DE1767747A1 - Process for the purification of the aqueous saline extracts in the recovery of the lead contained in lead-containing by-products - Google Patents

Description

V > rg. A. Grüneckf

Dr.-ir.j. H. Kinkeldey 1? RR

Or.-Ing. W. Stockn.air ^ ' * ~, U , Q

Λ M ::> chp.n 22. MaxtmiHanstr 43 17R77A7

F 2020

20 / 3cr

Mr. Carlos SEI? A MSCAlTO, LAS ARENAS (Vieoajra) - Savings

Process for cleaning the aqueous extracts in the production of lead containing lead

The present invention relates to physical-physical properties Process by which the aqueous salt-containing extracts are purified from lead-containing products and materials be, whereby aan in your way pralctisoh the Beeitivon As, Sb, Sn, Cu, CcI, Tl, In, Fe, Zn, Mh, Bi, Co

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BATHROOM OBlOLHAL

and Bl reached ι wao ordinary 7-impurities Bind, the be released simultaneously with the lead and from the said Materials originate.

Typical industrial by-products to the dae process are used in advance are lead-containing pyrite Cottrell dust, from the roasting of the aforementioned pyrites originates, and Bleisulf & i au3 dan cantern for the production of Sulfuric acid.

HatUrlioh are all substances that contain lead, daa before can be converted into the state of lead sulphate, and that of several or all of the impurities mentioned or are accompanied by tranquilizers, soluble in aqueous saline solutions "and consequently the cleaning process is to which I am referring to the present invention "

The mentioned lifting products contain several or allo mentioned Impurities in a more or less high amount, depending on the starting substance used, the type of treatment, to which the substance has been subjected and depends on the variations in a particular plant, weeh & lh the method according to the invention, which is independent of offer the possibility of all the fluctuations mentioned above Leaving lead free of other heavy metals in solution is a considerable advantage in the field of

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bring with it an idle salty leachate.

The process for the purification of lead in the lifting products by means of flowing arbaitae consists in submitting a large amount of original material, which is more or less covered with water, to an extraction with concentrated salt solutions and then to a precipitation in which one usually uses alkali hydroxides and / or odei carbonates, which in practice is restricted to the use of Solvay soda and caustic soda, one can also use some calcareous metal Lead or on a chemical wave in lead if at or in the same chemical way in black lead and the lead achieves its best sale and best profit.

The treatment of lead to divide lead urion, Lead sulphate or lead strength ale end product will be: L dar Ax? d-I «ugunesietllo4 · durob the white known in the area

and Terbtcserungec influenced, wrnron durob? "t" tit "jeechUtit ein. 80 be ^^ gt Ale 5 * & ug to mtnllifcohe · lead, that the method used does not bring a defined connection with external work, the reference to Lead sulphate ü.j ^; I call the eioh orgetamae Reini ^ nug, dl «received

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when the geniachton Hiedersohläge from Solvay-Sofla and caustic soda (the eil; the lead the hydroxides, carbonates and oxychlorides of the above notable impurities Bitauefallen) treated with excess sulphurous sulfuric acid finally, the reference to black lead sows a further development of the technology to ao fortechrittllcher than purity and crystalline conformity the lead oxides obtained are larger, and sets beforehand the precipitation precedes the dissolved lead as 0xyohlori3. Aue-C ,:, K- et the SaIa in, but roiner the final one Black lead.

If the production of a litharge of high quality is successful, the necessity arises to carry out a treatment of the aqueous salt-containing extract, this necessity being reinforced by the fact that without removing the accompanying impurities during the peeling of the oxychloride, the progressive and sometimes more difficult βε • 3loht is xsttglich that leaded lifting products inebeeondere from the roasting of pyrites "tasoDen, free of Betallisohtti unlöaliohen Yerunreini" tmf "Q in the Bxtn & ~ tlonelö8ui30en tu lateen, even strong," poisoning does not prevent the ealebaltigfiTi Extraktionelusung ₉ "if ·! The washing liquid and the solution itself are acidic or alkaline in economically reasonable quantities.

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In the cleaning method according to the invention it is eich la essential to three procedures interrelated la Aueaaß and in the pora <lcr Sntfermrag the errelohton impurities are different, whereby it should be noted that with each procedure a lead oxyohlorld is obtained with a Reiuhoit that is sufficient over a lcoBWJerBielle Bloiglp-l, tt to get as the end product if the extraction solution is kept within the constants.

In the following, the ⁵ hat-ptvrraliren, which brings the most intense affection with calibration, generally one, and then the other two methods are described in general.

