CN100469435C - A kind of preparation method of ferrocyanide/silicon dioxide hybrid material with high loading capacity - Google Patents

A kind of preparation method of ferrocyanide/silicon dioxide hybrid material with high loading capacity Download PDF

Info

Publication number
CN100469435C
CN100469435C CNB2007100644530A CN200710064453A CN100469435C CN 100469435 C CN100469435 C CN 100469435C CN B2007100644530 A CNB2007100644530 A CN B2007100644530A CN 200710064453 A CN200710064453 A CN 200710064453A CN 100469435 C CN100469435 C CN 100469435C
Authority
CN
China
Prior art keywords
ferrocyanide
silicon dioxide
hybrid material
add
nanoparticles
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.)
Expired - Fee Related
Application number
CNB2007100644530A
Other languages
Chinese (zh)
Other versions
CN101041123A (en
Inventor
刘海弟
赵璇
李福志
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.)
Tsinghua University
Original Assignee
Tsinghua University
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 Tsinghua University filed Critical Tsinghua University
Priority to CNB2007100644530A priority Critical patent/CN100469435C/en
Publication of CN101041123A publication Critical patent/CN101041123A/en
Application granted granted Critical
Publication of CN100469435C publication Critical patent/CN100469435C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicon Compounds (AREA)

Abstract

一种高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,涉及一种放射性核素离子吸收材料的制备方法。该方法是采用Mn、Sn、Ti、Fe、Ni、Co、Cr、Zr、Cu、Pb、Zn等金属离子的盐溶液和亚铁氰化钾(钠)进行反应,得到亚铁氰化物纳米粒子。将该粒子在水体系中用硅溶胶固定或在有机溶剂中用聚合烷基硅氧烷固定,再加入适量无机酸、有机胺或氨水,得到杂化凝胶。将所得凝胶烘干、研磨、过筛,即得到高负载量的亚铁氰化物/二氧化硅杂化材料。该材料亚铁氰化物负载量高,对核素离子吸附能力强,此外材料强度可以满足填充床的要求,粒径可控,避免了单独使用亚铁氰化物导致的床层水阻过大的问题。The invention discloses a method for preparing a ferrocyanide/silicon dioxide hybrid material with a high loading capacity, relating to a method for preparing a radionuclide ion absorbing material. The method is to react salt solutions of metal ions such as Mn, Sn, Ti, Fe, Ni, Co, Cr, Zr, Cu, Pb, Zn and potassium ferrocyanide (sodium) to obtain ferrocyanide nanoparticles . The particle is fixed with silica sol in the water system or polymerized alkyl siloxane in the organic solvent, and then an appropriate amount of inorganic acid, organic amine or ammonia water is added to obtain a hybrid gel. The obtained gel is dried, ground and sieved to obtain a ferrocyanide/silicon dioxide hybrid material with a high loading capacity. The material has a high loading capacity of ferrocyanide and strong adsorption capacity for nuclide ions. In addition, the material strength can meet the requirements of packed beds, and the particle size is controllable, which avoids the excessive water resistance of the bed caused by the use of ferrocyanide alone. question.

Description

一种高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法 A kind of preparation method of ferrocyanide/silicon dioxide hybrid material with high loading capacity

技术领域 technical field

本发明涉及一种放射性核素离子吸收材料的制备方法,特别涉及一种高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,属于材料制备及放射性废水处理技术领域。The invention relates to a preparation method of a radionuclide ion absorption material, in particular to a preparation method of a ferrocyanide/silicon dioxide hybrid material with a high loading capacity, and belongs to the technical field of material preparation and radioactive waste water treatment.

背景技术 Background technique

我国的能源政策已经从“适度发展核电”转变为“积极发展核电”。到2020年,国内核电装机容量将由现在的800万kW上升到4000万kW左右。2020年以后还会有更大的发展。核工业所产生的放射性废水能否妥善处置是关系到核安全性的关键环节之一。研究开发高效、高选择性的放射性废水处理技术,最大程度上实现废物小量化,是核工业领域非常有意义的工作。放射性废水的处理常用的方法有以下几种:my country's energy policy has changed from "moderately developing nuclear power" to "actively developing nuclear power". By 2020, the domestic nuclear power installed capacity will increase from the current 8 million kW to about 40 million kW. After 2020, there will be even greater development. Whether the radioactive wastewater produced by the nuclear industry can be properly disposed of is one of the key links related to nuclear safety. It is a very meaningful work in the field of nuclear industry to research and develop efficient and highly selective radioactive wastewater treatment technology to maximize the miniaturization of waste. The commonly used methods for the treatment of radioactive wastewater are as follows:

1)蒸发浓缩法:放射性废水经蒸发浓缩处理后,蒸残液固化后处置,蒸馏液经离子交换树脂处理后排放。这种方法能耗大,而且由于放射性废水含盐量高,对蒸发装置的腐蚀非常严重。1) Evaporation and concentration method: After the radioactive waste water is evaporated and concentrated, the distillation residue is solidified and disposed of, and the distillate is discharged after being treated with ion exchange resin. This method consumes a lot of energy, and due to the high salt content of radioactive waste water, the corrosion of the evaporation device is very serious.

2)天然硅铝酸盐处理法,该方法是采用高岭土、累托石、蛭石等具有一定离子交换能力的天然硅铝酸盐处理放射性废水,以期将放射性核素离子固定在这些材料内部,完成对废水的处理。然而这些材料离子交换能力有限,而且对核素离子选择性差,产生大量的放射性废物,需要进一步处理处置。2) Natural aluminosilicate treatment method, which is to use natural aluminosilicates such as kaolin, rectorite, and vermiculite to treat radioactive wastewater with certain ion exchange capabilities, in order to fix radionuclide ions inside these materials, Complete the treatment of waste water. However, these materials have limited ion exchange capacity and poor selectivity to nuclide ions, resulting in a large amount of radioactive waste, which requires further treatment and disposal.

3)沸石处理法:天然沸石或人工合成的沸石具有适宜的规则空间结构,可以吸附处理放射性核素。理论上沸石对Cs的交换容量可以达到2meq/g,但是实际中其它离子如钾离子,会强烈干扰Cs的去除,导致沸石的吸附容量非常低,每公斤沸石仅能处理10公斤废水。由于放射性废水处理中吸附剂不能再生,因此产生的大量的放射性废物,需要进一步处理处置。3) Zeolite treatment method: natural zeolite or artificially synthesized zeolite has a suitable regular space structure and can absorb and treat radionuclides. Theoretically, the exchange capacity of zeolite for Cs can reach 2meq/g, but in practice, other ions such as potassium ions will strongly interfere with the removal of Cs, resulting in a very low adsorption capacity of zeolite, which can only treat 10 kg of wastewater per kg of zeolite. Since the adsorbent cannot be regenerated in the treatment of radioactive wastewater, a large amount of radioactive waste generated needs further treatment and disposal.

4)离子交换树脂处理法;目前我国核设施用于处理中低放废液的离子交换树脂多为苯乙烯二乙烯苯为基体的强酸强碱型。通常情况下,树脂的吸附容量利用率不足30%。树脂对中低放废液中的放射性核素缺乏足够的选择性,树脂一次性使用,不再生,因此放射性废树脂产生量大,后期处置费用相当惊人。另外,树脂为有机材料,耐辐照性能差,辐照分解可能产生氢气,成为放射性废树脂长期存放的重大隐患。4) Ion-exchange resin treatment method; at present, the ion-exchange resins used by my country's nuclear facilities to treat low- and medium-level radioactive waste liquids are mostly strong-acid and strong-base types with styrene divinylbenzene as the matrix. Typically, the adsorption capacity utilization of the resin is less than 30%. The resin lacks sufficient selectivity to the radionuclides in the medium and low-level radioactive waste liquid, and the resin is used for one-time use without regeneration. Therefore, a large amount of radioactive waste resin is produced, and the post-processing cost is quite astonishing. In addition, the resin is an organic material with poor radiation resistance, and hydrogen gas may be generated by radiation decomposition, which has become a major hidden danger for long-term storage of radioactive waste resin.

