Texaco Inc.

Roger J Corbeels

Mitri S Najjar

Richard V Kessler

Charles G Sengenberger

Robert M Suggitt

Matthew A McMahon

Walter C Gates, Jr

John T Nolan, Jr

Stephen R Vasconcellos

Uygur Kokturk

Enrique F dePaz

Synthesis gas is produced by the partial oxidation of a high silicon and sulfur-containing heavy liquid hydrocarbonaceous fuel and/or petroleum coke having a nickel and vanadium-containing ash that includes calcium and sodium, in a mixture with an iron and/or copper containing additive in a vertical free-flow reaction zone lined with refractory A or a combination of refractory A and refractory B. Refractory A lining of the reaction zone comprises in wt %: Cr.sub.2 O.sub.3 about 20 to 82, MgO about 5.0 to 45, Fe.sub.2 O.sub.3 about 0 to 10.5 Al.sub.2 O.sub.3 about 0 to 6.2, CaO about 0 to 1.0, SiO.sub.2 about 0 to 2.5, and others about 0 to 1.3. Refractory B comprises in wt. %: Cr.sub.2 O.sub.3 about 0 to 40, MgO about 20 to 85, Fe.sub.2 O.sub.3 about 0 to 16, Al.sub.2 O.sub.3 about 0 to 9.0, SiO.sub.2 about 0 to 2.7, and others about 0 to 1.1. In the reaction zone separate portions of said Fe and/or Cu containing additive: (1) combine with portions of said Fe, Ni, and S to generate a liquid phase washing agent; (ii) combine with a portion of refractory components, and V, Fe, Ni and Al to form high melting spinel and oxide lath phases which are washed by said liquid phase washing agent; and (iii) combine with a portion of said Ni, Ca, Si, Al, Mg and Na to generate a liquid oxide silicate phase that fluxes substantially all of the remaining vanadium and other ash components.

Partial oxidation process

A process for the simultaneous partial oxidation and desulfurization of sulfur and silicate-containing solid carbonaceous fuel for the production of a gas stream comprising gaseous mixtures of H.sub.2 and CO and containing less than about 0.05 volume % of H.sub.2 S and COS, and entrained fly-ash, calcium sulfide, and particulate carbon. In the process, the solid carbonaceous fuel and a calcium-containing compound are entrained in a gaseous medium and are reacted by partial oxidation in the reaction zone of a free-flow unobstructed gas generator with a controlled amount of free-oxygen containing gas and with or without a temperature moderator so that an equilibrium oxygen concentration is provided in the gas phase in the reaction zone having a partial pressure which is less than about 10.sup.-12 atmosphere. The total moles of calcium in the reaction zone is at least equal to about 1.0 times the moles of sulfur in the solid carbonaceous fuel. The partial oxidation and desulfurization reactions take place simultaneously at a temperature which is at least about 400.degree. F. below the softening temperature of the ash in the solid carbonaceous fuel at an increased gasification efficiency. The sulfur in the solid carbonaceous fuel in the reaction zone is converted into calcium sulfide particulate matter which leaves the reaction zone along with the fly-ash entrained in the hot raw effluent gas stream.

Partial oxidation of sulfur-containing solid carbonaceous fuel

The hot effluent gas stream comprising H.sub.2 +CO and entrained molten slag from the partial oxidation of an ash-containing heavy liquid hydrocarbonaceous fuel, an ash-containing solid carbonaceous fuel, or mixtures thereof is passed in succession through a radiant or quench cooling zone, a metal gas transfer line and a convective cooling zone. By covering the metal surfaces of the gas transfer line or the gas transfer line and the convective cooler connected thereto with a high temperature resistant carbon-containing material, substantially no molten slag sticks to the metal heat transfer surfaces on the inside of the gas transfer line or to the surfaces of the gas transfer line and the convective cooler connected thereto which are contacted by the partially cooled gas stream leaving the radiant or quench cooling zones.

Synthesis gas is produced by the partial oxidation of a feedstock comprising petroleum coke and/or heavy liquid hydrocarbonaceous fuel containing sulfur and having an ash that contains nickel, vanadium and a low content of silicon. An iron-containing additive is introduced into the vertical free-flow unobstructed refractory lined reaction zone along with the feed to produce first and second types of liquid phase washing agents which collect and transport at least a portion of the vanadium-containing oxide laths and spinels and other ash components out of the reaction zone. The refractory lining of the reaction zone comprises in wt. %: MgO 85 to 98, Fe.sub.2 O.sub.3 0.03 to 3.0, Al.sub.2 O.sub.3 0.02 to 2.0, CaO 0.01 to 10, and SiO.sub.2 0.02 to 2.0. Elemental iron may be prevented from forming in the reaction zone by introducing sufficient supplemental oxygen-containing material and/or sulfur-containing material into the reaction zone so as to keep the partial pressure of oxygen and/or S.sub.2 gas in the reaction zone slightly above that calculated from Formulae I and/or II. The refractory substantially resists corrosion, erosion, and chemical attack by the molten slag. The life of the refractory is extended. Further, the molten slag is modified by contact with the refractory so that it runs more freely from the gasifier. By this method molten slag having a reduced viscosity and containing the nickel and vanadium-containing impurities from the feedstock and refractory components is readily removed from the gas generator.

