WO2019178654A1 - Method for chemical extraction of metals by means of processing of industrial waste and modular installation for its implementation - Google Patents

Method for chemical extraction of metals by means of processing of industrial waste and modular installation for its implementation Download PDF

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Publication number
WO2019178654A1
WO2019178654A1 PCT/BG2018/000032 BG2018000032W WO2019178654A1 WO 2019178654 A1 WO2019178654 A1 WO 2019178654A1 BG 2018000032 W BG2018000032 W BG 2018000032W WO 2019178654 A1 WO2019178654 A1 WO 2019178654A1
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extraction
zinc
industrial waste
oxides
module
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PCT/BG2018/000032
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French (fr)
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Emil Vasilev MINCHEV
Alexandar Stefanov KYURKCHIEV
Angel Georgiev ILIEV
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"Kcm"Ad
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    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

This patent application refers to a method and a modular plant for chemical and metallurgical processing of industrial waste, such as steel powders, filter dusts, sludges, insoluble residue originated from the extraction, sludges, drosses, sinters, slags, etc. by means of pyrometallurgical and hydrometallurgical processes until reaching the point of production of intermediate and end products such as zinc, zinc dust, zinc alloys, zinc sulphate salt, copper sulfate crystals, copper insoluble residue originated from the extraction for copper and copper products, lead insoluble residue originated from the extraction, cadmium, tellurium, gold, silver, etc. The method for the chemical (metallurgical) extraction of metals from industrial waste comprises the following steps: preparation of the batch of secondary industrial waste, activating materials and carbon containing reducing agent by mixing, granulating and wetting, after which the batch is fed into a rotary tube waelz furnace. Following the completion of the aforementioned actions rolling, cooling and filtration of the flue gases are performed. Zn, Pb, and Cd batch metals are reduced, evaporated and oxidized by the flow of air flowing in the opposite direction to the batch, whereby the exhaust gases containing Zn, Pb, Cd oxides are cooled and purified in a filtering module. The cleaned gases come into the atmosphere and the waelz oxides captured in the bag filters after transport and granulation are fed for oxidative roasting at a temperature of 900 ° C in a roasting tube rotary furnace. High-grade oxides rich in CI, F, Cd, Pb, Se, Te, Tl and As are removed from the upper end of the furnace, and from the lower end of the furnace the roasted waelz oxides are separated from where they move to a collecting vessel and are subjected to triple aqueous alkaline cleaning to purify the metal oxides from CI, F, Se. This is followed by the extraction of Zn and Cd. The purification from Sb, Ge, As and Fe is accomplished by means of a neutralization processes until reaching the point of pH = 4.8 ÷ 5, oxidation, hydrolysis, precipitation and filtration, and neutralization processes to pH = 4.8 ÷ 5.2 are applied to Se, Te and Tl purification with subsequent precipitation, cementation, the purified zinc sulphate solution entering the basic zinc production scheme, and the resulting solid residue yielding salts or a solution of zinc sulphate. According to the invention, a modular installation for chemical extraction of metals has been created where industrial waste processing is implemented abd used, consisting of a secondary storage for secondary industrial waste, activators and a solid reducing agent, a batch preparation unit, a rotary tube waelz furnace for reducing batch roasting and a heavy suspension compartment for separating the clinker from the unreacted gear (coke), which are sequentially connected.

Description

METHOD FOR CHEMICAL EXTRACTION OF METALS BY MEANS OF PROCESSING OF INDUSTRIAL WASTE AND MODULAR INSTALLATION FOR
ITS IMPLEMENTATION
AREA OF THE STATE OF THE ART
The present application for invention relates to a method and a modular plant for chemical and metallurgical processing of industrial waste, such as steel powders, filter dusts, sludges, insoluble residue resulting from the extraction, sludges, drosses, sinters, slags, etc. performed by pyrometallurgical and hydrometallurgical processes production of intermediate and end products such as zinc, zinc dust, zinc alloys, zinc sulphate salt, copper sulfate crystals, copper insoluble residue resulting from the extraction for copper and copper products, lead insoluble residue resulting from the extraction, cadmium, tellurium, gold, silver, etc.
BACKGROUND OF THE ART
GB 2 004 854 A discloses a method for separating zinc and lead from waste materials containing ferric oxide. The process is carried out in an inclined rotary kiln using a carbon- reducing agent. The feedstock in the form of granules enters the furnace together with the carbon-reducing agent where it is heated to a temperature lower than the melting temperature of the material where reduction process undergoes, and ferrum is released at the lower end of the furnace and in the upper exhaust gases containing zinc and lead are removed.
Document EP 0 508 166 A discloses a method and an installation for the reduction of zinc, lead and cadmium in the form of oxides. The process is carried out in a rotary furnace, and carbonaceous material is used as the reducing agent.
US 5 906 671 A discloses a method for separating and recovering metals from industrial waste containing zinc, lead, cadmium, arsenic, ferrum, mercury and selenium. The metals and their oxides are mixed with a reducing agent and additives, they are agglomerated, heated to about 800 0 C and mixed with a stream of inert gases (reducing or poorly oxidizing), where the metals are separated from the solid waste product.
Document US 2006 123 952 Al relates to a method and apparatus for extracting zinc from a material containing ferrum oxides by heating the reduction area to a temperature below the melting temperature of the ferrum but sufficient to form the carbon reducer required for reducing the zinc oxide to zinc vapor which is cooled to form a liquefied or solid zinc.
In CN 1 358 283 A a process is disclosed for the continuous melting of metals in a rotary furnace wherein the material is heated to the point of evaporation of zinc, lead, etc. in the form of gas, and then cooled to obtain powdered zinc oxide, lead oxide, etc.
Document EP 2 216 419 A2 relates to a method and apparatus for the refining of zinc, cadmium and lead from metal scrap rich in ferrum. Metal waste is mixed with reducing and binding agents. The reducing medium is created by the addition of high carbon containing materials. The processing of metal waste treatment is performed out in one or more rotary furnaces with periodic or continuous refill of raw materials. When the reduction temperature range is from 900 ° C to 1350 0 C, oxides are formed in a solid state, and when the temperature is above 1150 ° C, the oxides exist in the liquid physical state.
