of 582: 2 'g has insisted

Sb 1.43 %. 8.3 g

Bi 0.31 % 1.8 g

Ag 5.41 % 31.5 g

As' 0.24 % 1.4 g

Cu '0.096 % 0.6 g

Pb .. 63.07 % .367.2 g

Dia chloride solution 24 ₄ which is to be fed to the step for separating the metal contained therein and has a volume of 43.400 1, composed of:

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Sb 75.35 g / l 3270.2 g

Bi 15.79 g / l 685.3 g

Ag 0.20 g / l 3.7 g

As - 11.26 g / l 488, 7 g

Cu 4.54 g / l 197.0 g

Pb 2.69 g / l 115.7 g

The hydrolysis is carried out at a temperature of 70 ⁰ C, then cooled to 20 C *

The neutralization 35 is carried out with a final pH of 1.7, while the washing in 30 reaches a hpdrpJi of I. The residue 33 with a 'Λ', ^ * of 7573.7 g. and a s * w * of 4300 x 6 g. composed:

Sb 66.62 % 2865.0 g

Bi 0.25 % 10.7 g

Ag 0.092 % 3.9 g

As''2.30 % 98.9'^{; i} 'g'^;

Cu ^ '0> 02'.: -% 0,8 '"g

Pb 0.28 % 12.0 g

The antirone deprived solution 39 of 23-5.59 l consists of;

Sb 0.46 g / l 108.4 g

Bi 2.21 g / L 520.6 g

Ag 0.0081 g / L 1.9 g

As 1.35 g / l 218.0 g

Cu ^: 0.82 g / l 193.2 g

Pb; -0.26 g / l 61.2 g

The Schlararastroffl 38, which returned to the hydrolysis stage

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and having a w »w of 3179/6 g and a s # vv, of 1012.47 g, contains:

Sb 29.39 % 297.5 g

Bi 15.13 % 153.2 g

Ag 0.277 % 2.3g

As 7.05 % . 71.4 g

Cu 0.22 % 2.2 g

Pb 4.27 % 43.2 g

The antimony-entrained solution 39 is neutralized at 40 to a final pH of 2: 3. "

Subsequent wash 44 is carried out to a final pH of 2.3, containing 'residue' 48% by weight, of 2269 g and a s w * of 926 g.

Sb 6.82 % 63.1 g

Bi 55.89 % 517.5 g

Ag ⁰ » ^063! ^ 0.6 g

As i'vOS % "' ^: 9.7 g

Cu O ₄ 097 W 0.9 "g

Pb ·. 5.27 % 58.1 g

The vvisraut-depleted solution 44 of 228.506 1 contains:

Sb 0.193 g / l 44.1 g

Bi · 0.0175 g / l 4.0 g

Ag 0.0057 g / l. 1.3 g

As 1.35 g / l '308.5 g

Cu 0.84 g / L 192.0 g

Pb 0.015 g / l 3.4 g

Claims (6)

