缚酸剂对RaneyNi催化氢解TPD制1,3-丙二醇的影响

Effect of Acid Binding Agent on Hydrogenation of TPD under the Catalysis of Raney Ni

甘油的间接氢解是新近发展的制备1,3-丙二醇的方法。研究发现甘油的间接氢解中间体TPD(2-对甲苯磺酰氧基-1,3-丙二醇)加氢过程产生的对甲苯磺酸腐蚀催化剂,导致催化剂无法重复利用。为了避免催化剂被腐蚀,选用几种缚酸剂,研究了缚酸剂对TPD加氢反应的影响,通过单因素实验考察了温度、压力和催化剂(Raney Ni)用量对反应的影响,并对反应机理作了讨论。结果表明:三乙胺作为缚酸剂时较优的反应条件为:温度100℃,压力4 MPa,催化剂用量2.0 g(TPD质量的57%),在此反应条件下,TPD转化率为89.1%,1,3-丙二醇的选择性为33.7%。催化剂重复实验结果表明加入缚酸剂能在一定程度上保护催化剂。

Indirect hydrogenolysis of glycerol is a newly-developed method to prepare 1,3-propanediol.However,the catalyst is totally destroyed by the acid formed during the hydrogenation of the intermediate TPD（2-tosyloxy-1,3-propanediol）.To avoid the corrosion of catalyst（Raney Ni）,some bases were used separately as acid binding agent to protect the catalyst from corrosion in this work,and the influences of these bases on the hydrogenolysis were investigated;the effects of temperature,hydrogen pressure and the used amount of Raney Ni on the selectivity of 1,3-propanediol were studied as well.The mechanism of the hydrogenation of TPD was discussed.It was found from the experimental results that the triethylamine is the better base for using as the acid binding agent.The optimized reaction conditions were found as follows： that the temperature is 100℃,the hydrogen pressure is 4 MPa,and the dosage of Raney Ni is 2.0 g（57% of used amount of TPD）.Under these conditions,the conversion of TPD is 89.1%,and the selectivity of 1,3-propanediol is 33.7%.It was also found from the experimental results that the acid binding agent can protect the catalyst to a certain extent.