Document BG 61917 reveals a technological line for extraction of zinc from zinc- containing materials comprising unit for acceptance of zinc-containing materials, an activator and a solid reducer, a batch preparation compartment, a rotary tube furnace for reducing roasting of furnace charge batch, cooling and filtering systems, auger transport system and a rotary tube furnace for reducing roasting of the furnace charge batch, after which metal oxides undergo hydrometallurgical processing. When performing processing of a wide range of zinc- containing wastes, deposits on the interior of the furnace appear which are related to the necessity of a sharp increase in the supply of coke and other activators until reaching the point of melting of the coating. When applying this technological line it turns out to be difficult to use a wide range of secondary industrial waste with increased impurity content due to the impossibility of completing intermediate and final products containing high levels of impurities. The use of a waelz installation for the extraction of precious metals from secondary industrial waste does not constitute an instrument that is a to fully extent eficcient. Many extra costs for reagents and activators are incurred.
SUMMARY OF THE INVENTION
In the course of production of base metals in the colored [non-ferrous metallurgy] and black metallurgy, significant quantities of industrial (secondary) waste containing useful components are generated. The production of these industries forms the largest amount of semi-products and technological waste, the disposal of which is costly, causes a negative impact on the environment and is in contradiction with the progressively stringent legal requirements for environmental protection. These products are defined as secondary and can be processed for the purposes of production of metals. The new trend comprises increasing use of secondary sources for the production of zinc, lead, cadmium, antimony, selenium, tellurium, indium, silver, gold and other accompanying metals.
A significant source of secondary waste constitutes the portion related to the steel powder, which has constantly increased over the last years. They contain a significant amount of zinc, insignificant amount of copper, sulphide and sulphate anion of sulfure but have an increased content of impurities (Fe, Pb, Cd, Cl and F).
Another significant source of secondary waste is metallurgical insoluble residue originated from the extraction, filter facilities' dusts, drosses, sinters, slags, etc., which contain significant amounts of Se, Te, Tl, Sb, Ge, As, Pb, Cd, Fe, Si02,CaO, MgO, Ag, Au, etc. In the course of production of zinc metal, zinc alloys, zinc sulphates, metallic lead and its alloys, significant amounts of secondary waste are processed to final products. The expansion of the raw material base represented by secondary waste leads to appearance of increasing variety of impurities, forms of non-ferrous metals, thermal properties, characteristics, chemistry for reaction, etc. The aforementioned circumstances require the development of new technological schemes for the treatment of secondary waste.
In the metallurgical practice, Zn, Pb, Cd, Sb, Se, Te, In, Ag, Au and other metals are extracted from basic raw materials and from secondary waste via pyrometallurgical and hydrometallurgical lines. The utilization of industrial secondary waste requires the use of different production lines in one of which these materials, following the required preparation, are subjected to reduction, evaporation and oxidation of the volatile components conducted in a rotary tube furnace widely known in the art as a WAELZ kiln, and the other line method is based on hydrometallurgicsd extraction.
The purpose of the present ptent application is to provide a method and a modular plant for the chemical and metallurgical processing of industrial wastes, to create a flexible technological line for the maximum utilization of the useful components (metals) in the effective combination of preparatory, pyrometallurgical and hydrometallurgical processes, to provide processing of a wide range of secondary industrial waste with variable input composition to obtain high quality zinc, lead and cadmium and intermediate or end products for direct use in different industries and to avoid the deficiencies of existing recycling lines which have limited capacities with regard to inbound and outbound products.
The aim is sorted out by means of the method and modular installation disclosed in the present patent application, which are distinguishable from the prior art, due to the fact that they process a very large number of heterogeneous source materials as well as the surprising result , consisting in obtaining a significant number of precious metals, such as end products, as well as semi-products used in various economic sectors. On the one hand, the result obtained constitutes a result of the optimal selection of the steps of the chemical metal extraction method associated with the effective combination of the sequence and the conditions of its implementation. On the other hand, the achievement of this result is due to the construction of the requested chemical extraction plant, which comprises selection and combination of the individual technological lines in a way that ensures effective implementation of the method.
The method and the modular plant for the chemical and metallurgical processing of industrial waste for the purpose of extracting metals that constitutes object of the present patent application belongs to the so-called waste-free technologies, as they involve the processing of various in terms of type and quality industrial waste including
steel powders, filter installation dusts, slurries, insoluble residue resulting from the extraction, sediments, dross, sinters, slags, etc. to the extraction of precious metals such as zinc, lead, cadmium, copper, antimony, selenium, tellurium, silver, gold, etc.
The main effect of the claimed method and modular plant for industrial waste treatment is the receipt of a large number of final and intermediate products, which constitutes an evidence of a flexible technological process, for whose performance an installation consisting of separate units /modules/ is built, combined in such way as to provide efficient and economical production of a large number of products. The end products are: zinc - 99.995% (SHG), Z2 - 99.99% min .; Z3 - 99.95%, zinc dust, zinc alloys (ZA, CAM and SGG), zinc sulphate salt - brand A, B and C, copper sulphate crystals (CuS04 x 5H20), zinc sulphate salt for industry, insoluble residue resulting from the extraction for production copper and copper products, cadmium - 99.95%, lead residue resulting from extraction, to lead and other end products. The lead insoluble residue resulting from the extraction constitutes the basis for subsequent end products such as lead metal - 99.99% and 99.97%, lead bismuth - Bi - 7%, lead antimony alloy - PbSb 6.0AsCu and PbSb 5.0AsCu, lead antimony alloy - PbSb3 - Sb = 2 % ÷ 3.5%; PbSb4.5 - Sb = 4% ÷ 4.5%; PbSb6 - Sb = 6% ÷ 6,5%, lead antimony alloy for batteries - PbSb3Se antimony lead alloys, tin alloys - K-16; K- 83, tin lead alloys lead copper matte; zinc sulphate solution for the manufacture of crop protection products, synthetic fibers and reagents for various industries, insoluble residue resulting from the extraction for the production of copper and copper products - powder, electrolytic copper, copper salts and reagents for different industries. Amon the high quality end products also included are tellurium - brand 99.93%, gold - Au 99.99%; Au 99.98%; Au 99.95% and golden articles, silver - Ag 99.99% .; Ag 99.96%, high quality silver - Ag 99.995%; Ag 99.996% .; Ag 99.997%; Ag 99.998%; Ag 99.999%, technical silver nitrate.
