Hri, Inc.

Hydrocarbon Technologies, Inc.

Other

Energy Catalysis Incorporated

Pcp Consulting and Research, Inc.

Partha S Ganguli

Alfred G Comolli

Sankaran Sundaresan

A method and apparatus for catalytic hydroconversion processing of less volatile carbonaceous material to volatile liquid products is disclosed. The process is carried out in a plug-flow reactor system using nanosize metallic catalyst particles dispersed in the reactant slurry with compressed hydrogen/hydrogen-sulfide at a temperature between about 275&#xb0; C. and 525&#xb0; C. at a pressure of between about 800 psi and 6000 psi and a residence time in the reactors between about 1 minute and 4 hours.

Method and apparatus for hydroprocessing low-volatile hydrocarbon materials into volatile liquids

Stable carbonous catalyst particles composed of an inorganic catalytic metal/metal oxide powder and a carbonaceous binder material are formed having a basic inner substantially uniform-porous carbon coating of the catalytic powder, and may include an outer porous carbon coating layer. Suitable inorganic catalytic powders include zinc-chromite (ZnO/Cr03) and suitable carbonaceous liquid binders having molecular weight of 200-700 include partially polymerized furfuryl alcohol, which are mixed together, shaped and carbonized and partially oxidized at elevated temperature. Such stable carbonous catalyst particles such as 0.020-0.100 inch (0.51-2.54 mm) diameter extrudates, have total carbon content of 2-25 wt. % and improved crush strength of 1.0-5/mn, 50-300 m/g surface area, and can be advantageously utilized in fixed bed or ebullated/fluidized bed reactor operations. This invention also includes method steps for making the stable carbonous catalyst particles having improved particle strength and catalytic activity, and processes for utilizing the active stable carbonous carbon-coated catalysts such as for syn-gas reactions in ebullated/fluidized bed reactors for producing alcohol products and Fischer-Tropsch synthesis liquid products.

Stable carbonous catalyst particles and method for making and utilizing same

A hydrocarbon liquid feedstock containing at least 50 wt. % chemically digested organic-MSW material is catalytically hydroconverted utilizing either a single stage or two-stage catalytic reaction process to produce desirable lower-boiling hydrocarbon liquid products. The catalyst can be either a particulate supported type catalyst such as containing cobalt and/or molybdenum and/or nickel on alumina support, or a dispersed slurry type catalyst containing mainly iron oxide with anions of molybdate, phosphate, sulfate or tungstate, and combinations thereof. Broad useful reaction conditions are 600-860&deg; F. (315-460&deg; C.) temperature, 1000-3000 psi hydrogen partial pressure, and fresh feed rate of 20-60 pounds/hr/ft,reactor volume. Effluent material from the final stage catalytic reactor is phase separated and the resulting liquid portion is fractionated to produce the desired low-boiling hydrocarbon liquid products particularly useful as transportation fuels. If desired, the chemically digested organic-MSW feedstock can be blended with petroleum residua and/or particulate coal and/or mixed waste plastics and the blended feed material processed in catalytic two-stage reactors to produce similar desirable low-boiling hydrocarbon liquid products.

Catalytic hydroconversion of chemically digested organic municipal solid waste materials

Municipal solid waste (MSW) material is sized to provide a particulate material which is density separated into organic and inorganic portions using a suitable polar acidic organic liquid medium. The organic-MSW portion is digested in the polar acidic organic medium such as phenol at conditions of 500-850.degree. F. temperature, 300-2000 psig pressure and 5-100 minutes residence time. The digested organic material is then fractionated to produce gas, a light liquid boiling below about 170.degree. C., the polar acidic organic liquid medium such as phenol, boiling between 170 and 220.degree. C., and a liquid slurry boiling above about 220.degree. C. and including a powder material melting above about 400.degree. C. The recovered acidic organic liquid fraction is preferably recycled back to the density separation and/or digesting steps for further use in the process. The liquid slurry fraction product having heating value of 9,000-16,000 Btu/lb. can be utilized as a clean fuel for combustion such as in steam boilers, or it can be catalytically hydrogenated for producing lower boiling hydrocarbon liquid fuels.

