Hydrocarbon Technologies, Inc.

Headwaters Heavy Oil, LLC

Other

Headwaters Technology Innovation, LLC

Alberta Oil Sands Technology and Research Authority

Hydrocarbon Technology & Innovation, LLC

Lap-Keung Lee

Roger Kai Lott

Bing Zhou

Alfred G Comolli

Peizheng Zhou

Yijun Lu

Guohui Li

Vivek R Pradhan

Bruce P Pelrine

Jinglai Zhou

Michael A Rueter

Lawrence M Abrams

Baki Ozum

Theodore J Cyr

Leszek Lewkowicz

Hairong Wang

Naresh J Suchak

Zhixin Zhang

Peter C Quinn

Linyao Dong

A system and method for preparing and conditioning a heavy oil feedstock for hydroprocessing in a hydroprocessing system includes forming metal sulfide catalyst particles in situ within the heavy oil feedstock. The metal sulfide catalyst particles are formed in situ by (1) premixing a catalyst precursor with a hydrocarbon diluent to form a diluted precursor mixture, (2) mixing the diluted precursor mixture with the heavy oil feedstock to form a conditioned feedstock, and (3) heating the conditioned feedstock to decompose the catalyst precursor and cause or allow metal from the precursor to react with sulfur in the heavy oil feedstock to form metal sulfide catalyst particles in situ in the heavy oil feedstock. The in situ formed metal sulfide catalyst particles catalyze beneficial upgrading reactions between the heavy oil feedstock and hydrogen and eliminates or reduces formation of coke precursors and sediment.

Systems and methods for hydroprocessing heavy oil

A hydroprocessing method and system involves introducing heavy oil and well-dispersed metal sulfide catalyst particles, or a catalyst precursor capable of forming the well-dispersed metal sulfide catalyst particles in situ within the heavy oil, into a hydroprocessing reactor. The well-dispersed or in situ metal sulfide catalyst particles are formed by 1) premixing a catalyst precursor with a hydrocarbon diluent to form a precursor mixture, 2) mixing the precursor mixture with heavy oil to form a conditioned feedstock, and 3) heating the conditioned feedstock to decompose the catalyst precursor and cause or allow metal from the precursor to react with sulfur in the heavy oil to form the well-dispersed or in situ metal sulfide catalyst particles. The well-dispersed or in situ metal sulfide catalyst particles catalyze beneficial upgrading reactions between the heavy oil and hydrogen and eliminates or reduces formation of coke precursors and sediment.

Method for efficiently operating an ebbulated bed reactor and an efficient ebbulated bed reactor

A hydrocracking system involves introducing a heavy oil feedstock and a colloidal or molecular catalyst, or a precursor composition capable of forming the colloidal or molecular catalyst, into a hydrocracking reactor. The colloidal or molecular catalyst is formed in situ within the heavy oil feedstock by intimately mixing a catalyst precursor composition into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the precursor composition to form the colloidal or molecular catalyst. The colloidal or molecular catalyst catalyzes upgrading reactions between the heavy oil feedstock and hydrogen and eliminates or reduces formation of coke precursors and sediment. At least a portion of a resid fraction containing residual colloidal or molecular catalyst is recycled back into the hydrocracking reactor to further upgrade the recycled resid fraction portion and provide recycled colloidal or molecular catalyst within the hydrocracking reactor.

Methods for hydrocracking a heavy oil feedstock using an in situ colloidal or molecular catalyst and recycling the colloidal or molecular catalyst

An ebullated bed hydroprocessing system, and also a method for upgrading an existing ebullated bed hydroprocessing system, involves introducing a colloidal or molecular catalyst, or a catalyst precursor capable of forming the colloidal or molecular catalyst, into an ebullated bed reactor. The colloidal or molecular catalyst is formed by intimately mixing a catalyst precursor into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the catalyst precursor to form the colloidal or molecular catalyst in situ. The improved ebullated bed hydroprocessing system includes at least one ebullated bed reactor that employs both a porous supported catalyst and the colloidal or molecular catalyst to catalyze hydroprocessing reactions involving the feedstock and hydrogen. The colloidal or molecular catalyst provides catalyst in what would otherwise constitute catalyst free zones within the ebullated bed hydroprocessing system. Asphaltene or other hydrocarbon molecules too large to diffuse into the pores of the supported catalyst can be upgraded by the colloidal or molecular catalyst. A slurry phase reactor may be positioned upstream from one or more ebullated bed reactors or converted from an existing ebullated bed reactor.