Another effect of the claimed method and installation for processing of industrial waste is the implementation of a waste-free technology in which from secondary industrial waste a semi-product os produced for further processing in the existing technological installations of the main production of zinc, lead, cadmium or an end product is obtained that is used in other branches of industry. This is associated with the reduction of the harmful impact on the environment as the waste from the ferrous and non-ferrous metallurgy is processed to a finished product, the separated harmful substances and substances accompanying the processing of secondary waste being minimized. The wide range of industrial waste that can be processed by the claimed method and modular installation is of great importance, which have the following chemical composition: Zn - 15% ÷ 90%; Pb <15%; Fe <30%; Si02 <18%; CaO & lt; 20%; MgO & lt; 10%; With <3%; Cd <3%; As <0.03%; Sb <0.3%; Ni <0.05%; Co <0.05%; S <6%; Cl <10%; F <0.5%; Ge <40g / 1; Se <90 g / 1; Te <100 g / 1; Tl & lt; 40 g / 1; Hg <1 g / 1; maximum quantities In, Ag, Au.
The claimed method for the chemical (metallurgical) extraction of metals from industrial waste comprises the following steps: preparation of the batch of secondary industrial waste, activating materials and carbon containing reducing agent by mi ing; granulating and wetting, after which the batch is fed into a rotary tube waelz kiln. The following stage comprises the rolling, cooling and filtration of the flue gases. The metals from the batch -Zn, Pb, and Cd are reduced, evaporated and oxidized by the flow of air flowing in the opposite direction to the batch, whereby the exhaust gases containing Zn, Pb, Cd oxides are cooled and purified in a filtering module. The cleaned gases go into the atmosphere and the waelz pallets captured in the bag filters, after further transportation and granulation, are fed for oxidative roasting at a temperature of 900 ° C in a rotary tube furnace. Secondary waelz oxides rich in Cl, F, Cd, Pb, Se, Te, Tl and As are removed from the upper section of the furnace, and from the lower end of the furnace roasted waelz oxides are taken out, from where they are moved to a collecting vessel via a transport system, and subsequently are subjected to triple aqueous alkaline cleaning to purify the metal oxides of Cl, F, Se. During the next stage, Zn and Cd extraction is carried out in an acidic environment with the processed electrolyte from the zinc electrolysis, being the separated zinc sulphate subjected to chlorine scrubbing and the lead insoluble residue originated from the extraction obtained as filtrate is gravitationally discharged into metal lead production containers. The purification from Sb, Ge, As and Fe is accomplished by means of neutralization processes to pH = 4.8 ÷ 5, oxidation, hydrolysis, precipitation and filtration, where lead insoluble residue resulting from the extraction is produced for lead production and for purification from Se, Te and Tl neutralization processes are applied to pH = 4.8 ÷ 5.2, followed by precipitation, cementation, the purified zinc sulphate solution entering the basic zinc production scheme and the resulting solid residue yielding salts or zinc sulphate solution.
In cases where pure solutions are aimed for the production of a final product of zinc metal or salts for other industries, the method for chemical extraction of metals from industrial waste proceeds as follows: A portion of the washed alkaline wash, in particular the repellent insoluble residue resulting from the extraction after the second section, is fed to the neutralization, oxidation and hydrolysis module to remove impurities from the solutions Pb, Fe, Sb, Ge and As. A neutral water extraction process is carried out with a subsequent rotation of a portion of an aqueous suspension of water-alkaline washed squashes and fresh sulfuric acid to obtain a pulp of pH = 4.8-5.2 which is precipitated in a thickener with feeding a 0.1% aqueous solution of flocculant to give a neutral zinc-sulfate solution and a precipitate. The precipitate obtained after filtration is directed to the production of lead such as lead cachaza, and the resulting neutral zinc-sulfate solution is subjected to copper and cadmium purging by zinc dust cementation in a Cd, Se, Te, Tl solution. The filtrate, a solution of zinc sulphate, purified from copper and cadmium, is taken off as a finished product, and the cadmium insoluble residue resulting from the extraction resulting after filtration is passed to the production of cadmium for further processing to metal Cd.
One embodiment of the method for chemical extraction of metals comprises the process related to availability of secondary waelz oxides captured from the top end of a roasting tube rotary furnace where they are oriented directly to a module for extraction of secondary industrial waste and secondary waelz oxides for extraction with processed electrolyte and subsequent cementation of cadmium. Lead insoluble residue resulting from the extraction, which is directed to lead production, is obtained and the Zn and Cd-extracted filtrate is fed to the solution purification module by means of cementation, neutralization, oxidation and hydrolysis. A Cd cementation process takes place to produce a cadmiuih sponge which is led to produce cadmium, and a finished product zinc sulphate heptahydrafe is produced from the resulting filtrate.
In the case related to processing of secondary materials with increased content of elements Se> 50 g / 1, Te> 80 g / t, Tl> 50 g / t, Sb> 80 g / t, Ge> 20 g / t, As> 0.2 %, a change associated with movement of the roasted waelz oxides is carried out which, after passing through roasting tube rotary furnace, is fed to a neutralization, oxidation and hydrolysis module where the oxides are extracted with the relevant electrolyte obtained from the zinc electrolysis with subsequent hydrolysis precipitation of the harmful micro impurities. Zinc sulphate solution and precipitate are obtained, the zinc sulphate solution entering the chlorine scrubbing module, and the filtered precipitate in the form of lead insoluble residue resulting from the extraction for the production of lead.
