WO2008100123A1 - Procédé de transformation intégrée de matières premières de silicates d'aluminium - Google Patents

Procédé de transformation intégrée de matières premières de silicates d'aluminium Download PDF

Info

Publication number
WO2008100123A1
WO2008100123A1 PCT/KZ2007/000015 KZ2007000015W WO2008100123A1 WO 2008100123 A1 WO2008100123 A1 WO 2008100123A1 KZ 2007000015 W KZ2007000015 W KZ 2007000015W WO 2008100123 A1 WO2008100123 A1 WO 2008100123A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
leaching
cake
hydrochloric acid
aluminum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KZ2007/000015
Other languages
English (en)
Russian (ru)
Inventor
Alexandr Kosmukhambetov
Berik Kaniyev
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of WO2008100123A1 publication Critical patent/WO2008100123A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
    • C01F7/22—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with halides or halogen acids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C01F7/306—Thermal decomposition of hydrated chlorides, e.g. of aluminium trichloride hexahydrate

Definitions

  • the invention relates to non-ferrous metallurgy, in particular, to the technology of complex processing of oxidized raw materials containing aluminum and silicon oxides and can be used to obtain alumina, silica, and the separation of heavy non-ferrous metals from complex refractory raw materials.
  • the Bayer method is intended for the processing of high-quality bauxite with a low silica content, silicon module (the ratio of the content of Al 2 O 3 to SiOg) for which should be at least 7-8.
  • This limitation is associated with the formation of alkaline leaching of insoluble sodium aluminosilicate (permutite), with which aluminum oxide and sodium oxide are lost.
  • Closest to the proposed method for processing aluminosilicate raw materials is a method of sintering aluminosilicate raw materials with a high content of silica / A. Liner. Production of alumina. - M .: Metallurgizdat, 1961, p. 362-370 /.
  • the method is intended for processing raw materials with a silicon module of less than 7, consists in converting aluminum oxide into solid sodium aluminate due to its binding to soda and provides for the binding of silica to insoluble dicalcium silicate.
  • the method includes preparing a mixture consisting of feedstock, soda and a reagent having basic properties, which is limestone or lime, firing the mixture at a temperature of 1150-1250 0 C, leaching the obtained cake with reverse soda-alkaline solutions with dissolution of aluminum and transferring impurities into dump sludge, desiliconization of the solution, separation of aluminum hydroxide from the solution and its calcination to obtain alumina.
  • the method is intended primarily for producing alumina and does not provide complex processing of raw materials. In particular, silica in the form of dicalcium silicate is lost in the waste sludge.
  • the method is associated with a high consumption of soda, the need to use a significant amount of limestone or lime, high energy consumption.
  • Extraction of aluminum into the solution from the cake is in the range of 80-85% due to the insufficiently complete formation of sodium aluminate during sintering.
  • the disadvantage of this method is also a significant decrease in technological parameters during the processing of raw materials with a high iron content, which leads to the formation of low-melting iron silicate during sintering, the presence of which reduces the temperature range within which sintering takes place and leads to the formation of crusts in kilns.
  • the objective of the invention is to develop a method for the complex processing of complex refractory oxidized raw materials, mainly aluminosilicate raw materials containing, along with aluminum and silicon, metals such as copper, lead, zinc, tin, etc.
  • the technical result achieved by using the invention is to increase the extraction of aluminum into the solution during leaching, the extraction of silica in the form of marketable products, in particular in the form of amorphous highly dispersed silica, the reduction of the consumption of reagents and energy costs during sintering, the separation of related metals in the form of rich concentrates suitable for complex processing.
