US 2010O228065A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0228065 A1 Cheung et al. (43) Pub. Date: Sep. 9, 2010 (54) SELECTIVE HYDROGENATION CATALYST Publication Classification AND METHODS OF MAKING AND USING (51) Int. Cl. SAME C07C 5/03 (2006.01) BOI 3L/02 (2006.01) (75) Inventors: Tin-Tack Peter Cheung, Kingwood, TX (US); Zongxuan (52) U.S. Cl. ......................................... 585/277; 502/162 Hong, Houston, TX (US) (57) ABSTRACT A composition comprising a Supported hydrogenation cata Correspondence Address: lyst comprising palladium and an organophosphorous com CHEVRON PHILLIPS CHEMICAL COMPANY pound, the Supported hydrogenation catalyst being capable of 5601 Granite Parkway, Suite 750 selectively hydrogenating highly unsaturated hydrocarbons PLANO, TX 75024 (US) to unsaturated hydrocarbons. A method of making a selective hydrogenation catalyst comprising contacting a Support with (73) Assignee: CHEVRON PHILLIPS a palladium-containing compound to form a palladium Sup CHEMICAL COMPANY LP, The ported composition, contacting the palladium Supported Woodlands, TX (US) composition with an organophosphorus compound to form a catalyst precursor, and reducing the catalyst precursor to form Appl. No.: 12/710,781 the catalyst. A method of selectively hydrogenating highly (21) unsaturated hydrocarbons to an unsaturated hydrocarbon enriched composition comprising contacting a Supported (22) Filed: Feb. 23, 2010 catalyst comprising palladium and an organophosphorous compound with a feed comprising highly unsaturated hydro Related U.S. Application Data carbon under conditions suitable for hydrogenating at least a (60) Provisional application No. 61/157,491, filed on Mar. portion of the highly unsaturated hydrocarbon feed to form 4, 2009. the unsaturated hydrocarbon enriched composition. 10 20 30 40 Patent Application Publication Sep. 9, 2010 Sheet 1 of 2 US 2010/0228065 A1 FIG. I. 10 2O 30 40 Patent Application Publication Sep. 9, 2010 Sheet 2 of 2 US 2010/0228065 A1 FIG. 2 Ethylene vs. Temperature 78.000 74.000sooo 00 00 0 | 0 72.000 70,000 as 68.000 66.000 0 64.OOO 1OO 12O 140 16O 18O 2OO 220 Temperature (F) US 2010/0228.065 A1 Sep. 9, 2010 SELECTIVE HYDROGENATION CATALYST ings may have drawbacks such as decreased catalyst activity. AND METHODS OF MAKING AND USING Therefore, a need exists for a hydrogenation catalyst that has SAME a desired selectivity and activity. CROSS-REFERENCE TO RELATED SUMMARY APPLICATIONS 0010 Disclosed herein is a composition comprising a Sup 0001. This application claims priority to U.S. Provisional ported hydrogenation catalyst comprising palladium and an Patent Application Ser. No. 61/157,491, filed Mar. 4, 2009 organophosphorous compound, the Supported hydrogenation and entitled “Selective Hydrogenation Catalyst and Methods catalyst being capable of selectively hydrogenating highly of Making and Using Same,” which is hereby incorporated unsaturated hydrocarbons to unsaturated hydrocarbons. herein by reference in its entirety for all purposes. 0011. Also disclosed herein is a method of making a selec tive hydrogenation catalyst comprising contacting a Support STATEMENT REGARDING FEDERALLY with a palladium-containing compound to form a palladium SPONSORED RESEARCH ORDEVELOPMENT Supported composition, contacting the palladium Supported 0002. Not applicable. composition with an organophosphorus compound to form a catalyst precursor, and reducing the catalyst precursor to form REFERENCE TO AMICROFICHEAPPENDIX the catalyst. 0012. Further disclosed herein is a method of selectively 0003) Not applicable. hydrogenating highly unsaturated hydrocarbons to an unsat urated hydrocarbon enriched composition comprising con BACKGROUND tacting a Supported catalyst comprising palladium and an 0004. 1. Technical Field organophosphorous compound with a feed comprising highly 0005. The present disclosure relates to the production of unsaturated hydrocarbon under conditions suitable for hydro unsaturated hydrocarbons, and more particularly to a selec genating at least a portion of the highly unsaturated hydro tive hydrogenation catalyst and methods of making and using carbon feed to form the unsaturated hydrocarbon enriched SaC. composition. 