In the processing of high halide-content zinc materials, the resulting waelz oxides containing chlorine levels of Cl <7%, Fluorine F <0.2% and Selenium Se <50 g / 1 after the filtering module by changing the direction of movement of the transport system are directed to collector, from where they access the triple water alkaline cleaning module.
The modular installation for the chemical extraction of metals by processing of industrial waste consists of a receptacle for secondary industrial waste, activators and a solid reducer, a batch preparation unit, a rotary tubular furnace for reduction batch roasting and a heavy slurry separation unit for separating the clinker of the unreacted reducer (coke) which are sequentially connected. The rotary tubular furnace for reduction batch roasting is connected to the filtering unit with a system of transport facilities which is connected on one side with a roasting furnace for oxidative roasting of the raw waelz oxides and on the other with a triple water alkaline cleaning unit of the secondary industrial waste, roasted or raw waelz oxide connected with a purification module. The roasting tube rotary kiln is connected to the triple water-based alkaline cleaning unit on the one hand and on the other with the extraction module for secondary industrial waste and secondary waelz oxides, which is connected to a solution purification module by means of cementation, neutralization, oxidation and hydrolysis and the production of zinc sulphate solution and salts, the triple water alkaline washing of secondary industrial waste, roasted or raw waelz oxides is also connected to a module for acid extraction of cleaned secondary industrial waste oxides and hydrolysis to remove impurities from solutions - Pb, Fe, Sb, Ge and As is connected to a cementation module for purification of solutions of Cu, Cd, Se, Te, Tl, and on the other with a module for further chlorine purification of zinc sulphate solutions. The module for acid extraction of washed secondary industrial wastes and waelz oxides is connected to a module for further chlorine purification of zinc sulphate solutions. Repository for secondary industrial waste, activators and solid reducer via line 3 is connected to a module for extraction of secondary industrial waste and secondary waelz oxides. By means of a technological line 2 a connection is established between the secondary industrial waste storage facility, activators and the solid reducer (1) and the triple water alkaline cleaning unit of secondary industrial waste, rested or raw waelz oxides.
The following raw materials are stored in the warehouse: (a) secondary material from primary production and secondary industrial waste with Zn content above 15%; (b) activating materials affecting the modulus of the slag formed, the ratio (CaO + MgO) / Si02; namely Ca-containing material for an alkaline batch module and a Si-containing batch acidic batching material; (c) a carbon containing reducing agent.
The triple water alkaline cleaning module designed for use with regard to secondary industrial waste, roasted or raw waelz oxides serves to remove impurities (Cl, F, Na, K, As and Se) from solid materials. It consists of three sections connected in such a way as to provide a right flow of oxides arid a counter-flow of the filtrate, and each of the sections includes interconnected reactors and filter presses. In each of the sections, the solid is susperided in an aqueous solution containing sodium carbonate followed by dewatering of the suspension and separating the slurry solution by filtration. The separated solid phase passes into a reactor of the next section. The filtrate returns from a third section to a second, from a second to a wetting reactor, and after a first section rich in chlorine, fluorine, selenium and sulphates is released to a central sewage treatment plant. The insoluble residue originated from the extraction of the third section, to a maximum extend dewatered and cleaned with halogens, is fed to a buffer vessel.
The module for the acid extraction of cleaned secondary industrial wastes and waelz oxides is designed to dissolve solids and to partially remove impurities (Pb, Fe, Si, Ca, As, Sb, C and Ag) from solutions and constitutes a system of four sequentially connected reaction vessels the latter, being by gravity overflow of the pulp connected to a thickener whose overflow is placed over an auxiliary manifold for a solution of zinc sulphate and the lower terminal of the thickener, by means of a pump system is connected to an intermediate reactor which in turn is connected via a pump system to a membrane filter press, which coupled with collection of filtrate which a pump system for the filtrate is connected to the third reaction vessel, and the filter press is connected to a container for transport of the resulting lead insoluble residue originated from the extraction to the existing lead production unit.
The module for extra chlorine scrubbing of zinc sulphate solutions consists of parallelly connected reaction vessels, a thickener and a filter press, on the underside of which a chute is provided to remove the copper chlorine insoluble residue originated from the extraction obtained as a finished product.
The module of neutralization, oxidation and hydrolysis for removal of impurities from the solutions- Pb, Fe, Sb, Ge and As consists of a sequentially connected slurry reactor, three parallel reaction vessels, three thickening agents, the lower discharge of the thickeners being connected to two filter presses connected to a container for the transport of the resulting lead insoluble residue originated from the extraction as a raw material for lead production, upper plums from the zinc sulphate thickeners solution are connected to a piping system to the cementitious cleaning solution of the Cu, Cd, Se, Te, Tl and to the chlorine scrubbing module for zinc sulphate solutions.
The module for cementation purification of the solutions of Cd, Se, Te, Tl consists of a system of reactors comprising a receiver, two reactors connected to a filter press, a crystallizer and a furnace fluidized bed, a zinc sulphate solution for basic production and final zinc sulphate products solution or salt) for other branches of industry.
The module for extraction of secondary industrial waste and secondary waelz oxides consists of a reactor system comprising a receiver compartment, two reactors connected to a filter press, a press insoluble residue originated from the extraction connected to a container for transporting the resulting Pb insoluble residue originated from the extraction as feedstoc for intermediate and end products to existing lead production. The filter is oriented in two directions to a neutralization, oxidation and hydrolysis plant to remove impurities (Pb, Fe, Sb, Ge and As) from the solutions to obtain zinc sulphate solution for primary production and to the curing, neutralization, oxidation and hydrolysis of solutions to produce final products related to zinc sulphate solution and salts.
The module for solution cleaning perfomed by means of cementation, neutralization, oxidation and hydrolysis and the production of zinc sulphate solution and salts constitutes a system of reactors for cleaning zinc sulphate solutions of copper and cadmium by cementation and consists of a receiver collection, two reactors connected to a filter press and crystallizer, a filter press being coupled to a container for transporting the resulting cadmium insoluble residue originated from the extraction to a cadmium product for further processing to a metal Cd, and the filtrate from the filter press being coupled to the crystallizer, connected to produce the final product zinc sulphate salt for the industry.
