WO2015089777A1

WO2015089777A1 - Method for preparing light, ball-flower shaped nanometer magnesium hydroxide with high specific surface area

Info

Publication number: WO2015089777A1
Application number: PCT/CN2013/089902
Authority: WO
Inventors: 林璋; 陈伦泰; 王永好; 吴智诚; 洪杨平; 黄嘉魁
Original assignee: 中国科学院福建物质结构研究所
Priority date: 2013-12-18
Filing date: 2013-12-18
Publication date: 2015-06-25

Abstract

The present invention relates a method for preparing light, ball-flower shaped nanometer magnesium hydroxide with high specific surface area, comprising the following steps of: (1) preparing a magnesium salt aqueous solution with a certain concentration in a reaction vessel; (2) preparing an alkali solution with a certain concentration in a vessel; (3) adding a certain amount of dispersant into the solution of step (1) or the solution of step (2) before reaction; (4) dropping the solution of step (2) into the solution of step (1) slowly, or dropping the solution of step (1) into the solution of step (2) slowly, reacting and obtaining a white precipitate, centrifuging and cleaning the white precipitate (magnesium hydroxide) after aging to remove other impurity ions, thereby obtaining a white gelatinous solid. The method of the present invention provides a method for preparing a special morphological magnesium hydroxide, and the method has the characteristic of simple operation, nonpollution for environment, easy of enlarging scale production and low requirements for apparatus. The magnesium hydroxide synthesized by the method is mainly used for treatment of dyeing waste water, adsorption of heavy metal ion and desulphurizer of flue gas.

Description

说明书一种制造轻质、高比表面积、花球型纳米氢氧化镁的方法技术领域 Method for producing lightweight, high specific surface area, flower-sphere type nanometer magnesium hydroxide

本发明属于无机材料制备技术领域。具体是一种利用碱和镁盐在添加分散剂情况下反应制造具有特殊形貌的纳米氢氧化镁的方法。 The invention belongs to the technical field of inorganic material preparation. Specifically, it is a method of producing a nano-magnesium hydroxide having a special morphology by reacting a base and a magnesium salt with the addition of a dispersant.

背景技术 Background technique

氢氧化镁具有其他无机材料不具有的优点，因为其热稳定性好、分解温度高、无毒、及抑烟等，传统上主要作为高性能无机阻燃剂应用于高分子材料中。在酸雨土壤治理、食品与饲料添加剂、以及生物和医药制剂方面均有不同程度的应用，是一种公认的环境友好型的绿色化工产品。目前，氢氧化镁受到了各国重视，是发达国家在推行可持续发展战略、保护环境、有益生态发展进程中备受青睐和推崇的产品之一，被称为绿色安全中和剂、环境友好阻燃剂和第三种碱，有关研究生产活动十分活跃。除此之外，氢氧化镁还用于： Magnesium hydroxide has advantages that other inorganic materials do not have, because of its good thermal stability, high decomposition temperature, non-toxicity, and smoke suppression, it has been traditionally used as a high-performance inorganic flame retardant in polymer materials. It is a recognized environmentally friendly green chemical product with varying degrees of application in acid rain soil treatment, food and feed additives, and biological and pharmaceutical preparations. At present, magnesium hydroxide has been valued by all countries and is one of the products favored and respected by developed countries in the implementation of sustainable development strategies, environmental protection and beneficial ecological development. It is called green safe neutralizer and environmentally friendly. The fuel and the third alkali are very active in research and production activities. In addition to this, magnesium hydroxide is also used in:

1、环保的酸性废水的中和剂：绿色安全，中和后 pH不超过 9, 附带吸附重金属离子； 1. Neutralizer for environmentally friendly acidic wastewater: Green safe, pH is not more than 9, after adsorption, with heavy metal ions adsorbed;

2、印染废水处理：脱色效果明显； 2. Printing and dyeing wastewater treatment: The decolorization effect is obvious;

3、烟道气脱硫剂或燃煤固硫剂：脱硫率高达 95%-98%, 高于其他试剂； 3. Flue gas desulfurizer or coal-fired sulfur-fixing agent: Desulfurization rate is as high as 95%-98%, higher than other Reagent

4、重金属离子去除剂：能吸附 As³⁺、 M²⁺、 Pb²⁺、 Cd²⁺、 Mn²⁺、 Cr³⁺、 Cr⁶⁺、 U³⁺等、吸附效果明显。 4. Heavy metal ion remover: It can adsorb As ³⁺ , M ²⁺ , Pb ²⁺ , Cd ²⁺ , Mn ²⁺ , Cr ³⁺ , Cr ⁶⁺ , U ^{3+ ,} etc .

另外，氢氧化镁是一种重要的无机化工原料，特定形貌的纳米氢氧化镁可作为特定功能材料，纳米氢氧化镁的优异性能引起材料化学界的广泛关注。由于氢氧化镁颗粒的形貌及尺寸对其应用有 f艮大影响，所以探索合成具有特殊形貌及微细尺寸的氢氧化镁就显得非常必要。其中纳米氢氧化镁因尺寸小而具有很多独特的效应. 如小尺寸效应、量子尺寸效应、表面效应、宏观量子的隧道效应等，使得纳米氢氧化镁具有优异的化学和物理性能，扩大其的应用范围。 In addition, magnesium hydroxide is an important inorganic chemical raw material, and nano-magnesium hydroxide with specific morphology can be used as a specific functional material. The excellent performance of nano-magnesium hydroxide has attracted wide attention in the field of material chemistry. Since the morphology and size of magnesium hydroxide particles have a great influence on their application, it is necessary to explore the synthesis of magnesium hydroxide with special morphology and fine size. Among them, nanometer magnesium hydroxide has many unique effects due to its small size. For example, small size effect, quantum size effect, surface effect, macroscopic quantum tunneling, etc., make nanometer magnesium hydroxide have excellent chemical and physical properties, and expand its Application range.

