WO2018233690A1 - Method for preparing sodium aluminate by treating bayer red mud by using one-step alkali heat process of andradite - Google Patents

Method for preparing sodium aluminate by treating bayer red mud by using one-step alkali heat process of andradite Download PDF

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WO2018233690A1
WO2018233690A1 PCT/CN2018/092427 CN2018092427W WO2018233690A1 WO 2018233690 A1 WO2018233690 A1 WO 2018233690A1 CN 2018092427 W CN2018092427 W CN 2018092427W WO 2018233690 A1 WO2018233690 A1 WO 2018233690A1
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sodium aluminate
red mud
calcium
solid
bayer process
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PCT/CN2018/092427
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French (fr)
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
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • 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
    • C01B33/20—Silicates
    • 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
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
    • C01F7/066—Treatment of the separated residue

Definitions

  • the invention belongs to the technical field of sodium aluminate production, and particularly relates to a method for producing sodium aluminate by the Bayer process red mud by a one-step alkali heat treatment of calcium iron garnet.
  • Red mud is the waste residue produced by alumina in the production process. It is red because it contains a lot of iron oxide, so it is called red mud.
  • the output of red mud varies with ore grade, production method and technical level. Now, for every 1 t of alumina produced, 1.0 to 1.7 tons of red mud will be produced, and the accumulated red mud is more than 300 million tons. A large amount of red mud can not be effectively utilized, and can only rely on large-area yard stacking, which not only occupies a large amount of land, but also causes serious pollution to the environment because of the high alkalinity of red mud. As of 2016, the cumulative stockpiles of more than 400 million tons have become a major environmental hazard.
  • red mud composition Due to the different production methods of alumina, the red mud composition, nature and phase of the production are different.
  • the alkali content of red mud produced by Bayer method is high; the content of CaO in red mud produced by sintering method and combined method is high, and the content of alkali and iron is low.
  • This difference determines the different methods of red mud utilization.
  • domestic and foreign researchers have carried out a lot of fruitful research on the comprehensive utilization of red mud, including two aspects: one is to extract useful components in red mud, and recover high-priced metals such as iron oxide, aluminum oxide, sodium oxide, and oxidation. Silicon, calcium oxide, zinc oxide, etc.
  • the second is to use red mud as a raw material for the manufacture of low value-added building materials, such as wall materials, cement, glass-ceramics, etc.
  • low value-added building materials such as wall materials, cement, glass-ceramics, etc.
  • Lu Guilin et al. studied the process of leaching alumina from red mud with hydrochloric acid, using secondary leaching, in which the leaching rate of alumina reached 89.0%.
  • Zheng Xiufang treated the soaked Bayer red mud and sintered silicon residue with soda lime sintering method. The dissolution rates of alumina and sodium oxide were greater than 95% and 97%, respectively.
  • the methods for removing alkali from red mud include lime de-alkali method, water-eluting alkali method, salt de-alkali method, suspension carbonization and alkali removal method, lime-sulfuric acid combined alkali removal method, and other new alkali removal methods, such as ion film.
  • De-alkali method, bacterial de-alkali method and fire method for alkali removal all have different degrees of problems.
  • the lime de-alkali method is not satisfactory under normal pressure, but the cost is high under high pressure; the water washing method has low removal efficiency, and only the alkali is washed away.
  • the present invention provides a method for producing sodium aluminate by a one-step alkali thermal treatment of Bayer red mud by a calcium iron garnet, and uses a one-step alkali heat method to use red mud produced by the alumina industry as a raw material. , mixed with sodium ferrite (or calcium ferrite) and active lime, dissolved at high temperature, so that aluminum and sodium in red mud enter the solution in the form of sodium aluminate, while silicon, iron and calcium remain in the form of calcium iron garnet. Dissolve in the slag.
  • the method of the invention recovers the alumina in the red mud, realizes the recycling of the solid waste, and achieves the effect of green utilization of resources.
  • the main technical solutions adopted by the present invention include:
  • the polymer is prepared by a sodium aluminate solution to prepare a circulating mother liquid used in the step S1.
  • the total amount of iron, aluminum, calcium and silicon present in each form is determined by oxide, respectively, and the formulation is as follows:
  • the molar ratio of the total amount of iron oxide to the total amount of alumina is 0.5 to 1.5:1.
  • the molar ratio of the total amount of calcium oxide to the total amount of silicon oxide is 1 to 3:1.
  • the raw material slurry has a liquid to solid ratio of 2 to 5:1.
  • the polymer is prepared by reacting a caustic alkali concentration with a sodium aluminate solution to obtain a circulating mother liquor, wherein the concentration of the caustic in the circulating mother liquor is 150 to 250 g/L, and the molecular ratio is 5 to 25.
  • the temperature of the dissolution reaction in the step S2 is 150 to 250 ° C, and the reaction time is 0.5 to 2 h.
  • the method further includes:
  • Step S6 washing the eluted slag in step S3 and solid-liquid separation to obtain calcium garnet type slag and washing liquid;
  • Step S7 The washing liquid is used to dilute the dissolved ore slurry in step S3.
  • step S4 specifically includes the following steps:
  • the crystallization temperature in the step S41 is 85 to 40 ° C
  • the crystallization time is 10 to 30 h
  • the seed crystal addition amount is 10 to 200 g/L.
  • 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 invention recovers the alumina and the sodium oxide in the red mud, so that the alkali content in the dissolution slag is reduced to less than 0.5%, and the main component of the dissolution slag is calcium iron garnet, and the alkali-free calcium iron garnet is suitable for refining.
  • the calcium ferrite additive in the steel process the ideal aggregate for self-stressing, high-strength, quick-setting Portland cement and high-strength concrete such as highways and airport runways, and also high value-added products such as glass-ceramics and silicon fertilizers.
  • this method can greatly reduce the red mud, realize the recycling of red mud, and achieve the effect of green utilization of resources; the product sodium aluminate can be used as a reagent to prepare other aluminum-containing products, or Metallurgical grade alumina is prepared as a feedstock by a simple Bayer process.
