WO2017101746A1 - 一种铝土矿高效快速脱硅方法 - Google Patents

一种铝土矿高效快速脱硅方法 Download PDF

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WO2017101746A1
WO2017101746A1 PCT/CN2016/109501 CN2016109501W WO2017101746A1 WO 2017101746 A1 WO2017101746 A1 WO 2017101746A1 CN 2016109501 W CN2016109501 W CN 2016109501W WO 2017101746 A1 WO2017101746 A1 WO 2017101746A1
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silicon
bauxite
reaction
solution
desiliconization
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PCT/CN2016/109501
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French (fr)
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陈湘清
李花霞
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郑州中绿环保新材料有限公司
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Publication of WO2017101746A1 publication Critical patent/WO2017101746A1/zh

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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
    • 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
    • C01F7/0613—Pretreatment of the minerals, e.g. grinding
    • 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

Definitions

  • the invention relates to the field of bauxite desiliconization technology, in particular to a method for efficient and rapid desiliconization of bauxite.
  • the traditional production process of alumina production from bauxite is mainly Bayer process, sintering method and the like.
  • Bayer process consists of two main processes, namely two patents proposed by Bayer.
  • One is that he found a sodium aluminate solution with a molar ratio of sodium oxide to alumina of 1.8 at room temperature, as long as aluminum hydroxide is added as a seed.
  • the alumina in the solution can be precipitated as aluminum hydroxide until the molar ratio of sodium oxide to alumina is increased to 6, and most of the aluminum hydroxide has been precipitated.
  • the remaining solution can be dissolved when heated.
  • Alumina hydrate in bauxite which is also a process of dissolving bauxite by using seed mother liquor.
  • batches of bauxite can be batch-processed, and pure aluminum hydroxide products can be obtained therefrom to form Bayer. Law loop.
  • the iron oxide, calcium oxide and titanium dioxide in the ore do not react with sodium hydroxide, but form a solid precipitate which remains in the bottom of the reactor, but the dioxide in the ore Silicon reacts with sodium hydroxide to form sodium silicate which is also soluble in water.
  • the Bayer process accelerates the solution by slowly heating the solution, causing the silica, alumina and sodium hydroxide in the solution to form a sodalite structure of sodium hydrated sodium aluminosilicate, and the solid precipitate in the bottom of the reactor, such as iron oxide in the ore. Calcium oxide, titanium dioxide, etc. are directly discharged as red mud to achieve the purpose of removing silicon.
  • the alumina production process by the sintering method is an alkali-lime sintering method, and the bauxite is sintered with a certain amount of soda ash, lime (or limestone) to form a charge at a high temperature, and the silicon oxide and calcification are combined to form a water-insoluble silicic acid.
  • the Bayer process and the sintering process all discharge silicon into the red mud together, which results in a large amount of red mud.
  • the effective elements in the red mud such as valuable rare elements and radioactive elements
  • the content is low and therefore cannot be effectively recycled.
  • the landfill method is used to treat red mud at home and abroad.
  • the dumping site needs to be treated with anti-seepage treatment to prevent environmental pollution, and the investment is large;
  • the content of Al 2 O 3 in red mud is as high as 20% to 25%,
  • a /S is 1.2 to 2.0, and contains a large amount of rare rare earth elements, which wastes resources.
  • the currently used desiliconization method is demineralization of bauxite ore dressing, and then the selected high-aluminum-silicon ratio concentrate is used as raw material to produce alumina, that is, "mineralization-Bayer method".
  • the method has been widely applied in industrialization, but has shortcomings such as long process flow, large equipment investment, low alumina recovery rate, and the contribution to the benefit of alumina production is not obvious. In the end, due to the large loss of resource recovery rate and the increase in cost, the two sides have offset the slight advantage of improving A/S and have stopped.
  • Another desiliconization method is roasting-sodium hydroxide stripping desiliconization technology, and the processes mainly include roasting, dissolution, solid-liquid separation and lye regeneration, for example, roasting-sodium hydroxide dissolution desiliconization technology, the raw ore is After calcination at 1000 ° C for 60 min, and then leaching with 10% caustic soda solution for 2 h, 77% of SiO 2 can be removed, and the recovery of aluminum can reach 96% to 98%, and the ratio of aluminum to silicon is increased from 2.4 to 8.9. 9.8; This method is complicated in process and high in energy consumption.
  • alumina production is mainly divided into: dissolution process, decomposition process and evaporation process, and the cost is about 1/3 of each, and the process of decomposition process and evaporation process is basically stable and mature.
  • dissolution process and the red mud properties have been changing with the nature of the ore and the processing method, and the research has not been stopped in order to reduce the influence of the silicon mineral.
  • the technical problem mainly solved by the present invention is to provide a method for efficient and rapid desiliconization of bauxite.
  • the technical solution adopted by the present invention is: a high-efficiency and rapid desiliconization method for bauxite, the desiliconization method comprising the steps of:
  • Silicon dissolution step bauxite is mixed with lye to prepare a reaction slurry, the content of sodium oxide in the alkali solution is 20-280 g/L, and the liquid-solid ratio of the reaction slurry is 2-50, and the reaction material
  • the slurry is reacted and dissolved in a microwave reactor, the reaction temperature is 10 to 130 ° C, and the reaction time is 2 to 220 min.
  • the reaction liquid is subjected to solid-liquid separation, and the liquid phase is a silicon-containing solution, and the SiO 2 content in the silicon-containing solution is 0.3. ⁇ 50g/L.
  • the high-efficiency and rapid desiliconization method of bauxite further comprises the following steps: the silicon-containing solution is subjected to desiliconization treatment, and then sedimented and filtered to obtain a silicon-containing slag and a desiliconized solution having an iron content of less than 0.5%;
  • the silicon-containing solution is recycled at least once, and then subjected to desiliconization treatment, followed by sedimentation and filtration to obtain a silicon-containing slag and a desiliconized solution having an iron content of less than 0.5%;
  • the recycling of the silicon-containing solution means that the silicon-containing solution is returned for the silicon elution step, and specifically includes: mixing a silicon-containing solution with the alkali solution for preparing a reaction slurry.