目前纳米氢氧化镁粉体制备方法主要有沉淀合成法，水热法，反向沉淀法，沉淀-共沸蒸馏法等，但仍存在着许多问题： At present, nanometer magnesium hydroxide powder preparation methods mainly include precipitation synthesis method, hydrothermal method, reverse precipitation method, precipitation-azeotropic distillation method, etc., but there are still many problems:

1、如所制产品粒径大、纯度不高、粒径分布不均匀； 1. If the product is large in particle size, the purity is not high, and the particle size distribution is not uniform;

2、设备要求高、条件苛刻、操作复杂、产品的收率低等缺点， 2. Shortcomings such as high equipment requirements, harsh conditions, complicated operation, and low product yield.

3、工业化难、产量低、成本高。 3. Industrialization is difficult, production is low, and cost is high.

4、大部分企业生产氢氧化镁的工艺为卤水氨法工艺，副产物氨氮含量高，氨氮是国家严格限制排放的物质，排放会造成环境问题。其次是生产过程由于氨水的挥发性会产生刺激性气味。发明内容 4. The process of producing magnesium hydroxide in most enterprises is the brine ammonia process. The by-product ammonia nitrogen content is high. Ammonia nitrogen is a substance that is strictly restricted by the state, and emissions will cause environmental problems. Secondly, the production process produces a pungent odor due to the volatility of ammonia. Summary of the invention

本发明目的是为了克服现有技术制备纳米氢氧化镁存在的缺点，提供一种易生产特殊形貌氢氧化镁的方法，使用简单设备，操作容易，易于工业放大、对环境无污染、在室温下即可得到纳米氢氧化镁，最终产物易清洗，干燥后不团聚，并且纯度高。使用本法制备的氢氧化镁是一种轻质型的氢氧化镁，具有微-纳结构，氢氧化镁纳米薄片经自组装形成花球型结构，产物具有大的比表面积。 The object of the present invention is to overcome the shortcomings of the prior art for preparing nanometer magnesium hydroxide, and to provide a method for easily producing magnesium hydroxide with special morphology, which is easy to operate and easy to use. Industrial amplification, no pollution to the environment, nano magnesium hydroxide can be obtained at room temperature, the final product is easy to clean, does not agglomerate after drying, and has high purity. The magnesium hydroxide prepared by the method is a light-weight magnesium hydroxide having a micro-nano structure, and the magnesium hydroxide nanosheets are self-assembled to form a globular structure, and the product has a large specific surface area.

为实现上述目的，本发明通过如下技术方案实现： To achieve the above object, the present invention is achieved by the following technical solutions:

一种制备纳米氢氧化镁的方法，其特征在于，包括如下步骤： A method for preparing nanometer magnesium hydroxide, comprising the steps of:

(1)在反应容器中配制一定浓度镁盐水溶液； (1) preparing a certain concentration of magnesium salt aqueous solution in a reaction vessel;

(2)在容器中配制一定浓度的碱溶液； (2) preparing a certain concentration of an alkali solution in the container;

(3)反应前，在步骤（1)溶液或者步骤（2)溶液中添加一定量的剂，也可以在两种溶液中都添加分散剂； (3) before the reaction, adding a certain amount of the agent in the step (1) solution or the step (2) solution, or adding a dispersing agent in both solutions;

(4)将步骤（2) 中的溶液緩慢滴入步骤（1)的溶液中，或者将步骤（1)的溶液緩慢滴入步骤（2)的溶液中，反应得到白色沉淀，陈化后，将白色沉淀（氢氧化镁）离心清洗，洗涤除去其他杂质离子，得到白色凝胶状固体。 (4) slowly dropping the solution in the step (2) into the solution of the step (1), or slowly dropping the solution of the step (1) into the solution of the step (2) to obtain a white precipitate, and after aging, The white precipitate (magnesium hydroxide) was washed by centrifugation, and other impurity ions were removed by washing to obtain a white gelatinous solid.

根据本发明，所述步骤（3)优选在步骤（1)的溶液中添加一定量的分散剂，或者在步骤（2)的溶液中添加一定量的分散剂，或者在两种溶液中都添加分散剂。 According to the invention, the step (3) preferably adds a certain amount of a dispersing agent to the solution of the step (1), or adds a certain amount of a dispersing agent to the solution of the step (2), or adds both solutions. Dispersant.

根据本发明，优选将剂与步骤（1)或（2)的溶液进行均匀混合。 According to the present invention, it is preferred to uniformly mix the agent with the solution of the step (1) or (2).

根据本发明，其中步骤（ 3 )所述的分散剂选自低级二元醇或低级三元醇，例如 2-6个碳原子的二元醇或三元醇类，优选乙二醇、丙二醇、丙三醇、丁二醇、丁三醇或丁四醇；最优选乙二醇或丙三醇。 According to the present invention, the dispersing agent according to the step (3) is selected from a lower diol or a lower triol, for example, a diol or a trihydric alcohol having 2 to 6 carbon atoms, preferably ethylene glycol or propylene glycol. Glycerol, butanediol, butyltriol or butanol; most preferred is ethylene glycol or glycerol.