  • FIG. 1 is a process flow diagram of a method for producing sodium aluminate by a Bayer process red mud by a one-step alkali thermal treatment of calcium iron garnet of the present invention.
  • the red mud used in the embodiment of the present invention is a Bayer process red mud, and the red mud contains alumina and silica.
  • the red mud contains alumina and silica.
  • F/A the molar ratio of total iron oxide to total alumina
  • calcium oxide to total silica the molar ratio of total calcium oxide to total silica.
  • C / S raw material slurry solid mass ratio
  • L / S raw material slurry solid mass ratio
  • Calcium iron garnet one-step alkali heat treatment of Bayer process red mud production of sodium aluminate means that the dissolution slag is calcium iron garnet type slag
  • one-step alkali heat method refers to the use of lye (cycle mother liquor) to carry out one step of alumina
  • the method of hydrothermal dissolution treatment, the target product produced is sodium aluminate.
  • the hydraulic aluminite Bayer process red mud is used, and the main chemical components (mass percentage, wt%) are: alumina (Al 2 O 3 ) 21.62%, silicon dioxide (SiO 2 ) 16.11%, sodium oxide (Na) 2 O) 7.08%, calcium oxide (CaO) 16.50%, total iron (TFe) 14.80%, and its aluminum to silicon ratio is 1.34;
  • Sodium ferrite is sintered from iron-containing raw materials and industrial caustic soda
  • the concentration of caustic in the circulating mother liquor is 240 g / L, the molecular ratio is 25;
  • the concentration of the caustic alkali and the molecular ratio in the sodium aluminate solution produced in this step need to be adjusted to meet the parameter requirements of the circulating mother liquor, and is used for formulating the raw material slurry and performing the dissolution reaction;
  • step S6 washing the eluted slag in step S3 and solid-liquid separation to obtain calcium garnet type dissolution slag and washing liquid;
  • the alkali-free calcium iron garnet type slag is obtained after treatment, so that the silicon in the raw red mud and the added iron and calcium remain in the dissolution slag in the form of calcium iron garnet, and the calcium iron garnet type slag
  • the alkali content falls below 0.5% and the aluminum to silicon ratio drops to 0.5.
  • alkali-free calcium iron garnet type slag is effectively utilized due to the reduction of alkali content, such as calcium ferrite additive used in the steelmaking process, self-stressing, high Ideal aggregates for high-strength concrete such as strength, quick-setting Portland cement and highways, airport runways, and as potential raw materials for higher value-added products such as glass-ceramics and silicon fertilizers;
  • alkali content such as calcium ferrite additive used in the steelmaking process, self-stressing, high Ideal aggregates for high-strength concrete such as strength, quick-setting Portland cement and highways, airport runways, and as potential raw materials for higher value-added products such as glass-ceramics and silicon fertilizers;
  • step S7 using the washing liquid for diluting the dissolved pulp in step S3;
  • the washing liquid produced in this step is waste liquid, but the washing liquid is returned to the step S3 for diluting and dissolving the pulp, which not only reduces the treatment and discharge of the waste liquid, but also achieves the effect of recycling, and achieves the recycling of the material. use.
  • the obtained sodium aluminate is a product.
  • the filtered slag is an alkali-free calcium iron garnet type slag, and the rest of the materials are recycled, which meets the requirements for comprehensive utilization of resources.
  • This embodiment adopts Bayer process red mud, the main chemical composition (mass percentage, wt%) is: alumina (Al 2 O 3 ) 23.35%, silica (SiO 2 ) 23.23%, sodium oxide (Na 2 O) 15.61 %, calcium oxide (CaO) 0.51%, total iron (TFe) 16.16%, titanium dioxide (TiO 2 ) 5.37%, and its aluminum to silicon ratio is 1.01;
  • Calcium ferrite is sintered from iron-containing raw materials and lime
  • the concentration of caustic in the circulating mother liquor is 240 g / L, the molecular ratio is 25;
  • the alumina extraction rate can reach 80% or more
  • the concentration of the caustic alkali and the molecular ratio in the sodium aluminate solution produced in this step need to be adjusted to meet the parameter requirements of the circulating mother liquor, and is used for formulating the raw material slurry and performing the dissolution reaction;
  • step S6 washing the eluted slag in step S3 and solid-liquid separation to obtain calcium garnet type slag and washing liquid;
  • the alkali-free calcium iron garnet-type red mud residue is obtained after treatment, so that the silicon in the red mud and the added iron and calcium remain in the dissolution slag in the form of calcium iron garnet, and the red garnet type red mud
  • the sodium content in the slag was reduced to 0.11% and the aluminum to silicon ratio was reduced to 0.5. It not only reduces the alkali content in the red mud, but also makes the alkali-free calcium iron garnet-type red mud residue effectively utilized due to the reduction of the alkali content, such as calcium ferrite additive used in the steelmaking process, self-stressing, high strength.
  • Ideal aggregates for high-strength concrete such as quick-setting Portland cement and highways and airport runways, and as potential raw materials for higher value-added products such as glass-ceramics and silicon fertilizers;
  • step S7 using the washing liquid for diluting the dissolved pulp in step S3;
  • the washing liquid produced in this step is waste liquid, but the washing liquid is returned to the step S3 for diluting and dissolving the pulp, which not only reduces the treatment and discharge of the waste liquid, but also achieves the effect of recycling, and achieves the recycling of the material. use.
  • the obtained sodium aluminate is a product.
  • the filtered slag is an alkali-free calcium iron garnet-type red mud slag, and the rest of the materials are recycled, which meets the requirements for comprehensive utilization of resources.