5)磷钼酸铵处理法:磷钼酸铵对Cs+具有高度的选择性,然而磷钼酸铵为细小的微晶,无法进行填充床操作,这严重限制了它的工业应用。孙兆祥等人制备了磷钼酸铵和四价金属磷酸盐(如Ti、Zr、Sb等)杂化材料,实现了磷钼酸铵的颗粒化(离子交换与吸附,12,44-49,1996;核化学与放射化学,21,76-82,1999;北京师范大学学报:自然科学版,27,339-343,1991),但引入了较为昂贵的四价金属,增加了成本。从国际原子能机构2002年发布的放射性废物处理的技术报告看,磷钼酸铵系列材料还没有在放射性废水处理中得到大规模实际应用。5) Ammonium phosphomolybdate treatment method: Ammonium phosphomolybdate has a high selectivity to Cs + , however, ammonium phosphomolybdate is a fine crystal and cannot be operated in a packed bed, which severely limits its industrial application. Sun Zhaoxiang and others prepared hybrid materials of ammonium phosphomolybdate and tetravalent metal phosphate (such as Ti, Zr, Sb, etc.), and realized the granulation of ammonium phosphomolybdate (Ion Exchange and Adsorption, 12, 44-49, 1996 ; Nuclear Chemistry and Radiation Chemistry, 21,76-82,1999; Journal of Beijing Normal University: Natural Science Edition, 27,339-343,1991), but the introduction of more expensive tetravalent metals increases the cost. According to the technical report on radioactive waste treatment issued by the International Atomic Energy Agency in 2002, ammonium phosphomolybdate series materials have not yet been used in large-scale practical applications in radioactive wastewater treatment.

6)亚铁氰化物处理法:被过渡金属固定的亚铁氰化物对放射性的Cs+、Sr2+离子具有很好的选择性吸收能力。在Na+浓度5mol/L的情况下,该类材料对于Cs+的选择性系数(针对Na+)达到1500000(Nuclear Science and Engineering,137,206-214,2001)。然而亚铁氰化物颗粒内部传质条件差,吸附容量往往不能完全利用(核化学与放射化学,23,108-113,2001)。将亚铁氰化物负载在多孔材料载体上可以改善传质动力学条件。Mardan研究了采用溶剂蒸发法,采用已经成型的多孔二氧化硅作为载体,固定K2[CoFe(CN)6](Separation andPurification Technology 16,147-158,1999),其最高负载量只有1.36g-K2[CoFe(CN)6]/g-SiO2,且需要将溶剂蒸发步骤反复多次,步骤繁琐,需要消耗大量有机溶剂,实际应用的可能性不大(Talanta,17-23,955,1970)。王秋萍等在酸性条件下采用共沉淀的方法制备了亚铁氰化钙钾、亚铁氰化锌钾、亚铁氰化锰钾等多种材料,均具有较好的Cs离子吸附能力,但均由于颗粒的稳定性不佳,容易在实际操作中破碎粉化,无法用于放射废水的处理(离子交换与吸附,16(3),225~233,2000)。Terada(Talanta 1970,17,955-963)和Konecny(Radioanal.Chem.,1973,14,255-266)均报道了将亚铁氰化钾先固定在二氧化硅凝胶中,再用过渡金属离子来将其转化为亚铁氰化物吸收剂的方法。然而,由于转化反应在二氧化硅的孔隙内进行,所以其速度极其缓慢,需要使用大大过量的金属离子,且转化反应的产物成分难以控制,此外因为转化反应难以完全进行,不能防止二氧化硅凝胶中部分亚铁氰化钾在离子吸收过程中被浸出而流失。6) Ferrocyanide treatment method: Ferrocyanide immobilized by transition metals has good selective absorption capacity for radioactive Cs + and Sr 2+ ions. In the case of a Na + concentration of 5 mol/L, the selectivity coefficient (for Na + ) of this type of material to Cs + reaches 1,500,000 (Nuclear Science and Engineering, 137, 206-214, 2001). However, the internal mass transfer conditions of ferrocyanide particles are poor, and the adsorption capacity is often not fully utilized (Nuclear Chemistry and Radiation Chemistry, 23, 108-113, 2001). Loading ferrocyanide on porous material supports can improve the kinetic conditions of mass transfer. Mardan studied the use of solvent evaporation method and the use of porous silica as a carrier to immobilize K 2 [CoFe(CN) 6 ] (Separation and Purification Technology 16, 147-158, 1999), and the highest loading capacity was only 1.36g K 2 [CoFe(CN) 6 ]/g-SiO 2 , and the solvent evaporation step needs to be repeated many times, the steps are cumbersome, and a large amount of organic solvent is consumed, so the possibility of practical application is not great (Talanta, 17-23, 955, 1970) . Wang Qiuping and others prepared various materials such as calcium potassium ferrocyanide, zinc potassium ferrocyanide, and manganese potassium ferrocyanide by co-precipitation under acidic conditions, all of which have good adsorption capacity for Cs ions, but neither Due to the poor stability of the particles, they are easily crushed and pulverized in actual operation, and cannot be used for the treatment of radioactive wastewater (Ion Exchange and Adsorption, 16(3), 225-233, 2000). Terada (Talanta 1970, 17, 955-963) and Konecny (Radioanal.Chem., 1973, 14, 255-266) both reported that potassium ferrocyanide was first fixed in silica gel, and then transition metal ions to convert it into ferrocyanide absorbent. However, since the conversion reaction is carried out in the pores of silica, its speed is extremely slow, a large excess of metal ions needs to be used, and the product composition of the conversion reaction is difficult to control. Part of the potassium ferrocyanide in the gel was leached and lost during the ion absorption process.

发明内容 Contents of the invention

本发明的目的在于克服现有技术中亚铁氰化物负载量低、造粒困难、颗粒强度不高、亚铁氰化钾(钠)固定不充分的缺点,从而提供一种制备高负载量的亚铁氰化物/二氧化硅杂化材料的方法,同时保证材料具有高的吸附容量与选择性。The purpose of the present invention is to overcome the shortcomings of low ferrocyanide loading, difficult granulation, low particle strength, and insufficient fixation of potassium ferrocyanide (sodium) in the prior art, thereby providing a method for preparing high-loading ferrocyanide. The ferrocyanide/silica hybrid material method ensures that the material has high adsorption capacity and selectivity at the same time.

本发明的目的是通过如下的技术方案实现的:一种高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,其特征在于该方法按如下步骤进行:The purpose of the present invention is achieved by the following technical scheme: a kind of preparation method of ferrocyanide/silicon dioxide hybrid material of high loading capacity, it is characterized in that the method is carried out as follows:

1)预沉淀:将亚铁氰化钾或亚铁氰化钠溶于去离子水中,在剧烈搅拌下向其中加入Mn、Sn、Ti、Fe、Ni、Co、Cr、Zr、Cu、Pb、Zn过渡金属的可溶性盐溶液,六氰合铁酸根与金属离子的摩尔比为1:1~1:6,将沉淀物经多次离心洗涤,得到亚铁氰化物纳米粒子;1) Preprecipitation: Dissolve potassium ferrocyanide or sodium ferrocyanide in deionized water, add Mn, Sn, Ti, Fe, Ni, Co, Cr, Zr, Cu, Pb, Soluble salt solution of Zn transition metal, the molar ratio of hexacyanoferrate to metal ion is 1:1~1:6, and the precipitate is centrifuged and washed several times to obtain ferrocyanide nanoparticles;

2)凝胶固定:采用在水体系中用硅溶胶固定或在有机溶剂中用聚合烷基硅氧烷固定:2) Gel fixation: fixation with silica sol in water system or polymeric alkyl siloxane in organic solvent:

