摘要
钛硅沸石(TS-1)是八十年代出现的一类骨架中硅原子被钛原子部分取代的具有MFI结构的杂原子沸石分子筛。作为一种新的催化氧化材料,TS-1受到人们的广泛关注。在TS-1的合成方法的研究中,经典的以及改进的水热法特别是廉价体系的水热法得到了较快的发展,而二次合成法进展缓慢。二次法合成的ZSM-5型钛硅沸石一般记作Ti-ZSM-5沸石。本文对Ti-ZSM-5沸石的气固相法合成进行了较深入的研究,考察了不同母体合成的Ti-ZSM-5沸石的物化性能,筛选出较合适的母体;通过对母体合成条件的调节,对母体缺陷位的控制,以及对气固相反应条件的优化,制备了高效的Ti-ZSM-5催化剂,加深了对气固相法合成Ti-ZSM-5沸石机理的认识;考察了Ti-ZSM-5催化剂的丙烯环氧化以及苯酚羟基化反应性能。论文的主要内容如下:
一、以B-ZSM-5和Al-ZSM-5沸石为母体合成Ti-ZSM-5沸石的研究
分别以水热合成体系中配料(n)SiO_2/(n)B_2O_3=5的B-ZSM-5、硅铝比为30的Al-ZSM-5和硅铝比分别为239、600的高硅ZSM-5沸石为母体,经过预处理造成骨架缺陷位后,在高温下与TiCl_4进行气固相反应合成了Ti-ZSM-5沸石,考察了母体对钛进入骨架及其存在形式的影响。研究表明:母体本身的物化性质影响所合成的Ti-ZSM-5沸石中钛的含量及其存在形式。以脱硼ZSM-5沸石(de-[B]-ZSM-5)为母体,所合成的Ti-ZSM-5沸石中骨架钛含量高,非骨架钛含量低,催化性能最好,但其中残留的硼引入的酸中心使其环氧丙烷选择性降低;虽然含硼沸石在预处理过程中晶粒破碎,但是晶体结构没有被破坏,仍保持了较高的结晶度。Al-ZSM-5沸石中大量的Al不能脱除,使得后续合成的Ti-ZSM-5沸石中生成了较多的锐钛矿型非骨架钛,而且含有较多较强的酸中心,降低了其催化性能,导致环氧丙烷选择性降低。1,6-己二胺为模板剂制备的、硅铝比239的高硅沸石为母体合成的Ti-ZSM-5沸石,较四丙基溴化铵为模板剂制备的、硅铝比600的高硅沸石为母体合成的Ti-ZSM-5沸石具有更高的骨架钛含量和催化活性;后者中除锐钛矿型TiO_2以外,还生成了较多的金红石型TiO_2,而前者和Al-ZSM-5沸石为母体的Ti-ZSM-5沸石中只有锐钛矿型TiO_2生成,de-[B]-Ti-ZSM-5沸石
Ti一SM一沸石的气固相法合成、表征和催化性能研究
中只发现相对极少量的锐钦矿型TioZ。丙烯环氧化和苯酚轻基化反应中,过氧化氢的
无效分解都不能归因于锐钦矿型和/或金红石型非骨架钦的存在。催化剂在丙烯环氧化
反应中的活性主要由骨架钦含量决定。苯酚轻基化反应中,骨架钦含量与催化剂晶粒大
小同时起着重要的作用,强酸中心导致的苯酚质子化降低苯酚转化率。
对以B一SM一5和Al一SM一5沸石为母体气固相法制备Ti-zSM-5的过程进行分析,
发现Ti’+既可以通过占据沸石骨架空位形成骨架钦物种,也可以通过同晶置换硼或者铝
等杂原子进入骨架,这两种过程可以单独存在,也可以同时发生,特别是母体沸石中同
时存在较多的骨架缺陷位和骨架杂原子的时候。
二、以不同(n) 510了(n)B203的B一SM一5沸石为母体合成Ti-ZSM一5沸石的研究
以不同(n) 5 102/(I心BZo3的B一SM一5沸石为母体,经过相同的酸洗脱硼预处理过
程后,在高温下与TIC玩进行气固相反应合成了Ti-ZSM一5沸石,考察了水热合成B-
zSM一5时的配料(n) 5102/(I习BZo:对钦进入沸石骨架的影响。研究发现,通过调变配料
(n) 510了(n)B 203即母体B一SM-5的B含量,可以有效的控制气固相法制备的Ti-ZSM一5
沸石的骨架钦含量。随着配料(n) 5102/(n)B203的增加,即母体B一sM一5中B含量的
减少,所制得的Ti-ZsM一5的(n)Sioy(n)Tio:增大,即总钦含量降低;同时骨架钦含量
也降低,其丙烯环氧化活性降低。而由于其中残留的B含量的降低,引入的酸中心的
数量减少,其环氧丙烷的选择性升高。各样品中均生成一定量锐钦矿型蜘和金红石型
TIOZ。该系列催化剂的苯酚轻基化反应性能同时受到骨架钦含量和晶粒大小的影响。无
论是在丙烯环氧化反应还是苯酚轻基化反应中,过氧化氢的无效分解都不能归因于锐钦
矿型和金红石型TioZ。水热合成配料(n) 510扩(n)B203二5的B一SM-5沸石为母体制备
的Ti-zSM一5沸石具有最好的催化性能。
三、提高Ti-zSM-5沸石催化剂催化性能的研究
在前人的研究中,气固相法合成的Ti-ZSM-5沸石分子筛用于丙烯环氧化反应时虽
然具有较好的反应性能,但是,用于苯酚经基化反应均难以得到理想的催化效果。本文
从调变母体的性质入手,通过在合成母体的过程中进行低温晶化等手段,降低沸石晶粒
Titanium silicalite-1 (TS-1) is a titanium-containing zeolite with the MFI structure that was first synthesized in 1983. Because of the unique catalytic properties in organic reactions with aqueous hydrogen peroxide (30%) as the oxidant under mild conditions, TS-1 has received much attention of the researchers. There are two methods for the synthesis of TS-1, hydrothermal synthesis and secondary synthesis or post synthesis. In the past decades, the hydrothermal synthesis, especially the low cost system, developed fast. At the same time, the secondary synthesis developed slowly. In this paper, different ZSM-5 precursors were used to prepare Ti-ZSM-5 through gas-solid method. The effect of precursors on the chemical-physics properties of Ti-ZSM-5 was investigated to find a kind of precursor more suitable for the gas-solid synthesis of Ti-ZSM-5. Through modifying the synthesis conditions of the B-ZSM-5 precursor to control the amount of hydroxyl nests and the crystal size, and optimizing the gas-solid synthesis conditions, Ti-ZSM-5 with