WO2018233686A1 - Méthode de préparation d'oxyde d'aluminium de niveau métallurgique par traitement de la bauxite de qualité moyenne et basse au moyen d'un processus thermique alcalin en une étape d'andradite - Google Patents

Méthode de préparation d'oxyde d'aluminium de niveau métallurgique par traitement de la bauxite de qualité moyenne et basse au moyen d'un processus thermique alcalin en une étape d'andradite Download PDF

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WO2018233686A1
WO2018233686A1 PCT/CN2018/092422 CN2018092422W WO2018233686A1 WO 2018233686 A1 WO2018233686 A1 WO 2018233686A1 CN 2018092422 W CN2018092422 W CN 2018092422W WO 2018233686 A1 WO2018233686 A1 WO 2018233686A1
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calcium
medium
carbon
liquid
alumina
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PCT/CN2018/092422
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English (en)
Chinese (zh)
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于海燕
潘晓林
吴艳
毕诗文
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东北大学
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    • 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

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  • the invention belongs to the technical field of alumina production, and particularly relates to a method for producing metallurgical grade alumina in a medium-low grade bauxite by a one-step alkali heat treatment of calcium iron garnet.
  • the treatment methods of low-grade bauxite mainly include Bayer method, sintering method and Bayer-sintering method.
  • the enhanced Bayer method is a method based on the Bayer method to adapt to the treatment of low-grade bauxite, mainly including the beneficiation Bayer method and the lime Bayer method.
  • the beneficiation Bayer method uses the combination of smelting and smelting to treat medium and low grade bauxite.
  • the process is relatively simple, but there are problems such as difficulty in physical beneficiation, large consumption of raw ore, low recovery rate of alumina, and influence of Bayer process by flotation reagents.
  • the ore dressing process produces a large amount of aluminum and silicon tailings that are less than 2, which can not be used, resulting in great waste of resources.
  • the lime Bayer method is based on the Bayer method to increase the alkali consumption by adding excess lime, but the amount of lime added is large. The dissolution rate of alumina is greatly reduced, the red mud discharge is increased, and the red mud sedimentation load is increased.
  • the sintering method mainly includes the soda lime sintering method and the lime sintering method, but the high energy consumption and high production cost are the main shortcomings of the development.
  • the soda lime sintering method belongs to wet compounding and wet sintering.
  • Bayer-sintering combined method includes series method, parallel method and hybrid method, which can deal with medium and low grade bauxite, but it has complicated problems and high energy consumption. It has been basically replaced by Bayer method.
  • Other processes such as acid method and acid-base combination method mainly stay in the laboratory research stage, and there are many problems such as poor quality of alumina products and serious corrosion of equipment.
  • an object of the present invention is to provide a method for producing a metallurgical grade alumina in a medium-grade low-grade bauxite by a one-step alkali thermal treatment of calcium iron garnet, and adding sodium ferrite during high-temperature dissolution ( The method of calcium ferrite) and active lime, aluminum enters the solution in the form of sodium aluminate during high temperature dissolution, and the silicon remains in the dissolution slag in the form of calcium iron garnet.
  • the method of the invention can greatly improve the dissolution rate of the metallurgical grade alumina, and at the same time, the dissolution slag contains almost no alkali, and has the characteristics of short process and high efficiency, and the material realizes zero discharge in the whole process.
  • the main technical solutions adopted by the present invention include:
  • a method for producing metallurgical grade alumina of medium and low grade bauxite by one-step alkali heat treatment of calcium iron garnet comprising the following steps,
  • step S7 The carbon mother liquor obtained in step S5 is causticized with calcium oxide to obtain a caustic slurry, and the caustic slurry is subjected to liquid-solid separation to obtain a polymer ratio sodium aluminate solution and calcium carbonate, and the ratio of the polymer is The sodium aluminate solution is prepared as the circulating mother liquor in step S2.
  • the medium-low grade bauxite has a silicon to aluminum ratio of 2-6.
  • the total amount of iron, aluminum, calcium and silicon present in each form is determined by the oxide, and the formulation is as follows:
