阅读说明：本技术 从烃料流中去除硫醇的催化剂和方法 (Catalyst and process for removing mercaptans from a hydrocarbon stream ) 是由 S·派茨 H·雷克尔 R·布克尔 T·匡特 S·勒德 A·M·里克斯 A·沃尔夫 G· 于 2020-01-08 设计创作，主要内容包括：本发明涉及一种催化剂,其用于在高级二烯烃(特别是C5二烯)存在下,从烃料流(特别是C4料流)中去除硫醇和任选存在的二硫化物(如果存在)的方法。同时,本发明还涉及通过用多不饱和烃将硫醇硫醚化,在一个实施方案中,在1-丁烯的存在下,从烃料流(特别是C4料流)中去除硫醇和二硫化物(如果存在)的方法,其中该方法是在高级二烯烃(特别是C<Sub>5</Sub>二烯)存在下,在加入氢气的反应器中进行的。(The present invention relates to a catalyst for use in a process for removing mercaptans and optionally disulfides, if present, from a hydrocarbon stream, in particular a C4 stream, in the presence of higher diolefins, in particular C5 dienes. Also, the present invention relates to the thioetherification of mercaptans by using polyunsaturated hydrocarbons, in one embodiment, in the presence of 1-butene fromProcess for the removal of mercaptans and disulfides, if present, in a hydrocarbon stream, in particular a C4 stream, wherein the process is carried out in a higher diolefin, in particular a C 5 Diene) in the presence of hydrogen in a reactor to which hydrogen is added.)

1. Heterogeneous catalyst for the removal of mercaptans and optionally disulfides from a hydrocarbon stream in the presence of higher diolefins, wherein the catalyst is a shell catalyst, characterized in that the catalyst comprises alumina, silica gel or activated carbon as support material and palladium and platinum as catalytically active metals, wherein the catalyst has a palladium concentration of at most 2.0 wt.%, a platinum concentration of at most 1.0 wt.%, and a total metal dispersion of at least 70%.

2. Heterogeneous catalyst according to claim 1, characterized in that the catalyst has a palladium concentration of at most 1.0 wt. -%, preferably of at most 0.5 wt. -%.

3. Heterogeneous catalyst according to claim 1 or 2, characterized in that the catalyst has a platinum concentration of at most 0.5 wt. -%, preferably of at most 0.2 wt. -%.

4. The heterogeneous catalyst of any of claims 1 to 3, wherein the catalyst has at least 0.5m²A/g, preferably at least 1.0m²A/g, more preferably at least 1.5m²Total metal surface area in g.

5. The heterogeneous catalyst of any of claims 1 to 4, wherein the catalyst has a total metal dispersion of at least 80%.

6. A process for the removal of mercaptans and disulfides (if present) from a hydrocarbon stream by thioetherification of mercaptans with a polyunsaturated hydrocarbon in the presence of at least one higher diolefin, wherein the process is carried out in a reactor to which hydrogen is added, wherein the molar ratio of hydrogen to polyunsaturated hydrocarbon is not more than 1, characterized in that a heterogeneous catalyst used in the process comprises palladium and platinum as catalytically active metals, wherein the catalyst has a palladium concentration of at most 2.0 wt.%, a platinum concentration of at most 1.0 wt.%, and a total metal dispersion of at least 70%.

7. The process of claim 6 wherein said higher diolefin is C₅Dienes, preferably isoprene.

8. A process according to claim 6 or 7, characterized in that mercaptans are thioetherified with polyunsaturated hydrocarbons, wherein the polyunsaturated hydrocarbons are selected from: 1, 3-butadiene, but-3-en-1-yne and 1, 2-butadiene.

9. A method according to any one of claims 6-8, characterized in that at least ethanethiol and/or methanethiol is present as a thiol.

10. The process according to any one of claims 6 to 9, characterized in that the molar ratio of hydrogen to polyunsaturated hydrocarbons is between 0.01 and 0.8, preferably between 0.1 and 0.5.

11. A process according to any one of claims 6 to 10, characterized in that it is carried out in the presence of carbon monoxide, wherein the content of carbon monoxide in the reactor feed is less than 20ppm based on the mass of the feed.

12. A method according to any of claims 6-11, characterized in that the inlet temperature of the reactor feed is between 0 ℃ and 180 ℃, preferably between 60 ℃ and 150 ℃, most preferably between 80 ℃ and 130 ℃.

13. Process according to any one of claims 6 to 12, characterized in that it operates as a liquid phase process and hydrogen is completely dissolved in the liquid phase.

14. The method of any one of claims 6-13, wherein C is₄A hydrocarbon stream is used as a feed to the reactor.

15. The process according to any of claims 6 to 14, characterized in that the conversion of 1-butene to 2-butene by isomerization and/or hydrogenation to n-butane is less than 5%, preferably less than 3%, most preferably less than 2%, if the concentration of 1-butene in the hydrocarbon stream is higher than the concentration at thermodynamic equilibrium for the double bond isomerization of 1-butene to 2-butene.

Example 1 (not according to the invention):

the tubular reactor was filled with 540m L catalyst containing Al₂O₃0.5 wt.% Pd. The C4 mixture was passed through the reactor at 90 ℃ and 20 bar pressure in 4kg/h in succession. The C4 mixture had the following composition:

0.5 wt.% 1, 3-butadiene, 13.8 wt.% butane, 40.3 wt.% 2-butene, 20.3 wt.% 1-butene, 22.0 wt.% isobutene, and 3.1 wt.% C5 hydrocarbons, as well as 120 wt ppm isoprene, 2.8 wt ppm sulfur from ethanethiol, and 6.0 wt ppm sulfur from dimethyl disulfide.

4.4Nl/h of hydrogen are metered into this mixture upstream of the reactor. The composition of the effluent from the reactor was as follows:

0.4 wt.% 1, 3-butadiene, 14.1 wt.% butane, 40.3 wt.% 2-butene, 20.3 wt.% 1-butene, 21.8 wt.% isobutene, and 3.1 wt.% C5 hydrocarbons, as well as 100 wt ppm isoprene, 0.7 wt ppm sulfur from ethanethiol, and 2.2 wt ppm sulfur from dimethyl disulfide. 1.5 ppm by weight of sulfur from methyl mercaptan and 4.4 ppm by weight of sulfur from high boilers were also detected.

This corresponds to 75% of ethanethiol, and 38.3% of dimethyl disulfide is converted to high boiling sulfur compounds, 25% of dimethyl disulfide is converted to methanethiol.

Complete conversion of ethanethiol is not achieved and, in addition, for methanethiol, additional thiols are formed from dimethyl disulfide.