Partial oxidation process

Claim 2

A process for the production of gaseous mixtures comprising H 2 +CO by the partial oxidation of a fuel feedstock comprising a heavy liquid hydrocarbonaceous fuel having a nickel, iron, and vanadium-containing ash or petroleum coke having a nickel, iron, 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 0.5 ppm nickel, and a minimum of 0.5 ppm iron, said process comprising: (1) mixing together a copper-containing additive with said fuel feedstock; wherein the weight ratio of copper-containing additive to ash in said fuel feedstock is in the range of about 1.0-10.0, and there is at least 10 parts by weight of copper for each part by weight of vanadium; (2) reacting said mixture from (1) at a temperature in the range of 2200° F. to 2900° F. and a pressure in the range of about 5 to 250 atmospheres in a free-flow refractory lined partial oxidation reaction zone with a free-oxygen containing gas in the presence of a temperature moderator and in a reducing atmosphere to produce a hot raw effluent gas stream comprising H 2 +CO and entrained molten slag; and where in said reaction zone said copper-containing additive combines with at least a portion of said nickel and iron 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 (3) separating nongaseous materials from said hot raw effluent gas stream.

Claim 3

The process of claim 1 wherein said copper-containing additive comprises a copper compound selected from the group consisting of oxide, sulfide, sulfate, carbonate, cyanide, chloride, nitrate, and mixtures thereof.

Claim 4

The process of claim 1 wherein said copper-containing additive comprises a cuprous or cupric organic compound selected from the group consisting of naphthenates, oxalates, acetates, benzoates, oleates, tartrates, and mixtures thereof.

Claim 5

The process of claim 1 wherein of said copper-containing additive is a water soluble copper salt.

Claim 6

The process of claim 1 wherein said heavy liquid hydrocarbonaceous fuel having a nickel, iron, and vanadium-containing ash feedstock is selected from the group consisting of crude residue from petroleum distillation and cracking process operations, petroleum distillate, reduced crude, whole crude, asphalt, coal tar, coal derived oil, shale oil, tar sand oil, and mixtures thereof.

Claim 7

The process of claim 1 wherein the fuel feedstock comprises a pumpable slurry of petroleum coke in water, liquid hydrocarbonaceous fuel, or mixtures thereof.

Claim 8

The process of claim 1 wherein in (1) said copper-containing additive is introduced into the feed to or the bottoms from a vacuum distillation unit.

Claim 9

The process of claim 1 wherein said mixture of copper-containing additive and fuel feedstock from (1) has a particle size such that substantially all of said material passes through a sieve in the range of ASTM E-11 Standard Sieve Designation about 425 microns to 38 microns, or below.

Claim 10

The process of claim 1 wherein a comparatively small amount of a comminuted second additive comprising a compound from the group of elements consisting of iron, calcium, magnesium, chromium, and mixtures thereof is mixed with the copper-containing additive and the fuel feedstock in (1).

Claim 11

The process of claim 1 wherein substantially all of the sulfur in said feedstock is converted into the sulfides of copper, iron, and nickel and leaves the reaction zone in the slag.

Claim 12

The process of claim 1 wherein a supplemental iron and/or calcium compound is introduced into the reaction zone of the partial oxidation reaction zone only at start-up to reduce the softening temperature of the copper-containing addition agent, and then the introduction of said iron and/or calcium compound is discontinued.

Claim 13

The process of claim 11 wherein said iron compound is selected from the group consisting of oxide, sulfate, sulfide carbonate, cyanide, chloride, nitrate, and mixtures thereof; and said calcium compound is selected from the group consisting of oxide, sulfate, sulfide, carbonate, and hydroxide.

Claim 14

The process of claim 11 wherein said supplemental iron compound may be introduced into the reaction zone in the amount of about 1.0 to 10.0 wt. % of said copper-containing addition agent; and said supplemental calcium compound may be introduced into the reaction zone in the amount of about 2.0 to 8.0 wt. % of said copper-containing addition agent.

Claim 15

The process of claim 1 wherein an additional magnesium and/or chromium compound is introduced in the total amount of about 1.0 to about 10.0 wt. % of said copper-containing additive.

Claim 16

The process of claim 14 wherein said magnesium and chromium compounds are selected from the group consisting of oxides, hydroxides, carbonates, sulfates, nitrates, and mixtures thereof.

Claim 17

The process of claim 1 wherein said liquid phase washing agent substantially comprises in wt. %: copper sulfide about 75 to 95, nickel sulfide about 0.5 to 3.0, copper oxide about about 2 to 9, iron sulfide about 0.4 to 2.0; and iron oxide about 0.1 to 1.0.

Claim 18

A process for the production of gaseous mixtures comprising H 2 +CO by the partial oxidation of a feedstock comprising a heavy liquid hydrocarbonaceous fuel having a nickel, iron, and vanadium-containing ash or petroleum coke having a nickel, iron, 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 0.5 ppm nickel and a minimum of 0.50 ppm iron; said process comprising: (1) mixing together a copper-containing additive with said feedstock; wherein the weight ratio of copper-containing additive to ash in the fuel feedstock is in the range of about 1.0-10.0, and there is at least 10 parts by weight of copper for each part by weight of vanadium. (2) coking said mixture from (1) to produce petroleum coke having a nickel, iron, and vanadium-containing ash and having dispersed therein said copper-containing additive; (3) introducing the petroleum coke from (2) into the partial oxidation reaction zone in (4) 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; and (4) reacting said petroleum coke from (3) at a temperature in the range of b 2200° F. to 2900° F. and a pressure in the range of about 5 to 250 atmospheres in said free-flow refractory lined partial oxidation reaction zone with a free-oxygen containing gas in the presence of a temperature moderator and in a reducing atmosphere to produce a hot raw effluent gas stream comprising H 2 +CO and entrained molten slag; and where in said reaction zone said copper-containing additive combines with a portion of said nickel and iron constituents and sulfur found in the feedstock to produce a liquid phase washing carrier that collects and transports a portion of the vanadium-containing oxide laths and spinels and other ash components and refractory out of the reaction zone, and; (5) separating nongaseous materials from said hot raw effluent gas stream.