2.1)在水体系中用硅溶胶固定2.1) Fixed with silica sol in water system

在剧烈搅拌下向所得亚铁氰化物纳米粒子加入碱性硅溶胶水溶液,亚铁氰化物纳米粒子与硅溶胶中的二氧化硅的质量比为0.2:1~7:1,再于水浴中将体系加热至40~80℃,加入无机酸,选自盐酸、硫酸、硝酸或磷酸的任一种或其几种的混合物;将体系的pH调节至2~7,将所得凝胶置于恒温烘箱中烘干至恒重,得到亚铁氰化物/二氧化硅杂化材料;Add alkaline silica sol aqueous solution to the obtained ferrocyanide nanoparticles under vigorous stirring, the mass ratio of ferrocyanide nanoparticles to silicon dioxide in the silica sol is 0.2:1~7:1, and then put the ferrocyanide nanoparticles in a water bath Heat the system to 40-80°C, add an inorganic acid, any one or a mixture of several selected from hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; adjust the pH of the system to 2-7, and place the resulting gel in a constant temperature oven Dry to constant weight in medium to obtain ferrocyanide/silicon dioxide hybrid material;

2.2)在有机溶剂中用聚合烷基硅氧烷固定2.2) Fixation with polymeric alkyl siloxane in organic solvent

将烷氧基硅烷溶于有机溶剂中,烷氧基硅烷选自四甲氧基硅烷、四乙氧基硅烷和四丙氧基硅烷中的1~3种的混合物,有机溶剂选自甲醇、乙醇和丙酮中的1~3种混合物;搅拌下加入去离子水和浓盐酸,形成混合液,有机溶剂的加入量是烷氧基硅烷体积的1~2倍,HCl和H2O的加入量分别为烷氧基硅烷的摩尔量的0.01~0.1倍和0.4~1.8倍;将混合液回流加热至60~90℃,保持2~8hr,得到聚烷基硅氧烷的溶液;将步骤1)中制备的亚铁氰化物纳米粒子用乙醇洗涤,再分散于聚烷基硅氧烷溶液中,且亚铁氰化物与体系中的二氧化硅的质量比为0.2:1~7:1;充分搅拌分散后,在搅拌下滴加氨水、甲胺、乙胺和乙二胺中的1~4种的混合物,加入量为原烷氧基硅烷体积的1/20~1/10,形成凝胶,将所得凝胶在恒温烘箱中烘干至恒重,得到亚铁氰化物/二氧化硅杂化材料。Dissolve the alkoxysilane in an organic solvent, the alkoxysilane is selected from a mixture of 1 to 3 kinds of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane, and the organic solvent is selected from methanol, ethanol and 1 to 3 mixtures in acetone; add deionized water and concentrated hydrochloric acid under stirring to form a mixed solution, the amount of organic solvent added is 1 to 2 times the volume of alkoxysilane, and the amount of HCl and H2O added is alkoxysilane 0.01 to 0.1 times and 0.4 to 1.8 times the molar weight of oxysilane; heat the mixed solution to reflux to 60 to 90°C and keep it for 2 to 8 hours to obtain a solution of polyalkylsiloxane; prepare the polyalkylsiloxane in step 1) Ferrocyanide nanoparticles are washed with ethanol, and then dispersed in polyalkylsiloxane solution, and the mass ratio of ferrocyanide to silicon dioxide in the system is 0.2:1~7:1; after fully stirring and dispersing , add a mixture of 1 to 4 kinds of ammonia water, methylamine, ethylamine and ethylenediamine dropwise under stirring, and the addition amount is 1/20~1/10 of the volume of the original alkoxysilane to form a gel, and the obtained The gel was dried in a constant temperature oven to a constant weight to obtain a ferrocyanide/silica hybrid material.

本发明的技术特征还在于;所述步骤1)中的六氰合铁酸根与金属离子的优选摩尔比为1:1.5~1:3。所述步骤2.1)和2.2)中亚铁氰化物纳米粒子和二氧化硅的优选质量比0.5;1~4:1。所述步骤2.1)中于水浴将体系加热至的优选温度为70~80℃。所述步骤2.2)中聚合反应在高于溶剂沸点5~10℃的温度下进行。The technical feature of the present invention is also that; the preferred molar ratio of hexacyanoferrate and metal ions in the step 1) is 1:1.5-1:3. The preferred mass ratio of ferrocyanide nanoparticles to silicon dioxide in the steps 2.1) and 2.2) is 0.5; 1-4:1. The preferred temperature to which the system is heated in a water bath in the step 2.1) is 70-80°C. The polymerization reaction in the step 2.2) is carried out at a temperature 5-10° C. higher than the boiling point of the solvent.

本发明所述步骤2.1)中的碱性硅溶胶水溶液中的二氧化硅含量为10~35wt%,其中二氧化硅粒子粒径为10~40nm,密度1.1~1.3g/mL。The silicon dioxide content in the alkaline silica sol aqueous solution in step 2.1) of the present invention is 10-35 wt%, wherein the silicon dioxide particles have a particle size of 10-40nm and a density of 1.1-1.3g/mL.

本方法避免了采用已经成型的多孔二氧化硅作为载体,而是采用二氧化硅的液态前驱体(硅溶胶或聚硅氧烷)和亚铁氰化物混合后引发凝胶反应,从而得到了亚铁氰化物负载量很高的杂化材料。具有以下优点:(a)亚铁氰化物负载量大:本方法获得的材料其亚铁氰化物的负载量可达80%以上。(b)材料中的亚铁氰化物以微小颗粒的形式分散在杂化材料中,而二氧化硅起到了亚铁氰化物载体的作用,能够满足强度要求。(c)所制备的亚铁氰化物/二氧化硅杂化材料具有多孔结构,可以改善吸附动力学条件,提高吸附速率。(d)本发明所制备的材料既发挥了纳米级亚铁氰化物高效的吸附性能,又满足了填充床操作需要的颗粒尺寸与强度。This method avoids the use of formed porous silica as a carrier, but uses a liquid precursor of silica (silica sol or polysiloxane) to mix with ferrocyanide to initiate a gel reaction, thereby obtaining a ferrocyanide. Hybrid materials with high ferricyanide loading. The method has the following advantages: (a) Large ferrocyanide load: the ferrocyanide load of the material obtained by the method can reach more than 80%. (b) The ferrocyanide in the material is dispersed in the hybrid material in the form of tiny particles, and the silica acts as a carrier of ferrocyanide, which can meet the strength requirements. (c) The prepared ferrocyanide/silica hybrid material has a porous structure, which can improve the adsorption kinetic conditions and increase the adsorption rate. (d) The material prepared by the present invention not only exerts the high-efficiency adsorption performance of nano-scale ferrocyanide, but also satisfies the particle size and strength required for packed bed operation.

本方法所制备的吸附材料可以在浓度为0.5mol/L的Na+和浓度为0.5mol/L的H+的干扰下将水中Cs+浓度从1000μg/L降低到8μg/L以下,而吸附剂用量仅为2g/L。The adsorption material prepared by this method can reduce the concentration of Cs + in water from 1000 μg/L to below 8 μg/L under the interference of 0.5 mol/L Na + and 0.5 mol/L H + , while the adsorbent The dosage is only 2g/L.

