摘要
在廉价体系中,水热法合成了小晶粒钛硅分子筛TS-1,并采用不同有机碱对小晶粒TS-1进行改性,进一步提高了其催化活性。通过考察酸碱性对丙烯环氧化反应性能的影响,提出了可能的反应机理。根据实验室小试得到的反应条件对丙烯环氧化反应进行了中试放大,分析了中试催化剂失活的原因,并研究了其再生条件。得到的主要结果如下：
1.在四丙基溴化铵-乙胺体系中,采用纳米TS-1母液作为晶种,合成出晶粒尺寸为600nm×400nm×250nm的小晶粒TS-1分子筛,并对小晶粒TS-1分子筛合成条件进行系统地考察,发现当Si/Ti摩尔比为50,晶种/Si02质量比为0.06,晶化48h,静置洗涤3次的样品催化性能最佳,其催化丙烯环氧化反应时,X(H202)及S(PO)可分别达到92%及98%,催化苯酚羟基化反应时,X(PHE)达到22%。其高催化性能的原因是：(1)比表面积较大且表面较粗糙,能为催化反应提供更多的外表面活性中心,使反应物转化率提高；(2)与微米TS-1相比,颗粒尺寸较小,平均孔径较大,扩散阻力较小,使反应物转化率及产物选择性提高；(3)少量Na+存在,能够覆盖TS-1表面酸中心,提高丙烯环氧化反应选择性。
2.在固定床反应器上优化了挤条小晶粒TS-1催化丙烯环氧化的反应条件,并在优化条件(40℃,3.0MPa,n(C3H6)/n(H2O2)=3,丙烯、甲醇及H202的WHSV分别为0.6、2.5及0.16h-1, NH3-H2O浓度为1.2mmol·L-1)下考察了其长运转性能,反应1000h后,X(H2O2)及S(PO)仍能达到95%以上
3.采用不同有机碱改性小晶粒TS-1,发现不同有机碱改性对TS-1二次晶化的方向取向有很大影响,TPA+及TBA+对晶粒内部的骨架钛具有保护作用。采用0.06mol·L-1四丙基氢氧化铵改性72h的样品,催化苯酚羟基化反应活性最高。
4.考察不同有机碱作为添加剂,对丙烯环氧化反应性能的影响,并根据反应结果、表征及DFT计算,推测了丙烯环氧化反应的机理,认为酸中心对丙烯环氧化反应具有重要的促进作用。
5.对微米TS-1(EPO-08)催化过氧化氢制环氧丙烷(HPPO)中试过程及结果进行讨论,该催化剂在采用丙酮／甲醇混合溶剂或纯甲醇溶剂时,均能表现出优异的催化性能。
6.将EPO-08催化剂用于HPPO中试1700h后,活性有所下降,从中试反应器入口至出口,催化剂活性逐渐降低。造成催化剂失活的主要原因是环氧丙烷低聚物的堵孔。失活的EPO-08可以采用体外或原位再生使其恢复活性,原位再生更适合工业化生产。
Titanium silicalite-1(TS-1) with a small crystal size (small-crystal TS-1) was synthesized in a TPABr-ethylamine hydrothermal system. The as-synthesized small-crystal TS-1was modified with different organic bases to further improve its catalytic activity. By investigating the influence of acid/base on the catalytic performance of propylene epoxidation, a new reaction mechanism is presented. According to the experiment in laboratory, a pilot plant of propylene epoxidation was carried out. The deactivated catalysts were characterized to study the reason for the deactivation and were regenerated under different conditions. The main results are shown as follows:
1. Small-crystal TS-1with a crystal size of about600nm×400nm×250nm, was synthesized in a TPABr-ethylamine hydrothermal system using the mother liquor of nano-sized TS-1as seeds. The synthesis conditions were systematically studied. When the molar ratio of Si/Ti was50, the weight ratio of seed/SiO2was0.06, using precipating separation for three times and the gel was crystallized for48h, the highest catalytic properties were obtained. The X(H2O2) and S(PO) were92%and98%, respectively, for the epoxidation of propylene, and the XPHE) was22%for the hydroxylation of phenol. The reasons for its high catalytic properties were considered as follows:(1) Larger surface area and rougher surface provided more active sites for the reactions, so that the reactant conversions were higher.(2) Smaller crystal size and larger pore diameter than micro-sized TS-1decreased the internal diffusion limitation, so that the selectivity of the main product in propylene epoxidation increased.(3) A small amount of sodium ions could improve the selectivity of propylene oxide by covering the acid centers on the TS-1.
2. The reaction conditions of propylene epoxidation over small-crystal TS-1extrudates were optimized in a fixed-bed reator. A long term test was performed under the optimal conditions (40℃,3.0MPa, n(C3H6)/n(H2O2)=3, WHSVs of propylene, methanol and H2O2were0.6,2.5and0.16h-1, and the NH3·H2O concentration was1.2mmol·L-1). The X(H2O2) and S(PO) were both more than95%after1000h reaction.
3. Different organic bases were used to modify the small-crystal TS-1. The direction of recrystallization depended on the kind of bases. TPA+and TBA+show a protection effect on the framework Ti in the crystals. When0.06mol·L-1TPAOH solution was adopted to treat the TS-1for72h, the highest conversion of phenol was obtained in phenol hydroxylation.
4. The influences of different organic base additives on the propylene epoxidation were investigated. A new mechanism of propylene epoxidation is presented, according to the experimental data, characterization and DFT calculations. Acid centers were considered to be promotors for the epoxidation reactions.
5. The process and results of the HPPO pilot plant over EPO-08were dicussed. The EPO-08showed excellent catalytic performances both in acetone/methanol mixed solvent and in pure methanol solvent.
6. The EPO-08deactivated partly after1700h pilot plant. The activity decreased from the entrance of the pilot-plant reactor to the exit. The main reason for the deactivation was blocking of pores by propylene oxide oligomers. The deactivated EPO-08could be regenerated by external and in-situ regeneration, while the in-situ regeneration was preferred in industry.
引文
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