  • the grinding fineness of the bauxite in the reaction slurry is -200 mesh content of 60% to 100%.
  • the microwave reactor has a frequency of 300 MHz to 300 GHz.
  • the reaction slurry has a liquid to solid ratio of 2 to 20.
  • the reaction slurry is reacted to dissolve silicon in a microwave reactor at a reaction temperature of 50 to 105 ° C and a reaction time of 3 to 120 min.
  • the bauxite may be a diaspore type bauxite or a gibbsite type bauxite or a boehmite type bauxite.
  • the liquid phase silicon-containing solution obtained by solid-liquid separation is subjected to desiliconization treatment.
  • the desiliconized solution is a sodium hydroxide solution, and the sodium hydroxide solution is returned for formulating the reaction slurry;
  • the solid phase obtained by solid-liquid separation is directly used for producing alumina; or the solid phase obtained by solid-liquid separation is treated by a silicon dissolution step, followed by production of alumina.
  • the desiliconized solution obtained after the desiliconization treatment of the liquid phase silicon-containing solution is a sodium aluminate solution
  • the aluminate The sodium solution is decomposed to prepare aluminum hydroxide, and the remaining reaction solution after the decomposition reaction is concentrated by evaporation, and returned to prepare a reaction slurry;
  • the solid phase obtained by solid-liquid separation is washed with hot water of 50 to 100 ° C to obtain a solid phase slag.
  • solid phase slag is directly discharged as red mud
  • the solid phase slag is further treated by a silicon dissolution step, followed by washing with hot water of 50 to 100 ° C, and discharging as red mud.
  • the mineral morphology of silicon minerals can be changed under different energy density conditions and different total energy states. For example, it is found that kaolinite receives enough energy, and when it passes over the energy barrier, silicon will be in a soluble ion state. It is stable in solution for a long time, so that silicon can be separated from other elements by solid-liquid separation. Therefore, by changing and controlling the nature and form of silicon minerals in bauxite, it is possible to achieve the goal of continuously improving resource utilization with minimum energy consumption and raw material consumption.
  • the high-efficiency and rapid desiliconization method of bauxite provided by the invention is based on the study of the structure of silicon minerals, and it is found that the silicon minerals generate high-frequency vibration under the action of microwaves, especially at lower temperatures.
  • High-frequency vibrations vary between minerals, while There are also differences in the molecular bonds between the same mineral molecules.
  • the difference in vibration between different molecular bonds of silicon-containing minerals causes a significant difference in molecular bond activity, so that a large amount of sodium ions present in the lye can be substituted with hydrogen ions in the most active hydrogen bond of the outermost layer of the silicon mineral molecule.
  • Competing for silicon mineral molecules, sodium silicate can be formed under microwave oscillation without increasing temperature.
  • silicon minerals are continuously attracted to the lye by sodium ions, causing continuous dissolution of silicon minerals. Since the dissolution rate of the silicon mineral is faster under the action of the microwave and the dissolution time is short, the solid-liquid separation can be performed when the silicon mineral has not precipitated, and the dissolution and separation of the silicon mineral can be realized.
  • the beneficial effects of the invention are as follows: the high-efficiency and rapid desiliconization method of the bauxite provided by the invention is carried out in the microwave reactor for desiliconization, and the solid solution ratio, the reaction temperature and the reaction time of the reaction slurry are determined.
  • the invention provides a high-efficiency and rapid desiliconization method for bauxite. By mixing bauxite and sodium hydroxide solution, the silicon is rapidly dissolved at a low temperature under the action of microwave, so that SiO 2 in the bauxite enters the alkali solution to reach the bauxite. The purpose of desiliconization.
  • the method of the invention realizes the purification and recovery of the silicon mineral so as not to enter the red mud, thereby greatly reducing the amount of red mud produced in the alumina production, thereby increasing the valuable precious metal content in the red mud to the available level.
  • the content of valuable rare elements in red mud can be increased to more than 10 times of the existing level, which facilitates the recycling of useful rare earth elements in red mud.
  • the pure silicon-containing slag produced can be further prepared into 4A zeolite. It can be utilized to generate greater economic benefits.
  • the high-efficiency and rapid desiliconization method of bauxite provided by the invention realizes the comprehensive utilization of efficient and rapid desiliconization of bauxite and red mud.
  • the high-efficiency desiliconization method of bauxite avoids the high energy consumption required for roasting bauxite, has the advantages of short desiliconization time and good desiliconization effect, and alumina at the same time as the conventional roasting-dissolution method.
  • the recycling rate has also been greatly improved. Compared with the beneficiation desiliconization method, the equipment investment cost is greatly saved, no tailings are produced, and the influence of the flotation agent addition on the subsequent alumina dissolution is avoided.
  • Examples 1-10 a high-efficiency and rapid desiliconization method for a bauxite-type bauxite, and the composition analysis results of the bauxite are shown in Table 1.
  • Silicon dissolution step bauxite is mixed with lye to prepare a reaction slurry.
  • the content of sodium oxide in the alkali solution is 20-700 g/L, and the liquid-solid ratio of the reaction slurry is 2.5-20, and the alumina in the reaction slurry is The grinding fineness of the ore is -200 mesh content of 90%, and the reaction slurry is reacted to dissolve silicon in a microwave reactor.
  • the frequency of the microwave reactor is 2450 MHz, the reaction temperature is 90-135 ° C, and the reaction time is 3-20 min.
  • the reaction solution was subjected to solid-liquid separation, and the obtained liquid phase was a silicon-containing solution.
  • the test results are shown in Table 2.
  • the dissolution of silicon minerals in the diaspore-type bauxite can be achieved in the range of the alkali Na 2 O concentration of 20 g/L to 700 g/L, and the reaction time and reaction can be adjusted.