根据本发明，所述分散剂的加入量为步骤（ 1 )或（ 2 )中溶液的 1-50% 重量，优选 5-40%重量，更优选 10-30%重量，最优选 20-30%重量。 According to the invention, the dispersing agent is added in an amount of from 1 to 50% by weight, preferably from 5 to 40% by weight, more preferably from 10 to 30% by weight, most preferably from 20 to 30% by weight of the solution in the step (1) or (2) weight.

根据本发明的优选技术方案： Preferred technical solution according to the invention:

( 1 )配置一定量的分散剂溶液，然后加入一定浓度的镁盐水溶液，任选再加入一定量的剂，混合均匀； (1) arranging a certain amount of dispersant solution, then adding a certain concentration of magnesium salt aqueous solution, optionally adding a certain amount of the agent, and mixing uniformly;

( 2 )在容器中配制一定浓度的碱溶液； (2) preparing a certain concentration of an alkali solution in the container;

( 4 )将步骤（2 )中的溶液緩慢滴入步骤（1 )的溶液中，或者将步骤（1 )的溶液緩慢滴入步骤（2 )的溶液中，反应得到白色沉淀，陈化后，将白色沉淀（氢氧化镁）离心清洗，洗涤除去其他杂质离子，得到白色皿状固体。 (4) slowly dropping the solution in the step (2) into the solution of the step (1), or slowly dropping the solution of the step (1) into the solution of the step (2) to obtain a white precipitate, and after aging, The white precipitate (magnesium hydroxide) was washed by centrifugation, and other impurity ions were removed by washing to obtain a white dish-like solid.

( 1 )配置一定浓度的镁盐水溶液； (1) arranging a certain concentration of magnesium salt aqueous solution;

( 2 )配置一定量的分散剂溶液，然后在容器中配制一定浓度的碱溶液，任选再加入一定量的剂，混合均匀； (2) arranging a certain amount of dispersant solution, and then preparing a certain concentration of alkali solution in the container, optionally adding a certain amount of the agent, and mixing uniformly;

( 4 )将步骤（ 2 )中的溶液緩慢滴入步骤（ 1 )的溶液中，或者将步骤（1 )的溶液緩慢滴入步骤（2 )的溶液中，反应得到白色沉淀，陈化后，将白色沉淀（氢氧化镁）离心清洗，洗涤除去其他杂质离子，得到白色皿状固体。根据本发明的优选技术方案： (4) slowly dropping the solution in the step (2) into the solution of the step (1), or slowly dropping the solution of the step (1) into the solution of the step (2) to obtain a white precipitate, and after aging, The white precipitate (magnesium hydroxide) was washed by centrifugation, and other impurity ions were removed by washing to obtain a white dish-like solid. Preferred technical solution according to the invention:

(1)配置一定量的分散剂溶液，然后加入一定浓度的镁盐水溶液，任选再加入一定量的剂，混合均匀； (1) Configuring a certain amount of dispersant solution, and then adding a certain concentration of magnesium salt aqueous solution, optionally adding a certain amount of the agent, and mixing uniformly;

(2)配置一定量的分散剂溶液，然后在容器中配制一定浓度的碱溶液，任选再加入一定量的剂，混合均匀； (2) Configuring a certain amount of dispersant solution, and then preparing a certain concentration of alkali solution in the container, optionally adding a certain amount of the agent, and mixing uniformly;

(4)将步骤（2)中的溶液緩慢滴入步骤（1)的溶液中，或者将步骤（1)的溶液緩慢滴入步骤（2)的溶液中，反应得到白色沉淀，陈化后，将白色沉淀（氢氧化镁）离心清洗，洗涤除去其他杂质离子，得到白色皿状固体。 (4) The solution in the step (2) is slowly dropped into the solution of the step (1), or the solution of the step (1) is slowly dropped into the solution of the step (2), and the reaction is white precipitated, and after aging, The white precipitate (magnesium hydroxide) was washed by centrifugation, and other impurity ions were removed by washing to obtain a white dish-like solid.

根据本发明，其中步骤（ 1 )所述的镁盐可以为硫酸镁 (无水硫酸镁或者七水硫酸镁）、氯化镁（无水氯化镁或者六水氯化镁），硝酸镁（无水硝酸镁或者六水硝酸镁)。优选地，所述镁盐选自硫酸镁或氯化镁。 According to the present invention, the magnesium salt in the step (1) may be magnesium sulfate (anhydrous magnesium sulfate or magnesium sulfate heptahydrate), magnesium chloride (anhydrous magnesium chloride or magnesium chloride hexahydrate), magnesium nitrate (anhydrous magnesium nitrate or six). Water magnesium nitrate). Preferably, the magnesium salt is selected from magnesium sulfate or magnesium chloride.

根据本发明，所述镁盐水溶液的浓度优选为 0.1-4mol/L, 优选为 0.3-1.5mol/L; 更优选为 0.5-lmol/L。 According to the invention, the concentration of the aqueous magnesium salt solution is preferably from 0.1 to 4 mol/L, preferably from 0.3 to 1.5 mol/L; more preferably from 0.5 to 1 mol/L.

根据本发明，其中步骤（2)所述的碱溶液选自氢氧化锂、氢氧化钠、氢氧化钾或者氨水等。优选地，所述碱溶液为氢氧化钠或氢氧化钾。 According to the invention, the alkali solution described in the step (2) is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonia water. Preferably, the alkali solution is sodium hydroxide or potassium hydroxide.

根据本发明，所述碱溶液的浓度优选为 0.5-20mol/L, 优选为 l-10mol/L。 According to the invention, the concentration of the alkali solution is preferably from 0.5 to 20 mol/L, preferably from 1 to 10 mol/L.

