IT202000017134A1 - THERMAL-ELECTROLYTIC PROCESS WITH REDUCED ENVIRONMENTAL IMPACT FOR THE RECOVERY OF LEAD FROM THE MIXTURE OF LEAD OXIDES AND SULPHATE PRESENT IN THE BATTERIES AT THE END OF THEIR LIFE. - Google Patents
THERMAL-ELECTROLYTIC PROCESS WITH REDUCED ENVIRONMENTAL IMPACT FOR THE RECOVERY OF LEAD FROM THE MIXTURE OF LEAD OXIDES AND SULPHATE PRESENT IN THE BATTERIES AT THE END OF THEIR LIFE. Download PDFInfo
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- IT202000017134A1 IT202000017134A1 IT102020000017134A IT202000017134A IT202000017134A1 IT 202000017134 A1 IT202000017134 A1 IT 202000017134A1 IT 102020000017134 A IT102020000017134 A IT 102020000017134A IT 202000017134 A IT202000017134 A IT 202000017134A IT 202000017134 A1 IT202000017134 A1 IT 202000017134A1
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- lead
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- 238000000034 method Methods 0.000 title claims description 18
- 238000011084 recovery Methods 0.000 title claims description 10
- 229910000464 lead oxide Inorganic materials 0.000 title claims description 6
- 229910021653 sulphate ion Inorganic materials 0.000 title claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims description 4
- 239000000203 mixture Substances 0.000 title description 5
- 230000007613 environmental effect Effects 0.000 title description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 239000001166 ammonium sulphate Substances 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- 229910000003 Lead carbonate Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 5
- WBLCSWMHSXNOPF-UHFFFAOYSA-N [Na].[Pb] Chemical compound [Na].[Pb] WBLCSWMHSXNOPF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 4
- 206010011906 Death Diseases 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000010411 cooking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000002013 dioxins Chemical class 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000007425 progressive decline Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 sulphate ions Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Secondary Cells (AREA)
Description
DESCRIZIONE dell?invenzione avente per TITOLO: ?Processo misto termico -elettrolitico a ridotto impatto ambientale per il recupero di piombo dalla miscela di ossidi e solfato di piombo presente nelle batterie a fine vita? DESCRIPTION of the invention having the TITLE: ?Mixed thermal-electrolytic process with reduced environmental impact for the recovery of lead from the mixture of lead oxides and lead sulphate present in end-of-life batteries?
Le batterie a fine vita rappresentano la principale fonte di piombo poich? il costo del suo recupero ? notevolmente inferiore partendo dai minerali. In una batteria a fine vita sono presenti i seguenti materiali: leghe metalliche del piombo, plastiche leggere, plastiche pesanti, elettrolita (acido solforico diluito), miscela di ossidi e solfato di piombo (denominata pastello). Il trattamento di recupero delle leghe metalliche e delle plastiche leggere ? agevole e poco costoso. Le plastiche pesanti e l?elettrolita rappresentano un onere poich? non trovano applicazioni utili e sono inviati in discariche speciali con costi elevati. Il recupero del piombo dal pastello ? universalmente attuato con un processo pirometallurgico che prevede i seguenti stadi: trattamento del pastello con una soluzione di carbonato di sodio al fine di convertire in carbonato il solfato di piombo e produrre una soluzione di solfato di sodio, miscelazione della risultante massa solida con ferro metallico e carbone (riducenti) e con soda e vetro (flussanti-scorificanti), trattamento alla temperatura di 1.100-1 .200?C per almeno 4 ore, scarico della risultante massa e separazione della fase metallica dalla scoria, spegnimento della scoria con acqua, stagionatura e inertizzazione prima di procedere alla sua messa in discarica per materiali pericolosi, raffinazione della fase metallica. Durante il trattamento termico si liberano gas solforosi-solforici, NOx, polveri contenenti composti del piombo, silice, particolato di carbone. E? necessario, pertanto, un trattamento dei gas che prevede: un post combustore per distruggere le eventuali diossine, furani, idrocarburi policiclici aromatici, un raffreddatore - scrubber alimentato con una soluzione di carbonato di sodio per abbattere i gas acidi, le polveri e altre sostanze trascinate. I solidi che si separano da questo trattamento sono riciclati al trattamento