Hri, Inc.

Hydrocarbon Research, Inc.

Hydrocarbon Technologies, Inc.

Senergy LLC

Other

Energy Catalysis Incorporated

Alfred G Comolli

Joseph B McLean

Lap-Keung Lee

James B MacArthur

Partha S Ganguli

Edwin J Hippo

David L Tanner

Vivek R Pradhan

Michael C Chervenak

Bruce P Pelrine

Salvatore J Antieri

Robert O'Brien

A process for making a carbonaceous material and a carbonous residue from scrap tires is disclosed. Tires are digested in an oil product. Steel and glass fibers are separated. A product enhancing additive comprising halogen based organic or inorganic compounds is added. The resulting carbonaceous material is then cured to create the final product. The produced carbonous residue is well suited for capture of mercury. The present invention has the benefits of providing a use for scrap tires that would otherwise require disposal in a landfill, and also produces a product useful for capturing a harmful element, thereby providing multiple environmental and economic benefits.

Tire recycling method generating carbonous reside

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

A process for making a carbonous residue from scrap tires is disclosed. Tires are digested in an oil product. Steel and glass fibers are separated. A product enhancing additive comprising halogen based organic or inorganic compounds is added. The resulting carbonaceous material is then cured to create the final product. The produced carbonous residue is well suited for capture of mercury. The present invention has the benefits of providing a use for scrap tires that would otherwise require disposal in a landfill, and also produces a product useful for capturing a harmful element, thereby providing multiple environmental and economic benefits.

Tire recycling method generating carbonous residue

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 multi-stage catalytic hydrogenation and hydroconversion process for heavy hydrocarbon feed materials such as coal, heavy petroleum fractions, and plastic waste materials. In the process, the feedstock is reacted in a first-stage, back-mixed catalytic reactor with a highly dispersed iron-based catalyst having a powder, gel or liquid form. The reactor effluent is pressure-reduced, vapors and light distillate fractions are removed overhead, and the heavier liquid fraction is fed to a second stage back-mixed catalytic reactor. The first and second stage catalytic reactors are operated at 700-850&deg; F. temperature, 1000-3500 psig hydrogen partial pressure and 20-80 lb./hr per ft,reactor space velocity. The vapor and light distillates liquid fractions removed from both the first and second stage reactor effluent streams are combined and passed to an in-line, fixed-bed catalytic hydrotreater for heteroatom removal and for producing high quality naphtha and mid-distillate or a full-range distillate product. The remaining separator bottoms liquid fractions are distilled at successive atmospheric and vacuum pressures, low and intermediate-boiling hydrocarbon liquid products are withdrawn, and heavier distillate fractions are recycled and further upgraded to provide additional low-boiling hydrocarbon liquid products. This catalytic multistage hydrogenation process provides improved flexibility for hydroprocessing the various carbonaceous feedstocks and adjusting to desired product structures and for improved economy of operations.

Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds

A highly dispersed iron-based ionic liquid or liquid-gel catalyst which may be anion-modified and metals-promoted has high catalytic activity, and is useful for hydrocracking/hydrogenation reactions for carbonaceous feed materials. The catalyst is produced by aqueous precipitation from saturated iron salt solutions such as ferric sulfate and ferric alum, and may be modified during preparation with anionic sulfate (SO.sub.4.sup.2-) and promoted with small percentages of at least one active metal such as cobalt, molybdenum, palladium, platinum, nickel, or tungsten or mixtures thereof. The resulting catalyst may be used in a preferred ionic liquid form or in a liquid-gel form, and either fluidic form can be easily mixed and reacted with carbonaceous feed materials such as coal, heavy petroleum fractions, mixed plastic waste, or mixtures thereof. The invention includes methods for making the ionic liquid or liquid-gel catalyst, and processes for using the fluidic catalysts for hydroprocessing the carbonaceous feed materials to produce desirable low-boiling hydrocarbon liquid products.

