Abstract: Improved alkylation catalysts, alkylation methods, and methods of making alkylation catalysts are described. The alkylation method comprises reaction over a solid acid, zeolite-based catalyst and can be conducted for relatively long periods at steady state conditions. The alkylation catalyst comprises a crystalline zeolite structure, a Si/Al molar ratio of 20 or less, less than 0.5 weight percent alkali metals, and further having a characteristic catalyst life property. Some catalysts may contain rare earth elements in the range of 10 to 35 wt %. One method of making a catalyst includes a calcination step following exchange of the rare earth element(s) conducted at a temperature of at least 575° C. to stabilize the resulting structure followed by an deammoniation treatment. An improved method of deammoniation uses low temperature oxidation.

Abstract: This invention describes methods of alkylating isobutane which include a catalytic reaction system comprising a crystalline zeolite catalyst and a rare earth-modified molecular sieve adsorbent (RE-MSA). The crystalline zeolite catalyst comprises sodalite cages and supercages, a Si/Al molar ratio of 20 or less, less than 0.5 weight percent alkali metals; and up to 5 wt % of Pt, Pd and or Ni, and acid-site density (including both Lewis and Brønsted acid sites) of at least 100 mole/gm. The RE-modified molecular sieve adsorbent (Re-MSA) comprising sodalite cages and supercages, a Si/Al molar ratio of 20 or less, less than 1 wt % of alkali metals, RE (rare earth elements) in the range of 10 to 30 wt % and transition metals selected from groups 9-11 in the range from 2 wt % to 10 wt; and acid-site density of no more than 30 mole/gm. The invention also includes methods of making RE-MSA.

Abstract: Methods of simultaneously converting butanes and methanol to olefins over Ti-containing zeolite catalysts are described. The exothermicity of the alcohols to olefins reaction is matched by endothermicity of dehydrogenation reaction of butane(s) to light olefins resulting in a thermo-neutral process. The Ti-containing zeolites provide excellent selectivity to light olefins as well as exceptionally high hydrothermal stability. The coupled reaction may advantageously be conducted in a staged reactor with methanol/DME conversion zones alternating with zones for butane(s) dehydrogenation. The resulting light olefins can then be reacted with iso-butane to produce high-octane alkylate. The net result is a highly efficient and low cost method for converting methanol and butanes to alkylate.

Abstract: The invention relates to a catalyst composition suitable for the dehydrogenation of paraffins having 2-8 carbon atoms comprising zinc oxide and titanium dioxide, optionally further comprising oxides of cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), terbium (Tb), ytterbium (Yb), yttrium (Y), tungsten (W) and Zirconium (Zr) or mixtures thereof, wherein said catalyst composition is substantially free of chromium and platinum. The catalysts possess unique combinations of activity, selectivity, and stability. Methods for preparing improved dehydrogenation catalysts and a process for dehydrogenating paraffins having 2-8 carbon atoms, comprising contacting the mixed metal oxide catalyst with paraffins are also described. The catalyst may also be disposed on a porous support in an attrition-resistant form and used in a fluidized bed reactor.

Abstract: A catalyst, methods of making, and process of dehydrogenating paraffins utilizing the catalyst. The catalyst includes at least 20 mass % Zn, a catalyst support and a catalyst stabilizer. The catalyst is further characterizable by physical properties such as activity parameter measured under specified conditions. The catalyst may also be disposed on a porous support in an attrition-resistant form and used in a fluidized bed reactor.

Abstract: A catalyst, methods of making, and process of dehydrogenating paraffins utilizing the catalyst. The catalyst includes at least 20 mass % Zn, a catalyst support and a catalyst stabilizer. The catalyst is further characterizable by physical properties such as activity parameter measured under specified conditions. The catalyst may also be disposed on a porous support in an attrition-resistant form and used in a fluidized bed reactor.

