Texaco Inc.

Other

Michael W Becker

Mitri S Najjar

John Saunders Stevenson

Arnulf Muan

James R Muenger

Americo R Catena

John M Veillon

Anthony E Bergin

Allen M Robin

Synthesis gas is produced by the partial oxidation of a feedstock comprising sulfur and ash-containing heavy liquid hydrocarbonaceous fuels, solid carbonaceous fuels, or mixtures thereof. An iron-containing additive is introduced into the reaction zone along with the feed to produce first and second liquid phase washing agents that collect and transport the vanadium-containing oxide laths and spinels and other ash components out of the reaction zone. A gaseous slag fludizing agent is also introduced into the top of the reaction zone so tha the gasifier is operated at a uniform temperature throughout under conditions that maximize the fluidity of the molten slag over the full opereating temperature range in the gasifier. Equilibrium oxygen and sulfur concentrations are provided in the gas phase in the reaction zone which provide specific partial pressures. By this method substantially all of the molten slag having a reduced viscosity and containing the nickel and vanadium-containing impurities from the feedstock are readily removed from the walls of the gas generator at a lower temperature. Simultaneously, in-situ desulfurization of the feedstock takes place in the gasifier so that the raw effluent product gas may leave the gasifier containing less than about 1.00 mole % of H.sub. 2 S and COS. In one embodiment, an additional supplemental gas e.g. free-oxygen, H.sub.2 S, COS, SO.sub.2, and mixtures thereof may be introduced into the gasifier so as to increase the carbon conversion without increasing the temperature in the reaction zone; or to prevent the formation of free-iron.

Partial oxidation process

Reactor for gasifying a carbonaceous fuel to produce a usable gas, and comprising an insulated outer shell. A reaction chamber within the shell receives a fuel mixture from an injection burner. The products or effluent of gasification include hot produced gases which are passed through a constricted throat to be cooled in a liquid bath. A dip tube, which guides the hot effluent into the bath, is provided with a stream of coolant from a quench ring. The latter is supported below the reaction chamber and is provided with a thermal barrier along its surface that is exposed to the hot produced gas. The barrier will reduce thermal stress in the quench ring and reduce drain of heat from the gasifier throat, thus avoiding premature chilling of the slag component.

Thermally insulated quench ring for a gasifier

Synthesis gas is produced by the partial oxidation of a feedstock comprising petroleum coke and/or heavy liquid hydrocarbon fuel containing sulfur and having an ash that contains nickel, vanadium and silicon. An iron-containing or an iron and calcium-containing additive is introduced into the reaction zone along with the feed. The additive combines with at least a portion of the iron and nickel constituents and sulfur found in the feedstock to produce a liquid phase washing agent that collects and transports at least a portion of the vanadium-containing oxide laths and spinels and other ash components out the reaction zone. Slag and other particulate matter is separated from the effluent gas stream and ground to produce a heterogeneous mixture of magnetic and non-magnetic solid particles. The particles have various degrees of magnetic susceptibility and are thereby separated into the following three separate portions of magnetic particles: (1) particles of an Fe-Ni alloy, and a minor amount of magnetite particles; (2) particles of an oxysulfide phase of iron and nickel, a minor amount of particles of vanadium compounds, and particles of iron silicate and calcium silicate; and (3) particles of vanadium-containing spinels, and particles of metal silicates. The first and third portions are sent to a metal refiner to recover nickel and vanadium respectively. The second portion of magnetic particles having an increased Fe/V wt. ratio is recycled through the gasifier.

Partial oxidation process with magnetic separation of the ground slag

An assembly of a quench liquid distribution ring and dip-tube with or without a draft tube for use in a hot effluent gas quench cooling zone containing a pool of quench liquid in the bottom in combination with a vertical cylindrical free-flow refractory lined reaction zone of a partial oxidation gas generator. The hot effluent gas from the reaction zone passes through a bottom central discharge outlet and passage and then through a coaxial vertical dip-tube that extends down into a pool of quench liquid. A quench liquid distribution ring that includes an annular rectangular shaped bottom feed quench liquid distribution channel, surrounds the outside diameter of the dip-tube at its upstream end. A quench ring face and cover is provided that comprises a vertical cylindrical shaped leg portion and a top horizontal flat ring plate portion that extends perpendicularly outward from the upstream end of the leg portion. The cylindrical shaped leg portion extends downward and overlaps the inside surface of the inner wall of said annular rectangular shaped quench liquid distribution channel thereby providing an annular shaped gap therebetween. The top horizontal flat ring plate portion provides a gas and liquid tight cover with the annular quench liquid distribution channel when the two parts are bolted to a floor flange connected to the support floor for the refractory that lines the reaction zone of the gas generator. A plurality of slot orifices pass through the inner wall of said annular distribution channel to provide free passage for the quench liquid between the distribution channel and the annular gap. The annular gap may be kept full of quench liquid and free from gas and vapor pockets, thereby avoiding poor heat transfer. A spiralling layer of quench liquid may be supplied to and distributed over the inside surfaces of the inner wall of the quench liquid distribution channel and the cylindrically shaped dip-tube.

Quench ring and dip-tube assembly

This invention pertains to the use of an ash-removal additive in the production of hot raw gaseous mixtures comprising H.sub.2 +CO and containing entrained molten slag by the partial oxidation of a feedstock comprising a heavy liquid hydrocarbonaceous fuel having a nickel and vanadium-containing ash or petroleum coke having a nickel and vanadium-containing ash. Sticking and build-up of molten slag on the surfaces of a steel quench ring and heat exchanger which may be contacted by the molten slag entrained in the hot raw effluent gas stream is prevented by the high temperature electrodeposition of a protective metal e.g. aluminum or titanium. The protective metal is electrodeposited from an electrolytic bath comprising molten fluorides and diffuses beneath the surface and forms an alloy or solid solution with the subsurface metal.