  • the mass ratio of the total amount of iron oxide to the total amount of alumina is 0.2 to 0.6:1;
  • the molar ratio of the total amount of calcium oxide to the total amount of iron oxide is from 3 to 6:1.
  • the liquid-solid ratio of the raw material slurry is 2 to 5:1.
  • the concentration of caustic in the circulating mother liquor in step S2 is 150 to 250 g/L, and the molecular ratio is 5 to 25.
  • the temperature of the dissolution reaction in the step S3 is 150 to 250 ° C, and the reaction time is 0.5 to 2 h.
  • step S5 carbon dioxide gas is introduced into the sodium aluminate obtained after elution and seed crystals are added to carry out carbon fractionation to obtain a slurry of crude aluminum hydroxide, followed by liquid-solid separation to obtain a carbon mother liquor and crude aluminum hydroxide.
  • step S5 the carbon content temperature is 60 to 90 ° C, the carbon end point is a decomposition rate of 90% or more, and the seed crystal addition coefficient is 0 to 1.0.
  • the method further includes:
  • Step S8 washing the eluted slag in step S4 and solid-liquid separation to obtain calcium garnet type slag and washing liquid;
  • Step S9 The washing liquid is used to dilute the dissolved slurry in step S4.
  • the method further comprises the step S10: calcining and decomposing the calcium carbonate obtained in the step S7 to obtain carbon dioxide gas and calcium oxide, and the obtained carbon dioxide gas is used for carbon separation in the step S5, and the obtained calcium oxide is used in the step.
  • Caustic treatment in S7 is used in the step S10.
  • the sodium ferrite in the step S1 is formed by sintering an iron-containing raw material and an industrial carbon base; the calcium ferrite is obtained by sintering the iron-containing raw material and the lime.
  • the method of the present invention produces a dissolution slag base content of 0.5% or less, and the slag contains almost no alkali;
  • the method of the invention has the characteristics of short process and high efficiency, and the material realizes zero discharge in the whole process.
  • FIG. 1 is a process flow diagram of a method for producing a metallurgical grade alumina in a low-grade bauxite by a one-step alkali thermal treatment of calcium iron garnet according to the present invention.
  • the ratio of silicon to aluminum (hereinafter referred to as A/S) is 2-6.
  • A/S the ratio of silicon to aluminum
  • F/A the mass ratio of the total amount of iron oxide to the total amount of alumina
  • C/F the total amount of calcium oxide
  • L/S The raw material slurry solid mass ratio
  • Calcium iron garnet one-step alkali heat treatment of medium-low grade bauxite to produce metallurgical grade alumina means that the dissolved slag is calcium iron garnet type slag, and the one-step alkali heat method refers to the oxidation of lye (circulating mother liquor)
  • the aluminum is subjected to a one-step hydrothermal dissolution treatment, and the produced product is metallurgical grade alumina.
  • a medium-low grade bauxite is used, and the main chemical components (mass percentage, wt%) are: alumina (Al 2 O 3 ) 60.60%, silica (SiO 2 ) 17.5%, others are impurities, and aluminum thereof
  • the silicon ratio is 3.5;
  • Calcium ferrite is sintered from iron-containing raw materials and lime
  • the concentration of caustic in the circulating mother liquor is 200 g / L, the molecular ratio is 25;
  • the extraction rate of alumina can reach 83%
  • step S7 The carbon mother liquor obtained in step S5 is causticized with lime milk to obtain a caustic slurry, and the caustic slurry is subjected to liquid-solid separation to obtain a polymer ratio sodium aluminate solution and calcium carbonate.
  • the sodium aluminate solution is prepared as the circulating mother liquor in step S2;
  • the carbon mother liquor is treated, and the obtained polymer can be used as a circulating mother liquor to participate in other process processes after adjusting the sodium aluminate solution, so that the process has no efflux and no pollution;
  • step S8 washing the eluted slag in step S4 and solid-liquid separation to obtain calcium garnet type slag and washing liquid;
  • the alkali-free calcium iron garnet type slag is obtained after treatment, so that the silicon and the added iron and calcium remain in the dissolution slag in the form of calcium iron garnet, thereby reducing the alkali content in the slag;
  • step S9 using the washing liquid for diluting the dissolved pulp in step S4;
  • the generated washing liquid is waste liquid, but the washing liquid is returned to the step S4 for diluting the dissolved pulp, which not only reduces the treatment and discharge of the waste liquid, but also achieves the effect of recycling, and achieves the recovery of the material. Reuse;
  • the decomposition and reuse of calcium carbonate realizes the recycling of resources, avoids waste of resources, and saves costs.
  • the resulting metallurgical grade alumina is the product.
