甲醇气相羰化非铑非卤素新催化体系研究 I.新的硫化物催化剂制备方法及其羰化性能

Study of a halide and rhodium free catalytic system for vapor phase carbonylation of methanol Ⅱ. A novel method for preparation of sulfided catalysts and their carbonylation behavior

采用（ＮＨ４）２Ｓ溶液硫化制备了一系列Ｃｒ、Ｍｏ、Ｗ硫化物负载型催化剂，结果表明，用此方法制备的硫化物催化剂比用Ｈ２与ＣＳ２（或Ｈ２Ｓ）气相硫化法制备的催化剂具有高的羰化活性与选择性，除硫化的ＣｒＣｏ／Ｃ催化剂无羰化活性外，其余在无任何促进剂下均对甲醇气相羰化具有活性，其羰化活性顺序为：ＭｏＣｏ／Ｃ＞ＭｏＮｉ／Ｃ＞ＷＣｏ／Ｃ＞ＷＮｉ／Ｃ＞ＭｏＦｅ／Ｃ。实验还发现，添加第３组分（Ｃｕ、Ａｇ、Ｚｎ、Ｓｎ、Ｐｂ）。

A series of supported Cr,Mo and W catalysts are prepared by sulfidization with (NH 4) 2S in an aqueous solution.It is found that the sulfided Cr,Mo and W catalysts thus prepared have much higher activity and selectivity for vapor phase carbonylation of methanol than the catalyst sulfidized by CS 2(or H 2S)in hydrogen atmosphere.All the sulfided catalysts except for the sulfided CrCo/C are active in the carbonylation without addition of any promoters such as halide to the feed.The order of activity for carbonylation is as follows:MoCo/C>MoNi/C>WCo/C>WNi/C>MoFe/C.The experimental results also show that addition of Cu,Ag,Zn,Sn or Pb to the sulfided CrCo/C catalyst has no promotion to carbonylation activity.