# US 5,349,114 A · Shape selective hydrocarbon conversions over modified catalyst > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,349,114 A - Document ID: US5349114A - Status: Granted - Kind: A - Application number: 08/042,431 - Filed: 1993-04-05 - Granted: 1994-09-20 - Earliest claimed: 1993-04-05 - Assignees: Mobil Oil Corporation - Inventors: Rudolph M. Lago; David O. Marler; Sharon B. McCullen - Web page: https://patentgrep.com/patent/US5349114A ## CPC - C07C 6/123: {of only one hydrocarbon} - B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively - C07C 1/20: starting from organic compounds containing only oxygen atoms as heteroatoms - C07C 2/12: with crystalline alumino-silicates {or with catalysts comprising} molecular sieves - C07C 2/66: Catalytic processes - C07C 5/2708: {with crystalline alumino-silicates, e.g. molecular sieves} - B01J 2229/12: to alter the outside of the crystallites, e.g. selectivation - B01J 2229/26: to stabilize the total catalyst structure - B01J 2229/32: Reaction with silicon compounds, e.g. TEOS, siliconfluoride - B01J 2229/36: Steaming - B01J 2229/42: Addition of matrix or binder particles - C07C 2529/42: containing iron group metals, noble metals or copper - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract A process for shape selective hydrocarbon conversion involves contacting a hydrocarbon feedsteam under conversion conditions with a modified catalytic molecular sieve which has been modified by being pre-selectivated with a first silicon source, then steamed. The feedstream may also contain a second silicon source which is a high efficiency para-xylene selectivating agent. The method for modifying the molecular sieve is also described. ## Claims ### Claim 1 A process for a shape selective hydrocarbon conversion comprises contacting a reaction stream comprising hydrocarbon to be converted, under conversion conditions, with a catalytic molecular sieve comprising ZSM-5 which has been modified by being (i) pre-selectivated with a first silicon-containing compound selected from the group consisting of silicones and propylamine silane polymers and (ii) subsequently steamed at about 280.degree. C. to 400.degree. C. ### Claim 2 (depends on 1) The process of claim 1 wherein the shape selective hydrocarbon conversion is selected from a group consisting of dewaxing of paraffins, isomerization of alkylaromatics, oligomerization of olefins, transalkylation of aromatics, alkylation of aromatics, conversion of oxygenates to hydrocarbons, rearrangement of oxygenates and conversion of paraffins and olefins to aromatics. ### Claim 3 (depends on 1) The process of claim 1 wherein the conversion conditions comprise a temperature of from about 100.degree. C. to about 760.degree. C., a pressure of about 0.1 atmosphere to about 200 atmospheres, a weight hourly space velocity of from about 0.08 hr.sup.-1 to about 2000 hr.sup.-1, and a hydrogen/hydrocarbon molar ratio of from about 0 to about 100. ### Claim 4 (depends on 1) The process of claim 1 wherein the shape selective hydrocarbon conversion is toluene disproportionation. ### Claim 5 (depends on 1) The process of claim 1 wherein the molecular sieve comprises a zeolite having an initial Constraint Index from about 1 to about 12. ### Claim 6 (depends on 1) The process of claim 1 wherein the molecular sieve contains ions selected from a group consisting of hydrogen, hydrogen precursor, metals of Periodic Table Group VIII and combinations thereof. ### Claim 7 (depends on 1) The process of claim 1 wherein the molecular sieve is incorporated with binder before being modified. ### Claim 8 (depends on 1) The process of claim 1 wherein the molecular sieve is incorporated with binder after being modified. ### Claim 9 (depends on 1) The process of claim 1 wherein the molecular sieve is contacted with steam under conditions comprising from about 5 to about 100% water vapor, a pressure from about 0.1 to about 50 psig for a time from about 2 to about 12 hours. ### Claim 10 (depends on 1) The process of claim 1 wherein the molecular sieve is modified in an as-synthesized condition. ### Claim 11 A process for toluene disproportionation comprising: contacting a reaction stream which comprises toluene, under conversion conditions, with a modified catalytic molecular sieve comprising ZSM-5 wherein the catalytic molecular sieve has been modified by being (i) pre-selectivated with a first silicon source selected from the group consisting of silicones and propylamine silane polymers and (ii) subsequently steamed at about 280.degree. C. to 400.degree.. ### Claim 12 (depends on 11) The process of claim 11 wherein the conversion conditions comprise a temperature between about 200.degree. C. and about 600.degree. C., a pressure between about 0.1 psig and about 100 psig, a weight hourly space velocity (WHSV) between about 0.1 hr.sup.-1 and about 20 hr.sup.-1, and a hydrogen/hydrocarbon mole ratio from about 2 to about 20. ### Claim 13 (depends on 11) The process of claim 11 wherein the molecular sieve comprises a zeolite having an initial Constraint Index from about 1 to about 12. ### Claim 14 (depends on 11) The process of claim 11 wherein the catalytic molecular sieve contains ions selected from the group consisting of hydrogen, hydrogen precursor, metals of Periodic Table Group VIII and combinations thereof. ### Claim 15 (depends on 11) The process of claim 11 wherein the molecular sieve has been incorporated with binder before being modified. ### Claim 16 (depends on 11) The process of claim 11 wherein the molecular sieve has been incorporated with binder after being modified. ### Claim 17 (depends on 11) The process of claim 11 wherein the molecular sieve is steamed under conditions comprising between about five and about 100 percent water vapor, a pressure of from about 0.1 to about 50 psig and for a time of from about 2 to about 12 hours. ### Claim 18 (depends on 11) The process of claim 11 wherein the molecular sieve is modified in an as-synthesized condition. ### Claim 19 (depends on 11) The process of claim 11 wherein the reaction stream further comprises a second silicon-containing compound which is a high efficiency para-xylene selectivating agent. ### Claim 20 (depends on 19) The process of claim 19 wherein the second silicon-containing compound is fed with the reaction stream for at least one hour. ### Claim 21 (depends on 19) The process of claim 19 wherein the high efficiency para-xylene selectivating agent comprises a silicone compound. ### Claim 22 (depends on 20) The process of claim 20 wherein the silicone compound comprises a mixture of phenylmethylsilicone and dimethylsilicone. ### Claim 23 (depends on 22) The process of claim 22 wherein the reaction stream comprises at least 80% toluene and at least 0.1% silicone compound. ### Claim 24 (depends on 19) The process of claim 19 wherein the contacting provides a single pass para-xylene product purity, relative to all xylene products of at least about 90% with at least about 15% toluene conversion.