具体实施方式 Detailed ways

本发明提供的一种高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,其具体工艺步骤如下:The preparation method of a ferrocyanide/silicon dioxide hybrid material with a high loading capacity provided by the present invention, its specific process steps are as follows:

1)预沉淀:将亚铁氰化钾或亚铁氰化钠溶于去离子水中,在剧烈搅拌下向其中加入Mn、Sn、Ti、Fe、Ni、Co、Cr、Zr、Cu、Pb、Zn过渡金属的可溶性盐溶液,六氰合铁酸根与金属离子的摩尔比为1:1~1;6,优选为1:1.5~1:3;将沉淀物经多次离心洗涤,得到亚铁氰化物纳米粒子;1) Preprecipitation: Dissolve potassium ferrocyanide or sodium ferrocyanide in deionized water, add Mn, Sn, Ti, Fe, Ni, Co, Cr, Zr, Cu, Pb, Soluble salt solution of Zn transition metal, the molar ratio of hexacyanoferrate to metal ion is 1:1~1;6, preferably 1:1.5~1:3; the precipitate is centrifuged and washed several times to obtain ferrous iron Cyanide nanoparticles;

2)凝胶固定:采用在水体系中用硅溶胶固定或在有机溶剂中用聚合烷基硅氧烷固定:2) Gel fixation: fixation with silica sol in water system or polymeric alkyl siloxane in organic solvent:

2.1)在水体系中用硅溶胶固定2.1) Fixed with silica sol in water system

在剧烈搅拌下向所得亚铁氰化物纳米粒子加入碱性硅溶胶水溶液,碱性硅溶胶水溶液中的二氧化硅含量为10~35wt%,其中二氧化硅粒子粒径为10~40nm,密度1.1~1.3g/mL。亚铁氰化物纳米粒子与硅溶胶中的二氧化硅的质量比为0.2:1~7:1,优选质量比为0.5:1~4:1;再于水浴中将体系加热至40~80℃,优选为70~80℃,加入无机酸,选自盐酸、硫酸、硝酸或磷酸的任一种或其几种的混合物;将体系的pH调节至2~7,优选4~6;将所得凝胶置于恒温烘箱中烘干至恒重,得到亚铁氰化物/二氧化硅杂化材料;Add alkaline silica sol aqueous solution to the obtained ferrocyanide nanoparticles under vigorous stirring, the silica content in the alkaline silica sol aqueous solution is 10-35wt%, wherein the silica particles have a particle size of 10-40nm and a density of 1.1 ~1.3g/mL. The mass ratio of ferrocyanide nanoparticles to silica in silica sol is 0.2:1-7:1, preferably 0.5:1-4:1; then heat the system to 40-80°C in a water bath , preferably at 70-80°C, adding an inorganic acid, selected from any one of hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid or a mixture of several thereof; adjusting the pH of the system to 2-7, preferably 4-6; The glue was dried in a constant temperature oven to a constant weight to obtain a ferrocyanide/silica hybrid material;

2.2)在有机溶剂中用聚合烷基硅氧烷固定2.2) Fixation with polymeric alkyl siloxane in organic solvent

将烷氧基硅烷溶于有机溶剂中,烷氧基硅烷选自四甲氧基硅烷、四乙氧基硅烷和四丙氧基硅烷中的1~3种的混合物,有机溶剂选自甲醇、乙醇和丙酮中的1~3种混合物;搅拌下加入去离子水和浓盐酸,形成混合液,有机溶剂的加入量是烷氧基硅烷体积的1~2倍,HCl和H2O的加入量分别为烷氧基硅烷的摩尔量的0.01~0.1倍和0.4~1.8倍;将混合液回流加热至60~90℃,优选高于溶剂沸点5~10℃的温度;保持2~8hr,得到聚烷基硅氧烷的溶液;将步骤1)中制备的亚铁氰化物纳米粒子用乙醇洗涤,再分散于聚烷基硅氧烷溶液中,且亚铁氰化物纳米粒子与体系中的二氧化硅的质量比为0.2:1~7:1;充分搅拌分散后,在搅拌下滴加氨水、甲胺、乙胺和乙二胺中的1~4种的混合物,加入量为原烷氧基硅烷体积的1/20~1/10,形成凝胶,将所得凝胶在恒温烘箱中烘干至恒重,得到亚铁氰化物/二氧化硅杂化材料。Dissolve the alkoxysilane in an organic solvent, the alkoxysilane is selected from a mixture of 1 to 3 kinds of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane, and the organic solvent is selected from methanol, ethanol and 1 to 3 mixtures in acetone; add deionized water and concentrated hydrochloric acid under stirring to form a mixed solution, the amount of organic solvent added is 1 to 2 times the volume of alkoxysilane, and the amount of HCl and H 2 O added are respectively 0.01 to 0.1 times and 0.4 to 1.8 times the molar weight of alkoxysilane; heat the mixed solution to reflux to 60 to 90°C, preferably 5 to 10°C higher than the boiling point of the solvent; keep it for 2 to 8 hours to obtain polyalkane A solution of polyalkylsiloxane; the ferrocyanide nanoparticles prepared in step 1) are washed with ethanol, and then dispersed in the polyalkylsiloxane solution, and the ferrocyanide nanoparticles and the silicon dioxide in the system The mass ratio is 0.2:1 to 7:1; after fully stirring and dispersing, add a mixture of 1 to 4 kinds of ammonia water, methylamine, ethylamine and ethylenediamine dropwise under stirring, and the amount added is the original alkoxysilane 1/20-1/10 of the volume to form a gel, and the obtained gel is dried in a constant temperature oven to a constant weight to obtain a ferrocyanide/silicon dioxide hybrid material.

下面举出几个具体实施例,以进一步理解本发明。Several specific examples are enumerated below to further understand the present invention.

实施例1:Example 1:

将9g亚铁氰化钾溶解于50mL去离子水中,剧烈搅拌下缓慢加入50mL Co(NO3)2溶液,K4[Fe(CN)6])和Co离子的摩尔比=1:1.5,而后将体系搅拌30min,陈化24hr,过滤、洗涤。将所得纳米级K2[CoFe(CN)6]粒子分散在50mL去离子水中,加入二氧化硅含量为30%(wt)的碱性硅溶胶115mL,体系中K2[CoFe(CN)6]和二氧化硅的质量比为0.2/1。充分搅拌并混合均匀后在水浴中加热至80℃,再在剧烈搅拌下加入35%的浓盐酸,调节pH为5,将体系静置,1min后凝胶,将凝胶在100℃下烘干至恒重,研磨,过60目筛。得放射性核素离子吸收材料,其活性组分为K2[CoFe(CN)6]。Dissolve 9 g of potassium ferrocyanide in 50 mL of deionized water, slowly add 50 mL of Co(NO 3 ) 2 solution under vigorous stirring, the molar ratio of K 4 [Fe(CN) 6 ]) to Co ions=1:1.5, and then The system was stirred for 30min, aged for 24hr, filtered and washed. The obtained nanoscale K 2 [CoFe(CN) 6 ] particles were dispersed in 50 mL of deionized water, and 115 mL of alkaline silica sol with a silica content of 30% (wt) was added, and K 2 [CoFe(CN) 6 ] in the system The mass ratio to silicon dioxide is 0.2/1. Stir well and mix evenly, heat to 80°C in a water bath, then add 35% concentrated hydrochloric acid under vigorous stirring, adjust the pH to 5, let the system stand still, gel after 1min, and dry the gel at 100°C To constant weight, grind and pass through a 60-mesh sieve. The radionuclide ion absorbing material is obtained, and its active component is K 2 [CoFe(CN) 6 ].