  • the specified technical result is achieved by the fact that in the method of processing aluminosilicate raw materials, including sintering with sodium carbonate and a reagent having the basic properties, leaching of cake, extraction of aluminum from the solution, followed by obtaining alumina, it is envisaged to sinter the raw materials using sodium hydroxide as a reagent, having basic properties, and the resulting cake is leached with a hydrochloric acid solution to obtain a chloride solution and a solid residue.
  • More electropositive metals than aluminum are isolated from the chloride solution, after which the chloride solution is subjected to heat treatment to obtain an aluminum-rich oxide product and hydrochloric acid solution, and the solid leach residue is dissolved in an alkaline solution and the resulting solution is carbonized to obtain sodium carbonate solution and sediment of amorphous silica.
  • the ratio of sodium carbonate to caustic soda in the sintering mixture is in the range (2.5-3.5): 1 at a total flow rate of 40-50% in May. from the amount received for sintering raw materials.
  • Sinter leaching is carried out with a hydrochloric acid solution with an initial concentration of at least 4.4 geq / dm 3 at a ratio W: T of at least 10: 1 for 30-60 minutes at a temperature of 40-80 C, after which the solution is separated from solid residue, replenish with a solution of hydrochloric acid to a concentration of not less than 4.4 g-eq / dm 3 and used to leach a new portion of cake, repeating these operations until the aluminum concentration in the solution is not less than 70-80 g / dm 3 in terms of Al 2 O 3 .
  • a special case of cake leaching is continuous leaching, which is carried out with a solution of hydrochloric acid with a concentration of 4.4 g-equiv / dm for 30-60 minutes at a temperature of 40-80 0 C, after which the solution is separated from the solid residue, some of it is returned for leaching of cake, and the rest of the solution is sent to subsequent processing.
  • More electropositive metals as a collective product are isolated from the solution obtained by leaching the cake, and this operation can be carried out, in particular, by electrolysis in an electrolyzer with a separated anode and cathode space at a cathode current density of at least 500 A / m 2 .
  • the chloride solution purified from metals that are more electropositive than aluminum is subjected to heat treatment by evaporating the solution to obtain aluminum chloride hexahydrate in the first stage, calcining it at 400-600 0 C to obtain an oxide product in the second stage, and condensing the hydrochloric acid solution from heat-treated gases .
  • the solution obtained by alkaline dissolution of the solid cake leach residue is subjected to carbonization with a gas containing carbon dioxide, followed by separation of the precipitate of amorphous silica, washing and drying it at 300-400 0 C.
  • an additional gas containing chlorine for example, the anode gas of a chlorine membrane electrolyzer, can be added to the pulp.
  • Concentrated hydrochloric acid is introduced into the chloride solution to a concentration of 6.5-7.5 g-eq / dm 3, after which iron is isolated from the solution by extraction with a solution of tributyl phosphate in kerosene with the number of extraction stages not less than three.
  • the raffinates obtained during the subsequent re-extraction are used in the leaching of cake, and the re-extracts are used to obtain an oxide-containing iron-containing product and regeneration of hydrochloric acid.
  • the strips are treated with iron scrap and then evaporated by 85-90%, after which they are subjected to heat treatment in an oxidizing medium at 580-650 0 C to obtain an iron oxide product, and the hydrochloric acid is regenerated by condensation of the gases obtained during evaporation and heat treatment.
  • the proposed sequence of operations and their conditions are due to the fact that the set of essential features of the invention allows to extract aluminum from complex refractory raw materials in the form of industrial alumina suitable for processing by known methods, silica in the form of pure finely dispersed amorphous silica, heavy non-ferrous metals in the form of rich products also suitable for processing by known methods.
  • An important advantage of the proposed technology is the ability to regenerate the reagents used in the scheme.