The -aqueous saline extract of Cottrell dust, which is preferably has been washed with water beforehand, the solution of lead contains other metals at the same time, in general Arsenic, antimony, copper, zinc, and elsen in considerable amounts Quantities, tin, visiouth, thalliua, indium, manganese in small amounts and, in the whole of the tunnels, cobalt, and Hiokel in very small quantities.

step 1

The first stage consists of an oxidation of the ealebaltic extracts in order to convert the trivalent arsenic into five-valent arsenic, the monovalent thallium into trivalent thallium, the bi-

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valent tin in tetr & vßler.fcea uiun and da «bivaltntt manganese in tetravalentea Canaan u-3. ^r : i: woiidolu. This oxidation is carried out before Bugovsiao by means of sodium peroxide, which is added to solid ponodone and lsb jutigen extract. However, it is also possible to use other oxidizing agents, such as, for example, water peroxide, alkali metal perulfates and dsrgleiohen.

From queries about satisfaction, the addition of ewei Equivalents of XtJsnatroL per HcI Uatriuiuperoxid that for the Later Piillung doe EiseE3 air Sisen ~ III chloride required 1st, the production of HatriuEohlorid, dee gawöhnlioh Salt used in these ancestors, as a result of the Precipitation of the iron-III-hydroxyde and other V / irkelt 1st the said H & triu & peroxide daο preferred in the process Oxidizing agents.

Level 2

Sin · «wide Btbandlung btsttht in dtr addition of tin ·· Alkaliftrrooyanidt, Torsugsweitt dtr latriuaverbindune, red dta wäfirigtn aalihaltigen extract which occurs step bti the staptratur from 0 to ι0O ⁰ ι Ia general from 40 to 80 ⁰ C, the practical metal indium , Bisen »Cadaiua, copper» zinc and, in increased Auaaafl liokel, cobalt and e% n precipitates.

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With less effective action, an Alfcali ferrioyanid or a ttisoir, :: ^ ν in Jterrooyanid unÄ lerri oyanifl Tervendou, although treatments flow much more effective «** find all cases above boechriobeno.

step \

Without it being necessary to remove the bodily lump «α obtained, in a c / j £ dio preceding steps the following is followed by the third P tu Ca -.u η η v. III- ^r .'a] ::, vor- ^ A / o- ⁴ oc ϊ iüen-HT-chloride, given by nös eretoTiD der Ül '«r3chu3 of alkali ferrocyanide ont-? Srr: t and ßvreitß the solution to size Iron (III) ions are depleted, which are later converted into iron (III) hydroxide, which is necessary to absorb all dissolved arsenic, including previous oxidation, to ASc, which is realized in the 4th ereton stage, to bobandtln and so on . The BGBGB Bisen hann alc vorgebildenoe Eieen-III-hydroxy4 vied <? R oingofti ^ ixt, it is however then that in the epäler Oxyd & tion with Hatriuxaperoxya released hyaroxide is not used.

There are also other substances that are suitable for arsenic, such as Alurainium hydrate, AttlTiercee Ai-aainivacxyd, Bentonite, activated Kieaeröt and "Sei ¹ " f! Dicyan, however, the Vf.rxin cleanses me

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partially or to some extent in the aqueous salty Hediuia dissolved or are more expensive.

Level 4

In the fourth-tone stage an addition of alkali hydroxide, preferably HatriuflhydrOxya, to dom salty extract of the first stage carried out, the addition with solid Caustic soda or with ITatrou? ". R ^ e can be done. Sodium hydroxyl has the task of filling the Ei9en-III-chloride3 alo] iif; <ir.-III-hydroxyd au complete, the already partially c'roh dac in the Oxydatdonsotufe released hetrium hydroxide reaches i3t.

At the end of this stage, the pH is in the order of 4 to 5i, with the metals Sb, Sn, Bi and TI «are precipitated under hydrolysis, the ferric areenate insoluble iF.t utd the residues of the trivalent arsenic (not oxidized) ac den Eiaon-III-hydroxyä in Porn by baeieohea Eieottareenite are absorbed.

As a sign that the ReinheltsBvstandea (See contains saline extracts, (Jer && e 31ei), it is considered that the Sutaeit test for arsenic, which is based on the reduction of arsenic to areen hydrogen, is negative.

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1787747

The thorough removal of the arsenic is essential, there in the south-facing slope between the areas of a devouring one Mlshaltigen extract and the amount of Ci in the preserved platinum is present. Hit dom described above Process is achieved that the percentage content Cl in the litharge amounts to £ 0.006, which is a substantial slope is when nan ssiaht ssiaht that in practice the Extraktlonslueungea concentrated solutions from ITatritGE-ohlorid aind.

This negative effect of arsenic on the molten metal surface, which is finally obtained by lead oxychloride precipitated from caustic soda, is more or less increased by the effect of all the other remaining impurities, chiefly by the most common of these [11, Sb and Sn.