  • a medium-low grade bauxite is used, and the main chemical components (mass percentage, wt%) are: alumina (Al 2 O 3 ) 65.22%, silica (SiO 2 ) 12.66%, others are impurities, and aluminum thereof
  • the silicon ratio is 5.15;
  • Sodium ferrite is sintered from iron-containing raw materials and industrial carbon base
  • the concentration of caustic in the circulating mother liquor was 230 g/L and the molecular ratio was 20.
  • the extraction rate of alumina can reach 83.7%
  • step S7 The carbon mother liquor obtained in step S5 is causticized with calcium oxide to obtain a caustic slurry, and the caustic slurry is subjected to liquid-solid separation to obtain a polymer ratio sodium aluminate solution and calcium carbonate, and the ratio of the polymer is The sodium aluminate solution is prepared as the circulating mother liquor in step S2;
  • the carbon mother liquor is treated, and the obtained polymer can be used as a circulating mother liquor to participate in other process processes after adjusting the sodium aluminate solution, so that the process has no efflux and no pollution;
  • step S8 washing the eluted slag in step S4 and solid-liquid separation to obtain calcium garnet type slag and washing liquid;
  • the alkali-free calcium iron garnet type slag is obtained after treatment, so that the silicon and the added iron and calcium remain in the dissolution slag in the form of calcium iron garnet, thereby reducing the alkali content in the slag;
  • step S9 using the washing liquid for diluting the dissolved pulp in step S4;
  • the generated washing liquid is waste liquid, but the washing liquid is returned to the step S4 for diluting the dissolved pulp, which not only reduces the treatment and discharge of the waste liquid, but also achieves the effect of recycling, and achieves the recovery of the material. Reuse;
  • the decomposition and reuse of calcium carbonate realizes the recycling of resources, avoids waste of resources, and saves costs.
  • the resulting metallurgical grade alumina is the product.
  • the method of the invention has the characteristics of short process and high efficiency, and the final products of the whole process are metallurgical grade alumina and alkali-free calcium iron garnet type slag, and the rest of the materials are recycled, and the materials in the whole process realize zero discharge.
  • This alkali-free calcium iron garnet type slag has been effectively utilized due to the reduction of alkali content, such as calcium ferrite additive used in steelmaking process, self-stressing, high strength, quick-setting Portland cement and highways, airports. Ideal aggregate for high-strength concrete such as runways, and as a potential raw material for higher value-added products such as glass-ceramics and silicon fertilizers.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne une méthode de préparation d'oxyde d'aluminium de niveau métallurgique par traitement de bauxite de qualité moyenne et basse au moyen d'un processus thermique alcalin en une étape d'andradite. La méthode comprend les étapes suivantes : S1, concasser et broyer finement la bauxite de qualité moyenne et basse en poudre minérale ; S2, mélanger la poudre minérale, la ferrite de sodium ou la ferrite de calcium, la chaux activée et le liquide mère en circulation pour préparer de la pulpe minérale de matière première ; S3, permettre à la pulpe minérale de matière première d'avoir une réaction de dissolution thermique alcaline ; S4, diluer la pulpe minérale dissoute, et permettre au liquide dilué de subir une séparation liquide-solide ; S5, introduire un gaz de dioxyde de carbone dans une solution d'aluminate de sodium pour effectuer une décomposition par carbonatation, de façon à obtenir un hydroxyde d'aluminium brut et un liquide mère décomposé par carbonatation ; et S6, permettre à l'hydroxyde d'aluminium brut de subir un traitement de procédé bayer, de façon à obtenir l'oxyde d'aluminium de niveau métallurgique ; et S7, caustifier le liquide mère décomposé par carbonatation en utilisant du lait de chaux, et effectuer une séparation liquide-solide pour obtenir une solution d'hydroxyde de sodium, et utiliser la solution d'hydroxyde de sodium mélangée en tant que liquide mère en circulation à l'étape 2. Dans la méthode, en ajoutant la chaux et la ferrite de sodium ou la ferrite de calcium dans une procédure de dissolution, des scories de type andradite au lieu de scories dissoutes classiques sont générées dans la procédure de dissolution ; le taux de dissolution de l'oxyde d'aluminium peut être considérablement amélioré ; en outre, l'oxyde d'aluminium de niveau métallurgique est préparé ; la méthode présente les caractéristiques d'une procédure courte et d'une efficacité élevée, et aucun rejet de matériau n'est obtenu.
PCT/CN2018/092422 2017-06-23 2018-06-22 Méthode de préparation d'oxyde d'aluminium de niveau métallurgique par traitement de la bauxite de qualité moyenne et basse au moyen d'un processus thermique alcalin en une étape d'andradite WO2018233686A1 (fr)