  • the temperature causes the dissolution rate of silica to reach 50% or more.
  • the effect of liquid-solid ratio on silicon dissolution is that, due to the different solubility of silica under different alkali concentration conditions, the silicon concentration in the reaction solution can be made unsaturated by increasing the liquid-solid ratio, thereby promoting silicon in the solid phase.
  • the mineral reaction is dissolved in the liquid phase to increase the dissolution rate of the silicon mineral.
  • the liquid-solid ratio is too large, the production efficiency is seriously degraded.
  • the liquid-solid ratio is preferably 2 to 50, preferably 2 to 20.
  • the effect of reaction temperature on the dissolution of silicon is mainly manifested in the fact that as the reaction temperature increases, the reaction increases, the dissolution rate of silicon increases, and the purpose of dissolving silicon can be achieved in a shorter time, but the oxidation in the solid phase increases with increasing temperature.
  • Aluminum is also partially dissolved in the solution, which causes a decrease in solid phase recovery.
  • the reaction temperature cannot be too high. It can be seen from the above examples that when the reaction temperature is less than 105 ° C, the alumina does not substantially elute, and the obtained silicon-containing solution is mainly silicon.
  • the method of increasing the reaction time by reducing the reaction temperature can increase the dissolution rate of silica and reduce the dissolution rate of alumina.
  • the silica dissolution rate is above 50%, and the alumina dissolution rate is at most 0.32%, and the obtained silicon-containing solution has an alumina content of 0.
  • Examples 11-17 a high-efficiency and rapid desiliconization method for a bauxite-type bauxite, and the composition analysis results of the bauxite are shown in Table 1.
  • Silicon dissolution step bauxite is mixed with lye and formulated into a reaction slurry.
  • the content of sodium oxide in the alkali solution is 77.5 g/L, and the liquid-solid ratio of the reaction slurry is 15, and the bauxite in the reaction slurry is ground.
  • the fineness of the ore is -200 mesh content of 90%, and the reaction slurry is reacted to dissolve silicon in a microwave reactor.
  • the frequency of the microwave reactor is 2450 MHz
  • the reaction temperature is 50-105 ° C
  • the reaction time is 7-120 min
  • the reaction liquid is carried out after the reaction is completed.
  • the solid phase was separated, and the obtained liquid phase was a silicon-containing solution.
  • the test results are shown in Table 3.
  • Silicon dissolution step bauxite is mixed with lye and formulated into a reaction slurry.
  • the content of sodium oxide in the alkali solution is 77.5 g/L, and the liquid-solid ratio of the reaction slurry is 20, and the bauxite in the reaction slurry is ground.
  • the fineness of the ore is -200 mesh and the content is 90%.
  • the reaction slurry is reacted and dissolved in a microwave reactor.
  • the frequency of the microwave reactor is 2450 MHz, the reaction temperature is 80 ° C, and the reaction time is 5 min.
  • the reaction liquid is subjected to solid-liquid separation.
  • the resulting liquid phase is a silicon-containing solution.
  • the silicon-containing solution is not subjected to desiliconization treatment, and is directly returned for treatment of the next batch of bauxite, and the alkali solution is added to the silicon-containing solution to maintain the liquid-solid ratio of the prepared reaction slurry at 20:1.
  • the first cycle of the silicon-containing solution a total of 5 cycles were performed.
  • the contents of Al 2 O 3 and SiO 2 in the silicon-containing solution obtained after each cycle were measured, and the dissolution rate was calculated. The results are shown in Table 4.
  • the dissolution rate of SiO 2 is more than 50% according to the slag phase (solid phase obtained by solid-liquid separation).
  • the concentration of Al 2 O 3 and SiO 2 in the liquid silicon-containing solution gradually increases with the number of cycles. Therefore, the silicon solution can be used to dissolve the silicon in the bauxite.
  • the concentration of Al 2 O 3 and SiO 2 in the silicon-containing solution reaches a certain value, the separation and desiliconization treatment is performed, thereby saving processing cost and improving production efficiency. .
  • Silicon dissolution step bauxite is mixed with sodium hydroxide solution to prepare a reaction slurry.
  • the content of sodium oxide in the sodium hydroxide solution is 77.5 g/L, and the liquid-solid ratio of the reaction slurry is 20, and the aluminum in the reaction slurry.
  • the grinding fineness of the earth ore is -200 mesh content of 60%, the reaction slurry is reacted and dissolved in the microwave reactor, the frequency of the microwave reactor is 2450 MHz, the reaction temperature is 70 ° C, the reaction time is 10 min, and the reaction liquid is ⁇ after the reaction is completed.
  • Hot fast solid-liquid separation the obtained liquid phase is a silicon-containing sodium hydroxide solution, and the obtained solid phase is washed with hot water of 50 to 100 ° C, and then subjected to secondary silicon dissolution treatment;
  • the obtained solid phase is subjected to secondary silicon dissolution treatment: the obtained solid phase is ground to a particle size of -200 mesh or less and 100%, and then mixed with a sodium hydroxide solution, and the Na 2 O concentration of the sodium hydroxide solution is 77.5 g/L.
  • the secondary reaction slurry is obtained, the liquid-solid ratio of the secondary reaction slurry is 10, and the secondary reaction slurry is desiliconized again in the microwave reactor, the reaction temperature is 70 ° C, the reaction time is 5 min, and the reaction is hot and fast after solidification.
  • the liquid phase is separated, and the obtained liquid phase is a silicon-containing sodium hydroxide solution, and the obtained solid phase is washed with hot water of 50 to 100 ° C to obtain a high aluminum-silicon ratio bauxite, and the high aluminum-silicon ratio bauxite is produced by the Bayer process.
  • Alumina Alumina.
  • the two obtained silicon-containing sodium hydroxide solutions are combined, and the 4A zeolite is formed by liquid phase desiliconization reaction, and then precipitated, and then solid-liquid separation, and the obtained sodium hydroxide solution is returned for the silicon dissolution step, and the solid product is 4A zeolite. .