An ebullated bed hydroprocessing system, and also a method for upgrading a pre-existing ebullated bed hydroprocessing system, involves introducing a colloidal or molecular catalyst, or a precursor composition capable of forming the colloidal or molecular catalyst, into an ebullated bed reactor. The colloidal or molecular catalyst is formed by intimately mixing a catalyst precursor composition into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the precursor composition to form the colloidal or molecular catalyst in situ. The improved ebullated bed hydroprocessing system includes at least one ebullated bed reactor that employs both a porous supported catalyst and the colloidal or molecular catalyst to catalyze hydroprocessing reactions involving the feedstock and hydrogen. The colloidal or molecular catalyst provides catalyst in what would otherwise constitute catalyst free zones within the ebullated bed hydroprocessing system. Asphaltene or other hydrocarbon molecules too large to diffuse into the pores of the supported catalyst can be upgraded by the colloidal or molecular catalyst. A slurry phase reactor may be positioned upstream from one or more ebullated bed reactors or converted from a pre-existing ebullated bed reactor.

Ebullated bed hydroprocessing systems

An expanded bed hydroprocessing system and related method includes at least one expanded bed reactor that employs a solid catalyst to catalyze hydroprocessing reactions involving hydrogen and a high molecular weight hydrocarbon feedstock (e.g., a Fischer-Tropsch wax) that is contaminated with solid particulates. Hydroprocessing the high molecular weight hydrocarbon feedstock in an expanded bed reactor results in formation of a hydroprocessed material from the hydrocarbon feedstock, while eliminating the risk of plugging of the supported catalyst bed by the solid particulates as compared to a reactor including a stationary catalyst bed.

Expanded bed reactor system and method for hydroprocessing wax produced by Fischer-Tropsch reaction and contaminated with solids

Methods and systems for hydroprocessing heavy oil feedstocks to form an upgraded material involve the use of a colloidal or molecular catalyst dispersed within a heavy oil feedstock, a hydrocracking reactor, and a hot separator. The colloidal or molecular catalyst promotes hydrocracking and other hydroprocessing reactions within the hydrocracking reactor. The catalyst is preferentially associated with asphaltenes within the heavy oil feedstock, which promotes upgrading reactions involving the asphaltenes rather than formation of coke precursors and sediment. The colloidal or molecular catalyst overcomes problems associated with porous supported catalysts in upgrading heavy oil feedstocks, particularly the inability of such catalysts to effectively process asphaltene molecules. The result is one or more of reduced equipment fouling, increased conversion level, and more efficient use of the supported catalyst if used in combination with the colloidal or molecular catalyst.

Hydroprocessing method and system for upgrading heavy oil using a colloidal or molecular catalyst

A fixed bed hydroprocessing system, and also a method for upgrading a pre-existing fixed bed hydroprocessing system, involves preliminarily upgrading a heavy oil feedstock in one or more slurry phase reactors using a colloidal or molecular catalyst and then further hydroprocessing the upgraded feedstock within one or more fixed bed reactors using a porous supported catalyst. The colloidal or molecular catalyst is formed by intimately mixing a catalyst precursor composition into a heavy oil feedstock and raising the temperature of the feedstock to above the decomposition temperature of the precursor composition to form the colloidal or molecular catalyst in situ. Asphaltene or other hydrocarbon molecules otherwise too large to diffuse into the pores of the fixed bed catalyst can be upgraded by the colloidal or molecular catalyst. One or more slurry phase reactors may be built and positioned upstream from one or more fixed bed reactors of a pre-existing fixed bed system and/or converted from one or more pre-existing fixed bed reactors.

Fixed bed hydroprocessing methods and systems and methods for upgrading an existing fixed bed system

Ebullated bed hydroprocessing methods and systems and methods of upgrading an existing ebullated bed system

A particulate supported noble metal phase-controlled catalyst material having 5-1000 &#x3bc;m surface area of 50&#x3bc;500 m/gm is provided for use in direct catalytic production of hydrogen peroxide (HO) product from hydrogen and oxygen-containing feedstreams. The catalyst is made by depositing phase controlled crystals of a noble metal such as palladium on a suitable particulate support material such as carbon black, by utilizing a precursor solution of the metal and a suitable control ionic polymer having molecular weight of 300-8000 such as sodium polyacrylate in a selected metal to polymer molar ratio of 1:0.1 to 1:10, which procedure provides desired phase control of the noble metal atoms to form widely dispersed minute noble metal crystals on the support material. The invention includes methods for making the catalyst, and also a process for utilizing the catalyst to directly produce high yields of hydrogen peroxide (HO) product from hydrogen and oxygen-containing gaseous feedstreams.