Treating municipal solid waste for producing hydrocarbon fuel products

Three-way precious metal catalysts useful for conversion treatment of pollutants in fuel combustion gases from automotive exhausts, or gas emissions from stationary fuel combustion sources, have chemical activity and thermal stability of the catalysts appreciably enhanced by utilizing a composite oxygen-ion conducting support material. Such composite supports are composed of zirconia stabilized by yttria, calcia, magnesia or scandia, and at least 40 wt. % inert support material such as alumina or titania, and have surface area of 20-300 m.sup.2 /gm. The catalysts can be supported by composites of yttria-stabilized-zirconia (YSZ) and alumina, and contain 0.01-3.0 wt % total active metals, which may consist of major metals platinum or palladium and minor metals rhodium or ruthenium dispersed on the support. Such three-way catalysts are thermally stable, achieve a high level of pollutants (CO, NO.sub.x, H.sub.2 and hydrocarbons) removal, and have long catalyst life without requiring undesirably high loading of expensive precious active metals on the catalyst support material.

Precious metal catalysts utilizing composites of oxygen-ion conducting

Three-way catalysts used for treatment of automobile exhaust gas or gas emissions from stationary combustion sources, which typically have consisted of platinum and rhodium and sometimes palladium and rhodium dispersed on an .gamma.-alumina support, can have the activities of the active metals in the catalysts appreciably enhanced by using an oxygen-ion conducting material such as yttria-stabilized-zirconia (YSZ) as the support material. Support material surface area is 20-300 m.sup.2 /gm, and useful concentrations of yttria on zirconia support are 1.0-50 wt. %. Useful concentrations of platinum or palladium on the support material is 0.01-2 wt. %, and the weight ratio of rhodium/platinum or rhodium/palladium is 0.01-0.1. YSZ-supported catalysts can achieve a substantially higher level of pollutants (CO, NO.sub.X, H.sub.2 and hydrocarbons) removal, without requiring increased loading of expensive precious active metals on the support material.

Precious metal catalysts with oxygen-ion conducting support

Supported carbon-coated catalyst material and a method for producing and using same in catalytic reaction processes, preferably in ebullated or fluidized catalyst beds. The catalyst materials are prepared by depositing a porous carbon layer on a support material of a selected metal oxide or compound to produce 5-40 wt. % carbon thereon, then preferentially treating the carbon based layer by partial oxidation, pyrolysis or reduction to enhance and activate the carbon layer on the catalyst. Promoter materials can also be advantageously added either to the support material or to the carbon layer in 0.5-10 wt. % to provide an improved composite carbon-coated catalyst having total pore volume of 0.3-1.0 cc/gm, substantially increased surface area of 80-600 M.sup.2 /gm, low surface acidity, particle strength of 1.8-5 lb/mm with reduced particle attrition losses and improved catalyst performance characteristics.

Porous metal oxide supported carbon-coated catalysts and method for

Used catalyst containing carbon and sulfur deposits is continuously regenerated by staged burnoff of the carbon and sulfur using a multiple zone treatment vessel containing thin beds of catalyst. The catalyst is exposed to successively increased temperatures and oxygen concentrations to effectively remove substantially all the carbon and sulfur deposits. The used catalyst can be that removed from hydroconversion processes, such as from H-Oil, H-Coal and fluid catalystic cracking processes, and processed in a multizone treatment vessel in combination with proper auxiliary heating equipment for continuous step-wise regeneration of the catalyst. Operating conditions of catalyst temperature, oxygen concentration of gas, and catalyst residence time in each stage of the catalyst regeneration process are carefully controlled to provide staged burnoff of carbon and sulfur deposits for superior regenerated catalyst results. The hot regenerated catalyst withdrawn from the last zone is cooled against make-up air to improve the overall thermal efficiency of the process.