termico. I gas sono infine inviati in filtri a maniche per la depurazione finale e le polveri separate, unitamente alle tele dei filtri, sono riciclate al forno. La soluzione risultante dal trattamento con soda del pastello ? depurata e concentrata fino secchezza ottenendo solfato di sodio anidro. Con i prezzi attuali del piombo, il trattamento descritto permette un ritorno economico solamente se sono trattate grandi masse di batterie a fine vita non sempre facilmente disponibili. Siffatto processo, infine, ha un impatto ambientale molto elevato che obbliga a operare in zone remote, lontano dai centri abitati con notevoli disagi dal punto logistico. End-of-life batteries are the main source of lead since the cost of its recovery? considerably lower starting from minerals. In an end-of-life battery, the following materials are present: metal alloys of lead, light plastics, heavy plastics, electrolyte (diluted sulfuric acid), mixture of lead oxides and sulphate (called crayon). The recovery treatment of metal alloys and light plastics? easy and inexpensive. The heavy plastics and the? Electrolyte represent a burden since? they do not find useful applications and are sent to special landfills with high costs. The recovery of lead from pastel? universally implemented with a pyrometallurgical process which involves the following stages: treatment of the pastel with a solution of sodium carbonate in order to convert lead sulphate into carbonate and produce a solution of sodium sulphate, mixing the resulting solid mass with metallic iron and coal (reducing agents) and with soda and glass (fluxing-slagging agents), treatment at a temperature of 1,100-1,200?C for at least 4 hours, discharge of the resulting mass and separation of the metal phase from the slag, quenching of the slag with water, curing and inerting before placing it in a landfill for hazardous materials, refining the metallic phase. During the heat treatment, sulphurous-sulphuric gases, NOx, powders containing lead compounds, silica, coal particles are released. AND? therefore, a gas treatment is necessary which includes: an afterburner to destroy any dioxins, furans, polycyclic aromatic hydrocarbons, a cooler - scrubber fed with a sodium carbonate solution to break down acid gases, dust and other entrained substances . The solids that separate from this treatment are recycled to the heat treatment. The gases are finally sent to bag filters for final purification and the separated powders, together with the filter cloths, are recycled to the furnace. The resulting solution from treating the pastel with soda? purified and concentrated until dryness obtaining anhydrous sodium sulphate. With current lead prices, the treatment described allows an economic return only if large quantities of end-of-life batteries are treated which are not always readily available. Lastly, this process has a very high environmental impact which forces it to operate in remote areas, far from inhabited centers with considerable logistical inconvenience.
Il nuovo processo, oggetto di questo brevetto, non presenta le criticit? presenti nel processo tradizionale. Non genera, infatti, residui tossici in qualsiasi forma (scorie, gas tossici, polveri, soluzioni acide), permette un recupero totale del piombo presente nel pastello, opera a temperatura pi? bassa di almeno 600?C, coproduce solfato di ammonio, un sale che trova moltissime applicazioni industriali ed ? anche usato come fertilizzante azotato. The new process, subject of this patent, does not present the critical points present in the traditional process. In fact, it does not generate toxic residues in any form (slag, toxic gases, powders, acid solutions), allows total recovery of the lead present in the crayon, operates at a lower temperature. low of at least 600?C, it co-produces ammonium sulphate, a salt that finds many industrial applications and is? also used as nitrogen fertilizer.
Le fasi salienti del processo, riportate nel disegno n. 1 , sono descritte di seguito. Nel reattore di carbonatazione 1 sono introdotti il pastello, l?acqua, l'ammoniaca e l anidride carbonica. La massa ? agitata energicamente al fine di attuare la reazione solido-soluzione: The main stages of the process, shown in drawing no. 1 , are described below. The pastel, water, ammonia and carbon dioxide are introduced into the carbonation reactor 1. The mass? vigorously stirred in order to implement the solid-solution reaction:
teressati dalla reazione. interested in the reaction.