实施例2:Example 2:

将15g亚铁氰化钠溶解于80mL去离子水中,剧烈搅拌下缓慢加入80mL Zn(NO3)2溶液,Na4[Fe(CN)6]和Zn离子的摩尔比=1:2,而后将体系搅拌60min,陈化12hr,过滤、洗涤。将所得Na2[CoFe(CN)6]粒子分散在80mL去离子水中,而后加入二氧化硅含量为25%(wt)的碱性硅溶胶50mL,体系中Na2[ZnFe(CN)6]和二氧化硅的质量比为0.9/1。充分搅拌并混合均匀后在水浴中加热至40℃,再在剧烈搅拌下加入65%的浓硝酸,调节pH为4,将所得凝胶体系静置,将凝胶在120℃下烘干至恒重,研磨,过60目筛,得放射性核素离子吸收材料,其活性组分为Na2[ZnFe(CN)6]。Dissolve 15g of sodium ferrocyanide in 80mL of deionized water, slowly add 80mL of Zn(NO 3 ) 2 solution under vigorous stirring, the molar ratio of Na 4 [Fe(CN) 6 ] to Zn ions=1:2, and then add The system was stirred for 60 minutes, aged for 12 hours, filtered and washed. The obtained Na 2 [CoFe(CN) 6 ] particles were dispersed in 80 mL of deionized water, and then 50 mL of alkaline silica sol with a silica content of 25% (wt) was added. In the system, Na 2 [ZnFe(CN) 6 ] and The mass ratio of silicon dioxide is 0.9/1. After fully stirring and mixing evenly, heat to 40°C in a water bath, then add 65% concentrated nitric acid under vigorous stirring, adjust the pH to 4, let the obtained gel system stand still, and dry the gel at 120°C until constant Heavy, ground, and passed through a 60-mesh sieve to obtain a radionuclide ion absorbing material, the active component of which is Na 2 [ZnFe(CN) 6 ].

实施例3:Example 3:

将1Kg亚铁氰化钾溶解于5.6L去离子水中,剧烈搅拌下缓慢加入5L Mn(NO3)2溶液,K4[Fe(CN)6]和Mn离子的摩尔比=1:1,而后将体系搅拌20min,陈化48hr,过滤、洗涤。将所得K2[MnFe(CN)6]纳米粒子分散于4L去离子水中,而后加入315mL二氧化硅含量为30%(wt)的碱性硅溶胶,体系中K2[MnFe(CN)6]和二氧化硅的质量比为7/1。充分搅拌并混合均匀后在水浴中加热至80℃,再在剧烈搅拌下加入硫酸(1:1),调节pH为5,将所得凝胶静置,于100℃下烘干至恒重,研磨,过50目筛,得放射性核素离子吸收材料,其活性组分为K2[MnFe(CN)6]。Dissolve 1Kg of potassium ferrocyanide in 5.6L of deionized water, slowly add 5L of Mn(NO 3 ) 2 solution under vigorous stirring, the molar ratio of K 4 [Fe(CN) 6 ] to Mn ions=1:1, and then The system was stirred for 20min, aged for 48hr, filtered and washed. Gained K 2 [MnFe(CN) 6 ] nanoparticles were dispersed in 4L deionized water, and then 315 mL of alkaline silica sol with a silicon dioxide content of 30% (wt) was added, and K 2 [MnFe(CN) 6 ] in the system The mass ratio to silicon dioxide is 7/1. After fully stirring and mixing evenly, heat to 80°C in a water bath, then add sulfuric acid (1:1) under vigorous stirring, adjust the pH to 5, let the obtained gel stand still, dry at 100°C to constant weight, and grind , through a 50-mesh sieve to obtain a radionuclide ion absorbing material, the active component of which is K 2 [MnFe(CN) 6 ].

实施例4:Example 4:

将15g亚铁氰化钾溶解于80mL水中,剧烈搅拌下缓慢加入100mL Cu(NO3)2溶液,K4[Fe(CN)6]和Cu离子的摩尔比=1:6,搅拌45min,陈化12hr,过滤、洗涤。将所得沉淀分散于50mL去离子水中,而后加入20mL二氧化硅含量为30%(wt)的碱性硅溶胶,体系中Cu2[Fe(CN)6]和二氧化硅的质量比为1.6/1。充分搅拌并混合均匀后在水浴中加热至70℃,再在剧烈搅拌下加入硫酸(1:1),调节pH为5,体系很快凝胶,将所得凝胶静置,于110℃下烘干至恒重,研磨,过50目筛,得放射性核素离子吸收材料,其活性组分为Cu2[Fe(CN)6]。Dissolve 15g of potassium ferrocyanide in 80mL of water, slowly add 100mL of Cu(NO 3 ) 2 solution under vigorous stirring, the molar ratio of K 4 [Fe(CN) 6 ] to Cu ions=1:6, stir for 45min, and stand After 12hr, filter and wash. Gained precipitation is dispersed in 50mL deionized water, then add 20mL silica content and be the alkaline silica sol of 30% (wt), the mass ratio of Cu 2 [Fe(CN) 6 ] and silica in the system is 1.6/ 1. Stir well and mix evenly, heat to 70°C in a water bath, then add sulfuric acid (1:1) under vigorous stirring, adjust the pH to 5, the system gels quickly, let the obtained gel stand still, and bake at 110°C Dry to constant weight, grind, and pass through a 50-mesh sieve to obtain a radionuclide ion absorbing material, the active component of which is Cu 2 [Fe(CN) 6 ].

实施例5:Example 5:

将50g亚铁氰化钾溶解于250mL去离子水中,剧烈搅拌下缓慢加入250mL Ni(NO3)2溶液,K4[Fe(CN)6]和Ni离子的摩尔比=1:5,搅拌30min,陈化24hr,过滤、洗涤。将所得沉淀分散于200mL去离子水中,而后加入60mL二氧化硅含量为25%(wt)的碱性硅溶胶,体系中Ni2[Fe(CN)6]和二氧化硅的质量比为2.16/1。混合均匀后水浴加热至80℃,加入60%浓硝酸调节pH至6,体系在30s内失去流动性并凝胶。将所得凝胶于80℃下烘干至恒重,研磨,过100目筛,得放射性核素离子吸收材料,其活性组分为Ni2[Fe(CN)6]。Dissolve 50g of potassium ferrocyanide in 250mL of deionized water, slowly add 250mL of Ni(NO 3 ) 2 solution under vigorous stirring, the molar ratio of K 4 [Fe(CN) 6 ] to Ni ions=1:5, and stir for 30min , aged for 24hr, filtered and washed. Gained precipitation is dispersed in 200mL deionized water, then add 60mL silica content and be the alkaline silica sol of 25% (wt), in the system Ni 2 [Fe(CN) 6 ] and the mass ratio of silica are 2.16/ 1. After mixing evenly, heat it in a water bath to 80°C, add 60% concentrated nitric acid to adjust the pH to 6, and the system loses fluidity and gels within 30 seconds. The obtained gel was dried at 80°C to constant weight, ground, and passed through a 100-mesh sieve to obtain a radionuclide ion absorbing material, the active component of which was Ni 2 [Fe(CN) 6 ].

实施例6:Embodiment 6:

将100g亚铁氰化钾溶解于700mL水中,剧烈搅拌下加入500mL Cu(NO3)2溶液,K4[Fe(CN)6]和Cu离子的摩尔比=1:4,搅拌40min,陈化48hr,过滤、洗涤。将所得沉淀分散于500mL去离子水中,而后加入35mL二氧化硅含量为30%(wt)的碱性硅溶胶,体系中Cu2[Fe(CN)6]和二氧化硅的质量比为6.3/1。混合均匀后水浴加热至80℃,加入60%浓硝酸调节pH至4,体系在10min内失去流动性并凝胶。将所得凝胶于100℃下烘干至恒重,研磨,过50目筛,得放射性核素离子吸收材料,其活性组分为Cu2[Fe(CN)6]。Dissolve 100g of potassium ferrocyanide in 700mL of water, add 500mL of Cu(NO 3 ) 2 solution under vigorous stirring, the molar ratio of K 4 [Fe(CN) 6 ] to Cu ions=1:4, stir for 40min, and age 48hr, filter and wash. Gained precipitation is dispersed in 500mL deionized water, then add 35mL of silica content and be the alkaline silica sol of 30% (wt), the mass ratio of Cu 2 [Fe(CN) 6 ] and silica in the system is 6.3/ 1. After mixing evenly, heat it in a water bath to 80°C, add 60% concentrated nitric acid to adjust the pH to 4, and the system loses fluidity and gels within 10 minutes. The resulting gel was dried at 100°C until constant weight, ground, and passed through a 50-mesh sieve to obtain a radionuclide ion absorbing material, the active component of which was Cu 2 [Fe(CN) 6 ].

