WO2018233686A1 - 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 - Google Patents

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 Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
calcium
medium
carbon
liquid
alumina
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/CN2018/092422
Other languages
English (en)
French (fr)
Inventor
于海燕
潘晓林
吴艳
毕诗文
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.)
Northeastern University China
Original Assignee
Northeastern University China
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 Northeastern University China filed Critical Northeastern University China
Publication of WO2018233686A1 publication Critical patent/WO2018233686A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/20Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts

Definitions

  • 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.

Landscapes

  • 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

提供一种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,包括下述步骤,S1:将中低品位铝土矿破碎磨细成矿粉;S2:将矿粉、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;S3:将原料矿浆进行碱热溶出反应;S4:将溶出矿浆进行稀释,并进行液固分离;S5:向铝酸钠溶液中通入二氧化碳气体进行碳分,得到粗氢氧化铝和碳分母液;S6:将粗氢氧化铝进行拜耳法处理,得到冶金级氧化铝;S7:将碳分母液采用石灰乳进行苛化并进行液固分离,得到氢氧化钠溶液,调制后作为步骤S2中的循环母液。该方法通过在溶出过程中添加石灰和铁酸钠或铁酸钙,使溶出过程生成钙铁榴石型渣来代替传统的溶出渣,能够大幅度提高氧化铝的溶出率,同时制备冶金级氧化铝,具有流程短、效率高的特点,物料实现了零排放。