better catalytic properties was successfully prepared. The mechanism of the gas-solid synthesis of Ti-ZSM-5 is highlighted through the work mentioned above.The main contents of this thesis are as follows:1. Ti-ZSM-5 samples were successfully synthesized by using B-ZSM-5 with a molar ratio of SiO_2 to B_2O_3 5 in the gel and Al-ZSM-5 zeolites with a molar ratio of SiO_2 to Al_2O_3 30, 239, 600, respectively, as the precursors. The gas-solid synthesis included two steps which were pretreatment in HCl solution or HNO_3 solution and titanation with gaseous TiCl_4. The results show that: The chemical-physics properties of the precursors play a very important role in the
incorporation of titanium into the zeolite framework. With B-ZSM-5 as the precursor, the synthesized Ti-containing samples have much more framework titanium species and less extra-framework titanium species which result in a higher activity in the oxidation reactions. At the same time, the acid sites from the residual boron in the Ti-containing samples lead to a low slectivity to PO. As to the Al-ZSM-5 with a molar ratio of SiO_2 to Al_2O_3 30, much Al atoms remain in the framework after the acid treatment. Ti-ZSM-5 with it as precursor has much acid sites which changed the catalytic properties. Ti-ZSM-5 starting with the silicon-rich ZSM-5 with a molar ratio of SiO_2 to Al_2O_3 239 has more framework titanium and better catalytic activity than that starting with the silicon-rich ZSM-5 with a molar ratio of SiO2 to Al_2O_3 600 does. The later has much anatase TiO_2 and rutile TiO_2, while the former and Ti-ZSM-5 starting with Al-ZSM-5 with a molar ratio of SiO_2 to Al_2O_3 30 contain only anatase TiO_2. The de-[B]-Ti-ZSM-5 contains trace of anatase TiO_2. Either for the reaction of propylene epoxidation or for the reaction of phenol hydroxylation, anatase TiO_2 or rutile TiO_2 does not accelerate the decomposing of H_2O_2. For the reaction of propylene epoxidation, the amount of framework titanium dominates the conversion of hydrogen peroxide. For the hydroxylation of phenol, the crystal size, as well as the amount of framework titanium, plays a very important role in the conversion of phenol. Phenol protonation caused by strong acid sites hindered the electrophilic reaction of phenol hydroxylation.Titanium can be incorporated into the zeolite framework through both the reaction of "hydroxyl nests" with TiCl_4 and the replacement of framework Al or B by Ti during the gas-solid reaction.2. Ti-ZSM-5 samples were successfully synthesized by using B-ZSM-5 with different molar ratio of SiO_2 to B_2O_3 as the precursors. The effect of (n)SiO_2/(n)B_2O_3 on the incorporation of titanium into the framework was investigated. Propylene epoxidation and phenol hydroxylation properties were also investigated. The results show that (n)SiO_2/(n)TiO_2 in the samples increased with an increase in the (n)SiO_2/(n)B_2O_3 in the precursors. The conversion of H_2O_2 increased with the decreasing of (n)SiO_2/(n)B_2O_3 or (n)SiO_2/(n)TiO_2, and
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