The tube waelz furnace constitutes a rotary tube furnace operating on the counterflow principle at a temperature in the hottest range of 1150° C to 1400° C. The furnace is inclined, and when rotated, the material moves to the lower end. The Waelz kiln operated in continuous mode, without idling, by periodically changing the slag module - alkaline, neutral and acidic - in the range of 5 to 0.3 and vice versa: alkaline (CaO - 13,5 ÷ 14,8%; MgO - 2.0 ÷ 2.55%, Si02 - 3.72 ÷ 3.95%), neutral (CaO - 5.21 ÷ 5.47%, MgO - 0.71 ÷ 0.77%, Si02 - 5.67 ÷ 5,75%) and acidic (CaO - 1,65 ÷ 2,07%; MgO - 0,50 ÷ 0,55%; Si02 - 6,04 ÷ 6,34%). The switching of the slag module allows the processing of various secondary materials under different technological conditions in the same plant. The advantages of these actions comprise reduction of the formation of deposits inside the furnace by chemical self-cleaning, which in turn leads to coke economy, increase with regard to the production capacity of the waelz kiln and extension of the life-cycle of the furnace.
DESCRIPTION OF ENCLOSED DRAWING
Fig. 1 displays a scheme of a modular installation for chemical extraction, of metals by processing of secondary industrial waste as follows:
1. secondary industrial waste storage, activators and hard reducing agent;
2. batch preparation compartment;
3. rotary pipe waelz kiln for reduction roasting of the shaft;
4. a filter module with a system of transportation facilities;
5. roasting tube rotary furnace for oxidative roasting of crude waelz oxides;
6. module for triple water alkaline cleaning of secondary industrial waste, roasted or raw waelz oxides;
7. module for acid extraction of washed secondary industrial waste and waelz oxides;
8. neutralization, oxidation and hydrolysis module to remove impurities from solutions - Pb, Fe, Sb, Ge and As; 9. Module for cementation of solutions of Cu, Cd, Se, Te, Tl;
10. module for additional chlorine cleaning of zinc sulphate solutions;
11. a module for the extraction of secondary industrial waste and secondary waelz oxides;
12. a module cleaning solution by means of cementation, neutralization, oxidation and hydrolysis and production of solution and salts of zinc sulphate;
13. a heavy slurry separating clinker from unreacted reducer (coke);
EMBODIMENTS
Line 1 designed for processing by means of rolling with itinerary (1) -® (2) ® (3) ® (4) (5) (6) ® (7) (10) and (6) - (7) ® (9). It is used for the processing of secondary industrial waste with a high content of Fe, Ca, Si02. Zn content above 15%.
In the storehouse 1 by means of a grab crane, materials are homogenized to an optimum zinc content of 21% ÷ 25%. The mixture obtained from various raw materials is premoistened, mixed and aerated.
From the receptacle 1, the materials enter a batch preparation section 2 where, according to predetermined operating parameters, a batch of zinc containing a material containing Ca or Si containing an activator is prepared. The prepared batch is mixed, granulated and dampened to the required moisture by means of the addition of recycle zinc solutions from the existing hydrometallurgical production to remove the accumulated alkali elements from the production cycle resulting in deterioration in zinc metal production. Using conveyor belts materials - the waelz batch and reducing agent are fed to a hopper system equipped with precision dosing belt feeders which feed a rotary tubular waelz furnace 3.
At the lower end of the tubular furnace, a spent clinker is ejected, which is granulated and discharged to regenerate the carbon containing reducing agent in a heavy shirry compartment 13. The batch metals Zn, Pb, Cd are reduced, evaporated and oxidized by the airflow moving in countercurrent to the batch. The exhaust gases containing Zn, Pb, Cd oxides are cooled and purified in a filtering module 4 with a system of transport facilities. The cleaned gases are released into the atmosphere, and the pellets are collected in the filter bags, after transport and granulation, for oxidative roasting in a roasting tube 5 for partial purification of the waelz oxides from Cl, F, Se, Te, Tl, As, Cd, Pb and Fe2+.
In the roasting tube rotary furnace 5, oxidation roasting takes place at a temperature of 900° C and the air is fed in countercurrent with regard to the movement of the waelz oxides. Secondary waelz oxides rich in Cl, F, Cd, Pb, Se, Te, Tl and As are extracted from the upper end of the furnace. From the bottom of the furnace, the roasted waelz oxides are separated from where they are transmitted to a collecting vessel (silo) through a transport system.
From the collecting vessel (silo), the waelz oxides, by means of two sequentially connected screws, mounted on a strain gauge platform to track the weight of incoming oxides are fed to the wetting (suspending) reactor. The wetting is performed with the filtrate from the triple water alkaline cleaning unit 6 to purify the metal oxides from Cl, F, Se.
The triple water-alkaline cleaning module 6 consists of three sections connected to provide a jet-flow of oxides and a counterflow of the filtrate, and each of the sections includes interconnected reactors and filter presses. In each of the sections, the solid is suspended in an aqueous solution containing sodium carbonate followed by dewatering of the slurry and separating the slurry solution by filtration. The separated solid phase passes into a reactor in a subsequent section. The filtrate returns from a third section to a second, from a second to a wetting reactor, and after a first section, which is rich in chlorine, fluorine, selenium and sulphates, it is released to a central sewage treatment plant. The insoluble residue originated from the extraction of the third section, maximally dewatered and cleaned from halogens, is fed to a buffer vessel.
The process is carried out with an alkalinity amounting to about pH> 10, which ensures that no heavy metals may appear into the wastewater. The first wash is performed at a temperature of about 50° C. Duringthis stage, the chlorine contained in the oxides and a small portion of the fluorine are washed away. The second wash is carried out at a temperature of about 95° C, cleaning the residues of chlorine and a significant portion of the fluorine. The third wash also takes place at a temperature of 95 ° C and, in addition to sodium carbonate, hydrogen peroxide (H202) is added to increase the rate of extraction of metals such as Fe, As, Sb and Ge.