根据本发明，在进行步骤（4)之前还包括如下步骤：任选加入其它有机辅助溶剂，混合均匀。根据本发明，所述有机辅助溶剂还可以在分散剂与步骤（1 )或（2 ) 的溶液混合之前加入到反应器中。 According to the present invention, the following steps are further included before the step (4): optionally adding other organic auxiliary solvent, and mixing is uniform. According to the invention, the organic auxiliary solvent can also be added to the reactor before the dispersant is mixed with the solution of step (1) or (2).

根据本发明，所述有机辅助溶剂选自：低级一元醇类、醚类或低级酮类有机辅助溶剂，例如 1-6个碳原子的一元醇类或 1-6个碳原子的醚类或 1-6个碳原子的低级酮类，优选为曱醇、乙醇或丙酮，更优选乙醇。 According to the present invention, the organic auxiliary solvent is selected from the group consisting of: a lower monohydric alcohol, an ether or a lower ketone organic auxiliary solvent, for example, a monohydric alcohol of 1 to 6 carbon atoms or an ether of 1 to 6 carbon atoms or 1 The lower ketone of -6 carbon atoms is preferably decyl alcohol, ethanol or acetone, more preferably ethanol.

根据本发明，所述有机辅助溶剂优选以溶液形式加入到反应器中，例如优选体积比为 1: 1-1: 4, 例如 1: 2-1: 3的低级醇的水溶液，例如乙醇水溶液的形式加入到反应器中。 According to the invention, the organic auxiliary solvent is preferably added to the reactor in the form of a solution, for example, an aqueous solution of a lower alcohol having a volume ratio of 1:1-1:4, for example 1:2:3, such as an aqueous ethanol solution. The form is added to the reactor.

根据本发明，所述步骤（4 ) 中，优选将步骤（2 ) 中的溶液緩慢滴入步骤（1 )的溶液中。 According to the invention, in the step (4), the solution in the step (2) is preferably slowly dropped into the solution of the step (1).

根据本发明，所述滴加在 20-60。C , 例如室温下进行。 According to the invention, the addition is at 20-60. C, for example, at room temperature.

根据本发明，所述反应在室温下在一定的搅拌速率下进行。所述搅拌速率为 100-5000转 /分，优选 700-3000转 /分。搅拌时间为 5-48小时，优选 10-24小时。 According to the invention, the reaction is carried out at room temperature at a certain agitation rate. The agitation rate is from 100 to 5,000 rpm, preferably from 700 to 3,000 rpm. The stirring time is 5-48 hours, preferably 10-24 hours.

根据本发明，所述步骤（4 ) 中，陈化时间为 1-8小时，优选 2-6小时。 According to the invention, in the step (4), the aging time is from 1 to 8 hours, preferably from 2 to 6 hours.

根据本发明，所述步骤（4 )中，将离心清洗后的白色沉淀用去离子水洗涤，优选数次，例如 1-4次。 According to the invention, in the step (4), the white precipitate after centrifugation washing is washed with deionized water, preferably several times, for example, from 1 to 4 times.

根据本发明，所述步骤（4 )中，在洗、涤至无其他杂质离子后，再使用无水乙醇洗、涤一次，即得到白色凝胶状固体。 According to the present invention, in the step (4), after washing and washing until no other impurity ions are present, it is washed with anhydrous ethanol and once, to obtain a white gelatinous solid.

根据本发明，所述步骤（4 )中，将白色固体在一定温度下干燥至恒重，即得到氢氧化镁粉体。优选地，所述干燥温度为 30^eC-340^eC , 优选干燥温度为 60-200。C。 According to the invention, in the step (4), the white solid is dried to a constant temperature at a constant temperature. Heavy, that is, magnesium hydroxide powder is obtained. Preferably, the drying temperature is from 30 ^e C to 340 ^e C, preferably from 60 to 200. C.

根据本发明，所制备得到的氢氧化镁烘干前为凝胶状；最终得到的氢氧化镁为具有微-纳结构、轻质、高比表面积、花球型纳米氢氧化镁。优选氢氧化镁的松装密度： < 0.15_g/mL , 并且具有大的比表面积： >50m²/g, 优选 >100m²/g。 According to the present invention, the prepared magnesium hydroxide is in the form of a gel before drying; the finally obtained magnesium hydroxide is a nano-magnesium hydroxide having a micro-nano structure, a light weight, a high specific surface area, and a flower ball type. Preference is given to a bulk density of magnesium hydroxide: < 0.15 _g /mL and a large specific surface area: > 50 m ² /g, preferably > 100 m ² /g.

本发明与现有技术相比的有益效果是：在生产过程中，通过使用丙三醇或者乙二醇等为添加剂，在室温下反应即可得到的产品为纳米花球型氢氧化镁，干燥后不团聚，得到粉末状氢氧化镁。所需反应的设备简单，易操作，易放大、对环境无污染。使用本发明方法合成的氢氧化镁粒径均匀，分散性好，纯度高，易于大量合成。如果需要生产大量的氢氧化镁产量，只需按下面所述的实施例按比例放大即可。使用本办法合成的氢氧化镁主要用于印染废水处理、重金属离子吸附、烟道气脱硫剂。 The beneficial effects of the present invention compared with the prior art are: in the production process, by using glycerol or ethylene glycol as an additive, the product obtained by the reaction at room temperature is nano-flower-type magnesium hydroxide, dried. After the agglomeration, powdered magnesium hydroxide was obtained. The equipment required for the reaction is simple, easy to operate, easy to amplify, and environmentally friendly. The magnesium hydroxide synthesized by the method of the invention has uniform particle size, good dispersibility, high purity and easy synthesis in a large amount. If it is desired to produce a large amount of magnesium hydroxide production, simply scale up as described in the examples below. Magnesium hydroxide synthesized by this method is mainly used for printing and dyeing wastewater treatment, heavy metal ion adsorption, and flue gas desulfurizing agent.