  • the method of the invention not only recovers the alumina in the red mud, but also reduces the alkali content in the red mud, realizes the recycling of the solid waste, and achieves the effect of green utilization of resources.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • Analytical Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Treatment Of Sludge (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Compounds Of Iron (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

A method for preparing sodium aluminate by treating bayer red mud by using a one-step alkali heat process of andradite. The method comprises the following steps: S1: mixing red mud, sodium ferrite or calcium ferrite, active lime and a circulating mother liquid to prepare raw material mineral pulp; S2: allowing the raw material mineral pulp to carry out an alkali heat dissolution reaction to obtain dissolved-out mineral pulp; S3: diluting the dissolved-out mineral pulp to obtain a diluted solution, carrying out liquid-solid separation to obtain dissolved-out slag and a dissolved-out solution; S4: evaporating the dissolved-out solution, adding seed crystals, crystallizing and carrying out solid-liquid separation to obtain a sodium aluminate solid and a high-molecular-ratio sodium aluminate solution; and S5: blending the high-molecular-ratio sodium aluminate solution to prepare the circulating mother liquid used in step S1.

Description

钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法Method for producing sodium aluminate by Bayer process red mud by one-step alkali heat treatment of calcium iron garnet 技术领域Technical field
本发明属于铝酸钠生产的技术领域，具体涉及一种钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法。The invention belongs to the technical field of sodium aluminate production, and particularly relates to a method for producing sodium aluminate by the Bayer process red mud by a one-step alkali heat treatment of calcium iron garnet.
背景技术Background technique
赤泥是氧化铝在生产过程中产生的废渣，因含有大量氧化铁而呈红色，故被称为赤泥。赤泥的产出量，因矿石品位、生产方法、技术水平而异。现在每生产1t氧化铝，伴随着就会产生1.0～1.7t的赤泥，目前累积堆存的赤泥超过三亿吨。大量的赤泥不能得到有效利用，只能依靠大面积的堆场堆放，不但占用了大量土地，同时因为赤泥的高碱性，也对环境造成了严重污染。截止到2016年，累计堆存量达4亿吨以上，成为一大环保隐患。Red mud is the waste residue produced by alumina in the production process. It is red because it contains a lot of iron oxide, so it is called red mud. The output of red mud varies with ore grade, production method and technical level. Now, for every 1 t of alumina produced, 1.0 to 1.7 tons of red mud will be produced, and the accumulated red mud is more than 300 million tons. A large amount of red mud can not be effectively utilized, and can only rely on large-area yard stacking, which not only occupies a large amount of land, but also causes serious pollution to the environment because of the high alkalinity of red mud. As of 2016, the cumulative stockpiles of more than 400 million tons have become a major environmental hazard.
由于氧化铝的生产方法不同，其生产的赤泥成分、性质、物相各异。拜耳法产生的赤泥中碱金属含量高；烧结法和联合法产生的赤泥CaO含量高，碱和铁含量较低。这种差异决定了赤泥利用的不同方法。国内外学者在赤泥的综合利用方面进行了大量卓有成效的研究，主要包括两个方面：一是提取赤泥中的有用组分，回收高价金属，如回收氧化铁、氧化铝、氧化钠、氧化硅、氧化钙、氧化锌等。二是将赤泥作为原材料用于制造低附加值的建筑材料，如做墙体材料、水泥、微晶玻璃等。但是由于赤泥中的碱含量较高，不利于赤泥在建筑材料中的应用。Due to the different production methods of alumina, the red mud composition, nature and phase of the production are different. The alkali content of red mud produced by Bayer method is high; the content of CaO in red mud produced by sintering method and combined method is high, and the content of alkali and iron is low. This difference determines the different methods of red mud utilization. Domestic and foreign scholars have carried out a lot of fruitful research on the comprehensive utilization of red mud, including two aspects: one is to extract useful components in red mud, and recover high-priced metals such as iron oxide, aluminum oxide, sodium oxide, and oxidation. Silicon, calcium oxide, zinc oxide, etc. The second is to use red mud as a raw material for the manufacture of low value-added building materials, such as wall materials, cement, glass-ceramics, etc. However, due to the high alkali content in the red mud, it is not conducive to the application of red mud in building materials.
目前关于从赤泥中回收铝的方法主要有浮选，石灰烧结法及浸出等工艺。范先锋等人对拜耳法赤泥进行了浮选工艺研究。小型闭路浮选试验表明，可以丢弃45.74％的赤泥，回收65.52％的Al 2O 3，其中铝硅比为7.53的占62.01％，可直接返回拜尔法溶浸，而铝硅比4.78的占2.86％，可作为烧结法的原料。周秋生等采用烧结法处理拜耳法高铁赤泥回收其中的氧化铝，熟料中的Al 2O 3回收率可达85％～90％。鲁桂林等研究了采 用盐酸浸出赤泥中的氧化铝的工艺，采用二次浸出，其中氧化铝的浸出率可达89.0％。郑秀芳用碱石灰烧结法处理泡合的拜耳法赤泥和烧结法硅渣，氧化铝和氧化钠溶出率分别大于95％和97％。 At present, there are mainly methods for recovering aluminum from red mud, such as flotation, lime sintering and leaching. Fan Xianfeng and others conducted a flotation process on Bayer's red mud. Small closed-circuit flotation tests show that 45.74% of red mud can be discarded, and 65.52% of Al 2 O 3 can be recovered, of which 62.01% of aluminum-silicon ratio is 7.53, which can be directly returned to Bayer process, while aluminum-silicon ratio is 4.78. It accounts for 2.86% and can be used as a raw material for the sintering method. Zhou Qiusheng et al. used the sintering method to treat the alumina in the Bayer process high-iron red mud, and the recovery rate of Al 2 O 3 in the clinker can reach 85% to 90%. Lu Guilin et al. studied the process of leaching alumina from red mud with hydrochloric acid, using secondary leaching, in which the leaching rate of alumina reached 89.0%. Zheng Xiufang treated the soaked Bayer red mud and sintered silicon residue with soda lime sintering method. The dissolution rates of alumina and sodium oxide were greater than 95% and 97%, respectively.