From the triplicate aqueous alkaline cleaning module 6, the washed waelz oxides are fed to the scrubbing oxide module 7. The extraxtion of Zn and Cd is carried out in an acidic environment with the relevant electrolyte from the zinc electrolysis in a system of four successively connected reaction vessels, and from the last one the resulting pulp runs oer gravitationally to a thickener, the top fusion of zinc sulphate solution containing zinc 140-150 g / 1, chlorine 200-220 mg / 1, fluorine 40-44 mg / 1, via an auxiliary manifold enters a module for further chlorine purification of zinc sulphate solutions (10) comprising a system of aggregates where the lower compressor slurry is pumped to intermediate reactor and is directed to a membrane filter press from which the filtrate is collected in a filtrate collection where it is pumped for recycling to the third reaction vessel and then removed together with the top discharge of the thickener. The insoluble residue originated from the extraction obtained by the filter press with a moisture content below 17%, lead over 37-43%, zinc below 7% and iron below 6% is gravitationally released into containers and transported to existing lead production in the form of lead residue for metal lead production.
The system of aggregates in the additional chlorine scrubbing unit of zinc sulphate solutions 10 consists of parallel connected reaction vessels, thickener and filter press. The solutions obtained from the acid extraction module 7 are treated with cadmium-precipitated copper insoluble residue originated from the extraction. The resulting pulp is subjected to precipitation in a thickener. The clear solution of zinc sulphate goes into the basic SHG zinc production scheme and the compressed pulp after precipitation flows into a filter press and the copper chlorine insoluble residue originated from the extraction obtained is packaged as a commercially available product.
One part of the top of the zinc sulphate solution from the rinsing oxide acid extraction module 7 is fed through a pump installation into a neutralization, oxidation and hydrolysis module 8.
The neutralization, oxidation and hydrolysis module 8 consists of a receiver collection volume of 100 m3 for the slurry connected by a system of pipelines with three parallel working reaction vessels with a working volume of 80 m3 and with mechanical a|itation which in turn are connected to three thickener, one of which characterized by- 660m 3 two - by 180 m3. The module is further equipped with two filter presses. Depending on the types and levels of impurities, different processes are performed - neutralization, oxidation and hydrolysis. For cleaning from Sb, Ge, As and Fe, neutralization processes are applied to pH = 4.8 ÷ 5, oxidation, hydrolysis, precipitation and filtration, where insoluble residue originated from the extraction is released and transported to the lead plant. The top of the thickener and filtrate from the filter presses is fed to the main SHG zinc production scheme.
For purification from Se, Te and Tl neutralization processes are applied to pH = 4.8 ÷ 5.2 with subsequent precipitation, after which the resulting discharge of 180 m3 of thickeners is fed to the Se, Te and Tl " 9, the purified zinc sulphate solution enters the basic zinc production scheme SHG. The resulting solid residue is used as a raw material for the production of technical zinc sulphate salts for other branches of industry.
The module for cementation cleaning of Se, Te and and Tl 9 solutions consists of a receiver collection, two reactors connected to a filter press, a crystallizer, and a furnace fluid bed. This module produces a solution of zinc sulphate for basic production and final products of zinc sulphate (solution or salt) for other industries.
For the preparation of particularly pure solutions for final product zinc metal of SHG quality or salts for other productions, the connection (6) ® (8) ® (9) is carried out. Part of the washings in a triple water alkaline wash module 6 of the pellets, in particular repulped insoluble residue originated from the extraction after the second section (aqueous suspension) having a solids content of 250-300 g / 1 or a relative weight of 1360-1400 g / 1, is supplied by a pump installation to the neutralization, oxidation and hydrolysis module to remove impurities from solutions - Pb, Fe, Sb, Ge and As 8. The neutral extraction process is carried out in a reaction vessel of 80 m3 with a water supply up to a volume of 25m3 with subsequent rotation of a portion of an aqueous suspension of water-alkaline waelz oxides and fresh sulfuric acid to obtain a pulp of pH = 4.8-5 , 2 and a relative weight of 1360-1400 g / 1, which is fed to the subsequent sedimentation operation in a 180 m3 thickener by feeding 0.1% aqueous flopulant flopam to give a neutral zinc sulphate solution and a precipitate , which after filtration is directed to the production of lead such as lead insoluble residue originated from the extraction. The resulting neutral zinc-sulphate solution is subjected to copper and cadmium purging by zinc dust cementation in a Cd, Se, Te, Tl 9 solution. The filtrate, a solution of zinc sulphate, purified from copper and cadmium, is used as a commercial product (raw material in the manufacture of crop protection products) or after crystallisation in the form of a technical salt of zinc sulphate crystalline hydrate is used as a commercial product in other industries in silk production, fertilizers, feed additives, paints and varnishes, enrichment factories, etc.). The cadmium insoluble residue originated from the extraction obtained after the filter press is taken to produce cadmium for further processing to metal Cd.
The secondary waelz oxides captured from the top end of a roasting tube rotating furnace 5 are directed to a secondary industrial waste recovery and secondary waelz oxide extraction unit 11 for a conventional exhaustion with the relevant electrolyte and subsequent cementation of cadmium. The divalent iron compounds as a result of roasting in a roasting tube rotary kiln 5 are oxidized to a third valence and are thus a reagent for hydrolytic purification of the solutions which reduces the consumption of the oxidant. Lead insoluble residue originated from the extraction is produced, which is directed to lead production. The filtrate with the extracted Zn and Cd is fed to the solution purification module by cementation, neutralization, oxidation, and hydrolysis 12 where a Cd cementation process takes place. After the cementation of the solution, a cadmium sponge is produced, which is led to the - production of cadmium, and a product of zinc sulphate heptahydrate for the industry is produced from the resulting filtrate. Depending on the type of zinc-containing materials processed and in particular on the level of the impurities contained therein, the proposed process line is executed in the described sequence of the technological units, installations and facilities and, if necessary or for economic reasons, the waelz oxidesare subjected either to (5) ® (8), or aqueous-alkaline flushing with subsequent sulfur-acid extraction along the route (6) ® (7).