Continuous process for catalyst regeneration by staged burnoff of carbon

Spent catalysts removed from a catalytic hydrogenation process for hydrocarbon feedstocks, and containing carbon undesired metals contaminants deposits, are rejuvenated for reuse. Following solvent washing to remove process oils, the catalyst is treated either with chemicals which form sulfate or oxysulfate compounds with the metals contaminants, or with acids which remove the metal contaminants, such as 5-50 W % sulfuric acid in aqueous solution and 0-10 W % ammonium ion solutions to substantially remove the metals deposits. The acid treating occurs within the temperature range of 60.degree.-250.degree. F. for 5-120 minutes at substantially atmospheric pressure, after which the rejuvenated catalyst containing carbon deposits can be effectively reused in the catalytic hydrogenation process.

Catalyst rejuvenation process for removal of metal contaminants

A process for improving the upgrading/conversion of hydrocarbonaceous materials such as coals, petroleum residual oils, shale oils and tar sand bitumens. In the process, the free radicals formed from thermal cracking of the hydrocarbons are reacted with the free radicals formed by the thermal cracking of a free radical forming chemical reactant, such as dimethyl ether, to yield stable low molecular weight hydrocarbon distillate products. The hydrocarbonaceous feed material is preheated to a temperature of 600.degree.-700.degree. F. and the hydrocarbon and the free radicals forming chemical, such as dimethyl ether, are passed through a flow reactor at temperature of 750.degree.-900.degree. F., pressure of 200-1000 psi, and liquid hourly space velocity of 0.3 to 5.0 LHSV. Free radicals formed from the hydrocarbon feed material and from the ether material react together in the reactor to produce low molecular weight hydrocarbon liquid materials. The weight ratio of ether material to hydrocarbon feed material is between about 0.3 and about 2.0.

Use of ethers in thermal cracking

A process for high hydroconversion of heavy hydrocarbon liquid feedstocks such as petroleum residua containing at least about 50 V % material boiling above 975.degree. F. to produce lower boiling hydrocarbon liquid and gas products, wherein heavy RCR materials and metals compounds are removed in-situ from the reactor effluent liquid by solvent vapor extraction using a process-derived solvent vapor at supercritical conditions. In the process, the feedstock is catalytically hydroconverted at 780.degree.-860.degree. F. temperature, and the resulting liquid fraction is contacted with a process-derived solvent vapor fraction having a normal boiling range of 250.degree.-400.degree. F. and heated to supercritical temperature to dissolve and extract substantially all the hydrocarbon liquid fractions, and separate heavy RCR materials and the metals compounds contained therein. The resulting supercritical solvent vapor with dissolved liquid fraction is pressure-reduced and distilled to recover the needed solvent fraction and to provide a hydrocarbon liquid fraction product. The hydrogenation step preferably uses an ebullated catalytic bed. Also, if desired, the supercritical solvent vapor extraction step can be used intermediate two hydroconversion reaction zones connected in series to produce additional desired lower boiling desulfurized hydrocarbon liquid fraction products.

Hydroconversion process for hydrocarbon liquids using supercritical

Spent catalysts removed from a catalytic hydrogenation process for hydrocarbon feedstocks, and containing undesired metals contaminants deposits, are regenerated. Following solvent washing to remove process oils, the catalyst is treated either with chemicals which form sulfate or oxysulfate compounds with the metals contaminants, or with acids which remove the metal contaminants, such as 5-50 W % sulfuric acid in aqueous solution and 0-10 W % ammonium ion solutions to substantially remove the metals deposits. The acid treating occurs within the temperature range of 60.degree.-250.degree. F. for 5-120 minutes at substantially atmospheric pressure. Carbon deposits are removed from the treated catalyst by carbon burnoff at 800.degree.-900.degree. F. temperature, using 1-6 V % oxygen in an inert gas mixture, after which the regenerated catalyst can be effectively reused in the catalytic process.

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Princeton, NJ, United States of America

Partha S Ganguli