关于赤泥脱碱的方法主要有石灰脱碱法、水洗脱碱法、盐类脱碱法、悬浮碳化脱碱法、石灰-硫酸联合脱碱法，及其他新型脱碱方法，如离子膜脱碱法、细菌脱碱法和火法脱碱。然而，上述脱碱方法均存在不同程度的问题，在常压下石灰脱碱法效果不理想，而在高压下则成本较高；水洗法脱除效率较低，仅能洗掉附着碱而对结合碱无效；氯化镁和氯化铵脱碱法中的氯离子会腐蚀设备，并不利于后续赤泥的应用；CO 2悬浮脱碱法，其中的CO 2仅对赤泥中的Na 2O·Al 2O 3、Na 2SiO 3和Na 2CO 3起作用，却对Na 2O·Al 2O 3·1.7SiO 2·nH 2O不起作用，而赤泥中大部分的钠是以Na 2O·Al 2O 3·1.7SiO 2·nH 2O的形态存在，因此该方法脱除效率不高；石灰一硫酸联合脱碱法中，酸法与碱法并存，易浪费原料，同时工艺较复杂，且使用了高压釜，成本较高。 The methods for removing alkali from red mud include lime de-alkali method, water-eluting alkali method, salt de-alkali method, suspension carbonization and alkali removal method, lime-sulfuric acid combined alkali removal method, and other new alkali removal methods, such as ion film. De-alkali method, bacterial de-alkali method and fire method for alkali removal. However, the above-mentioned alkali removal methods all have different degrees of problems. The lime de-alkali method is not satisfactory under normal pressure, but the cost is high under high pressure; the water washing method has low removal efficiency, and only the alkali is washed away. The combination of alkali is ineffective; the chloride ion in the magnesium chloride and ammonium chloride de-alkali method will corrode the equipment, which is not conducive to the application of the subsequent red mud; the CO 2 suspension de-alkali method, in which the CO 2 is only for the Na 2 O in the red mud. Al 2 O 3 , Na 2 SiO 3 and Na 2 CO 3 act but do not work for Na 2 O·Al 2 O 3 ·1.7SiO 2 ·nH 2 O, while most of the sodium in the red mud is Na 2 O·Al 2 O 3 ·1.7SiO 2 ·nH 2 O exists in the form, so the removal efficiency of the method is not high; in the lime-sulfuric acid combined with the alkali removal method, the acid method and the alkali method coexist, and the raw materials are easily wasted, and the process is It is more complicated and uses an autoclave at a higher cost.
发明内容Summary of the invention
(一)要解决的技术问题(1) Technical problems to be solved
为了解决现有技术的上述问题，本发明提供一种钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，利用一步碱热法，将氧化铝工业产生的赤泥作为原料，与铁酸钠(或铁酸钙)及活性石灰混合后高温溶出，使赤泥中的铝和钠以铝酸钠形式进入溶液，而硅、铁和钙以钙铁榴石的形式留在溶出渣中。本发明的方法回收了赤泥中的氧化铝，实现了固体废弃物的回收利用，达到了资源绿色利用的效果。In order to solve the above problems of the prior art, the present invention provides a method for producing sodium aluminate by a one-step alkali thermal treatment of Bayer red mud by a calcium iron garnet, and uses a one-step alkali heat method to use red mud produced by the alumina industry as a raw material. , mixed with sodium ferrite (or calcium ferrite) and active lime, dissolved at high temperature, so that aluminum and sodium in red mud enter the solution in the form of sodium aluminate, while silicon, iron and calcium remain in the form of calcium iron garnet. Dissolve in the slag. The method of the invention recovers the alumina in the red mud, realizes the recycling of the solid waste, and achieves the effect of green utilization of resources.
(二)技术方案(2) Technical plan
为了达到上述目的，本发明采用的主要技术方案包括：In order to achieve the above object, the main technical solutions adopted by the present invention include:
一种钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，包括下述步骤，Method for producing sodium aluminate by Bayer process red mud by one-step alkali heat treatment of calcium iron garnet, comprising the following steps
S1：将赤泥、铁酸钠(或铁酸钙)、活性石灰及循环母液混合制备 成原料矿浆；S1: mixing red mud, sodium ferrite (or calcium ferrite), active lime and circulating mother liquor into raw material pulp;
S2：将原料矿浆进行碱热溶出反应，反应结束后得到溶出矿浆；S2: subjecting the raw material slurry to an alkali thermal elution reaction, and after the reaction is finished, obtaining a dissolved pulp;
S3：将溶出矿浆稀释得到稀释液，将稀释液进行液固分离，得到溶出渣和溶出液，其中溶出液为铝酸钠溶液；S3: diluting the dissolved slurry to obtain a diluent, and performing liquid-solid separation on the diluted solution to obtain a dissolution slag and an eluate, wherein the eluate is a sodium aluminate solution;
S4：将铝酸钠溶液蒸发后，加晶种结晶并固液分离，得到铝酸钠固体和高分子比铝酸钠溶液；S4: after evaporating the sodium aluminate solution, adding seed crystals and separating the solid and liquid to obtain a sodium aluminate solid and a polymer ratio sodium aluminate solution;
S5：将所述高分子比铝酸钠溶液进行调制，制成步骤S1中所用的循环母液。S5: The polymer is prepared by a sodium aluminate solution to prepare a circulating mother liquid used in the step S1.
优选地，在赤泥、铁酸钠(或铁酸钙)、活性石灰组成的原料矿浆中，各形态存在的铁、铝、钙、硅总量分别以氧化物计，配料配方如下：Preferably, in the raw material slurry composed of red mud, sodium ferrite (or calcium ferrite) and activated lime, the total amount of iron, aluminum, calcium and silicon present in each form is determined by oxide, respectively, and the formulation is as follows:
氧化铁的总量与氧化铝的总量的摩尔比为0.5～1.5∶1The molar ratio of the total amount of iron oxide to the total amount of alumina is 0.5 to 1.5:1.
氧化钙的总量与氧化硅的总量的摩尔比为1～3∶1The molar ratio of the total amount of calcium oxide to the total amount of silicon oxide is 1 to 3:1.
优选地，所述原料矿浆的液固比为2～5∶1。Preferably, the raw material slurry has a liquid to solid ratio of 2 to 5:1.