A process for the partial oxidation of a sulfur- and silicate-containing carbonaceous fuel to produce a synthesis gas with reduced sulfur content which comprises partially oxidizing said fuel at a temperature in the range of 1800.degree.-2200.degree. F. in the presence of a temperature moderator, an oxygen-containing gas and a sulfur capture additive which comprises an iron-containing compound portion and a sodium-containing compound portion to produce a synthesis gas comprising H.sub.2 and CO with a reduced sulfur content and a molten slag which comprises (i) a sulfur-containing sodium-iron silicate phase and (ii) a sodium-iron sulfide phase. The sulfur capture additive may optionally comprise a copper-containing compound portion.

Process for production of synthesis gas with reduced sulfur content

A process for the simultaneous partial oxidation and desulfurization of an ash-containing solid carbonaceous fuel comprising (basis solid fuel) 0.2 to 8.0 wt. % sulfur and 0.1 to 30 wt. % of silicate compounds for the production of gaseous mixtures comprising H.sub.2 and CO and entrained molten slag. In the process, the solid carbonaceous fuel and supplemental iron-containing material are reacted by partial oxidation in the reaction zone of a free-flow unobstructed down-flowing vertical refractory lined gas generator with a controlled amount free-oxygen containing gas and a temperature moderator so that an equilibrium oxygen concentration is provided in the gas phase in the reaction zone having a partial pressure which is less than about 10.sup.-7 atmospheres. The partial oxidation and desulfurization reactions take place simultaneously at a temperature which is above 1900.degree. F. and about 10.degree. to 200.degree. F. above the fluid temperature of the slag at an increased thermal efficiency. The sulfur in the solid carbonaceous fuel in the reaction zone is converted into iron oxysulfide particulate matter which leaves the reaction zone along with the silicates of calcium and iron in the molten ash that is entrained in the hot raw effluent gas stream comprising H.sub.2 and CO. Less than about 0.6 mole % of H.sub.2 S and COS is in the effluent gas stream. Additional desulfurization in a fluidized bed of calcium and carbon containing materials may be optionally used to reduce the mole % of H.sub.2 S and COS.

A process for the simultaneous partial oxidation and desulfurization of sulfur and silicate-containing solid carbonaceous fuel for the production of gaseous mixtures comprising H.sub.2 and CO and containing less than about 0.05 volume % of H.sub.2 S and COS. In the process, the solid carbonaceous fuel and a calcium-containing compound are reacted by partial oxidation in the reaction zone of a free-flow unobstructed gas generator with a controlled amount of free-oxygen containing gas and a temperature moderator so that an equilibrium oxygen concentration is provided in the gas phase in the reaction zone having a partial pressure which is less than about 10.sup.-12 atmospheres. The total moles of calcium in the reaction zone is at least equal to about 1.0 times the moles of sulfur in the solid carbonaceous fuel. The partial oxidation and desulfurization reactions take place simultaneously at a temperature which is about 10.degree. to 200.degree. F. below the softening temperature of the ash in the solid carbonaceous fuel and below about 2000.degree. F. at an increased gasification efficiency. The sulfur in the solid carbonaceous fuel in the reaction zone is converted into calcium sulfide particulate matter which leaves the reaction zone along with the fly-ash entrained in the hot raw effluent gas stream.

A process for the simultaneous partial oxidation and desulfurization of an ash-containing solid carbonaceous fuel comprising (basis solid fuel) 0.2 to 6.0 wt. % sulfur and 0.1 to 30 wt. % of silicate compounds for the production of gaseous mixtures comprising H.sub.2 and CO and entrained molten slag. In the process, the solid carbonaceous fuel and first and second types of supplemental calcium-containing materials are reacted by partial oxidation in the reaction zone of a free-flow unobstructed down-flowing vertical refractory lined gas generator with a controlled amount of free-oxygen containing gas and a temperature moderator so that an equilibrium oxygen concentration is provided in the gas phase in the reaction zone having a partial pressure which is less than about 10.sup.-9 atmospheres. The partial oxidation and desulfurization reactions take place simultaneously at a temperature above about 1900.degree. F. and about 10.degree. to 100.degree. F. above the fluid temperature of the slag at an increased thermal efficiency. The sulfur in the solid carbonaceous fuel in the reaction zone is converted into calcium and iron sulfide particulate matter which leaves the reaction zone along with the silicates of calcium and iron in the molten ash that is entrained in the hot raw effluent gas stream. Additional desulfurization in a fluidized bed containing calcium-containing material in admixture with carbon-containing material may be used to reduce the amount of H.sub.2 S and COS in the effluent gas stream to less than about 0.05 volume %.