For example, when processing secondary materials with an increased content of Se> 50 g / 1, Te> 80 g / 1, Tl> 50 g / 1, Sb> 80 g / 1, Ge> 20 g / 0.2% in the modular installation by changing the direction of movement of the fried wax oxides after a frypot tube 5 are fed to a neutralization, oxidation and hydrolysis module 8. The oxides are recovered with spent electrolyte generated in zinc electrolysis, followed by hydrolysis precipitation of harmful microparticles to yield zinc sulphate solution and sludge. The zinc-sulphate solution enters the chlorine purification module 10, and the filtered lead sludge sludge slurry is added to produce lead.
In another case, when processing high halide containing zinc materials waelz oxides are produced containing levels of chlorine (Cl <7%), fluorine (F <0.2%) and selenium (Se <50 g / 1) are produced in the processing of high halide containing zinc materials. Following the filtering module 4, the raw, waelz oxides that are not roasted, by changing the direction of movement of the transport system, are directed to the collecting vessel (silo) from where they enter the triple water alkaline cleaning unit 6.
In each unit of the modular installation according to the present invention, the capture and recovery of all waters, solutions and filtrates are organized to minimize their amount upon their introduction into a purification plant.
The advantages provided by the method and the modular installation for processing of industrial waste are:
increasing the variety of processed secondary materials both in terms of composition and in terms of quality;
reducing the environmental impact of disposal of ferrous and non-ferrous metallurgy waste;
efficient use of secondary industrial waste to extract precious metals by utilizing impurities in intermediate and end products;
practical waste-free treatment of secondary industrial waste, after each technological process a semi-finished product is produced for subsequent processing in the existing schemes of the main zinc, lead, cadmium or end-use products for use in other branches of industry; the production of commercial products - solution and technical salts of zinc sulphate for other industries reduces the cost of production of the zinc metal unit;
a high degree of use by returning to the production cycle of working solutions, minimizing the amount of wastewater to a treatment plant and improving the water and metal balance of the entire production scheme;
reducing costs for different reagents;
pre-distillation of fluorine under oxidative roasting provides the possibility of using standard reactors at a temperature of 95°C throughout the hydrometallurgical purification stage.

Claims

PATENT CLAIMS
1. A method for chemical extraction of metals from industrial waste comprising preparation of the batch of secondary industrial waste, activating materials and carbon containing reducing agent by mixing, granulating and wetting, after which the batch is fed into a rotary tubular waelz furnace followed by rolling, cooling and filtration of furnace gases, characterized in that the Zn, Pb, Cd batch metals are reduced, evaporated and oxidized by the airflow moving in countercurrent to the batch, wherein the exhaust gases containing Zn, Pb, Cd oxides are cooled and purified in a filtering module 4, after which the cleaned gases are released into the atmosphere and the waelz oxides captured in the bag filters after transport and granulation are subjected to oxidative roasting at a temperature of 900 ° C in a roasting tube rotating furnace 5 where from the upper end of the furnace secondary waelz oxides rich in Cl, F, Cd, Pb, Se, Te, Tl and As are discharged, and the roasted pellets are removed from the lower end of the furnace, from where they are moved to a collecting vessel by means of a transport system, then subjected to triple water alkaline cleaning is to purify metal oxides from Cl, F, Se. The next step consists of the extraction of Zn and Cd in an acidic environment with the relevant electrolyte from the zinc electrolysis, the separated zinc sulphate being subjected to chlorine scrubbing, and the lead insoluble residue originated from the extraction obtained as a filtrate is gravitationally discharged into metal lead production containers, followed by purification from Sb, Ge, As and Fe by neutralization to pH = 4.8 ÷ 5, oxidation, hydrolysis, precipitation and filtration, which lead to the production of lead, and for purification from Se, Te and Tl the neutralization processes are applied to pH = 4.8 ÷ 5.2, with subsequent precipitation and cementation, the purified zinc sulphate solution enters the main circuit for the production of zinc and the resulting solid residue was obtained salts or zinc sulphate solution.
2. A method process for the chemical extraction of metals from industrial waste according to claim 1, characterized in that, for the preparation of pure metal zinc end products or salts for other industries, a part of the washings in a triple aqueous alkaline cleaning (6) in particular a repulped insoluble residue originated from the extraction after the second section, is fed into the neutralization, oxidation and hydrolysis module to remove impurities from the solutions - Pb, Fe, Sb, Ge and As (8), where a neutral extraction process is carried out by feeding water subsequent alternation of feed portion wt of a suspension of water-alkaline washed silica and fresh sulfuric acid to obtain a pulp of pH = 4.8-5.2 which is precipitated in a thickener by feeding 0.1% aqueous flocculant solution to produce neutral zinc sulfate solution and a sludge which after filtration is directed to the production of lead in the form of lead residue, and the resulting neutral zinc-sulfate solution is subjected to copper and cadmium scrubbing by means of zinc dust cementation in a cementitious cleaning solution of the Cd, Se , Te, Tl (9), the filtrate being a solution zinc sulphate, copper and cadmium cleaned, is taken off as a finished product, and the cadmium insoluble residue originated from the extraction resulting after filtration is taken to cadmium production for further processing to metal Cd.
3. A method for chemical extraction of metals from industrial waste according to claim 1, characterized in that the secondary waelz oxides caught from the upper end of a roasting furnace (5) are transmitted directly to a secondary industrial waste and secondary ferrous oxide extraction unit (11) for exhaustion with relevant electrolyte and subsequent cementation of cadmium, lead insoluble residue originated from the extraction is obtained which is directed to the production of lead and the filtrate with the extracted Zn and Cd is fed to the solution purification module by means of cementation, neutralization, oxidation and hydrolysis (12), wherein a process of cementation of Cd takes place to produce a cadmium sponge, which is conveyed to the manufacture of cadmium, and from the resulting filtrate a finished product of zinc sulfate heptahydrate is produced.