  • Silicon dissolution step bauxite is mixed with sodium hydroxide solution to prepare a reaction slurry.
  • the content of sodium oxide in the sodium hydroxide solution is 150 g/L, and the liquid-solid ratio of the reaction slurry is 10, and the alumina in the reaction slurry is The grinding fineness of the ore is 95% of the -200 mesh content.
  • the reaction slurry is dissolved in the microwave reactor.
  • the frequency of the microwave reactor is 2450 MHz, the reaction temperature is 105 ° C, the reaction time is 10 min, and the reaction liquid is hot after the reaction. Rapid solid-liquid separation, the obtained liquid phase is a silicon-containing sodium hydroxide solution, and the obtained solid phase is washed with hot water of 100 ° C, followed by secondary silicon dissolution treatment;
  • the obtained solid phase is subjected to secondary silicon dissolution treatment: the obtained solid phase is ground to a particle size of -200 mesh or less and 100%, and then mixed with a sodium hydroxide solution, and the Na 2 O concentration of the sodium hydroxide solution is 150 g/L.
  • the liquid-solid ratio of the secondary reaction slurry and the secondary reaction slurry is 10, and the secondary reaction slurry is desiliconized again in the microwave reactor, the reaction temperature is 100 ° C, the reaction time is 5 min, and the reaction is quenched and heated quickly.
  • the obtained liquid phase is a silicon-containing sodium hydroxide solution
  • the obtained solid phase is washed with hot water of 100 ° C to obtain a high aluminum-silicon ratio bauxite, and the high aluminum-silicon ratio bauxite is subjected to a Bayer process to produce alumina.
  • the two obtained silicon-containing sodium hydroxide solutions are combined, and the 4A zeolite is formed by liquid phase desiliconization reaction, and then precipitated, and then solid-liquid separation, and the obtained sodium hydroxide solution is returned for the silicon dissolution step, and the solid product is 4A zeolite.
  • Examples 21-26 a high-efficiency and rapid desiliconization method for gibbsite-type bauxite, and the composition analysis results of bauxite are shown in Table 8.
  • Silicon dissolution step bauxite is mixed with sodium hydroxide solution to prepare a reaction slurry.
  • the content of sodium oxide in the sodium hydroxide solution is 115 g/L, and the liquid-solid ratio of the reaction slurry is 15, and the alumina in the reaction slurry is The grinding fineness of the ore is -200 mesh content of 90%, and the reaction slurry is reacted to dissolve silicon in a microwave reactor.
  • the frequency of the microwave reactor is 2450 MHz, the reaction temperature is 50-100 ° C, and the reaction time is 5 min.
  • the reaction liquid is hot and rapid solid-liquid separation, and the obtained liquid phase is a silicon-containing sodium hydroxide solution, and the obtained solid phase is washed with hot water of a corresponding reaction temperature to obtain a solid phase slag.
  • the test results are shown in Table 9.
  • the dissolution process of the gibbsite-type bauxite silicon As the reaction temperature increases, the alumina and the silica are simultaneously dissolved in the sodium hydroxide solution, and reacted at 50 ° C for 5 min, that is, a small amount of aluminum Dissolution.
  • the dissolution and desiliconization applied to the gibbsite-type bauxite is a process in which aluminum and silicon simultaneously enter the alkali solution, thereby simultaneously separating aluminum, silicon and other minerals at a lower temperature, and then from the lye. The silicon is first removed, the sodium aluminate solution is obtained, and the sodium aluminate solution is decomposed to prepare aluminum hydroxide.
  • the remaining reaction liquid is concentrated by evaporation, and is returned to prepare a reaction slurry to dissolve the next batch of ore.
  • the dissolution temperature when the reaction temperature is 100 ° C and the reaction time is 5 min, the dissolution rate of the silica can be made greater than 50%, and the dissolution of the silica can be further extended by lowering the reaction dissolution time at a lower temperature. The rate is increased, and of course, further increasing the reaction temperature also allows the dissolution rate to be further increased.
  • the bauxite in preparing the reaction slurry, may be first ground, then mixed with the alkali solution, or may be ground after being mixed with the alkali solution.
  • the desiliconization treatment of the silicon-containing solution belongs to the prior art in the art, and the desiliconization treatment method may be performed by changing the temperature of the desiliconization solution, such as heating to raise the temperature or lowering the temperature, or desiliconizing by adding a desiliconizing agent.
  • the silicate ions in the silicon-containing solution are converted into solid phase silicon to precipitate.