0006 2. Background 0007 Unsaturated hydrocarbons such as ethylene and pro BRIEF DESCRIPTION OF THE DRAWINGS pylene are often employed as feedstocks in preparing value 0013 For a more complete understanding of the present added chemicals and polymers. Unsaturated hydrocarbons disclosure and the advantages thereof, reference is now made may be produced by pyrolysis or steam cracking of hydrocar to the following brief description, taken in connection with bons including hydrocarbons derived from coal, hydrocar the accompanying drawings and detailed description, bons derived from synthetic crude, naphthas, refinery gases, wherein like reference numerals represent like parts. ethane, propane, butane, and the like. Unsaturated hydrocar 0014 FIG. 1 depicts a process flow diagram of an embodi bons produced in these manners usually contain Small pro ment of a selective hydrogenation process. portions of highly unsaturated hydrocarbons such as acety 0015 FIG. 2 is a plot of ethylene weight percentage in lenes and diolefins that adversely affect the production of Subsequent chemicals and polymers. Thus, to form an unsat reactor effluent as a function of temperature for the sample urated hydrocarbon product Such as a polymer grade from Example 1. monoolefin, the amount of acetylenes and diolefins in the DETAILED DESCRIPTION monoolefin stream is typically reduced. For example, in poly mer grade ethylene, the acetylene content typically is less 0016. It should be understood at the outset that although an than about 2 ppm. illustrative implementation of one or more embodiments are 0008. One technique commonly used to reduce the provided below, the disclosed systems and/or methods may amount of acetylenes and diolefins in an unsaturated hydro be implemented using any number of techniques, whether carbon stream primarily comprising monoolefins involves currently known or in existence. The disclosure should in no selectively hydrogenating the acetylenes and diolefins to way be limited to the illustrative implementations, drawings, monoolefins. This process is selective in that hydrogenation and techniques illustrated below, including the exemplary of the monoolefinand the highly unsaturated hydrocarbons to designs and implementations illustrated and described saturated hydrocarbons is minimized. For example, the herein, but may be modified within the scope of the appended hydrogenation of ethylene or acetylene to ethane is mini claims along with their full scope of equivalents. mized. 0017. In an embodiment, a method of making a selective 0009. One challenge to the selective hydrogenation pro hydrogenation catalyst comprises contacting an inorganic cess is the potential for runaway reactions that lead to the catalyst Support with a palladium-containing compound to uncontrollable reduction of ethylene to ethane. One method form a palladium Supported composition and contacting the ology to minimize runaway reactions is to increase the palladium Supported composition with an organophosphorus amount of selectivity enhancers in the hydrogenation cata compound. Herein, the disclosure will focus on the use of lyst. Thus, catalyst preparations may comprise one or more phosphine oxides, phosphates, phosphinates, and phospho selectivity enhancers. Selectivity enhancers are materials nates as the organophosphorus compound, although phos Such as alkali metal halides that increase the catalyst selec phines phosphites, phosphinites, and phosphonites are also tivity for the hydrogenation of highly unsaturated olefins to contemplated organophosphorus compound precursors and unsaturated olefins. The use of additional amounts of selec will be described in more detail later herein. In an embodi tivity enhancers, also termed increased loadings, may lead to ment, the organophosphorus compound functions to increase improved catalyst selectivity; however, the increased load the selectivity of the hydrogenation catalyst for the conver US 2010/0228.065 A1 Sep. 9, 2010 sion of a highly unsaturated hydrocarbon to an unsaturated 0024. In an embodiment, the PPSC may be prepared using hydrocarbon. Herein, such catalysts are termed palladium, a palladium-containing compound in an amount of from organophosphorus supported catalysts (PPSC). about 0.005 wt.% to about 5 wt.% based on the total weight 0018. The PPSC may be used for selectively hydrogenat of the PPSC, alternatively from about 0.01 wt.% to about 3 ing highly unsaturated hydrocarbons to unsaturated hydro wt.%, alternatively from about 0.02 wt.% to about 1 wt.%. carbons. As used herein, a highly unsaturated hydrocarbon is alternatively from about 0.02 wt.% to about 0.04 wt.%. defined as a hydrocarbon containing a triple bond, two con alternatively from about 0.03 wt.% to about 0.05 wt.%. The jugated carbon-carbon double bonds, or two cumulative car amount of palladium incorporated into the PPSC may be in bon-carbon double bonds. As used herein, an unsaturated the range described herein for the amount of palladium-con hydrocarbon is defined as a hydrocarbon containing an iso taining compound used to prepare the PPSC. lated carbon-carbon double bond. Examples of highly unsat 0025. In an embodiment, the PPSC comprises an organo urated hydrocarbons include without limitation acetylene, phosphorus compound. In an embodiment, the organophos