8-frof e 5

SohlieQlioh verden in an optional fifth stage, which is the addition of elnea Aboorptiocsmittele, v ^ rsugeveine Activated charcoal, see below: ealxhaXtlgen extract of the pre-fcerlgtß grade is noted that in the solution Torhandecen Sieen-lXI-äaet «Ab- * OTbi © rt, with an eecondary tinting effect at the same time % reielt vixd.

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Although this stage can also be used bentonites, which are environmentally friendly, this is, however, not recommended, as they bring in alkaline earths into the Xtfeung.

The sets of eu vervendeadea that have been carried out in each stage of the process vtvsohledenen Realrtioneteilnehiaer, who advocated ale are mentioned vary widely depending on the used Auagange material and the initial aqueous treatment.

TtIr an aqueous saline extract formed which at the same time as lead are the metals just mentioned Contains impurities, D notifies the addition of the reactants as explained below.

Level 1. KvKttbe top Jatrlumoeroxyd

iet the oxidation of arsenic, thallium, and tin

dae Thalliumj sense and manganese auenacht a minimal part ia VerbÄltniB EEA arsenic provides that vorwendete latritraperoxyd pralctiech as "bie 2- 4-faohe represents the amount that theoretically iet erfordorlioh _f mm arsenic in arsenic fUnfttertiges uasuwandeln.

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17677 / !? Il

f 2. Zvut & Ta * TQB gatrluttferroQ, V3ni d In practice, the suzugebanOu slope is calculated in view of the egg, rapier and zinc. Reagent of precipitable metals, which lies in the lornings (IniiiKj, Cadaiuro, Lickol, cobalt »manganese)» small ie * and is covered by the opposite over-bus to IPerrocyaald.

This excess iat ir mu ± 9ux & gleioh the amount theoretically necessary for the biaon, dae Eupfer and aaa zinc, but in general 20 to 30% overobufl.

The Eeagfcnji can preferably also be solved be given in a Balslöeung.

3. giigftba von Bieen-III ^ ohlorid Se is Yormag? Veiae in solid Γογχε or also dissolved ic a Salßlöauug and given in an amount that makes up the maximum amount of double the kecge, which is "required, vm da" an * feeond'3 Ar «« c after the CxTdation as SlS9n> IXX- «reeclat ru fall, vnbei gevuhnlioh eis übericbnfi τοη 50 f» rorwn-

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ptufe 4 ,. 2gjg.be top

Suftbe vlrd 1 "general in Laugetfor * alt" ines 0eh £ Lt Toa 45 to 50 5 · HaOH carried out in an amount that des? Krag introduced · gleioh let, dl "theoretisoh erforderlloh let, tm Al · VKUmng ä- Iq * r d dritttn stage Eieen III ehlorlde to Terrolletandlgec, the partially duroh the Satr hydroxide like iet _r dae duroh daa Batrluapercxyd enengt

A * Sode of this ^ level, in which the pH between 4 and 5

Are all obea tea-related issues canceled?

CH 9 on the self side nlt dieeen is a small? Oil dee leads in

the Orttflenordcimg from 2 to 10 i " dee initially in the" wäfiri gen aalBfcaltifet) extract aaveeenden leads bit been filled in "

5. Absorptlyq old

Mese is in the ratio up to su Mudaal 1 kg / n ^? Lömmg added _y where the amount of 0.1 to 0.3 kg / » ³ is used.

The KocteJrteelt erforderliehe for the absorption of the Blsens and discoloration of Ißmrnz is wctIjwI 2 hours and the Seaporatur & concerning s * ^l> ^ - ■ '■ ^ O ⁰ CS norMlervtise 40

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to 8O ⁰ C.

The order of addition of the reagents to the aqueous The saline extract of the oleaginous materials can be changed in such a way that the addition of the hatriujahydroxyds before the HatriiHBperoxjäa is carried out, whereby this sequence for chemical and practical reasons has been chosen because uie is optimal.

A second method is to DurchjTUhruüe a first stage equal dor zv / öitan stage the optimum procedural ~ rene, followed by KatriuaJhydroxydzugabe to dsm aqueous saline extract at a Semperatur of 0 to 100 ⁰ C, in a Xquivalentmenge to bie au maximum 30 The lustful lead in Jonah will fall from PbOl (OH), so that while the pH of the saline medium is kept at 4-5 and 6, all of the above-mentioned metallic impurities are precipitated into the largest rope. This cleaning leaves in the solution after the Gutz "it ~? Robe analttelbart · species, the Men ^ el * dooh can be reduced very much if one carries out the partial precipitation of the leadioa in the present τοη Eieen-HI-hydroxyd" fias one preformed in A solution can also precipitate in situ.