Iron-based ionic liquid catalysts for hydroprocessing carbonaceous feeds

A dispersed fine-sized anion-modified and phosphorus-promoted iron-oxide slurry catalyst having high surface area exceeding 100 m.sup.2 /gm and high catalytic activity, and which is useful for hydrogenation and hydroconversion reactions for carbonaceous feed materials is disclosed. The catalyst is synthesized by rapid aqueous precipitation from saturated salt solutions such as ferric sulfate and ferric alum, and is promoted with phosphorus. The iron-based catalysts are modified during their preparation with anionic sulfate (SO.sub.4.sup.2-). The resulting catalyst has primary particle size smaller than about 50 Angstrom units, and may be used in a preferred wet cake or gel form which can be easily mixed with a carbonaceous feed material such as coal, heavy petroleum fractions, mixed waste plastics, or mixtures thereof. Alternatively, the catalyst can be dried and/or calcined so as to be in a fine dry particulate form suitable for adding to the feed material. The invention includes methods for making the catalyst and processes for using the catalyst for hydroprocessing of carbonaceous feed materials to produce desirable low-boiling hydrocarbon liquid products.

Dispersed anion-modified phosphorus-promoted iron oxide catalysts

A dispersed fine-sized anion-modified iron oxide slurry catalyst having high surface area exceeding about 100 m.sup.2 /gm and high catalytic activity, and which is useful for hydrogenation and hydroconversion reactions for carbonaceous feed materials is disclosed. The catalyst is synthesized by rapid aqueous precipitation from saturated salt solutions such as ferric alum or ferric sulfate, and is promoted with at least one active metal such as cobalt, molybdenum, nickel, tungsten and combinations thereof. The iron-based dispersed catalysts are modified during their preparation with anionic modifiers such as molybdate (MoO.sub.4.sup.2-), phosphate (PO.sub.4.sup.3-), sulfate (SO.sub.4.sup.2-), or tungstate (WO.sub.4.sup.2-). The resulting catalyst usually has primary particle size smaller than about 50 Angstrom units, and may be used in the form of a gel or wet cake which can be easily mixed with a hydrocarbonaceous feed material such as coal, heavy petroleum fractions, mixed waste plastics or mixtures thereof. Alternatively, the catalyst can be dried and/or calcined so as to be in a fine dry particulate form suitable for adding to the feed material. The invention includes methods for making the catalyst and processes for using the catalyst for hydroprocessing of the carbonaceous feed materials.

Dispersed anion-modified iron oxide catalysts for hydroconversion

A process for catalytic multi-stage hydrogenation and liquefaction of coal to produce high yields of low-boiling hydrocarbon liquids containing low concentrations of nitogen compounds. First stage catalytic reaction conditions are 700.degree.-800.degree. F. temperature, 1500-3500 psig hydrogen partial pressure, with the space velocity maintained in a critical range of 10-40 lb coal/hr ft.sup.3 catalyst settled volume. The first stage catalyst has 0.3-1.2 cc/gm total pore volume with at least 25% of the pore volume in pores having diameters of 200-2000 Angstroms. Second stage reaction conditions are 760.degree.-870.degree. F. temperature with space velocity exceeding that in the first stage reactor, so as to achieve increased hydrogenation yield of low-boiling hydrocarbon liquid products having at least 75% removal of nitrogen compounds from the coal-derived liquid products.

Catalytic two-stage coal liquefaction process having improved nitrogen

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

A process for the hydrogenation of undissolved coal and subsequent liquefaction of the hydrogenated coal particles to provide useful hydrocarbon liquid products including naphtha, gasoline and diesel fuel. These low boiling hydrocarbon liquids are produced by the process comprising: (a) mixing solid coal particles with a coal derived solvent in a solvent/coal ratio ranging from about 8/1 to about 1.5/1 to provide a flowable coal/oil slurry of solid coal particles; (b) passing the coal/oil slurry and hydrogen upwardly through a first reaction zone containing a coal-derived liquid and bed of particulate catalyst maintained at a temperature ranging from about 400.degree. to about 700.degree. F. and a hydrogen partial pressure of 100 to 2000 psig for a time sufficient to hydrogenate the solid coal particles; and (c) withdrawing the coal/oil slurry having the hydrogenated coal particles from the first reaction zone and passing the coal/oil slurry to a second reaction zone containing a catalytic bed which is maintained at a temperature of between about 700.degree. and about 850.degree. F. and a hydrogen partial pressure of 9 to 2000 psig to liquefy and convert the coal to useful hydrocarbon liquid fuel products. The first and second reaction zones may include the same or different catalysts such as Co/Mo on a porous substrate, or the second reaction zone can include a noble metal such as platinum on a porous substrate such as alumina or silica.