Description

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 技术领域
本发明属于氧化铝生产的技术领域,具体涉及一种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。
背景技术
现有铝土矿资源中绝大多数为中低品位铝土矿,具有高铝,高硅,低铝硅比(A/S)等特点。随着矿石品位的降低,各氧化铝生产工艺成本均在逐渐增加,其中拜耳法工艺增幅最大。根据拜耳法的基本工艺和原理,当铝土矿A/S下降到5以下时,将很难再用拜耳法处理。针对于低品位铝土矿,近年来氧化铝工业界主要采用如下几种方法。
中低品位铝土矿处理方法主要有强化拜耳法、烧结法、拜耳-烧结联合法等。强化拜耳法是在拜耳法基础上进行改进以适应处理中低品位铝土矿的方法,主要包括选矿拜耳法和石灰拜耳法。其中,选矿拜耳法采用选冶联合处理中低品位铝土矿,流程相对简单,但存在物理选矿难度大、原矿消耗量大、氧化铝回收率低、浮选药剂影响拜耳法流程等问题,同时选矿过程产生大量铝硅比低于2的尾矿无法利用,造成资源的极大浪费;石灰拜耳法是在拜耳法基础上通过添加过量石灰以达到降低碱耗等作用,但石灰添加量大导致氧化铝溶出率大幅降低、赤泥排出量增加、赤泥沉降负荷增大等问题。烧结法主要包括碱石灰烧结法和石灰烧结法,但能耗高、生产成本高是其发展的主要短板。碱石灰烧结法属于湿法配料、湿法烧结,在烧结过程生料浆中40%左右的水分蒸发极大增加了生产总能耗,且烧结熟料中2CaO·SiO 2稳定性较低,二次反应严重;石灰烧结法存在石灰配比高、弃渣量大、熟料氧化铝浸出率低等问题。拜耳-烧结联合法包括串联法、并联法和混联法,能够处理中低品位铝土矿, 但存在流程复杂、能耗高等问题,目前已基本被拜耳法所取代。其它如酸法和酸碱联合法等工艺目前主要停留在实验室研究阶段,存在氧化铝产品质量差、设备腐蚀严重等诸多问题。
纵观以上处理中低品位铝土矿的方法,烧结法和拜耳-烧结联合法由于其能耗和成本问题已基本被弃用,石灰拜耳法是特定历史时期为解决碱耗问题而研发的,目前只有选矿拜耳法在个别企业应用。然而,经过近些年的工业实践,选矿拜耳法日益暴露出的问题已经严重阻碍了生产过程的正常运行,成为其继续推广发展的瓶颈。
发明内容
(一)要解决的技术问题
为了解决现有技术的上述问题,本发明的目的在于提供一种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,在高温溶出过程中添加铁酸钠(铁酸钙)及活性石灰的方法,高温溶出过程中铝以铝酸钠形式进入溶液,而硅以钙铁榴石的形式留在溶出渣中。本发明的方法能够大幅度提高冶金级氧化铝的溶出率,同时使溶出渣中几乎不含碱,具有流程短效率高的特点,整个流程中物料实现了零排放。
(二)技术方案
为了达到上述目的,本发明采用的主要技术方案包括:
一种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,包括下述步骤,
S1:将中低品位铝土矿破碎磨细成矿粉;
S2:将矿粉、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;
S3:将原料矿浆进行碱热溶出反应,反应结束后得到溶出矿浆;
S4:将溶出矿浆进行稀释得到稀释液,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;
S5:向所述铝酸钠溶液中通入二氧化碳气体进行碳分,得到粗氢氧 化铝和碳分母液;
S6:将所述粗氢氧化铝进行拜耳法处理,得到冶金级氧化铝;
S7:将步骤S5中得到的碳分母液采用氧化钙进行苛化,得到苛化料浆,将苛化料浆进行液固分离,得到高分子比铝酸钠溶液和碳酸钙,将高分子比铝酸钠溶液进行调制,作为步骤S2中的循环母液。
优选地,所述中低品位铝土矿的硅铝比为2~6。
优选地,在铝土矿、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::
氧化铁的总量与氧化铝的总量的质量比为0.2~0.6∶1;
氧化钙的总量与氧化铁的总量的摩尔比为3~6∶1。
优选地,步骤S1中,原料矿浆的液固比为2~5∶1。
优选地,步骤S2中循环母液中的苛碱浓度为150~250g/L,分子比为5~25。
优选地,步骤S3中溶出反应的温度为150~250℃,反应时间为0.5~2h。
优选地,步骤S5中,向溶出后得到的铝酸钠内通入二氧化碳气体并加入晶种进行碳分,得到粗氢氧化铝料浆后进行液固分离,得到碳分母液和粗氢氧化铝,
步骤S5中碳分温度为60~90℃,碳分终点为分解率在90%以上,晶种添加系数为0~1.0。
优选地,所述方法还包括:
步骤S8:将步骤S4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;
步骤S9:将所述洗涤液用于步骤S4中稀释所述溶出矿浆。
优选地,所述方法还包括步骤S10:将步骤S7中得到的碳酸钙进行煅烧分解,得到二氧化碳气体和氧化钙,得到的二氧化碳气体用于步骤S5中碳分处理,得到的氧化钙用于步骤S7中苛化处理。
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。
(三)有益效果
本发明的有益效果是:
(1)与常规拜耳法相比,本发明的方法产生的冶金级氧化铝实际溶出率提高了15%以上,大幅度地提高了氧化铝的溶出率;
(2)与常规拜耳法相比,本发明的方法产生的溶出渣碱含量在0.5%以下,渣中几乎不含碱;
(3)本发明的方法具有流程短效率高的特点,整个流程中物料实现了零排放。
附图说明
图1为本发明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的工艺流程图。
具体实施方式
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。
本发明实施例中的中低品位铝土矿,硅铝比(以下简称A/S)为2~6。在铝土矿、铁酸钠(或铁酸钙)、活性石灰组成的原料矿中,氧化铁的总量与氧化铝的总量的质量比以下简写为F/A;氧化钙的总量与氧化铁的总量的摩尔比为简写为C/F。原料矿浆液固质量比以下简写为L/S。
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,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,生产的产品为冶金级氧化铝。
实施例1
本实施例采用中低品位铝土矿,主要化学成分(质量百分比,wt%)为:氧化铝(Al 2O 3)  60.60%,二氧化硅(SiO 2)  17.5%,其它为杂 质,其铝硅比为3.5;
铁酸钙为含铁原料与石灰烧结而成;
循环母液中的苛碱浓度为200g/L,分子比为25;
F/A=0.5∶1;
C/F=4.5∶1。
按照本图1所示的本发明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:
S1:将中低品位铝土矿破碎磨细成矿粉;
S2:将矿粉、铁酸钙、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矿浆;
S3: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2h,反应结束后得到溶出矿浆;
经过本步骤的溶出反应处理,氧化铝的提取率能够达到83%;
S4:将溶出矿浆进行稀释得到稀释液,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;
S5:将铝酸钠在80℃、晶种添加系数为0.8的条件下,通二氧化碳并加入晶种进行碳分(碳酸化分解)至分解率达到95%,得到粗氢氧化铝料浆,并进行液固分离,得到碳分母液和粗氢氧化铝;
S6:将步骤S5中得到的粗氢氧化铝进行拜耳法处理,得到冶金级氧化铝;
S7:将步骤S5中得到的碳分母液采用石灰乳进行苛化,得到苛化料浆,将苛化料浆进行液固分离,得到高分子比铝酸钠溶液和碳酸钙,将高分子比铝酸钠溶液进行调制,作为步骤S2中的循环母液;
本步骤中,将碳分母液进行处理,得到的高分子比铝酸钠溶液调整后能够作为循环母液参与其他工艺流程,使得工艺流程无外排无污染;
S8:将步骤S4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;
本步骤中,经过处理得到了无碱钙铁榴石型渣,使硅与加入的铁和钙以钙铁榴石的形式留在溶出渣中,降低了渣中的碱含量;
S9:将洗涤液用于步骤S4中稀释所述溶出矿浆;
本步骤中,产生的洗涤液为废液,但将洗涤液返回到步骤S4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;
S10:将步骤S7中得到的碳酸钙在1000℃下进行煅烧分解,得到二氧化碳气体和氧化钙,得到的二氧化碳气体用于步骤S5中碳分处理,得到的氧化钙用于步骤S7中苛化处理;
本步骤中,碳酸钙的分解再利用,实现了资源的回收利用,避免了资源的浪费,节约了成本。
得到的冶金级氧化铝即为产品。
实施例2
本实施例采用中低品位铝土矿,主要化学成分(质量百分比,wt%)为:氧化铝(Al 2O 3)  65.22%,二氧化硅(SiO 2)  12.66%,其它为杂质,其铝硅比为5.15;
铁酸钠为含铁原料与工业碳碱烧结而成;
循环母液中的苛碱浓度为230g/L,分子比为20。
F/A=0.6∶1;
C/F=4∶1。
按照本图1所示的本发明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:
S1:将中低品位铝土矿破碎磨细成矿粉;
S2:将矿粉、铁酸钠、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矿浆;
S3: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;
经过本步骤的溶出反应处理,氧化铝的提取率能够达到83.7%;
S4:将溶出矿浆进行稀释得到稀释液,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;
S5:将低分子比铝酸钠在80℃、晶种添加系数为0.8的条件下,通二氧化碳并加入晶种进行碳分,碳分终点为分解率95%以上。碳分得到粗氢氧化铝料浆后进行液固分离,得到碳分母液和粗氢氧化铝;
S6:将步骤S5中得到的粗氢氧化铝进行拜耳法处理,得到冶金级氧化铝;
S7:将步骤S5中得到的碳分母液采用氧化钙进行苛化,得到苛化料浆,将苛化料浆进行液固分离,得到高分子比铝酸钠溶液和碳酸钙,将高分子比铝酸钠溶液进行调制,作为步骤S2中的循环母液;
本步骤中,将碳分母液进行处理,得到的高分子比铝酸钠溶液调整后能够作为循环母液参与其他工艺流程,使得工艺流程无外排无污染;
S8:将步骤S4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;
本步骤中,经过处理得到了无碱钙铁榴石型渣,使硅与加入的铁和钙以钙铁榴石的形式留在溶出渣中,降低了渣中的碱含量;
S9:将洗涤液用于步骤S4中稀释所述溶出矿浆;
本步骤中,产生的洗涤液为废液,但将洗涤液返回到步骤S4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;
S10:将步骤S7中得到的碳酸钙在1000℃下进行煅烧分解,得到二氧化碳气体和氧化钙,得到的二氧化碳气体用于步骤S5中碳分处理,得到的氧化钙用于步骤S7中苛化处理;
本步骤中,碳酸钙的分解再利用,实现了资源的回收利用,避免了资源的浪费,节约了成本。
得到的冶金级氧化铝即为产品。
本发明的方法具有流程短、效率高的特点,全流程的最终产物为冶金级氧化铝和无碱钙铁榴石型渣,其余物料均实现了循环利用,整个流程中物料实现了零排放。这种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。