优选地，步骤S5中所述高分子比铝酸钠溶液进行苛碱浓度调制后得到循环母液，其中，循环母液中的苛碱浓度为150～250g/L，分子比为5～25。Preferably, in the step S5, the polymer is prepared by reacting a caustic alkali concentration with a sodium aluminate solution to obtain a circulating mother liquor, wherein the concentration of the caustic in the circulating mother liquor is 150 to 250 g/L, and the molecular ratio is 5 to 25.
优选地，步骤S2中溶出反应的温度为150～250℃，反应时间为0.5～2h。Preferably, the temperature of the dissolution reaction in the step S2 is 150 to 250 ° C, and the reaction time is 0.5 to 2 h.
优选地，所述方法还包括：Preferably, the method further includes:
步骤S6：将步骤S3中的溶出渣进行洗涤并固液分离，得到钙铁榴石型渣和洗涤液；Step S6: washing the eluted slag in step S3 and solid-liquid separation to obtain calcium garnet type slag and washing liquid;
步骤S7：将所述洗涤液用于步骤S3中稀释所述溶出矿浆。Step S7: The washing liquid is used to dilute the dissolved ore slurry in step S3.
优选地，步骤S4具体包括下述步骤：Preferably, step S4 specifically includes the following steps:
S41：将晶种加入到蒸发后的铝酸钠溶液中进行结晶，得到结晶浆料；S41: adding seed crystals to the evaporated sodium aluminate solution for crystallization to obtain a crystal slurry;
S42：将结晶浆料进行液固分离，得到高分子比铝酸钠溶液和铝酸钠。S42: The liquid crystal slurry is subjected to liquid-solid separation to obtain a polymer ratio sodium aluminate solution and sodium aluminate.
优选地，步骤S41中的结晶温度为85～40℃，结晶时间为10～30h，晶种添加量为10～200g/L。Preferably, the crystallization temperature in the step S41 is 85 to 40 ° C, the crystallization time is 10 to 30 h, and the seed crystal addition amount is 10 to 200 g/L.
优选地，步骤S1中的铁酸钠是含铁原料与工业碳碱烧结而成；铁酸 钙是含铁原料与石灰烧结而成。Preferably, 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.
(三)有益效果(3) Beneficial effects
本发明的方法回收了赤泥中的氧化铝和氧化钠，使溶出渣中的碱含量降低到0.5％以下，溶出渣的主要成分为钙铁榴石，这种无碱钙铁榴石适合炼钢过程的铁酸钙添加剂、做自应力、高强度、速凝硅酸盐水泥和高速公路、机场跑道等高强度混凝土的理想骨料，也是微晶玻璃、硅肥等附加值较高产品的潜在原料，此方法可对赤泥进行大宗消纳，实现了对赤泥的回收利用，达到了资源绿色利用的效果；产品铝酸钠即可单独做试剂用来制备其他含铝产品，也可作为原料通过简单的拜耳法制备冶金级氧化铝。The method of the invention recovers the alumina and the sodium oxide in the red mud, so that the alkali content in the dissolution slag is reduced to less than 0.5%, and the main component of the dissolution slag is calcium iron garnet, and the alkali-free calcium iron garnet is suitable for refining. The calcium ferrite additive in the steel process, the ideal aggregate for self-stressing, high-strength, quick-setting Portland cement and high-strength concrete such as highways and airport runways, and also high value-added products such as glass-ceramics and silicon fertilizers. Potential raw materials, this method can greatly reduce the red mud, realize the recycling of red mud, and achieve the effect of green utilization of resources; the product sodium aluminate can be used as a reagent to prepare other aluminum-containing products, or Metallurgical grade alumina is prepared as a feedstock by a simple Bayer process.
附图说明DRAWINGS
图1为本发明钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠方法的工艺流程图。1 is a process flow diagram of a method for producing sodium aluminate by a Bayer process red mud by a one-step alkali thermal treatment of calcium iron garnet of the present invention.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明，而不用于限制本发明的范围。The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are only illustrative of the invention and are not intended to limit the scope of the invention.
本发明实施例所用的赤泥为拜耳法赤泥，赤泥中含有氧化铝和二氧化硅。赤泥、铁酸钠(或铁酸钙)和石灰组成的原料矿中，总氧化铁与总氧化铝的的摩尔比以下简写为F/A；总氧化钙与总氧化硅的摩尔比以下简写为C/S；原料矿浆液固质量比以下简写为L/S。The red mud used in the embodiment of the present invention is a Bayer process red mud, and the red mud contains alumina and silica. In the raw ore consisting of red mud, sodium ferrite (or calcium ferrite) and lime, the molar ratio of total iron oxide to total alumina is abbreviated as F/A; the molar ratio of total calcium oxide to total silica is abbreviated below. For C / S; raw material slurry solid mass ratio is abbreviated as L / S.
钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，是指溶出渣为钙铁榴石型渣，一步碱热法是指利用碱液(循环母液)对氧化铝进行一步水热溶出处理的方法，生产的目标产品为铝酸钠。Calcium iron garnet one-step alkali heat treatment of Bayer process red mud production of sodium aluminate means that the dissolution slag is calcium iron garnet type slag, one-step alkali heat method refers to the use of lye (cycle mother liquor) to carry out one step of alumina The method of hydrothermal dissolution treatment, the target product produced is sodium aluminate.
实施例1Example 1
本实施例采用水硬铝石拜耳法赤泥，主要化学成分(质量百分比，wt％)为：氧化铝(Al 2O 3)21.62％，二氧化硅(SiO 2)16.11％，氧化 钠(Na 2O)7.08％，氧化钙(CaO)16.50％，全铁(TFe)14.80％，其铝硅比为1.34； In this embodiment, the hydraulic aluminite Bayer process red mud is used, and the main chemical components (mass percentage, wt%) are: alumina (Al 2 O 3 ) 21.62%, silicon dioxide (SiO 2 ) 16.11%, sodium oxide (Na) 2 O) 7.08%, calcium oxide (CaO) 16.50%, total iron (TFe) 14.80%, and its aluminum to silicon ratio is 1.34;
铁酸钠为含铁原料与工业烧碱烧结而成；Sodium ferrite is sintered from iron-containing raw materials and industrial caustic soda;
循环母液中的苛碱浓度为240g/L，分子比为25；The concentration of caustic in the circulating mother liquor is 240 g / L, the molecular ratio is 25;
F/A＝0.6∶1；F/A = 0.6:1;
C/S＝2.5∶1。C/S = 2.5:1.