Abstract

一种铝土矿高效快速脱硅方法，包括步骤：铝土矿与碱液混合，配制成反应料浆，反应料浆液固比2～50，反应料浆在微波反应器中反应溶出硅，反应温度10～130℃，反应时间2～220min，反应结束后反应液进行固液分离，所得液相为含硅溶液，含硅溶液中SiO 2含量为0.3～50g/L。该方法在微波反应器中进行反应脱硅，通过对反应料浆液固比、反应温度和反应时间的确定，实现了在较短的时间内，高效溶出铝土矿中硅的目的。该方法对铝土矿中硅矿物实现了纯化回收，使其不进入赤泥，因此大大降低了氧化铝生产中赤泥的产生量。

Description

一种铝土矿高效快速脱硅方法 技术领域
本发明涉及铝土矿脱硅技术领域，特别是涉及一种铝土矿高效快速脱硅方法。
背景技术
铝土矿生产氧化铝传统的生产工艺主要是拜耳法、烧结法等。现今为止，世界上90％的铝业公司都在使用拜耳法生产。拜耳法包括两个主要的过程，也就是拜耳提出的两项专利，一项是他发现氧化钠与氧化铝摩尔比为1.8的铝酸钠溶液在常温下，只要添加氢氧化铝作为晶种，不断搅拌，溶液中的氧化铝便可以呈氢氧化铝徐徐析出，直到其中氧化钠与氧化铝的摩尔比提高到6，已经析出了大部分氢氧化铝，剩余的溶液在加热时，又可以溶出铝土矿中的氧化铝水合物，这也是利用种分母液溶出铝土矿的过程，交替使用这两个过程就能够一批批处理铝土矿，从中得到纯的氢氧化铝产品，构成拜耳法循环。铝土矿矿石在和氢氧化钠反应时，矿石中的铁氧化物、氧化钙、二氧化钛基本不会和氢氧化钠发生反应，而是形成固体沉淀留在反应釜底部，但矿石中的二氧化硅则会和氢氧化钠反应，生成同样溶于水的硅酸钠。拜耳法通过缓慢加热溶液，促使溶液中的二氧化硅、氧化铝和氢氧化钠生成方钠石结构的水合铝硅酸钠沉淀，与留在反应釜底部的固体沉淀如矿石中的铁氧化物、氧化钙、二氧化钛等一起作为赤泥直接排放，从而达到除硅的目的。烧结法生产氧化铝工艺为碱-石灰烧结法，将铝土矿与一定量的纯碱、石灰(或石灰石)配成炉料在高温下进行烧结，使氧化硅与石灰化合成不溶于水的硅酸二钙，氧化铁与纯碱化合成可以水解的铁酸钠，而氧化铝与纯碱化合成可溶于水的铝酸钠；之后将烧结产物(熟料)用水溶出时，铝酸钠进入水，铁酸钠水解形成 氧化铁。氧化铁和硅酸二钙一起进入赤泥，而后用二氧化碳分解铝酸钠溶液便可析出氢氧化铝。
从以上氧化铝的生产工艺来看，拜耳法和烧结法工艺都是将硅一起排入了赤泥中，这样就造成赤泥量大，赤泥中的有效元素如有价稀有元素、放射性元素的含量低，因此不能有效回收利用。目前国内外都采用堆积填埋的方法来处理赤泥，同时堆放场所需要进行防渗处理，以防止对环境造成污染，投资大；赤泥中Al2O3含量高达20％～25％，A/S为1.2～2.0，同时含有大量的稀有稀土元素，资源浪费严重。因此，二氧化硅在铝土矿溶出过程中的行为和影响成为氧化铝生产的关注点，尤其是随着铝土矿品位的下降，高硅矿物进入氧化铝生产流程，吨氧化铝产出赤泥量急剧增加，氧化铝生产成本显著增加。
针对高硅矿物，需要先脱硅，以提高铝硅比A/S，之后再用于生产氧化铝。目前普遍采用的脱硅方法为铝土矿选矿脱硅，而后以选出的高铝硅比的精矿作为原料来生产氧化铝，即“选矿‐拜耳法”。该方法已经被广泛产业化应用，但是存在工艺流程长，设备投资大，氧化铝回收率低等缺点，对氧化铝生产的效益贡献不明显。最终因资源回收率损失大，成本增加两方面抵消了提高A/S带来的微弱优势，也停止不前。另一种脱硅方法为焙烧‐氢氧化钠溶出脱硅技术，其工艺主要包括焙烧、溶出、固液分离和碱液再生等作业，例如采用焙烧‐氢氧化钠溶出脱硅技术，将原矿在1000℃下焙烧60min，然后用10％的苛性钠溶液浸取2h，可使77％的SiO2脱除，而铝的回收率可达96％～98％，铝硅比从2.4提高到8.9～9.8；此方法流程复杂，能耗高。也有采用生物选矿脱硅技术，即以微生物分解硅酸盐和铝硅酸盐矿物，此方法虽然浸出条件温和，但是浸出时间长，效率低，无法满足生产需要。
目前，也出现了新的低品位铝土矿生产氧化铝方法的报道。其中公开号为CN 101289207A的专利申请中公开了一种铝土矿生产氧化铝的方法，将铝土矿直接用高浓度苛性碱液浸出其中的铝硅酸盐矿物，原理基于苛性碱液在一定的浓度和温度下能够分解高岭石和伊利 石等脉石矿物，不经过焙烧铝土矿达到大部分SiO2进入溶液而分离的脱硅目的。其缺点是使用的碱液浓度较高，溶出时间长，需要5～10小时。
回顾氧化铝的全工艺及发展历程，可以看出氧化铝生产主要分为：溶出过程、分解过程及蒸发过程，其成本大约各占1/3，而分解过程及蒸发过程的工艺已基本稳定成熟，但是溶出过程及赤泥性质一直随矿石的性质变动及加工方式而变动，并且为了降低硅矿物的影响，一直未停止过研究。
发明内容
本发明主要解决的技术问题是提供一种铝土矿高效快速脱硅方法。
为解决上述技术问题，本发明采用的技术方案是：一种铝土矿高效快速脱硅方法，所述脱硅方法包括步骤：
硅溶出步骤：铝土矿与碱液混合，配制成反应料浆，所述碱液中氧化钠的含量为20～280g/L，所述反应料浆的液固比为2～50，反应料浆在微波反应器中反应溶出硅，反应温度10～130℃，反应时间2～220min，反应结束后反应液进行固液分离，所得液相为含硅溶液，含硅溶液中SiO2含量为0.3～50g/L。
铝土矿高效快速脱硅方法，还包括以下步骤：所述含硅溶液进行脱硅处理，之后沉降、过滤，得到含铁量小于0.5％的含硅渣和脱硅后溶液；