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CN201710488114.9A CN107188209A (zh) 2017-06-23 2017-06-23 钙铁榴石一步碱热法处理中低品位铝土矿生产冶金级氧化铝的方法
CN201710488114.9 2017-06-23

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Publication number Priority date Publication date Assignee Title
CN107188209A (zh) * 2017-06-23 2017-09-22 东北大学 钙铁榴石一步碱热法处理中低品位铝土矿生产冶金级氧化铝的方法
CN107857285A (zh) * 2017-12-01 2018-03-30 东北大学设计研究院（有限公司） 一种利用低品位含铝原料生产铝酸钠晶体的方法
CN110436492B (zh) * 2019-08-19 2021-10-19 河北科技大学 一种综合利用低品位铝资源的方法
CN111039299B (zh) * 2019-12-13 2020-10-30 潘爱芳 一种铅锌尾矿高效资源化的方法

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US2992893A (en) * 1957-01-15 1961-07-18 Pechiney Prod Chimiques Sa Process for treating aluminum ores
CN101054626A (zh) * 2007-05-31 2007-10-17 中国铝业股份有限公司 一种一水硬铝石型铝土矿的溶出方法
CN101117230A (zh) * 2007-07-12 2008-02-06 中国铝业股份有限公司 一种拜耳法溶出方法
CN104445310A (zh) * 2013-09-25 2015-03-25 贵阳铝镁设计研究院有限公司 一种全湿法碱性体系下处理中低品位铝土矿的新工艺
CN107188209A (zh) * 2017-06-23 2017-09-22 东北大学 钙铁榴石一步碱热法处理中低品位铝土矿生产冶金级氧化铝的方法

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Publication number Priority date Publication date Assignee Title
US2992893A (en) * 1957-01-15 1961-07-18 Pechiney Prod Chimiques Sa Process for treating aluminum ores
CN101054626A (zh) * 2007-05-31 2007-10-17 中国铝业股份有限公司 一种一水硬铝石型铝土矿的溶出方法
CN101117230A (zh) * 2007-07-12 2008-02-06 中国铝业股份有限公司 一种拜耳法溶出方法
CN104445310A (zh) * 2013-09-25 2015-03-25 贵阳铝镁设计研究院有限公司 一种全湿法碱性体系下处理中低品位铝土矿的新工艺
CN107188209A (zh) * 2017-06-23 2017-09-22 东北大学 钙铁榴石一步碱热法处理中低品位铝土矿生产冶金级氧化铝的方法

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