15.9,1983 £ 4 3 4 Ό Ο U - 13 - 62 239/13 Erf indu nqsansp ruc _t h 1, Process for the recovery of metals of high commercial value of ^: a sludge, characterized in that this (anodes) sludge contains lead and antimony and is attacked at least once by a Naßmethoda with hydrochloric acid in aqueous solution, optionally accompanied by air or oxygen injection,,..:, 2 Method according to item 1, characterized in that the sludge containing lead and antimony is also composed of silver, arsenic, bismuth, copper, lead and antimony in the form of elements or their compounds. 3 * The method of item 2 _$ _ characterized in that "the sludge, consisting of silver, arsenic, bismuth, copper, lead and antimony is subjected in the form of elements or their compounds in the following steps': prefect aggressor! - de ^r s "Schlarafiis ^ nvi.i. ' Hydrochloric acid - ^in; wä'Br ^{strength: i: ';} L, ö "* -.- sung, accompanied by air or oxygen injection; b) decanting, siphoning and optionally filtering the sludge attacked in accordance with item a) to separate a thickened fraction of silver, from a solution depleted in it; c) attacking the thickened fraction of point b) with hydrochloric acid in aqueous solution, optionally accompanied by. * Air or oxygen injection; d) decanting, eliminating and optionally filtering the attacked thickened fraction from point c) .to the separation of a silver-containing residue from an aqueous solution rich in hydrochloric and dichloride; 15,9,1983 AP C 22 B / 249 468 62 239/18 e) washing and filtering the silver-containing residue of item d) to separate a purified silver-containing residue rich in silver chloride from an aqueous solution which is recycled to stage c); f.) cooling and filtering the solution of point b) to separate a residue * rich in dichloride, from a solution containing * antimony *, Wised *, · silver, * arsenic, copper and Sleichloridej (g) Cooling and filtration of the aqueous solution, rich in hydrochloric acid and lead chloride, in accordance with (d), to remove a residue rich in lead chloride from a solution of solution of hydrochloric acid, to which the hydrochloric acid is added tufs, a) is being returned, " 4 «A method according to item 3 ', characterized in that the Antision-, Wiscjut - _t ^ silver, arsenic, copper and Bleichlori'de containing solution from point f) is subjected to the following operations: i) hydrolyzing this solution; (ii) cooling and filtration are hydrolyzed in a solution to separate a residue containing antimony:,, from a solution which: is depleted of antimony; iii) washing the anti.mon-containing residue with hydrochloric acid in aqueous solution and then filtering to remove a residue containing anti-nonoxychloride, ..:. from - a solution: solution, which is returned to stage i); 09/15/1983 CQ Λ ^{ΑΡ C 22 Β / 249 468} ü 4 ö ο y ~ i5-02 239/18 iiii) neutralizing the depleted solution according to item ii) with Na ₂ CO or another neutralizing agent. Means and then filtering to remove a residue which is recycled to stage i) from an antironed solution containing bismuth, arsenic, silver. Copper «. ,, Lead and Antiraonchlorida * 5 * Method according to item 4, characterized in that the solution containing antiraon, bismuth, arsenic, silver, copper, lead and antimony chlorides of item iiii) is subjected to the following operations: J ...) ^, eij.txaio.jS.ia ^ rir ·e Lösung solution, ait- · .. bla? Contains CO or one other neutralizing agent, and then filtered to separate a residue which is bismuth, from a Wismutverarmten solution rich in copper soft "; _: un.d ... Arsenchlo.rid ^ n, is; .. ·.;. ·.; ,,. jj) washing the / wi ^ m-üthalticj.en · RückstarideaAmii- ^Sai: 2 ^ ^ä:; and, then, filtering to remove a residue consisting of bismuth oxychloride from an aqueous solution which is recycled to the hydrolysis step, i) 6 Method according to Item 3 ", characterized in that the purified silver-containing residue of Stuf 3 e '), which is rich in silver chloride, is converted into silver and dusted by reaction with" zinc "; Aaraonium hydroxide and water, 7 »Procedure closed. Item 3, characterized in that the purified silver-containing residue of stage 'e', which is rich in silver chloride, is converted by direct reduction in silver » 15.9.1983 AP C 22 3/249 468 - 15 - 62 239/18 8 "Process according to item 3", characterized in that the lead chloride-rich residue of points f) and g) is fed to the main lead treatment cycle s 9 "Method according to Item 3, characterized in that the residue rich in the chloride of lead, points f) and g), is recycled in the form of the pure salt." 10. Procedure according to point 3 ,; characterized in that the anode sludge is attacked in step a) at a temperature between 50 and 80 C y / uring a period between 0.5 and 3.0 hours * 11 »Procedure see item 3 ,. characterized in that the thickened fraction in step (c) is attacked at a temperature between 50 and 80 ^° C for a period of between 0.5 and 2 hours. ». 12 * Procedure according to point 3 ,. characterized in that the silver-depleted solution in step f) is cooled to a temperature between 15 and 25 ⁰ C _e 13 »Method geffläS point 3, characterized in that the solution rich in hydrochloric acid and Sleichlorid in. Stage g) is cooled to a temperature between 15 and 25 C, 14. The method according to item 3, characterized in that the molar concentration of salt is sow * ra · ^sV in ®aß rig ^βτ ν solution in the attack stage a) of the anode sludge between 3- and 8m selected * 15,9.1983 ί r η rs αρ c 22 Β / 249 468 4 | J α Q O U - 17 - 62 239/13 15, method according to item 3, characterized in that the molar concentration of hydrochloric acid in the aqueous solution in the attack of the thickened fraction stage c} 4- and Bm is selected. 15. ..Method according to item 4, characterized by _; that the antimony, bismuth, silver, arsenic, copper and bleach chloride-containing solution in step i) is hydrolyzed at a tare, temperature between 55 and 75 ⁰ C. 17, process according to item 4 », characterized in that the hydrolyzed solution in stage ii) is at a temperature between 15 and 25; ^{: 0} C is cooled ',, IB, method according to item 4, characterized in that the antiraonverarinized solution in stage iiii) is neutralized with NagCO to a final pH of between 1.2 and 2 * h.re.rt ... g ^ piäßÄ Punkt .4 /, gekörfrizeicfma * / " _Ä in that: in: stage iii), which comprises washing the antiraonhaltigen residue, the molar concentration of the aqueous hydrochloric acid solution between 0 / 5- and Oj7m wirä _f selected so that a final pH of from 1 to 1.2 reaches "yird * 20, method according to item 5, characterized in that the solution in step j) with Na ₂ CO ^ to a final pH value between 2 _f 0 and 2,8. is neutralized » 21 * Process according to item 5 * characterized in that - in step 3j) j which comprises the washing of the bismuth-containing residue, the molar concentration of the aqueous hydrochloric acid, between 0 * 0! and 0.1 is chosen so that a final pH VVert between 2.2 and 2.5. is reached.