实施例7:Embodiment 7:

将40g亚铁氰化钾溶解于220mL水中,剧烈搅拌下加入250mL Sn(NO3)2溶液,K4[Fe(CN)6]和Sn离子的摩尔比=1:1.6,搅拌20min,陈化24hr,过滤、洗涤。将所得沉淀分散于200mL去离子水中,而后加入60mL二氧化硅含量为20%(wt)的碱性硅溶胶,体系中K2[SnFe(CN)6]和二氧化硅的质量比为2.7/1。混合均匀后水浴加热至80℃,而后加入磷酸调节pH至5,体系凝胶。将所得凝胶于100℃下烘干至恒重,研磨,过100目筛,得放射性核素离子吸收材料,其活性组分为K2[SnFe(CN)6]。Dissolve 40g of potassium ferrocyanide in 220mL of water, add 250mL of Sn(NO 3 ) 2 solution under vigorous stirring, the molar ratio of K 4 [Fe(CN) 6 ] to Sn ions=1:1.6, stir for 20min, and age 24hr, filter and wash. The resulting precipitate was dispersed in 200mL deionized water, and then 60mL of alkaline silica sol with a silicon dioxide content of 20% (wt) was added, and the mass ratio of K 2 [SnFe(CN) 6 ] to silicon dioxide in the system was 2.7/ 1. After mixing evenly, heat in a water bath to 80°C, then add phosphoric acid to adjust the pH to 5, and the system gels. The obtained gel was dried at 100°C to constant weight, ground, and passed through a 100-mesh sieve to obtain a radionuclide ion absorbing material, the active component of which was K 2 [SnFe(CN) 6 ].

实施例8:Embodiment 8:

将20g亚铁氰化钾溶解于100mL水中,剧烈搅拌下加入120mL Pb(NO3)2溶液,K4[Fe(CN)6]和Pb离子的摩尔比=1:2,搅拌45min,陈化36hr,过滤、去离子水洗涤三次。分散于100mL聚四乙氧基硅烷的丙酮溶液中(二氧化硅含量为15g,其制备方法如下:取52g四乙氧基硅烷溶于100mL丙酮中,回流搅拌下加热至60℃,保持4hr,得110mL聚四乙氧基硅烷的丙酮溶液)体系中K2[PbFe(CN)6]和二氧化硅的质量比为1.57/1。搅拌下向该溶液中加入6.5mL30wt%氨水,体系很快凝胶,将所得凝胶于120℃下烘干至恒重,研磨,过100目筛,得放射性核素离子吸收材料,其活性组分为K2[PbFe(CN)6]。Dissolve 20g of potassium ferrocyanide in 100mL of water, add 120mL of Pb(NO 3 ) 2 solution under vigorous stirring, the molar ratio of K 4 [Fe(CN) 6 ] to Pb ions=1:2, stir for 45min, and age 36hr, filtered and washed three times with deionized water. Disperse in 100mL of polytetraethoxysilane in acetone solution (silicon dioxide content is 15g, its preparation method is as follows: take 52g of tetraethoxysilane dissolved in 100mL of acetone, heat to 60°C under reflux and stirring, keep for 4hr, The mass ratio of K 2 [PbFe(CN) 6 ] and silicon dioxide in the system was 1.57/1. Add 6.5mL of 30wt% ammonia water to the solution under stirring, and the system gels quickly. The resulting gel is dried at 120°C to constant weight, ground, and passed through a 100-mesh sieve to obtain a radionuclide ion-absorbing material. Divided into K 2 [PbFe(CN) 6 ].

实施例9:Embodiment 9:

将10g亚铁氰化钾溶解于100mL水中,剧烈搅拌下加入120mL CrCl3溶液K4[Fe(CN)6]和Cr离子的摩尔比=1:1.5,搅拌70min,陈化10hr,过滤、去离子水洗涤三次。分散于40mL聚四丙氧基硅烷的乙醇溶液中(其中二氧化硅含量为6g,其制备方法如下:取27g四丙氧基硅烷溶于50mL乙醇中,回流搅拌下加热至90℃,保持8hr,得53mL聚四丙氧基硅烷的乙醇溶液)体系中K[CrFe(CN)6]和二氧化硅的质量比为1.2/1。搅拌下向该溶液中加入2mL乙二胺,将所得凝胶于110℃下烘干至恒重,研磨,过100目筛,得放射性核素离子吸收材料,其活性组分为K[CrFe(CN)6]。Dissolve 10g of potassium ferrocyanide in 100mL of water, add 120mL of CrCl 3 solution K 4 [Fe(CN) 6 ] to Cr ion molar ratio = 1:1.5 under vigorous stirring, stir for 70min, age for 10hr, filter, remove Washed three times with deionized water. Disperse in 40mL of ethanol solution of polytetrapropoxysilane (the content of silicon dioxide is 6g, the preparation method is as follows: take 27g of tetrapropoxysilane and dissolve it in 50mL of ethanol, heat it to 90°C under reflux and stir, and keep it for 8hr , to obtain 53mL ethanol solution of polytetrapropoxysilane) The mass ratio of K[CrFe(CN) 6 ] and silicon dioxide in the system was 1.2/1. Add 2mL of ethylenediamine to the solution under stirring, dry the resulting gel at 110°C to constant weight, grind, and pass through a 100-mesh sieve to obtain a radionuclide ion-absorbing material, whose active component is K[CrFe( CN) 6 ].

实施例10:Example 10:

将18g亚铁氰化钾溶解于100mL去离子水中,剧烈搅拌下缓慢加入110mL Co(NO3)2溶液,K4[Fe(CN)6])和Co离子的摩尔比=1:1.5,而后将体系搅拌30min,陈化24hr,过滤、去离子水洗涤三次。分散于85mL聚四甲氧基硅烷的甲醇溶液中(其中二氧化硅含量为15g,其制备方法如下:取38g四甲氧基硅烷溶于47mL甲醇中,回流搅拌下加热至70℃,保持2hr,得85mL聚四甲氧基硅烷的甲醇溶液)体系中K2[CoFe(CN)6]和二氧化硅的质量比为1/1。搅拌下向该溶液中加入2.4mL甲胺,将所得凝胶于90℃下烘干至恒重,研磨,过100目筛,得放射性核素离子吸收材料,其活性组分为K2[CoFe(CN)6]。Dissolve 18g of potassium ferrocyanide in 100mL of deionized water, slowly add 110mL of Co(NO 3 ) 2 solution under vigorous stirring, the molar ratio of K 4 [Fe(CN) 6 ]) to Co ions=1:1.5, and then The system was stirred for 30 minutes, aged for 24 hours, filtered and washed with deionized water three times. Disperse in 85mL of methanol solution of polytetramethoxysilane (the content of silicon dioxide is 15g, the preparation method is as follows: dissolve 38g of tetramethoxysilane in 47mL of methanol, heat to 70°C under reflux and stirring, and keep for 2hr , to obtain 85 mL of methanol solution of polytetramethoxysilane) in the system, the mass ratio of K 2 [CoFe(CN) 6 ] to silicon dioxide was 1/1. Add 2.4 mL of methylamine to the solution under stirring, dry the resulting gel at 90°C until constant weight, grind, and pass through a 100-mesh sieve to obtain a radionuclide ion-absorbing material, the active component of which is K 2 [CoFe (CN) 6 ].

