Hydrocarbon Research, Inc.

Hri, Inc.

Govanon Nongbri

Michael C Chervenak

Ronald H Wolk

Axel R Johnson

Seymour B Alpert

Richard M Eccles

Susan M Brandt

An improved process for catalytic desulfurization of petroleum residua feedstocks to provide at least about 75% desulfurization of the liquid product while achieving low catalyst deactivation and increased catalyst age. In the process which uses an ebullated catalyst bed reactor, the reaction conditions are usually maintained at 790.degree.-860.degree. F. temperature, 1000-1800 psig hydrogen partial pressure, and 0.2-2.0 Vf/hr/Vr space velocity. To control carbon and metals deposition on the catalyst, used catalyst is withdrawn from the reactor, a minor portion of the catalyst is discarded to control metals deposition and maintain catalyst activity, and the remaining catalyst is regenerated to remove carbon by carbon burnoff and returned to the reactor for further use. If desired, the regenerated catalyst can be presulfided before returning it to the reactor. Following phase separation and distillation steps, the desulfurized hydrocarbon liquid products are withdrawn from the process. For feedstocks requiring higher desulfurization, two stages of catalytic reaction are provided in which the used catalyst is withdrawn from each stage reactor and regenerated to remove carbon and then returned to the same stage reactor. Alternatively, fresh catalyst is added to the second stage only, some used catalyst from the second stage reactor is transferred to the first stage reactor, and used catalyst is discarded from the first stage reactor.

Catalyst desulfurization of petroleum residua feedstocks

A process for high hydroconversion of petroleum residua containing at least about 25 V % material boiling above 975.degree. F. to produce lower boiling hydrocarbon liquid products and avoid undesirable precipitation of asphaltene compounds. In the process, the feedstock is at least about 80 percent catalytically hydroconverted to material boiling below 975.degree. F. and containing a mixture of gas and liquid fractions, after which the gas fraction is removed while maintaining the resulting liquid fractions temperature above about 730.degree. F. to avoid precipitation of asphaltene compounds which causes operations difficulties in the downstream equipment. Alternatively, the pressure-reduced liquid fraction can be stripped of material boiling below about 650.degree. F. before cooling the liquid to a temperature below about 730.degree. F. to prevent such precipitation of asphaltene compounds in the downstream equipment. The resulting liquid fraction is distilled to produce hydrocarbon liquid products, and a vacuum bottoms fraction is recycled to the catalytic reaction step to obtain increased percent conversion to lower boiling liquid products.

Sustained high hydroconversion of petroleum residua feedstocks

An improved process for upgrading a coal liquid where the coal liquid is catalytically converted by hydrogenating and hydrocracking. In the process of upgrading a coal liquid where the coal liquid is fed with hydrogen into a catalytic reactor, the improvement comprises the feeding of a sulfur-containing liquid with the coal liquid. The sulfur-containing liquid ranges from about 0.2 to about 2.0 weight percent of the coal liquid feed. The sulfur-containing liquid is a high boiling hydrocarbon sulfur compound of the formula RSR.sub.1, where R is an alkyl group having 2 to 20 carbon atoms or a phenyl group and R.sub.1 is H, an alkyl group having 2 to 20 carbon atoms or a phenyl group.

Catalyst activity in coal liquid upgrading

A process for the catalytic hydroconversion of special petroleum feedstocks, containing 10-28 W % asphaltenes, and having Ramsbottom carbon residue of 12-35 W %, such as Cold Lake and Lloydminster crude and residua materials. In the process, high percentage conversion (65-80 V %) to lower boiling hydrocarbon products can be achieved by maintaining a narrow range of reaction conditions, preferably in an ebullated bed catalytic reactor. Reaction temperature is 780.degree.-835.degree. F., hydrogen partial pressure is 2000-3000 psig, and space velocity is 0.25-5.0 V.sub.f /hr/V.sub.r. Higher conversion of about 80 to 95 volume percent can be obtained with recycle of 975.degree. F..sup.+ vacuum bottoms fraction to the reactor. Useful catalysts have total pore volume of about 0.5-0.9 cc/gm and include cobalt-molybdenum and nickel-molybdenum on alumina support.

Selective operating conditions for high conversion of special petroleum

In the catalytic demetallization of Venezuelan crude oil feedstocks, the rate of catalyst deactivation is reduced by controlling the level of demetallization at start-up. Operating conditions of pressure, temperature and space velocity are controlled to maintain the initial level of demetallization below 75 percent.

Extending life of demetallization catalyst

In producing low sulfur fuel oil by the ebullated bed hydroconversion of petroleum residue, the resulting heavy vacuum bottoms sulfur-containing residue material is utilized to produce hydrogen. The residue material from the hydroconversion operation is gasified to provide a fuel gas, which is then used to fire a steam-methane reformer. The chemical requirements for hydrogen production are met by feeding a portion of light gaseous products from the hydroconversion step to the catalytic side of the steam-methane reformer. A low sulfur fuel oil distillate product is recovered from the reactor effluent streams and can be further hydrotreated as desired. Thus, all hydrogen required in the H-Oil reactor for hydroconversion and desulfurization is ultimately produced from the residual oil feed material, by using the heavy product residue material to produce a fuel gas and converting the light hydrocarbons to hydrogen.

Production of low sulfur fuel oil and hydrogen from petroleum residium

The maximum conversion and desulfurization of residual petroleum oils having a high content of asphaltenes can be attained by first converting a maximum amount of the asphaltenes contained in these feeds by pretreating the feeds with hydrogen under a selected combination of operating conditions. Conditions of temperature between 700.degree. and 800.degree.F, liquid space velocity between 0.1 and 2.0 V.sub.f /hr/V.sub.r and hydrogen partial pressure between 1200 and 3000 psig, result in a maximum conversion of asphaltenes when 5 to 45 volume percent of the 975.degree.F+ fraction in the feedstock is converted to lower boiling fractions.

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Newtown, PA, United States of America

Govanon Nongbri