Se il pastello ? impregnato con acido solforico o ? ancora in sospensione nell?elettrolita, si pu? procedere lo stesso alla carbonatazione utilizzando una quantit? di ammoniaca in eccesso per salificare l?acido presente a dare solfato di ammonio che si aggiunge a quello generato dalla reazione di carbonatazione. Al fine di incrementare la solubilit? dei due gas in acqua, il reattore ? realizzato per operare sotto pressione. In tal modo si evitano, anche, le emissioni di ammoniaca in fase di reazione. A fine reazione la miscela ? scaricata curando, mediante eventuali aggiunte di anidride carbonica, che sia esente da ammoniaca libera. Segue la separazione liquido-solido nel filtro F1. La soluzione separata passa nel reattore 2. di purificazione, acidificata con acido solforico al fine di decomporre l'eventuale carbonato di ammonio presente formando solfato di ammonio e additivata con zinco metallico in polvere per cementare eventuali metalli pesanti presenti nella soluzione. La massa attraversa il filtro F2. separando i metalli cementati, mentre la soluzione ? inviata all?apparecchiatura per la concentrazione 3. al fine di ottenere solfato di ammonio secco. La massa solida separata in F1 ? lavata in W1 , filtrata in F3 e l?acqua di lavaggio ? riciclata al reattore di carbonatazione 1. Il solido ? inviato in cottura in 4. previa miscelazione con una piccola quantit? di idrossido di sodio al fine di operare in ambiente alcalino. La cottura ? condotta alla temperatura di 450-500?C per almeno 30 minuti al fine di decomporre formando ossido (II) il biossido e il carbonato di piombo. Non vengono aggiunti reattivi poich? le reazioni interessate sono le seguenti: If the pastel ? impregnated with sulfuric acid or ? still in suspension in the?electrolyte, can you? proceed the same to the carbonation using a quantity? of excess ammonia to salify the acid present to give ammonium sulphate which is added to that generated by the carbonation reaction. In order to increase the solubility? of the two gases in water, the reactor ? built to operate under pressure. In this way, ammonia emissions during the reaction phase are also avoided. At the end of the reaction the mixture ? discharged taking care, by possible additions of carbon dioxide, that it is free from free ammonia. This is followed by the liquid-solid separation in filter F1. The separated solution passes into the purification reactor 2., acidified with sulfuric acid in order to decompose any ammonium carbonate present forming ammonium sulphate and added with powdered metallic zinc to cement any heavy metals present in the solution. The mass passes through filter F2. separating the cemented metals, while the solution ? sent to the apparatus for concentration 3. in order to obtain dry ammonium sulphate. The solid mass separated in F1 ? washed in W1, filtered in F3 and the washing water? recycled to the carbonation reactor 1. The solid ? sent to cook in 4. after mixing with a small amount? of sodium hydroxide in order to operate in an alkaline environment. The cooking? conducted at a temperature of 450-500?C for at least 30 minutes in order to decompose, forming oxide (II), lead dioxide and carbonate. No reagents are added since? the reactions involved are the following:
(al riciclo al reattore 1. di carbonatazione) (to recycle to carbonation reactor 1.)
La CO2 che si libera ? riciclata al reattore 1 . di carbonatazione. The CO2 that is released? recycled to reactor 1. of carbonation.
La massa cotta passa al reattore di solubilizzazione 5., additivata con una soluzione di idrossido di sodio ? scaldata a 75-80?C al fine di facilitare la formazione di piombito di sodio secondo la reazione: The cooked mass passes to the solubilization reactor 5., with the addition of a sodium hydroxide solution ? heated to 75-80?C in order to facilitate the formation of sodium lead according to the reaction:
La massa ? chiarificata nel filtro F4 separando le impurezze solide mentre la soluzione liquida limpida ? inviata alla fase 6. in una cella elettrolitica CE per recuperare piombo metallico e separare la soluzione di NaOH da riciclare alla fase 5. The mass? clarified in the F4 filter separating the solid impurities while the clear liquid solution? sent to phase 6. in an electrolytic cell CE to recover metallic lead and separate the NaOH solution to be recycled to phase 5.