按照本图1所示的本发明钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法：The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali heat treatment of the calcium iron garnet of the present invention shown in FIG. 1 :
S1：将赤泥、铁酸钠和活性石灰混合后，按照L/S＝4∶1的比例与循环母液混合制备成原料浆；S1: mixing red mud, sodium ferrite and active lime, and mixing with the circulating mother liquor according to the ratio of L/S=4:1 to prepare a raw material slurry;
S2：将原料矿浆进行碱热溶出反应，溶出反应温度为250℃，溶出反应时间为1h，反应结束后得到溶出矿浆；S2: the raw material slurry is subjected to an alkali thermal elution reaction, the dissolution reaction temperature is 250 ° C, the dissolution reaction time is 1 h, and the eluted slurry is obtained after the reaction is completed;
S3：将溶出矿浆稀释得到稀释液，将稀释液进行液固分离，得到溶出渣和溶出液，其中溶出液为铝酸钠溶液；S3: diluting the dissolved slurry to obtain a diluent, and performing liquid-solid separation on the diluted solution to obtain a dissolution slag and an eluate, wherein the eluate is a sodium aluminate solution;
S41：将10g/L晶种加入到经蒸发后的铝酸钠溶液中，并在85～40℃进行蒸发结晶15h，得到结晶浆料；S41: adding 10 g/L of seed crystals to the evaporated sodium aluminate solution, and evaporating and crystallizing at 85-40 ° C for 15 h to obtain a crystal slurry;
S42：将结晶浆料进行液固分离，得到高分子比铝酸钠溶液和固体铝酸钠；S42: performing liquid-solid separation of the crystal slurry to obtain a polymer ratio sodium aluminate solution and solid sodium aluminate;
S5：将所述高分子比铝酸钠溶液进行调制，制成步骤S1中所用的循环母液；S5: preparing the polymer than the sodium aluminate solution to prepare the circulating mother liquor used in the step S1;
本步骤中产生的高分子比铝酸钠溶液中的苛碱浓度及分子比均需调整以达到循环母液的参数要求，用于配制原料浆并进行溶出反应；The concentration of the caustic alkali and the molecular ratio in the sodium aluminate solution produced in this step need to be adjusted to meet the parameter requirements of the circulating mother liquor, and is used for formulating the raw material slurry and performing the dissolution reaction;
S6：将步骤S3中的溶出渣进行洗涤并固液分离，得到钙铁榴石型溶出渣和洗涤液；S6: washing the eluted slag in step S3 and solid-liquid separation to obtain calcium garnet type dissolution slag and washing liquid;
本步骤中，经过处理得到了无碱钙铁榴石型渣，使原料赤泥中的硅与加入的铁和钙以钙铁榴石的形式留在溶出渣中，钙铁榴石型渣中碱含量降至0.5％以下，铝硅比降至0.5。不仅回收了赤泥中的氧化铝和氧化钠， 还使得无碱钙铁榴石型渣因碱含量的降低得到了有效利用，如用于炼钢过程的铁酸钙添加剂、做自应力、高强度、速凝硅酸盐水泥和高速公路、机场跑道等高强度混凝土的理想骨料，以及作为微晶玻璃、硅肥等附加值较高产品的潜在原料；In this step, the alkali-free calcium iron garnet type slag is obtained after treatment, so that the silicon in the raw red mud and the added iron and calcium remain in the dissolution slag in the form of calcium iron garnet, and the calcium iron garnet type slag The alkali content falls below 0.5% and the aluminum to silicon ratio drops to 0.5. Not only the alumina and sodium oxide in the red mud are recovered, but also the alkali-free calcium iron garnet type slag is effectively utilized due to the reduction of alkali content, such as calcium ferrite additive used in the steelmaking process, self-stressing, high Ideal aggregates for high-strength concrete such as strength, quick-setting Portland cement and highways, airport runways, and as potential raw materials for higher value-added products such as glass-ceramics and silicon fertilizers;
S7：将洗涤液用于步骤S3中稀释所述溶出矿浆；S7: using the washing liquid for diluting the dissolved pulp in step S3;
本步骤中产生的洗涤液为废液，但将洗涤液返回到步骤S3中用于稀释溶出矿浆，既减少了废液的处理和排放，又达到了重复利用的效果，达到了物料的回收再利用。The washing liquid produced in this step is waste liquid, but the washing liquid is returned to the step S3 for diluting and dissolving the pulp, which not only reduces the treatment and discharge of the waste liquid, but also achieves the effect of recycling, and achieves the recycling of the material. use.
得到的铝酸钠即为产品。滤出渣为无碱钙铁榴石型渣，其余物料均实现了循环利用，符合资源绿色化综合利用的要求。The obtained sodium aluminate is a product. The filtered slag is an alkali-free calcium iron garnet type slag, and the rest of the materials are recycled, which meets the requirements for comprehensive utilization of resources.
实施例2Example 2
本实施例采用拜耳法赤泥，主要化学成分(质量百分比，wt％)为：氧化铝(Al 2O 3)23.35％，二氧化硅(SiO 2)23.23％，氧化钠(Na 2O)15.61％，氧化钙(CaO)0.51％，全铁(TFe)16.16％，二氧化钛(TiO 2)5.37％，其铝硅比为1.01； This embodiment adopts Bayer process red mud, the main chemical composition (mass percentage, wt%) is: alumina (Al 2 O 3 ) 23.35%, silica (SiO 2 ) 23.23%, sodium oxide (Na 2 O) 15.61 %, calcium oxide (CaO) 0.51%, total iron (TFe) 16.16%, titanium dioxide (TiO 2 ) 5.37%, and its aluminum to silicon ratio is 1.01;
铁酸钙为含铁原料与石灰烧结而成；Calcium ferrite is sintered from iron-containing raw materials and lime;
循环母液中的苛碱浓度为240g/L，分子比为25；The concentration of caustic in the circulating mother liquor is 240 g / L, the molecular ratio is 25;
F/A＝0.5∶1；F/A = 0.5:1;
C/S＝3∶1。C/S = 3:1.