Claims (6)

1、一种高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,其特征在于该方法按如下步骤进行:1, a kind of preparation method of ferrocyanide/silicon dioxide hybrid material of high loading capacity, it is characterized in that the method is carried out as follows: 1)预沉淀:将亚铁氰化钾或亚铁氰化钠溶于去离子水中,在剧烈搅拌下向其中加入Mn、Ti、Fe、Ni、Co、Cr、Zr、Cu、Zn过渡金属的可溶性盐溶液,六氰合铁酸根与金属离子的摩尔比为1:1~1:6,将沉淀物经多次离心洗涤,得到亚铁氰化物纳米粒子;1) Preprecipitation: Dissolve potassium ferrocyanide or sodium ferrocyanide in deionized water, add Mn, Ti, Fe, Ni, Co, Cr, Zr, Cu, Zn transition metals to it under vigorous stirring Soluble salt solution, the molar ratio of hexacyanoferrate to metal ions is 1:1-1:6, and the precipitate is centrifuged and washed several times to obtain ferrocyanide nanoparticles; 2)凝胶固定:采用在水体系中用硅溶胶固定或在有机溶剂中用聚烷氧基硅烷固定:2) Gel fixation: fix with silica sol in water system or fix with polyalkoxysilane in organic solvent: 2.1)在水体系中用硅溶胶固定2.1) Fixed with silica sol in water system 在剧烈搅拌下向所得亚铁氰化物纳米粒子加入碱性硅溶胶水溶液,亚铁氰化物纳米粒子与硅溶胶中的二氧化硅的质量比为0.2:1~7:1,再于水浴中将体系加热至40~80℃,加入无机酸,选自盐酸、硫酸、硝酸或磷酸的任一种或其几种的混合物;将体系的pH调节至2~7,将所得凝胶置于恒温烘箱中烘干至恒重,得到亚铁氰化物/二氧化硅杂化材料;Add alkaline silica sol aqueous solution to the obtained ferrocyanide nanoparticles under vigorous stirring, the mass ratio of ferrocyanide nanoparticles to silicon dioxide in the silica sol is 0.2:1~7:1, and then dissolve the ferrocyanide nanoparticles in a water bath Heat the system to 40-80°C, add an inorganic acid, any one or a mixture of several selected from hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; adjust the pH of the system to 2-7, and place the resulting gel in a constant temperature oven Dry to constant weight in medium to obtain ferrocyanide/silicon dioxide hybrid material; 2.2)在有机溶剂中用聚烷氧基硅烷固定2.2) Fixed with polyalkoxysilane in organic solvent 将烷氧基硅烷溶于有机溶剂中,烷氧基硅烷选自四甲氧基硅烷、四乙氧基硅烷和四丙氧基硅烷中的1~3种的混合物,有机溶剂选自甲醇、乙醇和丙酮中的1~3种混合物;搅拌下加入去离子水和浓盐酸,形成混合液,有机溶剂的加入量是烷氧基硅烷体积的1~2倍,HCl和H2O的加入量分别为烷氧基硅烷的摩尔量的0.01~0.1倍和0.4~1.8倍;将混合液回流加热至60~90℃,保持2~8hr,得到聚烷氧基硅烷的溶液;将步骤1)中制备的亚铁氰化物纳米粒子用乙醇洗涤,再分散于聚烷氧基硅烷溶液中,且亚铁氰化物纳米粒子与体系中的二氧化硅的质量比为0.2:1~7:1;充分搅拌分散后,在搅拌下滴加氨水、甲胺、乙胺和乙二胺中的1~4种的混合物,加入量为原烷氧基硅烷体积的1/20~1/10,形成凝胶,将所得凝胶在恒温烘箱中烘干至恒重,得到亚铁氰化物/二氧化硅杂化材料。Dissolve the alkoxysilane in an organic solvent, the alkoxysilane is selected from a mixture of 1 to 3 kinds of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane, and the organic solvent is selected from methanol, ethanol and 1 to 3 mixtures in acetone; add deionized water and concentrated hydrochloric acid under stirring to form a mixed solution, the amount of organic solvent added is 1 to 2 times the volume of alkoxysilane, and the amount of HCl and H 2 O added are respectively 0.01 to 0.1 times and 0.4 to 1.8 times the molar weight of alkoxysilane; heat the mixed solution to reflux to 60 to 90°C and keep it for 2 to 8 hours to obtain a solution of polyalkoxysilane; prepare in step 1) The ferrocyanide nanoparticles were washed with ethanol, and then dispersed in the polyalkoxysilane solution, and the mass ratio of ferrocyanide nanoparticles to silicon dioxide in the system was 0.2:1 to 7:1; fully stirred After dispersion, add a mixture of ammonia water, methylamine, ethylamine and ethylenediamine dropwise under stirring. The amount added is 1/20 to 1/10 of the volume of the original alkoxysilane to form a gel. The resulting gel was dried in a constant temperature oven to a constant weight to obtain a ferrocyanide/silicon dioxide hybrid material. 2、如权利要求1所述的高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,其特征在于:所述步骤1)中的六氰合铁酸根与金属离子的摩尔比为1:1.5~1:3。2. The method for preparing ferrocyanide/silicon dioxide hybrid material with high loading capacity according to claim 1, characterized in that the molar ratio of hexacyanoferrate to metal ions in said step 1) It is 1:1.5~1:3. 3、如权利要求1或2所述的高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,其特征在于:所述的步骤2.1)中的碱性硅溶胶水溶液中的二氧化硅含量为10~35wt%,其中二氧化硅粒子粒径为10~40nm,密度1.1~1.3g/mL。3. The method for preparing ferrocyanide/silicon dioxide hybrid material with high loading capacity as claimed in claim 1 or 2, characterized in that: the dihydrogen in the alkaline silica sol aqueous solution in the step 2.1) The silicon oxide content is 10-35 wt%, wherein the silicon dioxide particles have a particle diameter of 10-40nm and a density of 1.1-1.3g/mL. 4、如权利要求1或2所述的高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,其特征在于:所述步骤2.1)和2.2)中亚铁氰化物纳米粒子与二氧化硅的质量比0.5:1~4:1。4. The method for preparing ferrocyanide/silicon dioxide hybrid material with high loading capacity as claimed in claim 1 or 2, characterized in that: in the steps 2.1) and 2.2), ferrocyanide nanoparticles and The mass ratio of silicon dioxide is 0.5:1 to 4:1. 5、如权利要求1所述的高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,其特征在于:所述的步骤2.1)中将体系加热至70~80℃。5. The method for preparing high-capacity ferrocyanide/silicon dioxide hybrid material according to claim 1, characterized in that: in the step 2.1), the system is heated to 70-80°C. 6、如权利要求1所述的高负载量的亚铁氰化物/二氧化硅杂化材料的制备方法,其特征在于:所述步骤2.2)聚合反应在高于溶剂沸点5~10℃的温度下进行。6. The method for preparing high-capacity ferrocyanide/silica hybrid material according to claim 1, characterized in that: said step 2.2) polymerizes at a temperature 5-10°C higher than the boiling point of the solvent next.
CNB2007100644530A 2007-03-16 2007-03-16 A kind of preparation method of ferrocyanide/silicon dioxide hybrid material with high loading capacity Expired - Fee Related CN100469435C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2007100644530A CN100469435C (en) 2007-03-16 2007-03-16 A kind of preparation method of ferrocyanide/silicon dioxide hybrid material with high loading capacity

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2007100644530A CN100469435C (en) 2007-03-16 2007-03-16 A kind of preparation method of ferrocyanide/silicon dioxide hybrid material with high loading capacity

Publications (2)

Publication Number Publication Date
CN101041123A CN101041123A (en) 2007-09-26
CN100469435C true CN100469435C (en) 2009-03-18

Family

ID=38807052

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2007100644530A Expired - Fee Related CN100469435C (en) 2007-03-16 2007-03-16 A kind of preparation method of ferrocyanide/silicon dioxide hybrid material with high loading capacity

Country Status (1)

Country Link
CN (1) CN100469435C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102217654A (en) * 2011-04-15 2011-10-19 中国科学院过程工程研究所 Method for preparing nano zinc/potassium ferrocyanide antibacterial material