或者，所述含硅溶液至少循环使用一次，之后再进行脱硅处理，之后沉降、过滤，得到含铁量小于0.5％的含硅渣和脱硅后溶液；
其中，所述含硅溶液循环使用是指：所述含硅溶液返回用于所述硅溶出步骤，具体包括：含硅溶液与所述碱液混合，用于配制反应料浆。
所述反应料浆中铝土矿的磨矿细度为-200目含量60％～100％。
所述微波反应器的频率为300MHz～300GHz。
优选的，所述反应料浆的液固比为2～20。
所述反应料浆在微波反应器中反应溶出硅，反应温度50～105℃，反应时间3～120min。
所述铝土矿可以为一水硬铝石型铝土矿或三水铝石型铝土矿或一水软铝石型铝土矿。
所述铝土矿为一水硬铝石型铝土矿或一水软铝石型铝土矿时，在硅溶出步骤中，固液分离所得的液相含硅溶液再经脱硅处理后得到的脱硅后溶液为氢氧化钠溶液，所述氢氧化钠溶液返回用于配制反应料浆；
在硅溶出步骤中，固液分离所得的固相直接用于生产氧化铝；或者，固液分离所得的固相再经硅溶出步骤处理，之后用于生产氧化铝。
所述铝土矿为三水铝石型铝土矿时，在硅溶出步骤中，所得液相含硅溶液再经脱硅处理后得到的脱硅后溶液为铝酸钠溶液，所述铝酸钠溶液进行分解反应制备氢氧化铝，分解反应后剩余的反应液经蒸发浓缩，返回用于配制反应料浆；
在硅溶出步骤中，固液分离所得的固相用50～100℃的热水洗涤，得到固相渣。
进一步的，所述固相渣直接作为赤泥排放；
或者，所述固相渣再经硅溶出步骤处理，之后用50～100℃的热水洗涤，再作为赤泥排放。
通过试验研究发现，硅矿物在不同能量密度条件及不同的总能量状态时，矿物形态可以变换，例如发现高岭石在接受了足够的能量，越过能垒时，硅元素将以可溶性的离子状态而在溶液中稳定较长时间，从而可以通过固液分离的方法将硅与其他元素实现分离。因此，通过改变和控制铝土矿中硅矿物的性质及形态，从而可以达到以最少的能源消耗及原材料消耗来实现资源利用率不断提高的目的。
本发明提供的铝土矿高效快速脱硅方法，正是在对硅矿物结构研究的基础上，发现硅矿物在微波作用下，尤其是较低温度下硅矿物分子即产生高频振动，这种高频振动在不同矿物之间会存在差异，同时 在同一矿物分子间的不同分子键也存在差异。含硅矿物不同分子键之间的振动差异引起其分子键活性差异显著，这样，碱液中大量存在的钠离子就可以与硅矿物分子最外层最为活跃的氢键中的氢离子发生取代反应争夺硅矿物分子，因此可以在微波振荡而未升高温度的条件下生成硅酸钠，随着反应的进程，硅矿物不断的被钠离子吸引至碱液中，造成硅矿物的不断溶出。由于在微波作用下硅矿物的溶出速度较快，溶出时间短，因此在硅矿物尚未沉淀时即进行固液分离，就可以实现硅矿物的溶出分离。
本发明的有益效果是：本发明提供的铝土矿高效快速脱硅方法，在微波反应器中进行反应脱硅，通过对反应料浆液固比、反应温度和反应时间的确定，实现了在较短的时间内，高效溶出铝土矿中硅的目的。本发明提供的铝土矿高效快速脱硅方法，通过将铝土矿和氢氧化钠溶液混合，在微波作用下低温快速溶出硅，使铝土矿中的SiO2进入碱液，达到铝土矿脱硅的目的。本发明方法对硅矿物实现了纯化回收，使其不进入赤泥，因此大大降低了氧化铝生产中赤泥的产生量，这样一方面使赤泥中的有价贵金属含量提高到可利用的水平，赤泥中有价稀有元素的含量可提高到现有水平的10倍以上，便于对赤泥中有用稀有稀土元素的回收利用，同时，产生的纯净的含硅渣还可以进一步制作成4A沸石等得以利用，产生更大的经济效益。本发明提供的铝土矿高效快速脱硅方法实现了铝土矿高效快速脱硅和赤泥的综合利用。
本发明提供的铝土矿高效脱硅方法，与常规的焙烧-溶出法相比，避免了焙烧铝土矿需要投入的高能耗，具有脱硅时间短，脱硅效果好的优点，同时氧化铝的回收率也大大的提高。与选矿脱硅方法相比，设备投资费用大大节省，无尾矿产生，且避免了浮选药剂的加入对后续氧化铝溶出的影响。
具体实施方式
下面通过具体实施例对本发明的技术方案进行详细说明。
实施例1-10，一水硬铝石型铝土矿高效快速脱硅方法，铝土矿的成分分析结果见表1。
表1
化学成分 Al2O3 SiO2 A/S
百分含量(％) 57.50 9.3 6.2
硅溶出步骤：铝土矿与碱液混合，配制成反应料浆，碱液中氧化钠的含量为20～700g/L，反应料浆的液固比为2.5～20，反应料浆中铝土矿的磨矿细度为-200目含量90％，反应料浆在微波反应器中反应溶出硅，微波反应器的频率为2450MHz，反应温度90～135℃，反应时间3～20min，反应结束后反应液进行固液分离，所得液相为含硅溶液，试验结果见表2。
表2
Figure PCTCN2016109501-appb-000001
由表2试验结果可知，在碱液Na2O浓度20g/L～700g/L范围内，均能实现一水硬铝石型铝土矿中硅矿物的溶出，且可以通过调节反应时间和反应温度使二氧化硅的溶出率达到50％以上。液固比对硅溶出的影响在于，由于二氧化硅在不同碱浓度条件下的溶解度不同，因此可以通过增加液固比使反应溶液中二氧化硅浓度处于非饱和状态，促进固相中的硅矿物反应溶解于液相，提高硅矿物的溶出率，但是液固比过大时，生产效率会严重下降，因此综合考虑，液固比选择为2～ 50，优选为2～20。反应温度对硅溶出的影响主要表现在，随着反应温度升高，反应加剧，硅溶出速率加快，可以在较短的时间达到溶出硅的目的，但是随着温度升高，固相中的氧化铝也会部分溶解于溶液中，会造成固相回收率下降，如实施例10，所以反应温度不能过高。由以上实施例可知，当反应温度小于105℃时，氧化铝基本不会溶出，得到的含硅溶液中主要为硅。因此，可以通过降低反应温度而延长反应时间的方法来达到提高二氧化硅溶出率、降低氧化铝溶出率的目的。以实施例1-实施例4为例，二氧化硅溶出率均在50％以上，而氧化铝溶出率最高为0.32％，得到的含硅溶液中氧化铝含量为0。
