WO2023056675A1 - Procédé de préparation d'hydrotalcite de magnésium-aluminium par circulation de liqueur mère - Google Patents

Procédé de préparation d'hydrotalcite de magnésium-aluminium par circulation de liqueur mère Download PDF

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Publication number
WO2023056675A1
WO2023056675A1 PCT/CN2021/128173 CN2021128173W WO2023056675A1 WO 2023056675 A1 WO2023056675 A1 WO 2023056675A1 CN 2021128173 W CN2021128173 W CN 2021128173W WO 2023056675 A1 WO2023056675 A1 WO 2023056675A1
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Prior art keywords
magnesium
aluminum
sodium bicarbonate
source
aluminum hydrotalcite
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PCT/CN2021/128173
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English (en)
Chinese (zh)
Inventor
刘志启
吴青山
赵鹏程
周自圆
李娜
焦玲丽
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安徽大学绿色产业创新研究院
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Publication of WO2023056675A1 publication Critical patent/WO2023056675A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • the invention relates to the field of preparation methods of magnesium aluminum hydrotalcite, in particular to a method for preparing magnesium aluminum hydrotalcite by circulating mother liquor.
  • Magnesium aluminum hydrotalcite is a layered double hydroxide compound. Because of its structural characteristics, it has important applications in medicine, water purification, and polymer heat stabilizers.
  • magnesium aluminum hydrotalcite Mg 6 Al 2 CO 3 (OH) 16 4H 2 O
  • synthetic magnesium aluminum hydrotalcite is used.
  • the main synthesis method of magnesium aluminum hydrotalcite is co-precipitation method.
  • the most notable feature of the co-precipitation method is that the target material structure can be synthesized by controlling the molar ratio of M 2+ and M 3+ , the type of interlayer anions, reaction time, temperature and pH value of the solution, and it is widely used.
  • the purpose of the present invention is to provide a method for preparing magnesium-aluminum hydrotalcite by circulating mother liquor, so as to solve the cumbersome operation, high cost of raw materials, generation of by-products and waste liquid, and the prepared finished product in the preparation method of magnesium-aluminum hydrotalcite in the prior art.
  • a method for preparing magnesium aluminum hydrotalcite by mother liquor circulation is characterized in that, comprises the following steps:
  • the ratio of the amount of magnesium source to the aluminum source is 1:1 to 5:1; the ratio of the amount and concentration of sodium bicarbonate to the aluminum source is 1:2 to 3:1; the solid content of the mixed slurry is 5% ⁇ 12%;
  • step S2 stirring and reacting the mixed slurry obtained in step S1 at a constant temperature, and suction filtering after the reaction to obtain a filter cake and a filtrate;
  • step S3 washing and drying the filter cake obtained in step S2 to obtain magnesium aluminum hydrotalcite
  • step S4 passing CO 2 into the filtrate obtained in step S3 to obtain a sodium bicarbonate solution;
  • step S4 sodium bicarbonate is added to the obtained sodium bicarbonate solution, so that the concentration of the sodium bicarbonate solution meets the requirements in step S1.
  • step S4 the amount of sodium bicarbonate added to the sodium bicarbonate solution is 0.01-0.05 mol/L.
  • step S1 the ratio of the amount of the magnesium source to the aluminum source is 2.5:1.
  • the ratio of the amount of sodium bicarbonate to the amount of aluminum source is 1:1.
  • the solid content of the finally obtained mixed slurry was 10%.
  • step S2 the mixed slurry is added into a hydrothermal reaction kettle for a constant temperature stirring reaction, the reaction temperature of the constant temperature stirring reaction is 100-200°C, the hydrothermal reaction time is 1-8h, and the stirring speed is 200-700r /min.
  • the optimum value of reaction temperature is 140°C
  • the optimum value of reaction time is 4h
  • the optimum value of stirring speed is 500r/min.
  • step S3 the filter cake is dried at a temperature of 60-90°C.
  • the optimal value of the temperature is 80°C.
  • step S4 the flow rate of CO 2 is 15-100ml/min, and the time of introduction is 0.5-8h. Among them, the optimal value of the flow rate is 50ml/min, and the optimal value of the time is 4h.
  • the present invention is a brand-new method for preparing magnesium aluminum hydrotalcite from mother liquor circulation, and the reaction expression of the present invention is:
  • reaction (1) sodium bicarbonate participates in the reaction and provides an alkaline environment for the reaction, and magnesium hydroxide and aluminum hydroxide are used as magnesium source and aluminum source respectively.
  • the entire reaction process does not introduce anions other than carbonate or bicarbonate ions, so the slurry after the reaction in (1) can be suction-filtered, the filtrate is collected and CO 2 is introduced, and the by-products after the reaction (1) Na 2 CO 3 is converted into NaHCO 3 according to the reaction (2), so as to realize the recycling of raw materials, no waste water discharge, and meet the relevant requirements of the national environmental protection.
  • the magnesium source and the aluminum source do not need to be treated separately, and can be directly used to participate in the preparation of magnesium aluminum hydrotalcite, and the constant temperature stirring reaction can be carried out, without adding other catalysts, etc., and without taking other measure.