Claim 19

A process for the production of gaseous mixtures comprising H 2 +CO by the partial oxidation of a feedstock comprising a heavy liquid hydrocarbonaceous fuel having a nickel, iron, and vanadium-containing ash or petroleum coke having a nickel, iron, 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 0.5 ppm nickel and a minimum of 0.50 ppm iron; said process comprising: (1) mixing together a copper-containing additive with said feedstock; wherein the weight ratio of copper-containing additive to ash in the fuel feedstock is in the range of about 1.0-10.0, and there is at least 10 parts by weight of copper for each part by weight of vanadium. (2) coking said mixture from (1) to produce petroleum coke having a nickel, iron, and vanadium-containing ash and having dispersed therein said copper-containing additive; (3) introducing the petroleum coke from (2) into the partial oxidation reaction zone in (4) 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; and (4) reacting said petroleum coke from (3) at a temperature in the range of b 2200° F. to 2900° F. and a pressure in the range of about 5 to 250 atmospheres in said free-flow refractory lined partial oxidation reaction zone with a free-oxygen containing gas in the presence of a temperature moderator and in a reducing atmosphere to produce a hot raw effluent gas stream comprising H 2 +CO and entrained molten slag; and where in said reaction zone said copper-containing additive combines with a portion of said nickel and iron constituents and sulfur found in the feedstock to produce a liquid phase washing carrier that collects and transports a portion of the vanadium-containing oxide laths and spinels and other ash components and refractory out of the reaction zone, and; (5) separating nongaseous materials from said hot raw effluent gas stream.

Claim 20

The process of claim 17 wherein said copper-containing additive comprises a copper compound selected from the group consisting of oxide, sulfide, sulfate, carbonate, cyanide, chloride, nitrate, and mixtures thereof.

Claim 21

The process of claim 17 wherein said mixture of copper-containing additive and feedstock from (1) has a particle size such that substantially all of said material passes through a sieve in the range of ASTM E-11 Standard Sieve Designation of about 425 microns to 38 microns or below.

Claim 22

The process of claim 17 wherein said copper-containing additive comprises an inorganic or organic compound of copper.

Claim 23

The process of claim 17 wherein said ash-containing heavy liquid hydrocarbonaceous fuel is a high boiling liquid petroleum feed to or the bottoms from a vacuum tower or a fractionator.

Claim 24

The process of claim 17 where in (2) the mixture from (1) at a temperature in the range of about 650° F. to 930° F. is introduced into a delayed coking zone where at a temperature in the range of about 800° F. to 895° F. and a pressure in the range of about 20 to 60 psig, uncondensed hydrocarbon effluent vapor and steam are removed overhead and said petroleum coke having a nickel, iron, and vanadium-containing ash and having uniformly dispersed therein said copper-containing additive is removed from the bottom.

Claim 25

The process of claim 17 where in (2) the mixture from (1) at a temperature in the range of about 550° F. to 750° F. is introduced into a fluidized bed coking zone where at a temperature in the range of about 1000° F. to 1200° F. and a pressure in the range of about 10 to 20 psig, uncondensed hydrocarbon efflent vapor and steam are removed overhead and said petroleum coke is removed from the bottom.

Claim 26

The process of claim 17 where in (5) said nongaseous materials are separated from said hot effluent gas stream by contacting the gas stream from (4) with a water or oil scrubbing medium.

Claim 27

The process of claim 17 wherein a comparatively small amount of a comminuted second additive comprising a compound from the group of elements consisting of iron, calcium, magnesium, chromium, and mixtures thereof is mixed with the copper-containing additive and the feedstock in (1); and said second additive is uniformly dispersed in the petroleum coke produced in (2).

Claim 28

The process of claim 17 wherein magnesium and/or chromium compound is introduced as said second additive in the total amount of about 1.0 to 10.0 wt. % of said copper-containing additive.

Claim 29

The process of claim 26 wherein said magnesium and chromium compounds are selected from the group consisting of oxides, hydroxides, carbonates, sulfates, nitrates, and mixtures thereof.

Claim 30

The process of claim 17 wherein substantially all of the sulfur in said feedstock is converted into the sulfides of copper, iron, and nickel and leaves the reaction zone in the slag.

Claim 31

The process of claim 17 wherein a supplemental iron and/or calcium compound is introduced into the reaction zone of the partial oxidation reaction zone only at start-up to reduce the softening temperature of the copper-containing addition agent, and then the introduction of said iron and/or calcium compound is discontinued.

Claim 32

The process of claim 29 wherein said iron compound is selected from the group consisting of oxide, sulfate, sulfide carbonate, cyanide, chloride, nitrate, and mixtures thereof; and said calcium compound is selected from the group consisting of oxide, sulfate, sulfide, carbonate, and hydroxide.

Claim 33

The process of claim 29 wherein said supplemental iron compound may be introduced into the reaction zone in the amount of about 1.0 to 10.0 wt. % of said copper-containing addition agent; and said supplemental calcium compound may be introduced into the reaction zone in the amount of about 2.0 to 8.0 wt. % of said copper-containing addition agent.