【作者】 何丽新；

【导师】 崔天顺； 赵临远；

【作者基本信息】 广西师范大学 ， 无机化学， 2002， 硕士

【摘要】 沸石是一族由[（Si，Al）O₄]四面体组成的、兼有架状构造的含水铝硅酸盐矿物，其晶体结构比较特殊——有许多大小均一的孔道和孔穴，而孔道和孔穴由阳离子与水分子占据。孔道中的水分子能可逆地吸附、脱附，而不破坏沸石的晶体结构，脱水后，沸石的孔穴变得空旷，可以吸附并储存大量极性分子，所以其具有吸附性能；沸石晶格中的阳离子和铝硅酸盐格架结合较弱，能可逆地被其它阳离子交换代替，同时也不破坏沸石的晶体结构，因而其具有离子交换性能。利用沸石的吸附和离子交换性能，它已广泛应用于农业、石油化工、建筑业、畜禽饲养、环境保护和能源利用等领域。与合成沸石相比，天然沸石矿藏丰富，价格低廉，所以其开发利用备受关注。 广西辉沸石矿储量大，纯度高，铁的含量很低，仅～0.27％，白度几乎接近90度，晶体大。它是一种质量较好、用途较广且罕见的沸石矿，也是目前国内外唯一具有工业意义的辉沸石矿。广西辉沸石自1989年发现以来已有10余年，但为其开发应用提供理论依据的理化性质尚无系统而全面的研究。对辉沸石吸附性能和离子交换性能的研究，是有效开发利用沸石矿物资源的前提。在现有实验条件的基础上，本文主要针对广西辉沸石的吸附和离子交换性能做了比较深入的研究。 针对辉沸石的吸附性能，本文讨论了它的加热活化方式，并与其酸浸泡活化方式进行了比较，其中以加热方式为佳。辉沸石最佳的活化与再生条件为200℃加热1h，经活化后其饱和吸水率约为12.4％。辉沸石的饱和吸水率受粒度和环境相对湿度的影响不大，经过再生后，其可以重复使用。预期辉沸石可以代替硅胶与活性炭作为吸附剂使用。 在室温下，广西辉沸石经不同浓度的酸碱溶液浸泡，再测定沸石的饱和吸水率，根据沸石吸附性能的变化，来判断辉沸石的耐酸碱性，其结果表明，室温下辉沸石的耐酸性：0.1～0.5NHCl浸泡24h后，沸石的结构不变，而同样条件下，4MHCl处理后，其结构完全破坏；其耐碱性：0.1～0.3MNaOH或浓氨水浸泡24h后，沸石的结构不变，而同样条件下，1MNaOH处理后，结构完全破坏。通过测定竞争阳离子对沸石铵交换容量的影响，可知一价、二价阳离子交换序列为：K⁺>Ag⁺>Na⁺>Li⁺、Ba²⁺>Cu²>Sr²⁺>Ca²⁺>Zn²⁺>Mg²⁺，辉沸石对K⁺、Ag⁺有优先选择交换的性能。 广西辉沸石属于钙型沸石，CaO含量为8.8％。将沸石原矿改成钠型，有利于离子交换能力的提高，而离子交换能力的提高有赖于改型完全，改型完全可根据沸 广酉师范大学硕士论文：广百尽佛石的研兑 — — 石中钙溶出的情形来判断。本文讨论了改型剂和改型方式，以及时间、固液比、“交换次数与粒度等因素对钙离子溶出的影响。将沸石原矿细化，再用氯化钠溶液 沸水浴力。热静态交换，可达到较好的改型效果。改型后，辉沸石的吸附性能和离 子交换性能都大大增强，例如，IQ00目沸石的吸水率由 9．88％升高到 16．0％，C．E．C 从1一5．6mmol／100g升高至22？．0mmol／1009。由此可见，改型沸石可广泛用作离子 交换剂。 辉沸石经改型处理后，交换上具有抗菌性能的金属离子 Cu’”和 Zn’”，可制备成 抗菌沸石。本文主要讨论了沸石粒度、反应温度、反应物用量与反应时间等因素 对沸石中金属离子含量的影响。粒度越小，反应温度越高，抗菌沸石的抗菌离子 含量也越高。抑茵试验表明，抗菌沸石的抗菌性能较好，沸石中的铜和锌对细菌 的抑制有协同效应。 总之，沸石原矿难以直接在工业上应用，广西辉沸石亦不例外。但将辉沸石加 热活化处理，其吸附性能大为改观，可代替硅胶与活性炭用作千燥剂和吸附剂； 将辉沸石改型处理，其离子交换性能大有提高，能广泛用作离子交换剂。更多还原