实施例11-17，一水硬铝石型铝土矿高效快速脱硅方法，铝土矿的成分分析结果见表1。
硅溶出步骤：铝土矿与碱液混合，配制成反应料浆，碱液中氧化钠的含量为77.5g/L，反应料浆的液固比为15，反应料浆中铝土矿的磨矿细度为-200目含量90％，反应料浆在微波反应器中反应溶出硅，微波反应器的频率为2450MHz，反应温度50～105℃，反应时间7～120min，反应结束后反应液进行固液分离，所得液相为含硅溶液，试验结果见表3。
表3
Figure PCTCN2016109501-appb-000002
由表3试验结果可知，在相同的反应时间条件下，随着反应温度的升高，硅的溶出率也随之提高。例如实施例17，90℃下反应7min，二氧化硅溶出率达到50.74％。在相同的反应温度条件下，随着反应时间的延长，硅的溶出率也随之提高。例如实施例12，50℃下反应 45min，二氧化硅溶出率达到50.55％。即在较低的温度下反应溶出硅时，随着反应时间的延长，二氧化硅的溶出率也将显著提高。因此在实际生产过程中可以综合反应温度和反应时间二因素，以达到二者的合理匹配。从表3还可以看出，反应温度在低于105℃条件下，均没有氧化铝的溶出。
实施例18
一水硬铝石型铝土矿高效快速脱硅方法，铝土矿的成分分析结果见表1。
硅溶出步骤：铝土矿与碱液混合，配制成反应料浆，碱液中氧化钠的含量为77.5g/L，反应料浆的液固比为20，反应料浆中铝土矿的磨矿细度为-200目含量90％，反应料浆在微波反应器中反应溶出硅，微波反应器的频率为2450MHz，反应温度80℃，反应时间5min，反应结束后反应液进行固液分离，所得液相为含硅溶液。
含硅溶液不进行脱硅处理，直接返回用于处理下一批铝土矿，并向含硅溶液中补加碱液使配制成的反应料浆的液固比保持在20:1，这视为含硅溶液的第一次循环，共经过5次循环。分别测定每次循环后得到的含硅溶液中的Al2O3和SiO2含量，计算溶出率，结果见表4。
表4
Figure PCTCN2016109501-appb-000003
根据表4循环试验结果可知，每批铝土矿矿石1次溶出硅后，根据渣相(固液分离所得固相)计算，SiO2溶出率均达到50％以上。液相含硅溶液中Al2O3和SiO2的浓度随循环次数增多逐渐递增。因此，可以采用含硅溶液循环溶出铝土矿中硅的方式，当含硅溶液中Al2O3和SiO2浓度达到一定值后再进行分离脱硅处理，这样可以节约处理 成本，提高生产效率。
实施例19
一水硬铝石型铝土矿高效快速脱硅方法，铝土矿的成分分析结果见表1。
硅溶出步骤：铝土矿与氢氧化钠溶液混合，配制成反应料浆，氢氧化钠溶液中氧化钠的含量为77.5g/L，反应料浆的液固比为20，反应料浆中铝土矿的磨矿细度为-200目含量60％，反应料浆在微波反应器中反应溶出硅，微波反应器的频率为2450MHz，反应温度70℃，反应时间10min，反应结束后反应液趁热快速固液分离，所得液相为含硅的氢氧化钠溶液，所得固相用50～100℃的热水洗涤，之后进行二次硅溶出处理；
所得固相进行二次硅溶出处理：将所得固相磨矿至粒度为-200目以下占100％，之后与氢氧化钠溶液混合，氢氧化钠溶液的Na2O浓度为77.5g/L，得到二次反应料浆，二次反应料浆的液固比为10，二次反应料浆在微波反应器中反应再次脱硅，反应温度70℃，反应时间5min，反应结束后趁热快速固液分离，得到的液相为含硅的氢氧化钠溶液，所得固相用50～100℃的热水洗涤，得到高铝硅比铝土矿，高铝硅比铝土矿进入拜耳法工艺生产氧化铝。两次得到的含硅的氢氧化钠溶液合并，通过液相脱硅反应生成4A沸石，之后沉淀析出，然后固液分离，得到的氢氧化钠溶液返回用于硅溶出步骤，固体产品为4A沸石。
本实施例的试验结果见表5。
表5
Figure PCTCN2016109501-appb-000004
实施例20
一水硬铝石型铝土矿高效快速脱硅方法，铝土矿的成分分析结果见表6。
表6
化学成分 Al2O3 SiO2 A/S
百分含量(％) 58.44 17.03 3.43
硅溶出步骤：铝土矿与氢氧化钠溶液混合，配制成反应料浆，氢氧化钠溶液中氧化钠的含量为150g/L，反应料浆的液固比为10，反应料浆中铝土矿的磨矿细度为-200目含量95％，反应料浆在微波反应器中反应溶出硅，微波反应器的频率为2450MHz，反应温度105℃，反应时间10min，反应结束后反应液趁热快速固液分离，所得液相为含硅的氢氧化钠溶液，所得固相用100℃的热水洗涤，之后进行二次硅溶出处理；
所得固相进行二次硅溶出处理：将所得固相磨矿至粒度为-200目以下占100％，之后与氢氧化钠溶液混合，氢氧化钠溶液的Na2O浓度为150g/L，得到二次反应料浆，二次反应料浆的液固比为10，二次反应料浆在微波反应器中反应再次脱硅，反应温度100℃，反应时间5min，反应结束后趁热快速固液分离，得到的液相为含硅的氢氧化钠溶液，所得固相用100℃的热水洗涤，得到高铝硅比铝土矿，高铝硅比铝土矿进入拜耳法工艺生产氧化铝。两次得到的含硅的氢氧化钠溶液合并，通过液相脱硅反应生成4A沸石，之后沉淀析出，然后固液分离，得到的氢氧化钠溶液返回用于硅溶出步骤，固体产品为4A沸石。