Supported noble metal, phase-controlled catalyst and methods for making and using the catalyst

A bi-functional oxidation catalyst and process for catalytic oxidation and removal of nitrogen oxides (NO) from combustion gases derived from combustion of carbonaceous fuels such as coal, oil, or natural gas. The bi-functional catalyst includes adsorption and oxidation function metal oxides provided in adjacent close intimate contact by utilizing a binding agent, such as carboxylic acid and calcining to provide a metal oxide complex having a crystalline form. Such nitrogen oxides (NO) contained in the combustion gases are initially catalytically oxidized to at least about 50 vol % NOand some higher oxides by contact with the bi-functional catalyst at 170-550&#xb0; F. temperature. The combustion gas containing the partially oxidized NOis then preferably further chemically oxidized by being mixed with a chemical oxidant such as ozone (O) in a molar ratio of the chemical oxidantto NOin the range of 0.5:1-1.2:1 to produce higher oxides of nitrogen such as substantially NO. The further treated combustion gas containing the NOis next scrubbed with a suitable scrubbing liquid such as water to effectively remove the nitrogen oxides (NO) and produce a clean treated flue gas stream containing less than about 15 ppm nitrogen oxides and suitable for environmentally safe discharge to the atmosphere.

Catalyst and process for oxidation and removal of nitrogen oxides (NOx) from combustion gases

A process for catalytically directly producing hydrogen peroxide (H O ) product from hydrogen and oxygen-containing feeds by contacting them with a supported noble metal phase-controlled catalyst and a suitable organic liquid solvent having a Solvent Selection Parameter (SSP) between 0.14&times;10 and 5.0&times;10 at reaction condition of 0-100&deg; C. temperature and 100-3,000 psig pressure. Unconverted feed gas and organic liquid solvent solution are usually recovered and recycled back to the reactor along with any recovered catalyst. If desired, the hydrogen peroxide product can be fed together with an organic chemical feedstock such as propylene and with the organic liquid solvent solution into a second catalytic reaction step which oxidizes the feedstock to produce a desired crude oxidized organic product such as propylene oxide, which may be purified by distillation steps and recovered from the solvent solution.

Catalytic direct production of hydrogen peroxide from hydrogen and oxygen feeds

Particulate skeletal iron catalyst is provided which contain at least about 50 wt. % iron with the remainder being a minor portion of a suitable non-ferrous metal and having characteristics of 0.062-1.0 mm particle size, 20-100 m,/g surface area, and 10-40 nm average pore diameter. Such skeletal iron catalysts are prepared and utilized for producing synthetic hydrocarbon products from CO and H,feeds by Fischer-Tropsch synthesis process. Iron powder is mixed with non-ferrous powder selected from aluminum, antimony, silicon, tin or zinc powder to provide 20-80 wt. % iron content and melted together to form an iron alloy, then cooled to room temperature and pulverized to provide 0.1-10 mm iron alloy catalyst precursor particles. The iron alloy pulverized particles are treated with NaOH or KOH caustic solution at 30-95&deg; C. temperature to extract and/or leach out most of the non-ferrous metal portion, and then screened and treated by drying and reducing with hydrogen and to provide the smaller size skeletal iron catalyst material. Such skeletal iron catalyst is utilized with CO&plus;H,feedstream for Fischer-Tropsch reactions in either a fixed bed or slurry bed type reactor at 180-350&deg; C. temperature, 0.5-3.0 mPa pressure and gas hourly space velocity of 0.5-3.0 L/g Fe/hr to produce desired hydrocarbon products.

Skeletal iron catalyst having improved attrition resistance and product selectivity in slurry-phase synthesis processes

Skeletal iron catalysts are prepared and utilized for producing hydrocarbon products from CO and H,feeds by Fischer-Tropsch synthesis process. Iron powder is mixed with aluminum, antimony, silicon, tin or zinc powder and 0.01-5 wt % metal promotor powder to provide 20-80 wt % iron content, then melted together, cooled to room temperature and pulverized to provide 0.1-10 mm iron alloy catalyst precursor particles. The iron alloy precursor particles are treated with NaOH or KOH caustic solution at 30-95&deg; C. to extract or leach out a major portion of the non-ferrous metal portion from the iron, and then dried and reduced under hydrogen atmosphere to provide the skeletal iron catalyst material. Such skeletal iron catalyst is utilized with CO&plus;H,feedstream in either fixed bed or slurry bed type reactor at 200-350&deg; C. temperature, 1.0-3.0 mPa pressure and gas hourly space velocity of 0.5-3.0 L/g Fe/h to produce desired hydrocarbon products.

Skeletal iron catalyst and its preparation for Fischer-Tropsch synthesis processes

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.

Growing community of inventors

West Windsor, NJ, United States of America

Lap-Keung Lee