  • the by-product of reaction can be directly prepared into sodium bicarbonate solution, and this sodium bicarbonate solution can be used as mother liquor for next time adopting the method of the present invention to prepare magnesium-aluminum hydrotalcite, so the present invention can form mother liquor circulation when preparing magnesium-aluminum hydrotalcite, The whole process is free of any useless by-products.
  • the advantage of the present invention is:
  • the invention has simple operation steps, low cost, no waste liquid generation, all liquids used can be recycled to participate in the reaction again, no by-products and waste water are generated, the atom utilization rate is high, and the concept of green chemistry and national environmental protection requirements are met.
  • the magnesium aluminum hydrotalcite product prepared by the invention has the characteristics of wide source of raw materials, small particle size distribution, few by-products, high purity, regular shape, no anions that are difficult to remove, and the like.
  • Fig. 1 is a flowchart of an embodiment of the present invention.
  • Fig. 2 is an XRD pattern of cyclically synthesized magnesium aluminum hydrotalcite in Example 1 of the present invention.
  • Embodiment 1 As shown in Figure 1, the process of Embodiment 1 is as follows:
  • Step 1 Use aluminum hydroxide as the aluminum source, the dosage is 19.5g; magnesium hydroxide is used as the magnesium source, the dosage is 36.25g; the dosage of sodium bicarbonate is 21g, add 550ml deionized water, and configure the concentration to be 0.36mol/L sodium bicarbonate solution; then aluminum hydroxide and magnesium hydroxide are added to the sodium bicarbonate solution to form a mixed slurry with a magnesium-aluminum ratio of 2.5:1 and a solid content of 10%.
  • Step 2 Add the mixed slurry obtained in Step 1 into a 2L hydrothermal reaction kettle, raise the temperature to 140° C., and stir for 4 hours at a stirring speed of 500 r/min.
  • Step 3 After the reaction in step 2, the filter cake and filtrate were obtained by suction filtration, wherein the filter cake was washed three times, and then dried at 85° C. for 10 h, and the obtained product was magnesium aluminum hydrotalcite.
  • Step 4 feed CO gas into the filtrate obtained in step 3 at a flow rate of 50ml/min, and the feed time continues for 2.5h to obtain sodium bicarbonate solution.
  • Step 5 in the sodium bicarbonate solution that step 4 obtains, add 0.53g sodium bicarbonate, make the concentration of sodium bicarbonate solution meet the requirement of step 1.
  • the present embodiment 2 is basically the same as the embodiment 1, except that in the present embodiment 2, the flow rate of CO2 gas is 25ml/min, and the feeding time is 3h.
  • Present embodiment 2 process is as follows:
  • Step 1 Use aluminum hydroxide as the aluminum source, the dosage is 19.5g; magnesium hydroxide is used as the magnesium source, the dosage is 36.25g; the dosage of sodium bicarbonate is 21g, add 550ml deionized water, and configure the concentration to be 0.36mol/L sodium bicarbonate solution; then aluminum hydroxide and magnesium hydroxide are added to the sodium bicarbonate solution to form a mixed slurry with a magnesium-aluminum ratio of 2.5:1 and a solid content of 10%.
  • Step 2 Add the mixed slurry obtained in Step 1 into a 2L hydrothermal reaction kettle, raise the temperature to 140° C., and stir for 4 hours at a stirring speed of 500 r/min.
  • Step 3 After the reaction in step 2, the filter cake and filtrate were obtained by suction filtration, wherein the filter cake was washed three times, and then dried at 85° C. for 10 h, and the obtained product was magnesium aluminum hydrotalcite.
  • Step 4 feed CO gas into the filtrate obtained in step 3 at a flow rate of 25ml/min, and the feed time continues for 3h to obtain sodium bicarbonate solution.
  • Step 5 in the sodium bicarbonate solution that step 4 obtains, add 0.53g sodium bicarbonate, make the concentration of sodium bicarbonate solution meet the requirement of step 1.
  • the present embodiment 3 is basically the same as the embodiment 1, except that in the present embodiment 3, the flow rate of CO2 gas is 75ml/min, and the feeding time is 1.5h.
  • Present embodiment 3 process is as follows:
  • Step 1 Use aluminum hydroxide as the aluminum source, the dosage is 19.5g; magnesium hydroxide is used as the magnesium source, the dosage is 36.25g; the dosage of sodium bicarbonate is 21g, add 550ml deionized water, and configure the concentration to be 0.36mol/L sodium bicarbonate solution; then aluminum hydroxide and magnesium hydroxide are added to the sodium bicarbonate solution to form a mixed slurry with a magnesium-aluminum ratio of 2.5:1 and a solid content of 10%.
  • Step 2 Add the mixed slurry obtained in Step 1 into a 2L hydrothermal reaction kettle, raise the temperature to 140° C., and stir for 4 hours at a stirring speed of 500 r/min.
  • Step 3 After the reaction in step 2, the filter cake and filtrate were obtained by suction filtration, wherein the filter cake was washed three times, and then dried at 85° C. for 10 h, and the obtained product was magnesium aluminum hydrotalcite.
  • Step 4 feed CO gas into the filtrate obtained in step 3 at a flow rate of 75ml/min, and the feed time continues for 1.5h to obtain sodium bicarbonate solution.
  • Step 5 in the sodium bicarbonate solution that step 4 obtains, add 0.53g sodium bicarbonate, make the concentration of sodium bicarbonate solution meet the requirement of step 1.