本实施例的试验结果见表7。
表7
Figure PCTCN2016109501-appb-000005
实施例21-26，三水铝石型铝土矿高效快速脱硅方法，铝土矿的成分分析结果见表8。
表8
化学成分 Al2O3 SiO2 A/S
百分含量(％) 56.00 8.78 6.38
硅溶出步骤：铝土矿与氢氧化钠溶液混合，配制成反应料浆，氢氧化钠溶液中氧化钠的含量为115g/L，反应料浆的液固比为15，反应料浆中铝土矿的磨矿细度为-200目含量90％，反应料浆在微波反应器中反应溶出硅，微波反应器的频率为2450MHz，反应温度50～100℃，反应时间均为5min，反应结束后反应液趁热快速固液分离，所得液相为含硅的氢氧化钠溶液，所得固相用相应反应温度的热水洗涤后得到固相渣。试验结果见表9。
表9
Figure PCTCN2016109501-appb-000006
由表9可知，三水铝石型铝土矿硅溶出过程，随着反应温度的升高，氧化铝和氧化硅同时溶出于氢氧化钠溶液中，在50℃反应5min，即有少量的铝溶出。可见，应用于三水铝石型铝土矿的溶出脱硅时，是铝和硅同时进入碱液的过程，实现在较低温度下同时让铝、硅和其它矿物分离，然后再从碱液中先脱除硅，得到铝酸钠溶液，铝酸钠溶液进行分解反应制备氢氧化铝，分解反应后剩余的反应液经蒸发浓缩，返回用于配制反应料浆溶出下一批矿石。根据溶出温度优选的结果，反应温度在100℃，反应时间5min时，即可使二氧化硅的溶出率大于50％，在较低的温度下进一步延长反应溶出时间也可使二氧化硅的溶出率提高，当然，进一步提高反应温度也可使溶出率进一步提高。
以上各实施例中，在配制反应料浆时，可以先对铝土矿进行磨矿，之后与碱液混合，也可以在与碱液混合后再进行磨矿。
对含硅溶液的脱硅处理属于本领域的现有技术，脱硅处理方法可以是通过改变脱硅溶液的温度如加热升高温度或降温进行脱硅，或者加入脱硅剂进行脱硅，使含硅溶液中的硅酸根离子转变成固相硅沉淀析出。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构变换，或直接或间接运用在其他相关的技术领域，均包括在本发明的专利保护范围内。

Claims (10)

  1. 一种铝土矿高效快速脱硅方法，其特征在于，所述脱硅方法包括步骤：
    硅溶出步骤：铝土矿与碱液混合，配制成反应料浆，所述碱液中氧化钠的含量为20～280g/L，所述反应料浆的液固比为2～50，反应料浆在微波反应器中反应溶出硅，反应温度10～130℃，反应时间2～220min，反应结束后反应液进行固液分离，所得液相为含硅溶液，含硅溶液中SiO2含量为0.3～50g/L。
  2. 根据权利要求1所述的铝土矿高效快速脱硅方法，其特征在于，所述含硅溶液进行脱硅处理，之后沉降、过滤，得到含铁量小于0.5％的含硅渣和脱硅后溶液；
    或者，所述含硅溶液至少循环使用一次，之后再进行脱硅处理，之后沉降、过滤，得到含铁量小于0.5％的含硅渣和脱硅后溶液；
    其中，所述含硅溶液循环使用是指：所述含硅溶液返回用于所述硅溶出步骤，具体包括：含硅溶液与所述碱液混合，用于配制反应料浆。
  3. 根据权利要求2所述的铝土矿高效快速脱硅方法，其特征在于，所述反应料浆中铝土矿的磨矿细度为-200目含量60％～100％。
  4. 根据权利要求3所述的铝土矿高效快速脱硅方法，其特征在于，所述微波反应器的频率为300MHz～300GHz。
  5. 根据权利要求4所述的铝土矿高效快速脱硅方法，其特征在于，所述反应料浆的液固比为2～20。
  6. 根据权利要求5所述的铝土矿高效快速脱硅方法，其特征在于，所述反应料浆在微波反应器中反应溶出硅，反应温度50～105℃，反应时间3～120min。
  7. 根据权利要求6所述的铝土矿高效快速脱硅方法，其特征在于，所述铝土矿为一水硬铝石型铝土矿或三水铝石型铝土矿或一水软铝石型铝土矿。
  8. 根据权利要求7所述的铝土矿高效快速脱硅方法，其特征在于，所述铝土矿为一水硬铝石型铝土矿或一水软铝石型铝土矿时，在硅溶出步骤中，固液分离所得的液相含硅溶液再经脱硅处理后得到的脱硅后溶液为氢氧化钠溶液，所述氢氧化钠溶液返回用于配制反应料浆；
    在硅溶出步骤中，固液分离所得的固相直接用于生产氧化铝；或者，固液分离所得的固相再经硅溶出步骤处理，之后用于生产氧化铝。
  9. 根据权利要求7所述的铝土矿高效快速脱硅方法，其特征在于，所述铝土矿为三水铝石型铝土矿时，在硅溶出步骤中，所得液相含硅溶液再经脱硅处理后得到的脱硅后溶液为铝酸钠溶液，所述铝酸钠溶液进行分解反应制备氢氧化铝，分解反应后剩余的反应液经蒸发浓缩，返回用于配制反应料浆；
    在硅溶出步骤中，固液分离所得的固相用50～100℃的热水洗涤，得到固相渣。
  10. 根据权利要求9所述的铝土矿高效快速脱硅方法，其特征在于，所述固相渣直接作为赤泥排放；
    或者，所述固相渣再经硅溶出步骤处理，之后用50～100℃的热水洗涤，再作为赤泥排放。
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