Partial oxidation of ash-containing liquid hydrocarbonaceous and solid

Process for the production of gaseous mixtures comprising H.sub.2 +CO e.g. synthesis gas, reducing gas, or fuel gas by the partial oxidation of a vanadium-containing liquid hydrocarbonaceous fuel, solid carbonaceous fuel, or mixtures thereof in a free-flow vertical refractory lined gas generator. The feed mixture to the gas generator comprises (i) a vanadium-containing fuel; (ii) supplemental copper-containing additive; and (iii) at least a portion of the remainder of the copper-containing slag after separation of an enriched vanadium-containing coarse slag fraction. Materials (ii) and (iii) combine in the partial oxidation reaction zone with at least a portion of the nickel and iron constituents and the sulfur found in the feedstock to produce a liquid phase washing agent that collect and transports at least a portion of the vanadium-containing oxide laths and spinels and other ash components out of the reaction zone as molten vanadium-containing slag. A coarse slag fraction having a decreased Cu/V weight ratio is produced when a portion of the molten slag entrained in the hot raw effluent gas stream from the partial oxidation reaction zone is deposited on the walls of a slag separation chamber located between the bottom discharge outlet in the reaction zone and the effluent gas quench tank located at the bottom of the gas generator. Chunks of the slag drop into the quench tank and the enriched vanadium containing coarse slag portion is separated from the remainder of the copper-containing slag comprising smaller sized particles. It is economically advantageous to recover by-product vanadium from the coarse slag fraction in a metal refining plant.

Partial oxidation of vanadium-containing heavy liquid hydrocarbonaceous

Process for the production of gaseous mixtures comprising H.sub.2 +CO e.g. synthesis gas, reducing gas, or fuel gas by the partial oxidation of a vanadium-containing liquid hydrocarbonaceous fuel, solid carbonaceous fuel, or mixtures thereof in a free-flow vertical refractory lined gas generator. The feed mixture to the gas generator comprises (i) a vanadium-containing fuel; (ii) supplemental iron-containing ash fusion temperature reducing agent; and (iii) at least a portion of the remainder of the iron-containing slag after separation of an enriched vanadium-containing coarse slag fraction. The coarse slag fraction has a decreased Fe/V weight ratio and is formed by depositing a portion of the slag entrained in the hot raw effluent gas stream from the partial oxidation reaction zone on the walls of a slag separation chamber located between the bottom discharge outlet in the reaction zone and the effluent gas quench tank located at the bottom of the gas generator. It is economically advantageous to recover by-product vanadium from the coarse slag fraction in a metal refining plant.

An ash fusion temperature reducing agent principally comprising at least 50.0 wt. % of a manganese compound, such as MnO, and the remainder of the agent comprising a silicon compound, such as SiO.sub.2 is mixed with an ash-containing fuel comprising a pumpable liquid hydrocarbonaceous material and/or petroleum coke to produce Mixture A. In one embodiment, the ash fusion temperature reducing agent comprises a comminuted pyrolusite ore in which the following elements are present in weight percent basis ore: manganese in the range of about 50-75, calcium in the range of about 0-1.0, silicon in the range of about 0-3.0, magnesium in the range of about 0-1.0, and aluminum in the range of about 0-1.0. Mixture A is reacted with a free-oxygen containing gas in a free-flow refractory lined reaction zone of a partial oxidation gas generator. A hot raw effluent gas stream comprising H.sub.2 +CO along with molten ash having a reduced initial deformation temperature are produced at a lower temperature. Alternatively, Mixture A may be first introduced into a coking zone and converted into petroleum coke in which the ash fusion temperature reducing agent is dispersed throughout. The petroleum coke entrained in a liquid or gaseous carrier is then introduced into the partial oxidation gas generator where a hot raw effluent gas stream comprising H.sub.2 +CO is produced along with molten ash having a reduced ash fusion temperature. The molten ash is readily separated from the effluent gas stream; and, the gas generator may be operated at a lower temperature thereby extending the life of the refractory lined reaction zone.

An ash fusion temperature reducing agent comprising a mixture of about 70-97 wt. % of an iron compound and the remainder comprising a silicon compound is mixed with an ash-containing fuel comprising liquid hydrocarbonaceous material and/or petroleum coke. The comminuted mixture is reacted in a free-flow partial oxidation reaction zone with a free-oxygen containing gas in the presence of a temperature moderator to produce a hot raw effluent gas stream comprising H.sub.2 +CO along with molten ash having a reduced initial deformation temperature. The weight ratio of ash fusion temperature reducing agent to ash in said ash-containing fuel is in the range of about 0.5 to 10, and the weight ratio of iron oxide to SiO.sub.2 in said molten ash is about 1.5, or more. The molten ash is then separated from the hot raw effluent gas stream. In another embodiment, the comminuted ash fusion temperature reducing agent is disseminated into an ash-containing heavy liquid hydrocarbonaceous material and the mixture is then coked to produce petroleum coke containing dispersed therein said ash fusion temperature reducing agent. The petroleum coke entrained in a liquid or gaseous carrier is then introduced into the partial oxidation reaction zone as at least a portion of the feedstock. The molten ash is readily separated from the effluent stream of raw synthesis gas. The gas generator may be operated at a lower temperature thereby extending the life of the refractory lined reaction zone.

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Westminster, CA, United States of America

Michael W Becker