Ulteriore prerogativa di questo trovato ? che durante la cottura del pastello carbonatato, le impurezze che lo accompagnano, costituite da sostanze organiche, sono distrutte e l?unica impurezza che permane ? quella inorganica, costituita dal solfato di bario, presente come additivo nelle paste elettrodiche. L?aggiunta di soda alla massa da cuocere elimina il pericolo della formazione di diossine in quanto, se sono presenti plastiche clorurate, l?acido cloridrico derivante dalla loro decomposizione termica ? salificato dalla soda impedendo cos? la sua reazione di ossidazione a cloro Poich? nel pastello sono anche presenti frammenti di griglie e poli, durante la cottura essi fondono e si raggrumano formando delle sferette, facilmente separabili per setacciatura per cui all?attacco alcalino ? avviato solamente pastello contenente composti del piombo puri, con innegabili vantaggi sulla qualit? del piombo recuperato. Altro vantaggio offerto da questo trovato ? l?assenza di fanghi anodici che tipicamente accompagnano il processo elettrolitico di recupero del piombo condotto con acido fluoborico. In questo nuovo trovato, rispetto al processo tradizionale, non si utilizzano riducenti (ferro e carbone) non si opera ad alta temperatura, non si impiegano flussanti e scorificanti, non si emettono polveri e gas tossici. L?unico reattivo utilizzato ? l?ammoniaca per salificare gli ioni solfato legati al solfato di piombo e, eventualmente, l?acido solforico ma la spesa ? ripagata dalla vendita del solfato di ammonio che si produce. La reazione elettrolitica di recupero del piombo ? condotta in soluzione alcalina con indiscutibili vantaggi nella scelta dei materiali di costruzione e con un miglioramento rilevante delle condizioni dell?ambiente di lavoro e senza generazione di fanghi anodici contenenti sostanze tossiche. Another prerogative of this invention? that during the cooking of the carbonated pastel, the impurities that accompany it, consisting of organic substances, are destroyed and the only impurity that remains? the inorganic one, consisting of barium sulphate, present as an additive in electrode pastes. The addition of soda to the mass to be cooked eliminates the danger of dioxin formation since, if chlorinated plastics are present, the hydrochloric acid deriving from their thermal decomposition is salified by the soda thus preventing? its oxidation reaction to chlorine Since? in the pastel there are also fragments of grids and poles, during cooking they melt and clot together forming small spheres, easily separable by sieving so the alkaline attack ? started only crayon containing pure lead compounds, with undeniable advantages on the quality? of the recovered lead. Another advantage offered by this invention? the absence of anode sludge which typically accompanies the electrolytic process of lead recovery conducted with fluoboric acid. In this new invention, compared to the traditional process, no reducing agents (iron and coal) are used, no high temperatures are used, no fluxes and slagging agents are used, no toxic gases and dusts are emitted. The only reagent used? the ammonia to salify the sulphate ions linked to the lead sulphate and, possibly, the sulfuric acid but the expense ? repaid by the sale of the ammonium sulphate that is produced. The lead recovery electrolytic reaction? carried out in alkaline solution with indisputable advantages in the choice of construction materials and with a significant improvement in working environment conditions and without the generation of anodic sludge containing toxic substances.
Le modalit? operative adottate in questo processo sono riportate nell? Esempio 1 che non si deve intendere limitativo delle potenzialit? di questo trovato. The modalities? operations adopted in this process are reported in the Example 1 that should not be understood as limiting the potential? of this find.
Esempio 1 Example 1
Una massa di 2.885 grammi di pastello lavato e essiccato ? stato introdotto in un reattore riscaldabile che pu? operare sotto pressione precedentemente riempito con 1.335 grammi di idrossido di ammonio al 30%. La massa ? stata energicamente agitata e contemporaneamente sono stati introdotti grammi 130 di anidride allo stato gassosa. Il procedere della reazione di carbonatazione del solfato di piombo ? stato indicato dalla progressiva diminuzione della pressione che regna nel reattore. Quando la pressione si ? approssimata a quella atmosferica sono stati aggiunti altri 10 grammi di anidride carbonica per essere certi di salificare anche l'ammonica residua. La massa ? stata, complessivamente, tenuta sotto agitazione per 1 ora per completare la reazione di conversione del solfato in carbonato di piombo. La miscela ? stata poi filtrata separando una fase liquida contenente essenzialmente solfato di ammonio ed un solido contenente ossidi di piombo e carbonato di piombo. In questo solido sono presenti le sostanze che tipicamente accompagnano il pastello come il solfato di bario, il carbon black, le colle, le plastiche provenienti dai