附图说明 DRAWINGS

图 1为实施例 1所的产物的扫描电镜照片（X2000)示意图 Figure 1 is a schematic view of a scanning electron micrograph (X2000) of the product of Example 1.

图 2为实施例 1所的产物的扫描电镜照片（xlOOOO)示意图 2 is a schematic view of a scanning electron micrograph (x100) of the product of Example 1.

图 3为实施例 1所的产物的扫描电镜照片（X30000)示意图 Figure 3 is a schematic view of a scanning electron micrograph (X30000) of the product of Example 1.

图 4为实施例 2制备的纳米氢氧化镁样品的粉末衍射图 4 is a powder diffraction pattern of a nanometer magnesium hydroxide sample prepared in Example 2.

具体实施方式: 物相分析：使用 JEOL公司生产的型号为 JSM-6700F扫描电子显微镜分析，本产品的氢氧化镁纳米片自组装聚合体的粒径在 ΙΟμιη左右 (如图 1所示)，纳米片厚度为 15 nm (如图 2、图 3所示)。用 BET方法测得的氢氧化镁比表面积为 110 m²/_g。由于氢氧化镁粉体的纳米化，氢氧化镁衍射图上的衍射峰展宽，并且粉末衍射图上未见其他杂质峰，说明得到的氢氧化镁纯度高 (如图 4所示)。 detailed description: Phase analysis: Using JXOL's model JSM-6700F scanning electron microscope analysis, the particle size of the self-assembled polymer of magnesium hydroxide nanosheets of this product is around ΙΟμιη (as shown in Figure 1), and the thickness of nanosheets is 15 Nm (as shown in Figure 2 and Figure 3). The specific surface area of magnesium hydroxide measured by the BET method was 110 m ² / _g . Due to the nanocrystallization of the magnesium hydroxide powder, the diffraction peak on the magnesium hydroxide diffraction pattern is broadened, and no other impurity peaks are observed on the powder diffraction pattern, indicating that the obtained magnesium hydroxide has high purity (as shown in FIG. 4).

实施例 1: Example 1:

A. 在反应容器中配制乙醇、水比例为 1:1的混合溶液，在此混合溶液中配制 0.5 mol/L的硫酸镁溶液，并加入 30% (质量分数）的丙三醇，混合均匀。 A. Prepare a mixed solution of ethanol and water in a ratio of 1:1 in the reaction vessel, prepare a 0.5 mol/L magnesium sulfate solution in the mixed solution, and add 30% (mass fraction) of glycerin to mix well.

B. 在容器中配制乙醇、水比例为 1:4的混合溶液，在此混合溶液中配制 1 mol/L氢氧化钠溶液。 B. Prepare a mixed solution of ethanol and water in a ratio of 1:4 in a container, and prepare a 1 mol/L sodium hydroxide solution in the mixed solution.

C. 在室温下将 1L的 B所述溶液緩慢滴入 1L的 A所述溶液，同时在 700转 /分的搅拌速度搅拌反应 20 h, 在反应容器 A中得到白色沉淀，陈化 2 h后，将白色沉淀过滤，用去离子水洗、涤数次，直到无硫酸根离子，再使用无水乙醇洗涤，得到白色固体，将白色固体在 60。C温度下干燥至恒重，即得轻质、高比表面积（90 m²/_g )、花球型纳米氢氧化镁。 C. 1 L of the solution of B was slowly dropped into 1 L of the solution of A at room temperature, while stirring at a stirring speed of 700 rpm for 20 h, a white precipitate was obtained in the reaction vessel A, and after aging for 2 h. The white precipitate was filtered, washed with deionized water and washed several times until there was no sulfate ion, and then washed with anhydrous ethanol to give a white solid. Drying to constant weight at C temperature gives a light weight, high specific surface area (90 m ² / _g ), and nano-magnesium hydroxide.

实施例 2: Example 2:

A. 在反应容器中配制 0.5 mol/L的硫酸镁水溶液，并加入 30% (质量分数）的丙三醇，混合均匀。 A. Prepare a 0.5 mol/L aqueous solution of magnesium sulfate in the reaction vessel and add 30% The amount of glycerol is mixed evenly.

B. 在容器中配制 1 mol/L氢氧化钠水溶液。 B. Prepare a 1 mol/L sodium hydroxide solution in the container.

C. 在室温下将 1L的 B所述溶液緩慢滴入 1L的 A所述溶液，同时在 700转 /分的搅拌速度搅拌反应 15 h, 在反应容器 A中得到白色沉淀，陈化 1.5 h后，将白色沉淀过滤，用去离子水洗、涤数次，直到无硫酸根离子，再使用无水乙醇洗涤，得到白色固体，将白色固体在 100。C温度下干燥至恒重，即得轻质、高比表面积（110 m²/_g )、花球型纳米氢氧化镁。 C. 1 L of the solution of B was slowly dropped into 1 L of the solution of A at room temperature, while stirring at a stirring speed of 700 rpm for 15 h, a white precipitate was obtained in the reaction vessel A, and aged for 1.5 h. The white precipitate was filtered, washed with deionized water and dried several times until no sulfate ion was taken and washed with anhydrous ethanol to give a white solid. Drying to constant weight at C temperature gives a light, high specific surface area (110 m ² / _g ), and a nano-magnesium hydroxide.