【Abstract】 Natural zeolite is a minieral of hydrated aluminium silicate,consisting of [(Si,Al)04] tetrahedroid. The crystral structures of zeolite are special because they have many equal -sized ducts and holes which are occupied by water moleculars and positive ions . The water moleculars can adsorp and deadsorp reversibly without destroying the crystral structures,After dehydration the holes will be able to hold more moleculars ,In result zeolite possess adsorption property. On the other hand,the positive ions in ducts and holes are weak in combining with negative ions of aluminium silicate,so they can be replaced by other cation ions reversibly ,still keeping the crystral structure. Because of the above properties of adsorption and ions’ exchange,natural zeolites can be widely used in various fields such as agriculture petrochemical indusdtry architecture livestock husbandry. enviormental protection and energy application . Compared with synthetical zeolite ,natural zeolite is not only rich in deposit but also low in price. Therefore,its exploitation and utilization are calling great attention from the people.The deposite of stilbites in Guangxi is the only one which possesses industrial importance both at home and abroad at present time. They have high purity and are low in iron element. Their whiteness is up to nearly 90 percents. It is estimated that the stilbite in Guangxi have a great potentiality for exploration because of their excellent properties in adsorption and exchange of ions. Though discovered in 1989,the stilbites haven’t received an overall and systematically study on their physical and chemical properties,even though it is necessary for the exploitation and utilization.To meet this end,this thesis deals mainly with the study made under the present experiment condition to properties of adsorption and ions exchange of the stilbites in Guangxi.In order to strenghen the adsorption capacity,two ways for activation are used in my study:roasting and inorganic acid dipping treatment. Between them the former one is better. The best condition for activation and regeneration is roasting at temperature of 200C for one hour. The adsorption capacity of activatied stilbites is 12.4%,and is affected little by the size and relative humidity of enviorment. By regeneration the stilbites can be used repeatly. They can also replace silica gel and activated charcoal as adsorbents.By soaking the stilbites into acid or base solution of various densities at room temperture,We can measure their adsorption capacity,And then the changes of adsorption capacity reflects the acid fastness and alkali fastness of stilbites. The results show that at room temperature the steady state of stilbite require an acid density of 0.1-0.5MHC1 or alkali density of 0.1-0.3MNaOH or strong ammoniao On the other hand ,the complete damage to their structures requires the acid density of 4MHC1 or alkali density of IMNaOH. By testing the influence from the competitive positive ions on the exchange amounts of NH4" in stilbite. it can be seen that the order for one valence or two valences of ions’exchange is K+ > Ag+> Na+>Li+,Ba2"1" >Cu2>Sr2+ >Ca2+>Zn2+> Mg2+ which shows K+ and Ag+ have the priority in the exchange with stilbite.The stilbites in Guangxi are rich in calcium ,the content of calcium oxide is 8.8%.Changing the raw stilbite into Na - exchanged zeolite will contrbute to the ions’exchange. The raise of ion exchange capacity depends on the degree of retrofitting,and which can be jundged by the end of calciun’s dissolving ?This thesis discusses the retrofitting solution ways and influences by the factors such as tirn ratio of mass and volume exchanging times and the size. To thin the raw stilbite and then exchange with 20% of sodium chloride solution at the boiling point for 1-2 hours can obtain better effect. After remaking,the property of adsorption and ions exchanging capacity will increase greatly. Then the water -contained rate of 1000 mesh zeolite powder rises from 9.88% to 16.0%,and the C.E.C(cation exchange capacity) fr更多还原