The level of this modification is the same as the fifth

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Graduates the main procedure.

third method is similar to the previous method ait dam only trnteraohied, dad nan instead of the Euroh " Carrying out a partial peeling of the dissolved lead · lead hydroxide zueetst, like the precautionary frlach and feuoht eats, in a kenge that is sufficient, tub the pH dee oali-containing medium on a Vart between 4i5 and 6 see below • rtifheu. VfIe in the second method causes the presence des iücan-III-bydroxyde that dia distance dd3 Araens is vrirkeamer.

For the sake of completeness, bingevleeon is used, since all impurities are recovered in the above process with lead oxychloride in fore clay.

de «faohsMum lie & ?, hlr« iohe JUHtademngen and lodifimett on hand that can be carried out without the Baharo der KrfinAting su ferlasaen.

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20981 1/0663

Claims (1)

Js- Claims ι 1, Process for the purification of aqueous salabelligea extremes with the extraction of lead-containing by-products, and materials containing? ^ G5j Blai »thereby d & 3 »to the extracts from the Senrper & tur ron O to 100 ⁰ C a« eratsn treatment is subjected, Äia ait an oxidationcB-ittol, before: ivgjwüisc Katriunperoxid, is carried out, which is added in solid Pcra 'cr \ A in oinor Mor> ge , oils hBchctene 5aa 4-fold-3 dor Menga botrügt, 31o thooretieoh necessary iat, m ^r ·. iac go ?. 3 β te Arc cn vom draiv / ertiger; Zujsua ftinJTwertigoB state em oxidize, uaa dinse vorvollatätidigt, by an Allralihyfirosyä, feetöß or dissolved Hstriunhyäroryd * in the indicates that theoretically necessary) vrx 41 «^ lllung des 3iis «J> -III * olllori <5H & lc Eieen-III-hyÖrozyC β« τβττοΐΐ- , which partly ready by also the Satriuofréigee tatee liatriurhydroxyd causes wcrtfea itt _r the pH of the otltbftltifen medium 9 ' 2nd <a di' e '2 Be' rviflöhen 4 and 5 lies. Anupruch 1, I ta * n eirt treatment as long as I «fit | die sit tit} · »AUcali- »Rcr & ugevelee JSatrixaferrooyanld, led ? in festor? crn or dissolved in eiii ^ r - 15 - 209811/0663 trier ten eali-containing solution and in a heap, the litfohetene dee is double the amount required for 4a « existing iron, copper and zinc atöobioeetriaoh required let. 3 # Yerfahreo according to claim 2, characterized in that a "wide B j band lung sit a Biaen-III-Bal", TCrsugaveiee Eieea-III-ohlorid, feet or dissolved in a concentrated saline solution, in a Henge anßjLll », C ;, äla Iköcfcetene double eo large as the tbeoretiaoh amount required to dissolve the arsenic later al · Eioen-III-areGTjiat?; U fäll on, voboi das Sleen-XXX ~ 3ali bsv. d & e Eiseu-III-chloride that removed from the previous treatment etannficmdec fhorcchuß of ferrooyanid ale Preußieohbla \) " Method according to claim 2, characterized in that aas ice treatment old of an alkali hydroxide, rorirage-Katrlicöiydroxyd, in attfohiosetrieoher Kenge snr 1 »> the Bdluni of high "30 ^ de · dissolved leads" FXtioxjciloriji oneohlieflt, vobtl the pH de · aaltfbaltl-Msdiimc swlaohen 4 «nd 6 rerbltlbt. 9 · VsTfiiltrin according to AoepraeH 2, dadnroh germ «lofaaet, BolMndluag sit Sleihydroxyd, Torsogcveiee lind feaobt, touched in a lot that - 16 ~ ß 3 BATH ORIQ _{1 TIME} auereioht, us den aaffaglU ^: "sa pH ues saline medium to» inta Vert «viaohen 4" -ad 6 su increase. 6. Method according to claim 4 or 5, daduroh • eiohnet that mn dio treatment asohritte In degemrort rtm Bleen-III-hydroxyd dur-oh leads, doa in auieerhftlb dee *! »- containing Brtraktas preformed form added or In d lea © a Ekt (each can be, Xetxtoreo »ittele aufdlnander reachatider addition s of bis-XXX-chloride and 9 * -triunhydroxyd, whereby the Kesge · 3βο Biaon-III-hydroxyde is in each case a maximum of double the amount of honey} the theorotiech necessary i ^ t, uia das To convert arsenic in solution into basieohee egg arsenite. 7. The method according to claim 1, 4, 5 or 6, characterized in that the aqueous alcohol-containing sxtseJct is subjected to ^{an optional final treatment of bit active charcoal during the Xempexetur τοη 0 to 10O 0} O, which aan in a Haxioalnesge clay 0.5 ^ g / n ^ solution suggests, whereby the treatment lasts 2 hours « - 17 - BAD ORlSiNAL 209811/0663