按照本图1所示的本发明钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法：The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali heat treatment of the calcium iron garnet of the present invention shown in FIG. 1 :
S1：将赤泥、铁酸钠和石灰混合后，按照L/S＝5∶1的比例与循环母液混合制备成原料浆(注意：赤泥中含有的铁不计入配方，赤泥中含有的氧化钙计入配方，同时配石灰时应考虑到原料中的TiO 2与石灰反应生成钛酸钙的影响)； S1: After mixing red mud, sodium ferrite and lime, the raw material slurry is prepared by mixing with the circulating mother liquor according to the ratio of L/S=5:1 (Note: the iron contained in the red mud is not included in the formulation, and the red mud contains The calcium oxide is included in the formulation, and the lime should be considered in consideration of the reaction of TiO 2 in the raw material with lime to form calcium titanate);
S2：将原料矿浆在反应釜中进行溶出反应，溶出反应温度为250℃， 溶出反应时间为1h，反应结束后得到溶出矿浆；S2: the raw material slurry is subjected to a dissolution reaction in the reaction vessel, the dissolution reaction temperature is 250 ° C, and the dissolution reaction time is 1 h, and the eluted slurry is obtained after the reaction is completed;
经过本步骤的溶出反应，氧化铝提取率能够达到80％以上；After the dissolution reaction in this step, the alumina extraction rate can reach 80% or more;
S3：将溶出矿浆稀释得到稀释液，将稀释液进行液固分离，得到溶出渣和溶出液，其中溶出液为低分子比铝酸钠溶液；S3: diluting the eluted slurry to obtain a diluent, and performing liquid-solid separation on the diluted solution to obtain a dissolution slag and an eluate, wherein the eluate is a low molecular ratio sodium aluminate solution;
S41：将50g/L晶种加入到蒸发后的低分子比铝酸钠溶液中，并在85～40℃进行结晶10h，得到结晶浆料；S41: adding 50 g/L seed crystals to the evaporated low molecular weight sodium aluminate solution, and performing crystallization at 85-40 ° C for 10 h to obtain a crystal slurry;
S42：将结晶浆料进行液固分离，得到高分子比铝酸钠溶液和铝酸钠；S42: performing liquid-solid separation of the crystal slurry to obtain a polymer ratio sodium aluminate solution and sodium aluminate;
S5：将所述高分子比铝酸钠溶液进行调制，制成步骤S1中所用的循环母液；S5: preparing the polymer than the sodium aluminate solution to prepare the circulating mother liquor used in the step S1;
本步骤中产生的高分子比铝酸钠溶液中的苛碱浓度及分子比均需调整以达到循环母液的参数要求，用于配制原料浆并进行溶出反应；The concentration of the caustic alkali and the molecular ratio in the sodium aluminate solution produced in this step need to be adjusted to meet the parameter requirements of the circulating mother liquor, and is used for formulating the raw material slurry and performing the dissolution reaction;
S6：将步骤S3中的溶出渣进行洗涤并固液分离，得到钙铁榴石型渣和洗涤液；S6: washing the eluted slag in step S3 and solid-liquid separation to obtain calcium garnet type slag and washing liquid;
本步骤中，经过处理得到了无碱钙铁榴石型赤泥渣，使赤泥中的硅与加入的铁和钙以钙铁榴石的形式留在溶出渣中，铁榴石型赤泥渣中钠含量降至0.11％，铝硅比降至0.5。不仅降低了赤泥中的碱含量，还使得无碱钙铁榴石型赤泥渣因碱含量的降低得到了有效利用，如用于炼钢过程的铁酸钙添加剂、做自应力、高强度、速凝硅酸盐水泥和高速公路、机场跑道等高强度混凝土的理想骨料，以及作为微晶玻璃、硅肥等附加值较高产品的潜在原料；In this step, the alkali-free calcium iron garnet-type red mud residue is obtained after treatment, so that the silicon in the red mud and the added iron and calcium remain in the dissolution slag in the form of calcium iron garnet, and the red garnet type red mud The sodium content in the slag was reduced to 0.11% and the aluminum to silicon ratio was reduced to 0.5. It not only reduces the alkali content in the red mud, but also makes the alkali-free calcium iron garnet-type red mud residue effectively utilized due to the reduction of the alkali content, such as calcium ferrite additive used in the steelmaking process, self-stressing, high strength. Ideal aggregates for high-strength concrete such as quick-setting Portland cement and highways and airport runways, and as potential raw materials for higher value-added products such as glass-ceramics and silicon fertilizers;
S7：将洗涤液用于步骤S3中稀释所述溶出矿浆；S7: using the washing liquid for diluting the dissolved pulp in step S3;
本步骤中产生的洗涤液为废液，但将洗涤液返回到步骤S3中用于稀释溶出矿浆，既减少了废液的处理和排放，又达到了重复利用的效果，达到了物料的回收再利用。The washing liquid produced in this step is waste liquid, but the washing liquid is returned to the step S3 for diluting and dissolving the pulp, which not only reduces the treatment and discharge of the waste liquid, but also achieves the effect of recycling, and achieves the recycling of the material. use.
得到的铝酸钠即为产品。滤出渣为无碱钙铁榴石型赤泥渣，其余物料均实现了循环利用，符合资源绿色化综合利用的要求。The obtained sodium aluminate is a product. The filtered slag is an alkali-free calcium iron garnet-type red mud slag, and the rest of the materials are recycled, which meets the requirements for comprehensive utilization of resources.