实施例 3: Example 3:

A. 在反应容器中配制 0.5 mol/L的氯化镁水溶液，并加入 15% (质量分数）的丙三醇，混合均匀。 A. Prepare a 0.5 mol/L aqueous solution of magnesium chloride in a reaction vessel and add 15% (mass fraction) of glycerol. Mix well.

B. 在容器中配制 1 mol/L氢氧化钾水溶液，并加入 15% (质量分数）的丙三醇，混合均匀。 B. Prepare a 1 mol/L potassium hydroxide solution in a container and add 15% (mass fraction) of glycerol. Mix well.

C. 在室温下将 1L的 B所述溶液緩慢滴入 1L的 A所述溶液，同时在 700转 /分的搅拌速度搅拌反应 8h, 在反应容器 A中得到白色沉淀，陈化 3 h后，将白色沉淀离心清洗，用去离子水洗、涤数次，直到无氯离子 ,再使用无水乙醇洗、涤一次 ,得到白色凝胶状固体，将白色固体在 150。C 下干燥至恒重，即得轻质、高比表面积（70 m²/_g )、花球型纳米氢氧化镁。 C. 1 L of the solution of B was slowly dropped into 1 L of the solution of A at room temperature, while stirring at 800 rpm for 8 h, a white precipitate was obtained in the reaction vessel A, and after aging for 3 h, The white precipitate was washed by centrifugation, washed with deionized water, and washed several times until there was no chloride ion, and then washed with anhydrous ethanol and washed once to obtain a white gelatinous solid. Drying to constant weight under C gives a light weight, high specific surface area (70 m ² / _g ), and a spherical nano-magnesium hydroxide.

实施例 4: Example 4:

A. 在反应容器中配制乙醇、水比例为 1:1的混合溶液，在此溶液中配制 0.5 mol/L的硫酸镁溶液。 A. Prepare a mixed solution of ethanol and water in a ratio of 1:1 in the reaction vessel, in which the solution is Prepare a 0.5 mol/L magnesium sulfate solution.

B. 在容器中配制乙醇、水比例为 1:1的混合溶液，在此溶液中配制 1 mol/L氢氧化钠溶液，并加入 30% (质量分数）的丙三醇，混合均匀。 B. Prepare a mixed solution of ethanol and water in a ratio of 1:1 in the container, prepare a 1 mol/L sodium hydroxide solution in this solution, and add 30% (mass fraction) of glycerin, and mix well.

C. 在室温下将 1L的 B所述溶液緩慢滴入 1L的 A所述溶液，同时在 700转 /分的搅拌速度搅拌反应 18h, 在反应容器 A中得到白色沉淀，陈化 2.5 h后，将白色沉淀离心清洗，用去离子水洗、涤数次，直到无硫酸根离子，再使用无水乙醇洗、涤一次，得到白色凝胶状固体，将白色固体在 60。C下干燥至恒重，即得轻质、高比表面积（80 m²/_g )、花球型纳米氢氧化镁。 C. 1 L of the solution of B was slowly dropped into 1 L of the solution of A, while stirring at a stirring speed of 700 rpm for 18 h, a white precipitate was obtained in the reaction vessel A, and after aging for 2.5 h, The white precipitate was washed by centrifugation, washed with deionized water, and washed several times until there was no sulfate ion, and washed with absolute ethanol to obtain a white gelatinous solid with a white solid at 60. Drying to constant weight under C gives a light weight, high specific surface area (80 m ² / _g ), and a nano-magnesium hydroxide.

实施例 5: Example 5

A. 在反应容器中配制 1 mol/L的氯化镁水溶液。 A. Prepare a 1 mol/L aqueous solution of magnesium chloride in the reaction vessel.

B. 在容器中配制 2 mol/L氢氧化钠水溶液，并加入 30% (质量分数 ) 的丙三醇，混合均匀。 B. Prepare a 2 mol/L sodium hydroxide solution in a container and add 30% (mass fraction) of glycerol. Mix well.

C. 在室温下将 1L的 B所述溶液緩慢滴入 1L的 A所述溶液，同时在 700转 /分的搅拌速度搅拌反应 10 h, 在反应容器 A中得到白色沉淀，陈化 2 h后，将白色沉淀离心清洗，用去离子水洗、涤数次，直到无氯离子，再使用无水乙醇洗涤一次，得到白色皿状固体，将白色固体在 60。C 下干燥至恒重，即得轻质、高比表面积（72 m²/_g )、花球型纳米氢氧化镁。 A. 在反应容器中配制 l mol/L的氯化镁水溶液。并加入 30% (质量分数）的乙二醇，混合均匀。 C. 1 L of the solution of B was slowly dropped into 1 L of the solution of A at room temperature, while stirring at 700 rpm for 10 h, a white precipitate was obtained in the reaction vessel A, and aged for 2 h. The white precipitate was washed by centrifugation, washed with deionized water, and washed several times until there was no chloride ion, and then washed once with absolute ethanol to obtain a white dish-like solid with a white solid at 60. Drying to constant weight under C gives a light weight, high specific surface area (72 m ² / _g ), and a spherical nano-magnesium hydroxide. A. Prepare a 1 mol/L aqueous solution of magnesium chloride in the reaction vessel. Add 30% (mass fraction) of ethylene glycol and mix well.