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101279249B (en) * 2008-05-23 2010-04-07 清华大学 Preparation method of zirconium potassium ferrocyanide with small ball silica gel as carrier
FR2945756B1 (en) * 2009-05-20 2011-08-05 Commissariat Energie Atomique NANOCOMPOSITE SOLID MATERIAL BASED ON HEXA AND OCTACYANOMETALLATES, PROCESS FOR PREPARING THE SAME, AND METHOD FOR FIXING MINERAL POLLUTANTS USING THE SAME
US9745202B2 (en) * 2012-03-28 2017-08-29 Board of Regents, U of Texas System Metal cyanometallate synthesis method
FR2996149B1 (en) * 2012-09-28 2014-10-31 Commissariat Energie Atomique SUPPORTED HEXA- AND OCTACYANOMETALLATE MEMBRANE-SUPPORTED MEMBRANE, PROCESS FOR PREPARING THE SAME, AND SEPARATION METHOD USING THE SAME
CN103274757B (en) * 2013-06-07 2014-06-25 苏磊 Function ceramic material for efficiently filtering radioactive iodine and cesium, and preparation method thereof
CN103695205B (en) * 2013-12-03 2016-01-20 中国人民解放军总参谋部工程兵科研三所 A kind of Self-broken decontamination liquid
CN105651816B (en) * 2014-11-12 2019-01-25 长沙理工大学 A new type of ammonia gas sensor and preparation method thereof
CN104923167B (en) * 2015-07-10 2017-01-04 山东大学 A kind of preparation method of stable nano-SiO2/tributyl phosphate composite adsorption material
CN105381780B (en) * 2015-12-07 2017-10-31 中国科学院生态环境研究中心 A kind of magnetic adsorbent for adsorbing superconduction Magneto separate arsenic removal antimony and preparation method thereof
CN105741897B (en) * 2016-03-30 2018-03-13 中国科学院上海应用物理研究所 A kind of halide radwaste glass solidified body and preparation method thereof
FR3055558B1 (en) 2016-09-08 2022-01-14 Commissariat Energie Atomique SOLID NANOCOMPOSITE MATERIAL BASED ON HEXA- OR OCTACYANOMETALLATES OF ALKALINE METALS, METHOD FOR PREPARING IT, AND METHOD FOR EXTRACTION OF METALLIC CATIONS.
CN108160048B (en) * 2018-01-04 2023-07-14 清华大学 Large-scale preparation method of high-stability cesium-removing adsorbent and its products and applications
CN111111621A (en) * 2018-11-01 2020-05-08 四川德天合盛环保科技有限公司 Method for fixing copper ferrocyanide on PVDF hollow fiber membrane
CN109967048A (en) * 2019-02-19 2019-07-05 江苏海普功能材料有限公司 The resin-base nano compound adsorbent and preparation method thereof of caesium is mentioned for brine
CN109911914B (en) * 2019-04-25 2020-06-12 江西省科学院应用物理研究所 A kind of preparation method of core-shell structure silver aluminum ferrocyanide nanomaterial
CN111167517B (en) * 2019-12-31 2021-09-10 青岛科技大学 Au-GSH@TiO2@ PDMS composite material and preparation method and application thereof
CN114516960B (en) * 2022-01-19 2023-03-24 山东共聚有机硅技术研究院有限公司 Iron cyano silicone resin heat-resistant liquid filler and preparation method thereof
CN115522068B (en) * 2022-09-16 2023-08-01 河北远大中正生物科技有限公司 Method for separating rubidium and cesium from high-salt mother solution
CN117160404B (en) * 2023-10-31 2024-08-23 江苏海普功能材料有限公司 Porous composite material and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Silica gel as a support for inorganic ionexchangersfor the determination of caesium-137 in natural waters. Kikuo Terada, et al.Talanta,Vol.17 . 1970 *
Sorption of cesium on copperhexacyanoferrate/polymer/silica composites in batchanddynamic conditions. S.Milonjic, et al.Journal of Radioanalytical and Nuclear Chemistry,Vol.252 No.3. 2002 *
亚铁氰化铜-硅胶对钴、锌、铯和铈吸附性能的研究. 秦学祥等.海洋环境科学,第12卷第1期. 1993 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102217654A (en) * 2011-04-15 2011-10-19 中国科学院过程工程研究所 Method for preparing nano zinc/potassium ferrocyanide antibacterial material
CN102217654B (en) * 2011-04-15 2013-05-01 中国科学院过程工程研究所 Method for preparing nano zinc/potassium ferrocyanide antibacterial material

Also Published As

Publication number Publication date
CN101041123A (en) 2007-09-26

Similar Documents

Publication Publication Date Title
CN100469435C (en) A kind of preparation method of ferrocyanide/silicon dioxide hybrid material with high loading capacity
US11065610B2 (en) Fenton-like catalytic material with dual reaction centers and preparation method thereof
Li et al. Ultrahigh uranium uptake by magnetic magnesium ferrite loaded hydrothermal carbon nanosheets under acidic condition
CN100551519C (en) Preparation method of titanium potassium ferrocyanide with small ball silica gel as carrier
Lin et al. Efficient removal of dyes from dyeing wastewater by powder activated charcoal/titanate nanotube nanocomposites: adsorption and photoregeneration
Hu et al. Magnetically hyper-cross-linked polymers with well-developed mesoporous: a broad-spectrum and highly efficient adsorbent for water purification
Liu et al. Adsorption performance of U (VI) by amidoxime-based activated carbon
CN101279249B (en) Preparation method of zirconium potassium ferrocyanide with small ball silica gel as carrier
Liao et al. Efficiency and mechanism of amidoxime-modified X-type zeolite (AO-XZ) for Cs+ adsorption
WO2018129773A1 (en) Pertechnetate adsorbent and synthesis process thereof and use thereof in treatment of radioactive wastewater
Dong et al. A comparative study of immobilizing ammonium molybdophosphate onto cellulose microsphere by radiation post-grafting and hybrid grafting for cesium removal
CN107457000B (en) A kind of method that New-type bifunctional preparation method of resin-base nano composite material, composite material and a kind of water depth remove trivalent arsenic
Tao et al. Copper hexacyanoferrate nanoparticle-decorated biochar produced from pomelo peel for cesium removal from aqueous solution
Wu et al. Efficient removal of Sr2+ and Cs+ from aqueous solutions using a sulfonic acid-functionalized Zr-based metal–organic framework
Mahir et al. Facile elaboration of arginine-functionalized PANI@ graphitic carbon nitride for efficient removal of hexavalent chromium
Sang et al. Selective separation and immobilization process of 137Cs from high-level liquid waste based on silicon-based heteropoly salt and natural minerals
CN106824272A (en) A kind of nuclear grade ion-exchange resins based composites and preparation method thereof
Li et al. Fabrication of amino-functionalized Ce/Mn bimetallic organic framework and its efficient performance on Uranium (VI) extraction in aqueous solutions
Wang et al. The adsorptive ability of 3D flower-like titanium phosphate for U (VI) in aqueous solution
Wang et al. Ultrafast removal of ReO4−/TcO4− by radiation-induced grafting of imidazole ionic liquid on alkylated nano-silica microspheres
Ye et al. Ethanol Treated Mn–Zr Compound for Fluoride Removal and its Adsorption Mechanism
Badeenezhad et al. Efficiency of the activated carbon and clinoptilolite particles coated with iron oxide magnetic nanoparticles in removal of methylene blue
CN106390913A (en) Preparation method and applications of silicon-coated magnetic nano ferroferric oxide
Chen et al. Facile synthesis of porous polymer using biomass polyphenol source for highly efficient separation of Cs+ from aqueous solution
CN103736446B (en) A kind of preparation method of magnetic responsiveness bentonite water treatment agent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090318