Synthesis gas, fuel gas, or reducing gas is produced by the noncatalytic partial oxidation of a sulfur-containing liquid hydrocarbonaceous fuel or a slurry of sulfur-containing solid carbonaceous fuel with a free-oxygen containing gas in the free-flow reaction zone of a refractory lined gas generator at an autogenous temperature in the range of about 1900.degree. F. to 2900.degree. F. and above the ash-fusion temperature of the slag formed in the reaction zone, so that about 75 to 95 weight percent of the carbon in the fuel feed to the reaction zone is converted into carbon oxides. At least a portion of the hot effluent gas stream from the reaction zone is passed through a free-flow radiant cooler in admixture with an iron-containing additive. In the radiant cooler at least a portion of the sulfur-containing gases e.g. H.sub.2 S and COS react with the iron-containing additive to produce particulate matter comprising iron oxysulfide. Further, a portion of this newly formed particulate matter and/or the iron-containing additive combine with molten slag and/or ash in the hot raw gas stream passing through the radiant gas cooler. The slag produced thereby has a reduced ash fusion temperature and a reduced viscosity. The remainder of the newly formed particulate matter comprising iron oxysulfide and particulate carbon are entrained in the effluent gas stream leaving the radiant syngas cooler and are separated from the effluent gas stream and optionally recycled to the partial oxidation reaction zone in admixture with fresh fuel feed.

POX process with high temperature desulfurization of syngas

A process for the simultaneous partial oxidation and desulfurization of sulfur and silicate-containing solid carbonaceous fuel for the production of gaseous mixtures comprising H.sub.2 and CO and containing less than about 0.05 volume % of H.sub.2 S and COS. In the process, an aqueous slurry of the solid carbonaceous fuel and a copper-containing compound are reacted by partial oxidation in the reaction zone of a free-flow unobstructed down-flowing vertical refractory lined gas generator with a controlled amount of free-oxygen containing gas and with optionally a temperature moderator so that an equilibrium oxygen concentration is provided in the gas phase in the reaction zone having a partial pressure which is less than about 10.sup.-6 atmosphere. The O/C atomic ratio is in the range of about 0.5 to 2.0. The H.sub.2 O/solid carbonaceous fuel weight ratio is in the range of about 0.2 to 0.7. Further, the total moles of copper in the reaction zone is at least equal to about 1.0 times the moles of sulfur in the solid carbonaceous fuel. The partial oxidation and desulfurization reactions take place simultaneously at a temperature which produces fly-ash or molten slag at an increased thermal efficiency. At least about 90 wt. % of the sulfur in the solid carbonaceous fuel in the reaction zone is converted into copper oxysulfide particulate matter which leaves the reaction zone along with the fly-ash or molten slag entrained in the hot raw effluent gas stream comprising H.sub.2, CO, CO.sub.2 at least one gas selected from the group consisting of H.sub.2 O, N.sub.2, CH.sub.4 and A; and less than about 0.05 volumne % of H.sub.2 S and COS. The mole ratio in the reaction zone for H.sub.2 O/H.sub.2 is in the range of about 0.4 to 3.0.

The problem of creaming during formation of disperse-slurry of coal liquefaction residue by ball milling with water is eliminated by use, as an anti-creaming additive, of a quaternary amine such as tallow trimethyl ammonium chloride.

Formation of disperse-slurry of coal liquefaction residue

Outlet structure of a powdered coal gasification generator. The bottom of the generator has an outlet throat with cylindrical walls that extend beyond the base. And, the walls terminate in an oblique manner with a face shaped to promote flow of slag from the generator to a single point in order to minimize reentrainment of slag into the gasification products.

Outlet structure for a downflow generator

Unconverted char in a mixture of particles formed in the partial oxidation of an ash-containing solid fuel is recovered by grinding the mixture and subjecting the ground material to froth flotation.

Partial oxidation with recycle of recovered carbon

A method of producing a thick slurry of powdered coal and water. It includes feeding less coal than is required for the thick slurry into a ball mill, and introducing all of the water required so that a thin slurry is produced. The remaining coal required is pulverized in a dry grinder, and the thin slurry and dry powdered coal are mixed to produce the desired thick slurry.

Method of producing a coal-water slurry of predetermined consistency

An extruder for feeding finely divided solids. And, in combination therewith, means for using gas in various ways to repulverize the finely divided solids. It lends itself to a procedure for continuously charging finely divided solids with water into a high pressure reactor. The high pressure is inherently contained, and the solids are repulverized for use in a reaction.

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Wappingers Falls, NY, United States of America

Roger J Corbeels