B. 在容器中配制 2 mol/L氢氧化钠水溶液。 B. Prepare a 2 mol/L sodium hydroxide solution in a container.

C. 在室温下将 1L的 B所述溶液緩慢滴入 1L的 A所述溶液，同时在 700转 /分的搅拌速度搅拌反应 10 h, 在反应容器 A中得到白色沉淀，陈化 2.5 h后，将白色沉淀离心清洗，用去离子水洗、涤数次，直到无氯离子，再使用无水乙醇洗涤一次，得到白色皿状固体，将白色固体在 60。C 下干燥至恒重，即得轻质、高比表面积（68 m²/_g )、花球型纳米氢氧化镁。 C. 1 L of the solution of B was slowly dropped into 1 L of the solution of A at room temperature, while stirring at a stirring speed of 700 rpm for 10 h, a white precipitate was obtained in the reaction vessel A, and aged for 2.5 h. The white precipitate was washed by centrifugation, washed with deionized water, and washed several times until there was no chloride ion, and then washed once with absolute ethanol to obtain a white dish-like solid with a white solid at 60. Drying to constant weight at C gives a light weight, high specific surface area (68 m ² / _g ), and a spherical nano-magnesium hydroxide.

实施例 7: Example 7

A. 在反应容器中配制 0.5 mol/L的硫酸镁水溶液，并加入 30% (质量分数）的丙三醇，混合均匀。 A. Prepare a 0.5 mol/L aqueous solution of magnesium sulfate in a reaction vessel and add 30% (mass fraction) of glycerol. Mix well.

C. 在室温下将 37.5 L的 B所述溶液緩慢滴入 30 L的 A所述溶液，同时在 700转 /分的搅拌速度搅拌反应 24 h,在反应容器 A中得到白色沉淀，陈化 6 h后，将白色沉淀离心清洗，用去离子水洗、涤数次，直到无硫酸根离子，再使用无水乙醇洗、涤一次，得到白色凝胶状固体，将白色固体在 60 。C下干燥至恒重，即得公斤级轻质、高比表面积（56 m²/_g )、花球型纳米氢氧化镁。最后应说明的是：以上所述实施例仅为本发明的优选实施例，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记栽的方案进行修改，或者对其中部分技术特征进行更改、等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 C. 37.5 L of the solution of B was slowly dropped into 30 L of the solution of A at room temperature, while stirring at a stirring speed of 700 rpm for 24 h, a white precipitate was obtained in the reaction vessel A, aged 6 After h, the white precipitate was washed by centrifugation, washed with deionized water and washed several times until no sulfate ions were used, and then washed with absolute ethanol to obtain a white gelatinous solid with a white solid at 60. Drying to constant weight under C gives a kilogram of light weight, high specific surface area (56 m ² / _g ), and nano-magnesium hydroxide. Finally, it should be noted that the above-described embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, although the present invention has been described in detail with reference to the foregoing embodiments, Those skilled in the art can still modify the schemes recorded in the foregoing embodiments, or modify or replace some of the technical features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims

权利要求 Rights request

1.一种制备纳米氢氧化镁的方法，其特征在于，包括如下步骤：A method for preparing nanometer magnesium hydroxide, comprising the steps of:

2.根据权利要求 1 的方法，其特征在于，所述步骤（3)优选在步骤 (1)的溶液中添加一定量的分散剂，或者在步骤（2)的溶液中添加一定量的分散剂，或者在两种溶液中都添加分散剂。 The method according to claim 1, characterized in that the step (3) preferably adds a certain amount of a dispersing agent to the solution of the step (1), or adds a certain amount of a dispersing agent to the solution of the step (2). , or add a dispersant to both solutions.

优选地，将^ t剂与步骤（1)或（2)的溶液进行均匀混合。 Preferably, the agent is uniformly mixed with the solution of step (1) or (2).

优选地，步骤（3)所述的分散剂选自低级二元醇或低级三元醇，例如 2-6个碳原子的二元醇或三元醇类，优选乙二醇、丙二醇、丙三醇、丁二醇、丁三醇或丁四醇；最优选乙二醇或丙三醇。 Preferably, the dispersing agent described in the step (3) is selected from a lower diol or a lower triol, for example, a diol or a trihydric alcohol having 2 to 6 carbon atoms, preferably ethylene glycol, propylene glycol, or propylene glycol. Alcohol, butylene glycol, butyl triol or tetramethylene alcohol; ethylene glycol or glycerol is most preferred.

所述分散剂优选为低级醇与水的混合溶液。优选体积比为 1: 1-1: 4, 例如 1: 2-1: 3的低级醇的水溶液，例如乙醇水溶液。 The dispersing agent is preferably a mixed solution of a lower alcohol and water. Preferably, the volume ratio is 1:1-1:4, for example, 1: 2-1: 3 aqueous solution of a lower alcohol, such as an aqueous ethanol solution.

3.根据权利要求 1或 2的方法，其特征在于，所述分散剂的加入量为步骤（ 1 )或（ 2 )中溶液的 1-50%重量，优选 5-40%重量，更优选 10-30% 重量，最优选 20-30%重量。 The method according to claim 1 or 2, wherein the dispersing agent is added in an amount of 1 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, most preferably 20 to 30% by weight of the solution in the step (1) or (2).