  • the ratio of sodium carbonate to caustic soda in the mixture fed to sintering in the range (2.5 - 3.5): 1 at a total flow rate of 40-50% in May. of the amount supplied to the sintering of raw materials, provides the binding of aluminum and silica to the corresponding compounds by reactions
  • Replacing limestone (lime) with sodium hydroxide in the composition of the mixture allows to reduce the consumption of reagents and energy costs in the sintering process. Leaching of cake in hydrochloric acid makes it possible to separate aluminum and non-ferrous metals passing into the solution from the precipitate of silicic acid, which is poorly soluble in an acidic solution and which forms upon reaction with acid.
  • Sinter leaching can also be carried out continuously using a mixture of hydrochloric acid solution with part of the solution obtained by separating it from the solid leach residue as a solvent in an amount that provides an initial W: T ratio of at least 10: 1.
  • the remaining part of the solution, containing 70-80 g / dm 3 Al 2 O 3 is withdrawn for subsequent processing.
  • Evaporation of the purified chloride solution and subsequent calcination of the mixture of sodium and aluminum chlorides in an oxidizing atmosphere in the presence of water vapor makes it possible to obtain an oxide product containing aluminum and sodium oxides, which can be processed into alumina using standard Bayer method technology. Condensation of the heat treatment gases makes it possible to obtain a hydrochloric acid solution suitable for reuse in the leaching of cake.
  • the solid cake leach acid leach residue consisting predominantly of silicic acid, is leached after a water wash with a soda-alkaline solution.
  • a sodium silicate solution is treated with a gas containing CO 2 , the solution is carbonized, accompanied by the precipitation of amorphous silica from the solution
  • Na 2 SiO 3 + CO 2 Na 2 CO 3 +
  • the raw material be purified from iron before the sintering process.
  • This process was proposed to be carried out by leaching in a concentrated solution of hydrochloric acid, and to intensify the process and increase the extraction of iron into the solution, it was proposed to additionally supply gaseous chlorine to the leaching pulp, which can be obtained, for example, by electrolysis of a solution of sodium chloride in a chlorine membrane electrolyzer. From the solution obtained by leaching, iron is extracted by extraction after acidification of the solution with hydrochloric acid.
  • the extraction is carried out, for example, with a solution of tributyl phosphate in kerosene in several stages (as a rule, at least three stages are required), followed by re-extraction.
  • the raffinate obtained during extraction contains 4.5 - 5 g-eq / dm 3 hydrochloric acid and non-ferrous metals that are converted into solution by hydrochloric acid leaching. This solution can be used for leaching cake.
  • the re-extract is treated with iron scrap to cement a small amount of non-ferrous metals that have passed into it during the extraction process, after which it contains up to 40-45 g / dm 3 of iron, which is extracted by evaporation of the solution and heat treatment of the iron-containing product in an oxidizing medium at 580 - 650 0 C.
  • the heat treatment produces iron oxide and gases, upon condensation of which hydrochloric acid is obtained.
  • T 2.5: 1
  • a temperature of 75-80 0 C intensive mechanical stirring and feeding into the pulp a chlorine-containing anode gas obtained in a membrane electrolyzer during the electrolysis of a solution of sodium chloride.
  • leaching for 6 hours 98% of iron, 94-96% of copper, lead and bismuth, 60-65% of tungsten, 20-25% of tin and titanium were extracted into the solution.
  • the solubility of aluminum does not exceed 10-1 1%, silica - not more than 2%.
  • the iron chloride solution was supported by concentrated hydrochloric acid to 7 g-equiv / dm 3 and was subjected to three-stage extraction with a 30% solution of tributyl phosphate in kerosene. Reextraction was carried out in countercurrent water.
  • the raffinate obtained by extraction with an acidity of 4.7 geq / dm J contained, g / dm 3 : Fe 2 O 3 less than 0.005; Al 2 O 3 - 1 1.6; SiO 2 - 3.4; TiO 2 -1, 6; Sn 0.22; Cu - 0.3; Pb 2.2; Bi - 0.45; W - 0.17 and was sent to the subsequent operation of the leaching cake.