本发明的方法不仅回收了赤泥中的氧化铝，还降低了赤泥中的碱含 量，实现了固体废弃物的回收利用，达到了资源绿色利用的效果。The method of the invention not only recovers the alumina in the red mud, but also reduces the alkali content in the red mud, realizes the recycling of the solid waste, and achieves the effect of green utilization of resources.

Claims (9)

  1. 一种钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，其特征在于：包括下述步骤，Method for producing sodium aluminate by Bayer process red mud by one-step alkali heat treatment of calcium iron garnet, characterized in that it comprises the following steps:
    S1：将赤泥、铁酸钠或铁酸钙、活性石灰及循环母液混合制备成原料矿浆；S1: mixing red mud, sodium ferrite or calcium ferrite, active lime and circulating mother liquor into raw material pulp;
    S2：将原料矿浆进行碱热溶出反应，反应结束后得到溶出矿浆；S2: subjecting the raw material slurry to an alkali thermal elution reaction, and after the reaction is finished, obtaining a dissolved pulp;
    S3：将溶出矿浆稀释得到稀释液，将稀释液进行液固分离，得到溶出渣和溶出液，其中溶出液为铝酸钠溶液；S3: diluting the dissolved slurry to obtain a diluent, and performing liquid-solid separation on the diluted solution to obtain a dissolution slag and an eluate, wherein the eluate is a sodium aluminate solution;
    S4：将铝酸钠溶液蒸发后加晶种结晶，固液分离，得到铝酸钠固体和高分子比铝酸钠溶液；S4: the sodium aluminate solution is evaporated, seed crystals are added, and solid-liquid separation is performed to obtain a sodium aluminate solid and a polymer ratio sodium aluminate solution;
    S5：将所述高分子比铝酸钠溶液进行调制，制成步骤S1中所用的循环母液。S5: The polymer is prepared by a sodium aluminate solution to prepare a circulating mother liquid used in the step S1.
  2. 根据权利要求1所述的钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，其特征在于：赤泥、铁酸钠或铁酸钙、活性石灰组成的原料矿浆中，各形态存在的铁、铝、钙、硅总量分别以氧化物计，配料配方如下：The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali thermal treatment of the calcium iron garnet according to claim 1, characterized in that: in the raw material slurry composed of red mud, sodium ferrite or calcium ferrite, and active lime, The total amount of iron, aluminum, calcium and silicon present in each form is determined by oxide, and the formulation is as follows:
    氧化铁的总量与氧化铝的总量的摩尔比为0.5～1.5∶1；The molar ratio of the total amount of iron oxide to the total amount of alumina is 0.5 to 1.5:1;
    氧化钙的总量与氧化硅的总量的摩尔比为1～3∶1。The molar ratio of the total amount of calcium oxide to the total amount of silicon oxide is from 1 to 3:1.
  3. 根据权利要求1所述的钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，其特征在于：所述原料矿浆的液固比为2～5∶1。The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali thermal treatment of the calcium iron garnet according to claim 1, wherein the raw material slurry has a liquid-solid ratio of 2 to 5:1.
  4. 根据权利要求1所述的钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，其特征在于：步骤S5中所述高分子比铝酸钠溶液进行苛碱浓度调制后得到循环母液，其中，循环母液中的苛碱浓度为150～250g/L，分子比为5～25。The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali thermal treatment of the calcium iron garnet according to claim 1, wherein the polymer in step S5 is prepared by reacting a caustic concentration with a sodium aluminate solution. The circulating mother liquor, wherein the concentration of caustic in the circulating mother liquor is 150-250 g/L, and the molecular ratio is 5-25.
  5. 根据权利要求1所述的钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，其特征在于：步骤S2中溶出反应的温度为150～250℃，反应时间为0.5～2h。The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali thermal treatment of the calcium iron garnet according to claim 1, wherein the temperature of the dissolution reaction in the step S2 is 150 to 250 ° C, and the reaction time is 0.5 to 2 h. .
  6. 根据权利要求1所述的钙铁榴石一步碱热法处理拜耳法赤泥生产 铝酸钠的方法，其特征在于：所述方法还包括：The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali thermal treatment of the calcium iron garnet according to claim 1, wherein the method further comprises:
    步骤S6：将步骤S3中的溶出渣进行洗涤并固液分离，得到钙铁榴石型渣和洗涤液；Step S6: washing the eluted slag in step S3 and solid-liquid separation to obtain calcium garnet type slag and washing liquid;
    步骤S7：将所述洗涤液用于步骤S3中稀释所述溶出矿浆。Step S7: The washing liquid is used to dilute the dissolved ore slurry in step S3.
  7. 根据权利要求1所述的钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，其特征在于：步骤S4具体包括下述步骤：The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali thermal treatment of the calcium iron garnet according to claim 1, wherein the step S4 specifically comprises the following steps:
    S41：将晶种加入到经蒸发后的铝酸钠溶液中进行结晶，得到结晶浆料；S41: adding seed crystals to the evaporated sodium aluminate solution for crystallization to obtain a crystal slurry;
    S42：将结晶浆料进行液固分离，得到高分子比铝酸钠溶液和固体铝酸钠。S42: The crystal slurry is subjected to liquid-solid separation to obtain a polymer ratio sodium aluminate solution and solid sodium aluminate.
  8. 根据权利要求7所述的钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，其特征在于：步骤S41中的结晶温度为85～40℃，结晶时间为10～30h，晶种添加量为10-200g/L。The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali thermal treatment of the calcium iron garnet according to claim 7, wherein the crystallization temperature in the step S41 is 85 to 40 ° C, and the crystallization time is 10 to 30 h. The seed crystal is added in an amount of 10 to 200 g/L.
  9. 根据权利要求1所述的钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法，其特征在于：步骤S1中的铁酸钠是含铁原料与工业碳碱烧结而成；铁酸钙是含铁原料与石灰烧结而成。The method for producing sodium aluminate by the Bayer process red mud by the one-step alkali thermal treatment of the calcium iron garnet according to claim 1, wherein the sodium ferrite in the step S1 is sintered by the iron-containing raw material and the industrial carbon base; Calcium ferrite is a sintered iron-containing material and lime.
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