4.根据权利要求 1-3任一项的方法，其特征在于，包括如下步骤： The method according to any one of claims 1 to 3, characterized in that it comprises the following steps:

5.根据权利要求 1-3任一项的方法，其特征在于，包括如下步骤： The method according to any one of claims 1 to 3, characterized in that it comprises the following steps:

6.根据权利要求 1-3任一项的方法，其特征在于，包括如下步骤： The method according to any one of claims 1 to 3, characterized in that it comprises the following steps:

(1)配置一定量的分散剂溶液，然后加入一定浓度的镁盐水溶液，任选再加入一定量的剂，混合均匀； (2)配置一定量的分散剂溶液，然后在容器中配制一定浓度的碱溶液，任选再加入一定量的剂，混合均匀； (1) Configuring a certain amount of dispersant solution, and then adding a certain concentration of magnesium salt aqueous solution, optionally adding a certain amount of the agent, and mixing uniformly; (2) arranging a certain amount of dispersant solution, and then preparing a certain concentration of alkali solution in the container, optionally adding a certain amount of the agent, and mixing uniformly;

(4)将步骤（2) 中的溶液緩慢滴入步骤（1) 的溶液中，或者将步骤（1) 的溶液緩慢滴入步骤（2) 的溶液中，反应得到白色沉淀，陈化后，将白色沉淀（氢氧化镁）离心清洗，洗涤除去其他杂质离子，得到白色凝胶状固体。 (4) slowly dropping the solution in the step (2) into the solution of the step (1), or slowly dropping the solution of the step (1) into the solution of the step (2) to obtain a white precipitate, and after aging, The white precipitate (magnesium hydroxide) was washed by centrifugation, and other impurity ions were removed by washing to obtain a white gelatinous solid.

7.根据权利要求 1-6任一项的方法，其中步骤（ 1 )所述的镁盐可以为硫酸镁 (无水硫酸镁或者七水硫酸镁）、氯化镁 (无水氯化镁或者六水氯化镁），硝酸镁（无水硝酸镁或者六水硝酸镁）。优选地，所述镁盐选自硫酸镁或氯化镁。 The method according to any one of claims 1 to 6, wherein the magnesium salt in the step (1) may be magnesium sulfate (anhydrous magnesium sulfate or magnesium sulfate heptahydrate), magnesium chloride (anhydrous magnesium chloride or magnesium chloride hexahydrate). , magnesium nitrate (anhydrous magnesium nitrate or magnesium nitrate hexahydrate). Preferably, the magnesium salt is selected from magnesium sulfate or magnesium chloride.

优选地，所述镁盐水溶液的浓度优选为 0.1-4mol/L, 优选为 0.3-1.5mol/L; 更优选为 0.5-lmol/L。 Preferably, the concentration of the aqueous magnesium salt solution is preferably from 0.1 to 4 mol/L, preferably from 0.3 to 1.5 mol/L; more preferably from 0.5 to 1 mol/L.

优选地，步骤（2)所述的碱溶液选自氢氧化锂、氢氧化钠、氢氧化钾或者氨水等。优选地，所述碱溶液为氢氧化钠或氢氧化钾。优选地，所 ¾^溶液的浓度优选为 0.5-20mol/L, 优选为 l-10mol/L。 Preferably, the alkali solution described in the step (2) is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonia water. Preferably, the alkali solution is sodium hydroxide or potassium hydroxide. Preferably, the concentration of the solution is preferably from 0.5 to 20 mol/L, preferably from 1 to 10 mol/L.

优选地，在进行步骤（4)之前还包括如下步骤：任选加入其它有机辅助溶剂，混合均匀。更优选地，所述有机辅助溶剂还可以在分散剂与步骤（1)或（2)的溶液混合之前加入到反应器中。 Preferably, before the step (4), the following steps are further included: optionally adding other organic auxiliary solvent, and mixing is uniform. More preferably, the organic auxiliary solvent may also be added to the reactor before the dispersant is mixed with the solution of step (1) or (2).

8.根据权利要求 1-7任一项的方法，其特征在于，步骤（4)中，所述滴加在 20-60。C, 例如室温下进行。 The method according to any one of claims 1 to 7, wherein in the step (4), the dropping is at 20-60. C, for example, at room temperature.

优选地，所述反应在室温下在一定的搅拌速率下进行。所述搅拌速率为 100-5000转 /分，优选 700-3000转 /分。搅拌时间为 5-48小时，优选 10-24小时。 Preferably, the reaction is carried out at room temperature at a certain agitation rate. Stirring rate It is 100-5000 rpm, preferably 700-3000 rpm. The stirring time is from 5 to 48 hours, preferably from 10 to 24 hours.

优选地，陈化时间为 1-8小时，优选 2-6小时。 Preferably, the aging time is from 1 to 8 hours, preferably from 2 to 6 hours.

优选地，将离心清洗后的白色沉淀用去离子水洗涤，优选数次，例如 1-4次。 Preferably, the white precipitate after centrifugation is washed with deionized water, preferably several times, for example 1-4 times.

优选地，在洗、涤至无其他杂质离子后，再使用无水乙醇洗、涤一次，即得到白色皿状固体。 Preferably, after washing and scrubbing to no other impurity ions, it is washed and washed once with absolute ethanol to obtain a white dish-like solid.

优选地，将白色固体在一定温度下干燥至恒重，即得到氢氧化镁粉体。优选地，所述干燥温度为 30^eC-340^eC , 优选干燥温度为 60-200。 ( 。 Preferably, the white solid is dried to a constant weight at a certain temperature to obtain a magnesium hydroxide powder. Preferably, the drying temperature is from 30 ^e C to 340 ^e C, preferably from 60 to 200. (

9.根据权利要求 1-8任一项的方法，其特征在于，所制备得到的氢氧化镁烘干前为凝胶状；最终得到的氢氧化镁为具有微-纳结构、轻质、高比表面积、花球型纳米氢氧化镁。优选氢氧化镁的松装密度： < 0.15_g/mL, 并且具有大的比表面积： >100m²/g。 The method according to any one of claims 1-8, characterized in that the prepared magnesium hydroxide is in the form of a gel before drying; the finally obtained magnesium hydroxide has a micro-nano structure, light weight, high Specific surface area, flower sphere type nano magnesium hydroxide. The bulk density of magnesium hydroxide is preferably < 0.15 _g /mL, and has a large specific surface area: >100 m ² /g.