  • the re-extract with an acidity of 2.4 g-equiv / dm 3 contained, g / dm 3 : Fe 2 O 3 - 60.0; Al 2 O 3 - 0.33; SiO 2 - 0.1; TiO 2 -0.03; Sn 0.05; Cu - 0.12; Pb - 0.07; Bi - 0.03; W - 0.004 and from it after treatment with iron scrap, an iron-containing product was released.
  • the re-extract was subjected to preliminary evaporation to obtain a solution with an iron concentration of 370–380 g / dm and subsequent heat treatment at 580–620 ° C, as a result of which chlorine was completely transferred to the gas phase in the form of hydrochloric acid vapor and an iron oxide concentrate containing, wt.% Was obtained : Fe 2 O 3 - 97.3; Al 2 O 3 - 0.44; SiO 2 0.14; Sn - 0.033; Cu - 0.084; Pb - 0.048; Bi - 0.027; CaO - 1, 21; MgO - 0.43; Na 2 O - 0.007, S total -0.12.
  • the extraction of iron in the concentrate was 95.2%.
  • the cake obtained as a result of acid treatment was mixed with sodium carbonate and concentrated sodium hydroxide solution, taken in an amount of 40% of the amount cakes at a ratio of soda to alkali 3: 1, until a homogeneous wet mass is formed, after which the mass is dried at 250-300 0 C and sintered in crucibles at a temperature of 880 0 C for 2 hours.
  • the resulting spec had a composition in May.
  • the resulting pulp was filtered on a vacuum filter and the filtrate after reinforcing with hydrochloric acid to 4.4 geq / dm 3 and bringing to the initial volume was fed to leach a new portion of spec and this operation was repeated three times.
  • the composition of the solution obtained after each leaching step is shown below.
  • amorphous silica with a specific surface area of 120 m 2 / g (phenol) containing, wt.%: SiO 2 - 98.5; Al 2 O 3 -0.08; CaO 0.14; MgO - 0.2; Na - 0.05; Cl is 0.008.
  • the purified solution contained, g / dm 3 : Al 2 O 3 - 75.1; Fe 2 O 3 - 1.5; SiO 2 0.7; Sn is 0.02; TiO 2 -3.9; Cu - 0.07; Pb - 0.026; Bi was 0.008, W was 0.03 and was evaporated until the aluminum chloride hexahydrate was completely crystallized, which was calcined at 400-600 0 C, as a result of which an oxide product was obtained containing max. %: Al 2 O 3 - 56.8; Fe 2 O 3 - 1.9; SiO 2 0.2; Sn is 0.02; TiO 2 -1.3; CaO - 2.1;
  • the oxide product can be processed into commercial alumina using the Bayer method, the condensation of gases obtained by heat treatment of a chloride solution and calcination of aluminum chloride allows us to regenerate hydrochloric acid and reuse it in the process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne la métallurgie non ferreuse et notamment une technologie de transformation intégrée de matières premières oxydées contenant des oxydes d'aluminium et de silicium; elle peut s'utiliser dans la fabrication d'alumine, de silice et dans l'extraction de métaux lourds non ferreux à partir de matière premières difficiles à enrichir. L'invention permet d'augmenter l'extraction d'aluminium dans une solution lors de la lixiviation, l'extraction de silice sous forme de produits exploitables commercialement,notamment sous forme de silice amorphe hautement dispersée, de réduire la consommation de réactifs et d'énergie lors du frittage, d'effectuer l'extraction de métaux secondaires sous la forme de concentrés riches convenant pour la transformation complexe. Selon l'invention, dans ce procédé de transformation de matières premières à base de silicates d'aluminium, qui comprend son frittage avec le carbonate de sodium et un réactif possédant des propriétés basiques, la lixiviation du cake, l'extraction d'aluminium de la solution suivi de la fabrication d'alumine, on prévoit d'effectuer le frittage des matières premières en utilisant le sodium caustique en tant que réactif possédant des propriétés basiques, et de lixivier le cake obtenu avec une solution d'acide chlorhydrique de manière à obtenir une solution chlorurée et un résidu solide. On extrait à partir de la solution de chlorure des métaux plus électropositifs que l'aluminium, après quoi la solution chlorurée est soumise à un traitement thermique de manière à obtenir un produit oxydé riche en aluminium et une solution d'acide chlorhydrique, le résidu de lixiviation solide étant dissous dans une solution alcaline et la solution obtenue étant carbonée pour obtenir une solution de carbonate de sodium et un résidu d'alumine amorphe.
PCT/KZ2007/000015 2007-02-14 2007-11-19 Procédé de transformation intégrée de matières premières de silicates d'aluminium Ceased WO2008100123A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KZ20070228 2007-02-14
KZ2007/0228.1 2007-02-14