Abstract: The invention relates to a catalyst composition suitable for the dehydrogenation of paraffins having 2-8 carbon atoms comprising zinc oxide and titanium dioxide, optionally further comprising oxides of cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), terbium (Tb), ytterbium (Yb), yttrium (Y), tungsten (W) and Zirconium (Zr) or mixtures thereof, wherein said catalyst composition is substantially free of chromium and platinum. The catalysts possess unique combinations of activity, selectivity, and stability. Methods for preparing improved dehydrogenation catalysts and a process for dehydrogenating paraffins having 2-8 carbon atoms, comprising contacting the mixed metal oxide catalyst with paraffins are also described. The catalyst may also be disposed on a porous support in an attrition-resistant form and used in a fluidized bed reactor.

Abstract: The invention relates to a catalyst composition suitable for the dehydrogenation of paraffins having 2-8 carbon atoms comprising zinc oxide and titanium dioxide, optionally further comprising oxides of cerium (Ce), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), terbium (Tb), ytterbium (Yb), yttrium (Y), tungsten (W) and Zirconium (Zr) or mixtures thereof, wherein said catalyst composition is substantially free of chromium and platinum. The catalysts possess unique combinations of activity, selectivity, and stability. Methods for preparing improved dehydrogenation catalysts and a process for dehydrogenating paraffins having 2-8 carbon atoms, comprising contacting the mixed metal oxide catalyst with paraffins are also described. The catalyst may also be disposed on a porous support in an attrition-resistant form and used in a fluidized bed reactor.

Abstract: Methods of simultaneously converting butanes and methanol to olefins over Ti-containing zeolite catalysts are described. The exothermicity of the alcohols to olefins reaction is matched by endothermicity of dehydrogenation reaction of butane(s) to light olefins resulting in a thermo-neutral process. The Ti-containing zeolites provide excellent selectivity to light olefins as well as exceptionally high hydrothermal stability. The coupled reaction may advantageously be conducted in a staged reactor with methanol/DME conversion zones alternating with zones for butane(s) dehydrogenation. The resulting light olefins can then be reacted with iso-butane to produce high-octane alkylate. The net result is a highly efficient and low cost method for converting methanol and butanes to alkylate.

Abstract: Improved alkylation catalysts, alkylation methods, and methods of making alkylation catalysts are described. The alkylation method comprises reaction over a solid acid, zeolite-based catalyst and can be conducted for relatively long periods at steady state conditions. The alkylation catalyst comprises a crystalline zeolite structure, a Si/Al molar ratio of 20 or less, less than 0.5 weight percent alkali metals, and further having a characteristic catalyst life property. Some catalysts may contain rare earth elements in the range of 10 to 35 wt %. One method of making a catalyst includes a calcination step following exchange of the rare earth element(s) conducted at a temperature of at least 575° C. to stabilize the resulting structure followed by an deammoniation treatment. An improved method of deammoniation uses low temperature oxidation.

Abstract: Methods of simultaneously converting butanes and methanol to olefins over Ti-containing zeolite catalysts are described. The exothermicity of the alcohols to olefins reaction is matched by endothermicity of dehydrogenation reaction of butane(s) to light olefins resulting in a thermo-neutral process. The Ti-containing zeolites provide excellent selectivity to light olefins as well as exceptionally high hydrothermal stability. The coupled reaction may advantageously be conducted in a staged reactor with methanol/DME conversion zones alternating with zones for butane(s) dehydrogenation. The resulting light olefins can then be reacted with iso-butane to produce high-octane alkylate. The net result is a highly efficient and low cost method for converting methanol and butanes to alkylate.

Abstract: A method of producing a high octane alkylate from ethylene and isobutane by reacting ethylene and isobutane under catalytic conversion conditions. The ethylene and isobutane are contacted with a first catalytic material comprising a dimerization catalyst (i.e, for dimerizing ethylene) and a second catalytic material comprising an alkylation catalyst. The first and second catalytic materials are separate and distinct from each other. A high octane alkylate is recovered as a result of reacting the ethylene and isobutane in the presence of the first and second catalytic materials.