Concordia University

Valorbec Societe En Commandite

Other

La Cooperative Forestiere Des Hautes Laurentides

Les Exploitations Jyb Papineau Inc.

Les Creations Madero Inc.

9078-0990

Valorbec, S.e.c., Represented by the Gestion Valeo, S.e.c.

Societe Quebecoise D'initiatives Petrolieres (Soquip)

11127012 Canada Inc.

Raymond Le Van Mao

Pierre Levesque

David Ohayon

Jianhua Yao

Jacques Dunnigan

Louise Dufresne

Gerald P McLaughlin

This invention relates to a method for the conversion of lignocellulosic biomass into ethyl esters of carboxylic acids. Said method consists of treating the biomass material with an oxidizing agent that is incorporated in an solution comprising one or more acids, one or more alcohols and water, and subsequently performing a catalytic reaction at a higher temperature using the same acidic solution into which a larger volume of alcohol is added, in such a way that the catalytic conversion occurs in a medium with a much higher concentration of alcohol, i.e. with a much higher alcohol-to-water wt ratio. Such a method results in relatively high yields of ethyl esters, such as ethyl esters of formic, acetic, and levulinic acids, while producing a low yield of dialkyl ethers, which are unwanted by-products. The concentration of the oxidizing agent in the pre-treatment step is preferably higher than 6.0 wt %. The oxidizing agent is preferably a Fenton or Fenton-type reagent, and most preferably hydrogen peroxide activated by Fe (II), and/or Ti (IV) ions. The alcohol is preferably ethanol, and when ethanol is used, diethyl ether is formed as the unwanted dialkyl ether by-product. Preferably, the biomass material is pelleted before treatment.

Catalytic conversion of lignocellulosic biomass into industrial biochemicals

Disclosed herein are cracking catalysts useful in the thermo-catalytic cracking (TCC)&#x2014;formerly called selective deep catalytic cracking (SDCC)&#x2014;of petroleum naphthas, gas oils and other heavy hydrocarbon distillates to selectively produce light olefins, said catalyst comprising mesoporous mixed oxides modified by the presence of inorganic compounds containing chemical elements selected from phosphorus, sulfur, chlorine and mixtures thereof, said catalyst being supported on yttria stabilized zirconium oxide and/or aluminum oxide. Preferably, the catalyst will have the the following formula:() MoOand/or WO; () LaO; () CeO; () P, S or Cl; () ZrO; () YO.Also preferably, the catalyst will be combined with a material selected from an acidic crystalline (modified or not) zeolite, an acidic silica molecular sieve and an acidic alumina. Also disclosed are methods of making said cracking catalysts. The cracking catalysts can be used in both mono- and dual reactor configurations. Furthermore, the catalysts of the present invention have a sufficiently high thermal (and steam atmosphere) resistance, enabling them to be used at significantly higher temperatures.

Catalyst formulations for the thermo-catalytic cracking of naphthas and gas oils

Provided herein is a method and apparatus for selective deep catalytic cracking of petroleum naphthas or other hydrocarbon feedstocks. The feed comprising the hydrocarbons to be cracked and steam, in well-defined proportions, is first sent into a precatalytic zone (Zone I) of a cracking reactor, preferably a tubular reactor. In a preferred embodiment, Zone I, contains beads of some catalytically mildly active porous material such as quartz or quartz doped with Cr&#x2014;Al, is set at a temperature T. The gas steam flows then through a catalyst bed, called Zone II, where the catalytic reaction takes place. Zone II is set at temperature Tand contains a zeolite type catalyst, preferably ZSM5 zeolite or, most preferably, a hybrid zeolite catalyst. It is shown that by moderately increasing the temperature Tof Zone I, it is possible to have an increased total conversion of n-hexane used as model molecule for petroleum naphthas and an increased yield of light olefins (and aromatics), when compared to the parent ZSM-5 zeolite catalyst The ethylene/propylene product ratio is closely dependent of the temperature T, if all other reaction parameters are kept constant and can be widely varied (from 1.0 to 2.0 for instance) for a limited range of variation of temperature T.

Method and apparatus for selective deep catalytic cracking of hydrocarbons

Provided herein are monocomponent and hybrid catalyst compositions for use in steam-cracking of hydrocarbon feeds to selectively produce light olefins. The catalyst compositions being characterized by a first catalytic component comprising oxides of aluminum, silicon, chromium, and optionally, oxides of monovalent alkaline metals, and further comprising a binder, preferably bentonite clay. Preferably, the catalyst compositions will comprise a catalytic component in accordance with the following formula: (a) SiO&#xb7;(b) A1O&#xb7;(c) CrO(d) alkO, with alk being a monovalent alkaline metal, preferably selected from sodium, potassium and lithium. The second catalytic component is selected from a crystalline zeolite or a silica molecular sieve. Also provided in the present invention are methods of making the catalyst compositions.