Claims (10)

  1. 一种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,其特征在于:包括下述步骤,
    S1:将中低品位铝土矿破碎磨细成矿粉;
    S2:将矿粉、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;
    S3:将原料矿浆进行碱热溶出反应,反应结束后得到溶出矿浆;
    S4:将溶出矿浆进行稀释得到稀释液,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;
    S5:将铝酸钠溶液中通入二氧化碳气体进行碳分,得到粗氢氧化铝和碳分母液;
    S6:将所述粗氢氧化铝进行拜耳法处理,得到冶金级氧化铝;
    S7:将步骤S5中得到的碳分母液采用石灰乳进行苛化,得到苛化料浆,将苛化料浆进行液固分离,得到氢氧化钠溶液和碳酸钙,将氢氧化钠溶液进行调制,作为步骤S2中的循环母液。
  2. 根据权利要求1所述的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,其特征在于:所述中低品位铝土矿的硅铝比为2~6。
  3. 根据权利要求1所述的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,其特征在于:铝土矿、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:
    氧化铁的总量与氧化铝的总量的质量比为0.2~0.6∶1;
    氧化钙的总量与氧化铁的总量的摩尔比为3~6∶1。
  4. 根据权利要求1或2所述的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,其特征在于:步骤S1中,原料矿浆的液固比为2~5∶1。
  5. 根据权利要求1所述的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,其特征在于:步骤S2中循环母液中的苛碱浓度为150~250g/L,分子比为5~25。
  6. 根据权利要求1所述的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,其特征在于:步骤S3中溶出反应的温度为150~250℃,反应时间为0.5~2h。
  7. 根据权利要求1所述的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,其特征在于:
    步骤S5中,向低分子比铝酸钠内通入二氧化碳气体并加入晶种进行碳分,得到粗氢氧化铝料浆后进行液固分离,得到碳分母液和粗氢氧化铝,
    步骤S5中碳分温度为60~90℃,碳分终点为分解率在90%以上,晶种添加系数为0~1.0。
  8. 根据权利要求1所述的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,其特征在于:所述方法还包括:
    步骤S8:将步骤S4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;
    步骤S9:将所述洗涤液用于步骤S4中稀释所述溶出矿浆。
  9. 根据权利要求1所述的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,其特征在于:所述方法还包括步骤S10:将步骤S7中得到的碳酸钙进行煅烧分解,得到二氧化碳气体和氧化钙,得到的二氧化碳气体用于步骤S5中碳分处理,得到的氧化钙用于步骤S7中苛化碳分母液。
  10. 根据权利要求1所述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,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。
PCT/CN2018/092422 2017-06-23 2018-06-22 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 Ceased WO2018233686A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
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