separatori e dalle scatole La fase liquida ? stata acidificata con acido solforico ed additivata con zinco metallico al fine di cementare eventuali metalli pesanti presenti. Dopo aver allontanato la piccola quantit? di metalli cementati, la massa ? stata inviata ad un evaporatore recuperando 752 grammi di solfato di ammonio secco. La fase solida, invece, ? stata lavata con acqua al fine di allontanare il solfato di ammonio che la impregnava e l?acqua di lavaggio riciclata al reattore di carbonatazione. La fase solida pulita ? stata miscelata con una piccola quantit? di idrossido di sodio al fine di rendere alcalino l?ambiente di reazione e trattata in un forno senza aggiunta di alcun reattivo, alla temperatura di 550?C per 1 ora. Durante la cottura si verifica la decomposizione del carbonato di piombo ad ossido (II) mentre l?ossido (IV) si decompone a ossido (II) liberando ossigeno. Durante questo trattamento termico si ossidano le sostanze organiche mentre le tracce di acido cloridrico prodotto dalla decomposizione di plastiche clorurate sono salificate dalla soda eliminando cos? la possibilit? di formazione di cloro e quindi di diossine. I frammenti di leghe di piombo presenti nel pastello, dopo il trattamento si ritrovano sottoforma di sferette ben separabili dal resto della massa. A mass of 2.885 grams of washed and dried pastel? been introduced in a heatable reactor that pu? operate under pressure previously filled with 1.335 grams of 30% ammonium hydroxide. The mass? vigorously stirred and at the same time 130 grams of gaseous anhydride were introduced. The progress of the lead sulphate carbonation reaction? was indicated by the progressive decrease of the pressure that reigns in the reactor. When the pressure is ? approximate to the atmospheric one, another 10 grams of carbon dioxide were added to make sure that the residual ammonia was also salified. The mass? was, as a whole, kept under stirring for 1 hour to complete the conversion reaction of the sulphate into lead carbonate. The mixture ? was then filtered separating a liquid phase essentially containing ammonium sulphate and a solid containing lead oxides and lead carbonate. This solid contains the substances that typically accompany pastels such as barium sulphate, carbon black, glues, plastics from separators and boxes. The liquid phase? acidified with sulfuric acid and added with metallic zinc in order to cement any heavy metals present. After removing the small amount? of cemented metals, the mass ? was sent to an evaporator recovering 752 grams of dry ammonium sulphate. The solid phase, on the other hand, ? was washed with water in order to remove the ammonium sulphate which impregnated it and the washing water recycled to the carbonation reactor. The clean solid phase? been mixed with a small amount? of sodium hydroxide in order to make the reaction medium alkaline and treated in an oven without adding any reagent, at a temperature of 550°C for 1 hour. During cooking, lead carbonate decomposes to oxide (II) while oxide (IV) decomposes to oxide (II), releasing oxygen. During this heat treatment the organic substances are oxidized while the traces of hydrochloric acid produced by the decomposition of chlorinated plastics are salified by the soda thus eliminating the possibility? formation of chlorine and therefore of dioxins. The fragments of lead alloys present in the pastel, after treatment, are found in the form of small spheres that can be easily separated from the rest of the mass.
Il solido cotto ? stato trattato 2.900 grammi di una soluzione d?idrossido di sodio al 30% al fine di solubilizzare gli ossidi con formazione di piombito di sodio solubile. La massa ? stata filtrata separando le impurezze solide mentre la fase liquida ? stata elettrolizzata in una cella elettrolitica con anodi realizzati in nichel e catodi di piombo. La densit? di corrente tipica impiegata ? stata di 650 A/m<2>. Dopo l?elettrolisi sono stati recuperati grammi 2.195 di piombo metallico. La soluzione di idrossido di sodio che si ? liberata alla fine dell?elettrolisi ? stata utilmente riciclata alla fase di dissoluzione dell?ossido di piombo. The cooked solid? 2,900 grams of a 30% sodium hydroxide solution was treated in order to solubilize the oxides with the formation of soluble sodium lead. The mass? been filtered by separating the solid impurities while the liquid phase ? been electrolysed in an electrolytic cell with anodes made of nickel and cathodes of lead. The density? of typical current used ? was 650 A/m<2>. After the electrolysis, 2,195 grams of metallic lead were recovered. The sodium hydroxide solution that is? released at the end of? electrolysis ? been usefully recycled to the lead oxide dissolution phase.
Claims (8)
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US4107007A (en) * | 1976-05-14 | 1978-08-15 | Gesellschaft Zur Forderung Der Forschung An Der Eidgenossischen Technischen Hochschule | Process for the recovery of lead from scrapped lead batteries |
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