4. A process for chemical extraction of metals from industrial waste according to claim 1, characterized in that, when processing secondary materials with an increased content of Se> 50 g / 1, Te> 80 g / 1, Tl> 50 g / 1, Sb> 80 g / 1, Ge> 20 g / 1, As> 0.2%, in the modular installation by changing the direction of movement of roasting waelz oxides after a roasting tube rotary furnace (5) are fed to a neutralization, oxidation module and hydrolysis (8), wherein the oxides are extracted with the releant electrolytes generated in zinc electrolysis with subsequent hydrolysis precipitation of the harmful micro impurities, yielding zinc- sulphate solution and precipitate and zinc sulphate solution enters module further purification chlorine (10), and the filtered precipitate in the form of lead insoluble residue originated from the extraction is transmitted for the production of lead.
5. A process for chemical extraction of metals from industrial waste according to claim 1, characterized in that, when processing zinc -content materials with high content of halide, the resulting waelz acids containing chlorine levels of Cl <7%, fluorine F <0.2% and selenium Se < 50 g / t after the filter module 4, by changing the direction of the transport system, are directed to the collection vessel from where they enter the triple water alkaline cleaning unit (6).
6. A modular installation for carrying out the method of chemical extraction of metals by processing industrial waste according to claim 1, comprising the connected successively storage for secondary industrial waste, activators and a solid reducing agent (1), a batch preparation unit (2), a rotary tubular roasting furnace (3) and a filtering module (4), characterized in that the rotary tube roasting furnace (3) is connected to a heavy slurry compartment for separating the clinker from the breeze (13), and the filtering unit (4), on the one hand, is connected to a roasting furnace for oxidative roasting of the raw waelz oxides (5). On the other hand, with a triple water alkaline wash of secondary industrial waste, roasted or raw waelz oxides (6), wherein the roasting (5) is connected to the triple water alkaline cleaning unit (6) on the one hand and on the other (11) is connected to a solution purification module by means of cementation, neutralization, oxidation and hydrolysis, and production of solution and salts of zinc sulphate (12) associated with the main production of cadmium, such as the module triple water alkaline washing of secondary industrial waste, fried or raw waelz oxides (6) is also associated with an acid extraction unit of washed secondary industrial waste and waelz oxides (7) connected to a neutralization, oxidation and hydrolysis module for impurities removal from the solutions Pb, Fe, Sb, Ge and As (8) associated with a cementitious cleaning solution of Cd, Se, Te, Tl (9) solutions associated with the basic zinc production such as the acid- secondary industrial waste and waelz oxides (7) is connected to the additive module for additional chlorine cleaning (10) which is connected to the module cementation cleaning of solutions from Cd, Se, Te, Tl (9), and the chlorine additional purification module for zinc sulphate solutions (10) is also connected to the main production of zinc on the one hand and the production of copper and copper products on the other, such as the acid extraction unit for washed secondary industrial waste and waelz oxides (7), is also related to the production of lead and lead products, and the secondary storehouse for secondary industrial waste, activators and hard reducing agent (1) via line 3 is directly connected to the secondary industrial waste recovery and secondary waelz oxides (11) and via line 2 a connection is made between the secondary waste industrial waste, activators and the solid reducer (1) and the module for triple alkaline washing of secondary industrial waste, fried or raw waelz oxides (6).
7. A modular installation as claimed in claim 6, characterized in that the triple water- alkaline cleaning unit of secondary industrial waste, roasted or raw waelz oxides (6) consists of three sections connected to provide a straight-forward oxidation movement and a countercurrent motion of the filtrate, and each of the sections includes interconnected reactors and filter presses.
8. Modular installation according to claim 6, characterized in that the module for acid extraction of washed secondary industrial waste and waelz oxides (7) is a system of four successively connected reaction vessels, the latter of them by gravity infusion of the pulp being connected to a thickener whose overflowdrain is over an auxiliary compartment for a zinc sulphate solution, and the lower opening of the thickener through a pump system is connected to an intermediate reactor, which in turn is connected via a pump system to a membrane filter are connected to a filtrate manifold which is connected by a filtration pump system to the third reaction vessel and the filter press is connected to a container for transporting the resulting lead insoluble residue originated from the extraction to the existing lead production.
9. Modular installation according to claim 6, characterized in that the neutralizing, oxidation and hydrolysis module for removing impurities from the solutions - Pb, Fe, Sb, Ge and As (8) consists of a sequentially connected slurry reactor, three parallel operating slurry vessels, three thickeners and two filter presses connected to a container for transporting the resulting lead insoluble residue originated from the extraction as the raw material for lead production.
10. Modular installation according to claim 6, characterized in that the cement purification unit of the solutions of Cd, Se, Te, Tl (9) consists of a system of reactors comprising a receptacle, two reactors connected to a filter press, a crystallizer and a furnace fluidized bed .
11. Modular installation according to claim 6, characterized in that the solution purification module using means related to cementation, neutralization, oxidation and hydrolysis and production of solution and salts of zinc sulphate (11) constitutes a system of reactors for cleaning zinc sulphate solutions from copper and cadmium by cementation and consists of a receiver compartment, two reactors connected to a filter press and a crystallizer, the filter press being connected to a container for transporting the resulting cadmium insoluble residue originated from the extraction to a cadmium plant.
12. A modular installation according to claim 6, characterized in that the module for extraction of secondary industrial waste and secondary waelz oxides (11) consists of a reactor system comprising a receiver collection, two reactors connected to a filter press bound to a container for transporting the resulting Pb insoluble residue originated from the extraction.
PCT/BG2018/000032 2018-03-22 2018-07-29 Method for chemical extraction of metals by means of processing of industrial waste and modular installation for its implementation WO2019178654A1 (en)

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CN112646980A (en) * 2020-09-11 2021-04-13 湖北大江环保科技股份有限公司 Copper soot purification system and use method thereof
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