Catalysts for deep catalytic cracking of petroleum naphthas and other hydrocarbon feedstocks for the selective production of light olefins and method of making thereof

Provided herein are hybrid catalysts that are used in the deep catalytic cracking of petroleum naphthas or other hydrocarbon feedstocks, for the selective production of light olefins, in particular ethylene and propylene and BTX aromatics. The hybrid catalysts of this invention contain a chemically treated microporous crystalline silicate such as the pentasil-type silicalite, a mesoporous silica-alumina or zirconium oxide co-catalyst, into which may be incorporated aluminum oxide, molybdenum oxide, lanthanum oxide, cerium oxide or a mixture of aluminum and molybdenum oxides, and an inorganic binder such as bentonite clay. These novel catalysts show several advantages with respect to the classical steam (thermal) cracking: i) higher combined production of ethylene and propylene; ii) lower ethylene/propylene ratio; iii) much lower production of methane; iv) much lower reaction temperature resulting in significant energy savings; v) easy in-situ regeneration using air as oxidant; vi) lower carbon dioxide and other volatile oxides emitted during the regeneration phase.

Hybrid catalysts for the deep catalytic cracking of petroleum naphthas and other hydrocarbon feedstocks

Provided herein is are acidic Z5M-5 zeollte materials which are highly active and selective in the synthesis of methyl tert-butyl ether (MTBE) and similar ethers. The materials are obtained by the preparation method comprising the main steps of: i) impregnation of zeolites with fluorine species using ammonium fluoride as precursor, preferably with a F loading of ca.1.9&times;10,mol.g,of zeolite; and ii) stepwise activation in air at preferably 250&deg; C. and then preferably at 300&deg; C. to 500&deg; C., preferably 450&deg; C. The method is preferably applied to desilicated ZSM-5 zeolite and provides conversion rates to MTBE superior to those obtained with prior art commercial AMBERLYSF&trade; resin (gas phase reaction at 70-80&deg; C.) is obtained. No by-products, commonly produced by prior art commercial organic resin catalyst, are detected in the product spectrum.

ZSM-5 zeolite materials doped with fluorine species for the synthesis of MTBE and other acido-catalyzed reactions

Disclosed herein are thermally stable ZSM-5 zeolite materials. The novel materials having substantially uniform micropores narrower (about 0.49 nm) or wider (about 0.55 nm and above) than those of conventional ZSM-5 zeolite (0.52-0.54 nm). Also disclosed is a preparation method (desilication/reinsertion/stabilization or DRS) for converting conventional ZSM-5 zeolite materials to the thermally stable zeolite materials of the present invention. The method of the present invention comprises the steps of sequentially treating ZSM-5 zeolite with aqueous solutions of sodium carbonate and sodium hydroxide to obtain a desilication of the zeolite, reinserting some of the silicon species (mainly sodium orthosilicate and sodium pyrosilicate) which have been selectively removed from the zeolite framework during the desilication operation, and activating the resulting materials in air or in the presence of steam at high temperatures. The amount of the reinserted silicon species depends on the pore size wanted.

Thermally stable modified ZSM-5 zeolite materials with micro porosities and method of making same

In accordance with the present invention, there is now provided a hybrid catalyst suitable for the aromatization of light paraffins and olefins, comprising a mixture of a pentasil type zeolite having the structure of ZSM-5 or ZSM-11, and a cocatalyst consisting of gallium oxide supported by an oxide selected from the group consisting of silica, alumina particles and chromium oxide particles.

Catalysts for the aromatization of light paraffins and olefins

An aromatization catalyst is obtained by physical mixing of a pentasil type zeolite, for example H-ZSM-5 and a zinc oxide-alumina co-precipitate. The weight ratio of the zeolite to the co-precipitate ranges from 4.3 to 28.3. The Zn/Al atomic ratio in the co-precipitate may range from about 0.16 to 25.0. The composite catalyst yields greater amounts of aromatics, particularly BTX aromatics, when contacted with an olefinic and/or paraffinic feedstock than the respective zeolite alone.

Catalyst for aromatization of olefins and paraffins

There is provided a process for converting diluted ethanol to ethylene which comprises heating an ethanol-containing fermentation broth thereby to vaporize a mixture of ethanol and water and contacting said vaporized mixture with a ZSM-5 zeolite catalyst selected from the group consisting of

Catalytic conversion of aqueous ethanol to ethylene

The present invention relates to a method for enhancing the water-retention capacity of soils and providing plant nutrients to same over an extended period of time. This method comprises the admixing of soils with from 2 to 30% by weight of a chryso-zeolite of type A/and or X which comprises a magnesium leached asbestos matrix having an SiO.sub.2 content of 37 to 60% wt %, an MgO content of 0.1 to 15% by weight, an Fe.sub.2 O.sub.3 content of 0.1 to 2.5% by weight and containing from 10 to 25% by weight of Al.sub.2 O.sub.3 and from 25 to 35% by weight of Na.sub.2 O, and/or K.sub.2 O, and/or CaO, and/or (NH.sub.4).sub.2 O.

Growing community of inventors

Saint-Laurent, Canada

Raymond Le Van Mao