Hydrogenation of coal and subsequent liquefaction of hydrogenated

A process for catalytic two-stage hydrogenation and liquefaction of coal with selective extinction recycle of all heavy liquid fractions boiling above a distillation cut point of about 600.degree.-750.degree. F. to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal feed is slurried with a process-derived liquid solvent normally boiling above about 650.degree. F. and fed into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils. The first stage reactor is maintained at 710.degree.-800.degree. F. temperature, 1000-4000 psig hydrogen partial pressure, and 10-90 lb/hr per ft.sup.3 catalyst space velocity. Partially hydrogenated material withdrawn from the first stage reaction zone is passed directly to the second stage catalytic reaction zone maintained at 760.degree.-860.degree. F. temperature for further hydrogenation and hydroconversion reactions. A 600.degree.-750.degree. F..sup.+ fraction containing 0-20 W % unreacted coal and ash solids is recycled to the coal slurrying step. If desired, the cut point lower boiling fraction can be further catalytically hydrotreated. By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, to provide significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of hydrocarbon gases, and no net production of undesirable heavy oils and residuum materials.

Catalytic two-stage coal hydrogenation process using extinction recycle

A process for two-stage catalytic co-processing of coal and heavy petroleum hydrocarbon liquid fractions to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal is slurried with a petroleum residuum and optionally with a process-derived hydrocarbon liquid solvent and fed into a first stage catalytic reaction zone operated at relatively mild conditions which promote controlled rate liquefaction of the coal while simultaneously hydrogenating the petroleum and hydrocarbon recycle oils at conditions favoring hydrogenation reactions. The first stage reactor is maintained at 650.degree.-800.degree. F. temperature, 1000-4000 psig hydrogen partial pressure and 10-100 lb/hr/ft.sup.3 space velocity for the total coal and oil feed. From the first stage reaction zone, the partially hydrogenated effluent material is passed directly to the close-coupled second stage catalytic reaction zone maintained at more severe conditions of 750.degree.-900.degree. F. temperature for further catalytic; and hydrogenation and hydroconversion reactions. By this process, the blended coal and petroleum feed materials are successively catalytically hydrogenated and hydroconverted at the selected conditions, which results in significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of undesirable residuum and unconverted coal and hydrocarbon gases, while catalyst life is substantially increased.

Two-stage co-processing of coal/oil feedstocks

A process for two-stage catalytic hydrogenation and liquefaction of coal to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal is slurried with a process-derived liquid solvent and fed at temperature below about 650.degree. F. into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils at conditions favoring hydrogenation reactions. The first stage reactor is maintained at 650.degree.-800.degree. F. temperature, 1000-4000 psig hydrogen partial pressure, and 10-60 lb coal/hr/ft.sup.3 reactor space velocity. The partially hydrogenated material from the first stage reaction zone is passed directly to the close-coupled second stage catalytic reaction zone maintained at a temperature at least about 25.degree. F. higher than for the first stage reactor and within a range of 750.degree.-875.degree. F. temperature for further hydrogenation and thermal hydroconversion reactions. By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, which results in significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of undesirable residuum and unconverted coal and hydrocarbon gases, with use of less energy to obtain the low molecular weight products, while catalyst life is substantially increased.

Catalytic two-stage coal hydrogenation and hydroconversion process

A coal hydrogenation and liquefaction process in which particulate coal feed is pressurized to an intermediate pressure of at least 500 psig and slurried with CO.sub.2 liquid to provide a flowable coal/CO.sub.2 slurry feedstream, which is further pressurized to at least 1000 psig and fed into a catalytic reactor. The coal particle size is 50-375 mesh (U.S. Sieve Series) and provides 50-80 W % coal in the coal/CO.sub.2 slurry feedstream. Catalytic reaction conditions are maintained at 650.degree.-850.degree. F. temperature, 1000-4000 psig hydrogen partial pressure and coal feed rate of 10-100 lb coal/hr ft.sup.3 reactor volume to produce hydrocarbon gas and liquid products. The hydrogen and CO.sub.2 are recovered from the reactor effluent gaseous fraction, hydrogen is recycled to the catalytic reactor, and CO.sub.2 is liquefied and recycled to the coal slurrying step. If desired, two catalytic reaction stages close coupled together in series relation can be used. The process advantageously minimizes the recycle and processing of excess hydrocarbon liquid previously needed for slurrying the coal feed to the reactor(s).

Growing community of inventors

Yardley, PA, United States of America

Alfred G Comolli