Abstract

Procédé de préparation d'hydrotalcite de magnésium-aluminium par circulation de liqueur mère. Le procédé comprend les étapes suivantes : S1, l'ajout d'une source de magnésium et d'une source d'aluminium à une solution de bicarbonate de sodium pour préparer une suspension mixte; S2, la soumission de la suspension mixte à une réaction sous agitation à température constante; S3, à l'issue de la réaction de l'étape S2, la réalisation d'une filtration par aspiration pour obtenir un gâteau de filtration et un filtrat, et l'obtention d'une hydrotalcite de magnésium-aluminium à partir du gâteau de filtration; S4, l'introduction de CO2 dans le filtrat pour obtenir une solution de bicarbonate de sodium; et S5, le recueil de la solution de bicarbonate de sodium obtenue à l'étape S4, et la répétition des étapes S1 à S4. Le procédé présente des étapes de fonctionnement simples, un faible coût et aucune génération de déchets liquides; tous les liquides utilisés dans ce dernier peuvent être recyclés et impliqués de manière répétée dans la réaction sans générer de sous-produits ni d'eaux usées; le taux d'utilisation d'atomes est élevé; et le concept de chimie verte et les exigences de protection environnementale nationale sont satisfaites. Le produit hydrotalcite de magnésium-aluminium préparé au moyen du procédé est caractérisé en ce qu'il présente de larges sources de matières premières, une faible distribution de taille de particules, peu de sous-produits, une grande pureté, une morphologie régulière, aucun anion qui sont difficiles à éliminer, etc.
PCT/CN2021/128173 2021-10-09 2021-11-02 Procédé de préparation d'hydrotalcite de magnésium-aluminium par circulation de liqueur mère WO2023056675A1 (fr)

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CN202111175388.5A CN113830806A (zh) 2021-10-09 2021-10-09 一种母液循环制备镁铝水滑石的方法
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CN114904457A (zh) * 2022-03-28 2022-08-16 自然资源部天津海水淡化与综合利用研究所 一种母液碳中和的碳酸根型层状氢氧化镁铝连续生产设备和工艺
CN114988451A (zh) * 2022-05-30 2022-09-02 安徽大学绿色产业创新研究院 一种利用碳酸镁合成镁铝插层材料的制备方法
CN115057460A (zh) * 2022-06-06 2022-09-16 安徽大学绿色产业创新研究院 一种天然水菱镁制备镁铝水滑石的方法

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CN107416872A (zh) * 2017-09-01 2017-12-01 上海华峰新材料研发科技有限公司 镁铝碳酸根型水滑石的制备方法
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