Publications (1)

Publication Number Publication Date
WO2008100123A1 true WO2008100123A1 (fr) 2008-08-21

Family

ID=39690291

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KZ2007/000015 Ceased WO2008100123A1 (fr) 2007-02-14 2007-11-19 Procédé de transformation intégrée de matières premières de silicates d'aluminium

Country Status (2)

Country Link
RU (1) RU2373152C2 (fr)
WO (1) WO2008100123A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2574252C2 (ru) * 2012-12-25 2016-02-10 Александр Равильевич Космухамбетов Способ переработки алюмосиликатного сырья

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2625470C1 (ru) * 2016-06-23 2017-07-14 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Способ очистки алюминийсодержащих хлоридных растворов
US11746021B2 (en) * 2019-04-18 2023-09-05 Nextchem, Llc High purity aluminum oxide via electrodialysis

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB857245A (en) * 1956-10-22 1960-12-29 Anaconda Co Improvements in production of alumina
US4224287A (en) * 1978-04-24 1980-09-23 Veb Mansfeld Kombinat Wilhelm Pieck Process for the preparation of pure aluminum oxide
WO1997022554A1 (fr) * 1995-12-15 1997-06-26 Mashal Alumina Industries Ltd. Procede pour recuperer de l'alumine et de la silice

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD284213A5 (de) * 1986-06-09 1990-11-07 Mansfeld Kombinat W Pieck Veb Verfahren zur herstellung von aluminiumoxid
GB2205558A (en) * 1987-05-18 1988-12-14 Lonhro Plc Recovery of alumina from aluminosilicates
CN1197765A (zh) * 1997-04-26 1998-11-04 钟正伟 一种用铝土矿提纯氧化铝的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB857245A (en) * 1956-10-22 1960-12-29 Anaconda Co Improvements in production of alumina
US4224287A (en) * 1978-04-24 1980-09-23 Veb Mansfeld Kombinat Wilhelm Pieck Process for the preparation of pure aluminum oxide
WO1997022554A1 (fr) * 1995-12-15 1997-06-26 Mashal Alumina Industries Ltd. Procede pour recuperer de l'alumine et de la silice

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LAINER A.I.: "Proizvodstvo glinozema, Gosudarstvennoe naucho-tekhnicheskoe idzatelstvo literatury po chernoi tsvetnoi metallurgii", M., 1961, pages 362 - 370 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2574252C2 (ru) * 2012-12-25 2016-02-10 Александр Равильевич Космухамбетов Способ переработки алюмосиликатного сырья

Also Published As

Publication number Publication date
RU2373152C2 (ru) 2009-11-20
RU2007143435A (ru) 2009-05-27

Similar Documents

Publication Publication Date Title
CN100567165C (zh) 活性金属氧化物的提取工艺方法
RU2597096C2 (ru) Способы получения оксида титана и различных других продуктов
KR102090348B1 (ko) 희토류 추출을 위한 시스템 및 방법
US4162294A (en) Process for working up nonferrous metal hydroxide sludge waste
AU2011376315B2 (en) Process for purifying zinc oxide
CN109790045B (zh) 冶炼级氧化铝生产方法(实施方式)
JP5370683B2 (ja) 銅硫化物からの銅の回収方法
CA1191698A (fr) Traitement des matieres alumineuses
RU2247788C1 (ru) Способ получения оксида скандия из красного шлама
AU2020343122A1 (en) Process for preparing alumina
WO2021097518A1 (fr) Production de composés d'aluminium à partir d'argile
EA009399B1 (ru) Способ обработки анодного шлама
US5997828A (en) Process for production of alumina from ore bodies containing aluminum
CA1324977C (fr) Procede de traitement des residus issus de la production hydrometallurgique du zinc
RU2483131C1 (ru) Способ получения оксида скандия из красного шлама
RU2373152C2 (ru) Способ комплексной переработки алюмосиликатного сырья
CA3231096A1 (fr) Procede de production d'alumine
WO2002010068A1 (fr) Production d'oxydes metalliques
RU2630117C1 (ru) Способ переработки отработанной углеродной футеровки алюминиевого электролизера
JP3796929B2 (ja) アルミドロス残灰の処理方法
RU2431690C1 (ru) Способ переработки отработанных химических источников тока марганцевоцинковой системы для комплексной утилизации
KR20160075688A (ko) 출발 물질들로부터 비소를 분리하는 방법 및 장치
CN105886797A (zh) 一种从多金属硫化物原料中制备海绵铟的方法
NO164665B (no) Fremgangsmaate for gjenvinning av aluminium fra avfallsmateriale.
US3923617A (en) Electrolytic recovery of zinc

Legal Events

Date Code Title Description
DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07860841

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07860841

Country of ref document: EP

Kind code of ref document: A1