Partial oxidation of ash-containing liquid hydrocarbonaceous and solid carbonaceous

In a process for the production of gaseous mixtures comprising H.sub.2 +CO by the partial oxidation of a heavy liquid hydrocarbonaceous fuel having a nickel and vanadium-containing ash, or mixtures thereof;

• and said feedstock includes a minimum of 0.5 wt. % of sulfur;
• and said ash includes a minimum of 5.0 wt. % vanadium, a minimum of 2.0 wt. % of nickel, and silicon;
• the improvement comprising:
• (1) introducing into a reaction zone along with said fuel, additive A comprising an iron-containing additive when the silicon content of said feedstock is less than about 350 ppm, or additive B comprising an iron and calcium-containing additive when the silicon content of said feedstock is about 400 ppm or more;
• wherein the weight ratio of additive A or B to ash in the reaction zone in (2) is in the range of about 1.0-10.0 to 1.0, and for each part by weight of vanadium there is at least 10 parts by weight of iron when additive A is used, or at least 10 parts by weight of iron plug calcium when additive B is used;
• (2) reacting said materials from (1) at a temperature in the range of about 2200.degree. F. to 3000.degree. F. and above the ash fusion temperature and a pressure in the range of about 5 to 250 atmospheres in said reaction zone comprising a free-flow refractory-lined partial oxidation reaction zone with a gas which contains free oxygen in the presence of a temperature moderator and in a reducing atmosphere to produce a hot raw effluent gas stream comprising H.sub.2 +CO and entrained molten slag;
• and where in said reaction zone when additive A is used said iron-containing additive combines with at least portion of said 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 and refractory out of the reaction zone as molten slag;
• and when additive B is used separate portions of said iron and calcium-containing additive will (i) combine with a portion of said nickel, calcium and sulfur to generate a liquid phase washing agent that collects and transports a portion of the vanadium-containing oxide laths and spinels and other ash components and refractory;
• and (ii) combine with a portion of said nickel, calcium, and silicon to generate a liquid oxide-silicate phase that fluxes substantially all of the remaining portion of said vanadium-containing oxide laths and spinels and other ash components to produce molten slag;
• and (3) removing sensible heat from said hot effluent gas stream from (2) in a cooling means by passing said effluent gas through a discharge outlet in the bottom of said reaction chamber and through either (i) a steel quench ring, and a vertical steel dip-tube into body of quench liquid below, or through (ii) a steel tubular heat exchanger in indirect heat exchange with a coolant fluid or (iii) simultaneously through (i) and (ii);
• wherein the metal surfaces of said steel quench ring and tubular heat exchanger that were directly contacted by said entrained molten slag were protected with a metal and metal alloy, and said protective metal was selected from the group of metals consisting of aluminum, and titanium which was electrodeposited at high temperature from a electolytic bath of molten fluorides of alkali metals and alkaline-earth metals maintained in an inert atmosphere;
• and immediately after deposition said protective metal diffused into and formed an alloy or solid solution with the subsurface metal of said cooling means;
• wherein sticking and build-up of slag upon contacting said cooling means were substantially reduced.

In a process for the production of gaseous mixtures comprising H.sub.2 +CO by the partial oxidation of a feedstock comprising a heavy liquid hydrocarbonaceous fuel having a nickel and vanadium-containing ash;

• and said feedstock includes a minimum of 0.5 wt. % of sulfur;
• and said ash includes a minimum of 5.0 wt. % vanadium, a minimum of 2.0 wt. % of nickel, and silicon;
• said process comprising:
• (1) mixing together with said feedstock, additive A comprising an iron-containing additive when the silicon content of said feedstock is less than about 350 ppm, or additive B comprising an iron and calcium-containing additive when the silicon content of said feedstock is about 400 ppm or more;
• wherein the weight ratio of additive A or B to ash in the reaction zone in (2) is in the range of about 1.0-10.0 to 1.0, and for each part by weight of vanadium there is at least 10 parts of weight of iron when additive A is used, or at least 10 parts by weight of iron plus calcium when additive B is used;
• (2) coking said mixture from (1) to produce petroleum coke having a nickel and vanadium-containing ash and having dispersed therein said additive A or B;
• (3) introducing the petroleum coke from (2) into a partial oxidation reaction zone as a pumpable slurry of petroleum coke in water, liquid hydrocarbonaceous fluid or mixtures thereof, or as substantially dry petroleum coke entrained in a gaseous transport medium;
• (4) reacting said petroleum coke from (3) at a temperature in the range of about 2200.degree. F. to 3000.degree. F. and above the ash fusion temperature and at a pressure in the range of about 5 to 250 atmospheres in said free-flow refractory-lined partial oxidation reaction zone with a gas containing free oxygen in the presence of a temperature moderator and in a reducing atmosphere to produce a hot raw effluent gas stream comprising H.sub.2 +CO and entrained molten slag, and where in said reaction zone when additive A is used said iron-containing additive combines with at a least a portion of said 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 and refractory out of the reaction zone;
• and when additive B is used separate portions of said iron and calcium-containing additive (I) combine with a portion of said nickel, calcium, and sulfur to generate a liquid phase washing agent that collects and transports a portion of the vanadium-containing oxide laths and spinels and other ash components and refractory;
• and (II) combine with a portion of said nickel, calcium and silicon to generate a liquid oxide-silicate phase that fluxes substantially all of the remaining portion of said vanadium-containing oxide laths and spinels and other ash components to produce molten slag;
• and (5) removing sensible heat from said hot effluent gas stream from (4) by passing said effluent gas through a discharge outlet in the bottom of said reaction zone chamber and through either (i) a steel quench ring and a vertical steel dip-tube into a body of quench liquid below, or through (ii) a steel tubular heat exchanger in indirect heat exchange with a coolant fluid, or (iii) simultaneously through (i) and (ii);
• wherein the metal surfaces of said steel quench ring and tubular heat exchanger that were directly contacted by said entrained molten slag were protected with a metal alloy, said protective metal was selected from the group of metals consisting of aluminum and titanium and was electrodeposited at high temperature from a electrolytic bath of molten fluorides of alkali metals and alkaline-earth metals maintained in an inert atmosphere, and wherein the electrodeposited metal rapidly diffused into and formed an alloy or solid solution with the subsurface metal, thereby reducing build-up of molten slag and plugging.