Publications (1)

Publication Number Publication Date
WO2018233686A1 true WO2018233686A1 (zh) 2018-12-27

Family

ID=59878712

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/092422 Ceased WO2018233686A1 (zh) 2017-06-23 2018-06-22 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

Country Status (2)

Country Link
CN (1) CN107188209A (zh)
WO (1) WO2018233686A1 (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
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
CN117865195A (zh) * 2023-12-27 2024-04-12 东北大学 一种钙化碱溶全碳化及钠钙碳循环生产氧化铝方法
CN117865194A (zh) * 2023-12-27 2024-04-12 东北大学 一种氯化-碱溶-全碳分生产氧化铝的方法

Citations (5)

* Cited by examiner, † Cited by third party
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1235802C (zh) * 2003-04-18 2006-01-11 中国铝业股份有限公司 一种拜尔法溶出方法
CN100390307C (zh) * 2006-07-18 2008-05-28 中国铝业股份有限公司 一种拜尔法溶出添加剂的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN107188209A (zh) 2017-09-22

Similar Documents

Publication Publication Date Title
WO2018233686A1 (zh) 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
RU2644169C1 (ru) Способ рекуперации щелочи и алюминия во время обработки получаемого в процессе байера красного шлама с применением технологии известкования и карбонизации
CN109516484B (zh) 一种用电石泥粉煤灰和煤矸石烧结法生产氧化铝的方法
WO2018233688A1 (zh) 钙铁榴石一步碱热法处理中低品位铝土矿生产氢氧化铝的方法
CN100582009C (zh) 一种石灰烧结-拜耳法联合生产氢氧化铝的方法
CN101928025B (zh) 串联法生产氧化铝的方法
US20100119426A1 (en) Process for recovery of silica followed by alumina from coal fly ash
CN105585039B (zh) 一种铝土矿高效快速脱硅方法
WO2018233687A1 (zh) 钙铁榴石一步碱热法处理中低品位铝土矿生产铝酸钠的方法
CN101306926B (zh) 一种从粉煤灰或炉渣中提取漂珠的方法
WO2018233689A1 (zh) 钙铁榴石一步碱热法处理拜耳法赤泥生产冶金级氧化铝的方法
CN111422878B (zh) 一种硅钙质胶磷矿的处理方法
CN106006688B (zh) 一种钙化‑碳化一步法处理拜耳法赤泥的方法
WO2018233690A1 (zh) 钙铁榴石一步碱热法处理拜耳法赤泥生产铝酸钠的方法
CN108975364A (zh) 一种拜耳法赤泥酸处理除碱回收钠的方法
CN116063015B (zh) 一种利用磷石膏制备α-半水石膏的方法
CN108892146B (zh) 一种含硅铝物料的脱硅方法
CN107586947A (zh) 一种综合回收含钒硅质页岩中钒、铝、钾、硅的选冶联合工艺
CN104071954B (zh) 一种碱法处理高铁赤泥深度脱碱与铁富集的方法
CN110055365A (zh) 一种钙化-碳化高铁赤泥回收铁及尾渣水泥化的方法
CN106044784A (zh) 一种利用粉煤灰生产高纯度二氧化硅的方法
CN104649279A (zh) 一种以粉煤灰为原料制取白炭黑的工艺
WO2020206832A1 (zh) 一种高铁赤泥提铁及直接水泥化的方法
WO2019019844A1 (zh) 钙铁榴石一步碱热法处理拜耳法赤泥生产4a沸石的方法
CN102173430B (zh) 利用水合硅酸钙制备硅灰石超细粉体的工艺

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18819700

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: 18819700

Country of ref document: EP

Kind code of ref document: A1