Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/46—Gasification of granular or pulverulent flues in suspension
  • C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/46—Gasification of granular or pulverulent flues in suspension
  • C10J3/466—Entrained flow processes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/72—Other features
  • C10J3/82—Gas withdrawal means
  • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
  • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
  • C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
  • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
  • C10K1/18—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids hydrocarbon oils
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0983—Additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only

Definitions

• This invention relates to a process for the partial oxidation of a sulfur-containing heavy liquid hydrocarbonaceous or solid carbonaceous fuel having a nickel, vanadium, and silicon-containing ash to produce gaseous mixtures comprising H2 + CO and entrained molten slag. More particularly, it pertains to an additive system for preventing the formation of toxic Ni3S2 in said molten slag.
• a major drawback for coking is the disposal of the product coke.
• the product coke With a reasonably clean coker feed, the product coke has been substituted for applications requiring relatively pure carbon, such as for electrode manufacture.
• the feed crudes With the feed crudes becoming poorer, there are compounding factors affecting coker operations. Since the crudes contain more contaminants, i.e. sulfur, metals (predominately vanadium, nickel, and iron), and ash which are concentrated in the product coke, petroleum coke made from such crude stock is of a much poorer quality and is excluded from many normal product applications. For example, the presence of toxic Ni3S2 in the coke ash severely limits its use.
• the Texaco partial oxidation gasification process offers an alternative processing route for use of the coke or the ash-containing heavy liquid hydrocarbonaceous fuel.
• water slurries of petroleum coke are reacted by partial oxidation in coassigned U.S. Patent No. 3,607,157.
• Gasification is often cited as a convenient means of coke disposition.
• the decision to use gasification as a coke disposal means is generally based on economics. The expect­ed rise in energy costs and legislation requiring total use of feed crude should shortly bring about a greater utilizat­tion of petroleum coke feeds to the partial oxidation gas generator.
• Ni3S2 toxic nickel subsulfide
• the fuel was fed to the gasifier in admixture with an upgraded recycle portion of slag and a copper-containing additive.
• the aforesaid process, and the fluxing as used in coal operations and in U.S. Patent Nos. 1,799,885 and 2,644,745 do not provide a solution to Applicant's problems involving troublesome nickel and sulfur.
• a first silicon-containing additive and a second copper and/or cobalt-containing additive react with the vanadium and nickel found in the ash of the sulfur-containing liquid hydrocarbonaceous fuel and/or solid carbonaceous fuel.
• the partial oxidation gasifier may be run continuously because the slag does not build-up on the walls of the gasifier, but runs freely down and out through the bottom of the reaction zone.
• the invention provides a process for the production of gaseous mixtures comprising H2 + CO by the partial oxidation of a fuel feedstock comprising a heavy liquid hydrocarbonaceous fuel containing sulfur and having an ash comprising nickel, vanadium and silicon and/or a solid carbonaceous fuel containing sulfur and having an ash comprising nickel, vanadium and silicon.
• a fuel feedstock comprising a heavy liquid hydrocarbonaceous fuel containing sulfur and having an ash comprising nickel, vanadium and silicon and/or a solid carbonaceous fuel containing sulfur and having an ash comprising nickel, vanadium and silicon.
• said feedstock includes a minimum of about 0.2 wt. % of sulfur, such as about 1.5 to 6.5 wt.
• said feedstock includes a minimum of about 0.5 ppm (parts per million) of nickel, such as about 2.0 to 4,000 ppm; a minimum of about 1.0 ppm of vanadium, such as about 20 to 5,000 ppm; and a minimum of about 5.0 ppm of silicon, such as about 5.0 to 20,000 ppm, or more.
• An additive system is provided which prevents the formation of toxic nickel subsulfide (Ni3S2) in slags generated during the partial oxidation of said feedstocks without raising the activity and pressure of sulfur-bearing gases e. g. H2S and COS. The cost of a downstream gas purification system is thereby minimized.
• the process includes the steps of (1) mixing together a copper and/or cobalt-containing material with said fuel feedstock; wherein the weight ratio of copper and/or cobalt to nickel in said mixture is in the range of about 0.2 to 10; and the weight ratio of copper and/or cobalt to silicon in said mixture is in the range of about 0.0001 to 0.04; (2) reacting said mixture from (1) by partial oxidation with a free-oxygen containing gas in a reducing atmosphere and in the presence of a temperature moderator at a pressure in the range of about 2 to 250 atmospheres in a down-flowing free-flow unobstructed vertical reaction zone with refractory lined walls in a partial oxidation gas generator, and at a temperature in the range of about 1800°F to 2900°F; an equilibrium oxygen concentration is provided in the gas phase in the reaction zone with a partial pressure in the range of about 1.7 x 10 ⁇ 15 to 2.3 x 10 ⁇ 8 atmospheres; an equilibrium sulfur concentration is provided in the gas phase in the reaction zone with a partial pressure in
• said copper and/or cobalt-containing material combines with at least a portion of said nickel, sulfur, and silicon constituents in the fuel feedstock in said reaction zone to produce said slag with at least a portion e.g. about 10.0 to 98.0 wt. % depositing on the inside walls of said reaction zone and comprising the following phases in wt. %: (i) about 0.1 to 10 wt. % of a Cu-Ni alloy phase and/or Co-Ni alloy phase, wherein the weight ratio of Cu and/or Co to Ni is in the range of about 0.2 to 0.9; (ii) from about 5.0 to 85 wt.
• Ni3S2 and there is a reduction of about 1 to 20 wt. % in the mole ratio H2S + COS/H2 + Co in the raw effluent gas stream over said mole ratio when said partial oxidation reaction takes place in the absence of said Cu and/or Co-containing materials; and, (3) separating non-gaseous material containing substantially no Ni3S2 from said hot raw effluent gas stream.
• the gas generator is shut down.
• the reducing atmosphere in the reaction zone is changed to oxidizing.
• the slag on the walls of the reaction zone is oxidized so that the fusion temperature and viscosity are reduced.
• the molten slag, substantially free from Ni3S2 flows by gravity down to the bottom of the gas generator.
• the invention provides a process for the production of gaseous mix­tures comprising H2 + CO by the partial oxidation of a fuel feedstock comprising a heavy liquid hydrocarbonaceous fuel containing sulfur and having an ash comprising nickel, vanadium and silicon and/or a solid carbonaceous fuel con­taining sulfur and having an ash comprising nickel, vanadium and silicon.
• a fuel feedstock comprising a heavy liquid hydrocarbonaceous fuel containing sulfur and having an ash comprising nickel, vanadium and silicon and/or a solid carbonaceous fuel con­taining sulfur and having an ash comprising nickel, vanadium and silicon.
• said feedstock includes a minimum of about 0.2 wt. % of sulfur, such as about 1.5 to 6.5 wt.
• said feedstock includes a minimum of about 0.5 ppm (parts per million) of nickel, such as about 2.0 to 4,000 ppm; a minimum of about 1.0 ppm of vanadium, such as about 20 to 2,000 ppm; and a minimum of about 5.0 ppm of silicon, such as about 5.0 to 10,000 ppm, or more.
• An additive system is provided which prevents the formation of toxic nickel subsulfide (Ni3S2) in slags generated during the partial oxidation of said feedstocks without raising the activity and pressure of sulfur-bearing gases e.g. H2S and COS. The cost of a downstream gas purification system is thereby minimized.
• the process includes the steps of (1) mixing together with said fuel feedstock a first additive comprising a silicon-containing material comprising from about 25 to 65 wt. % of silicon; wherein the wt. ratio of silicon in said first additive plus the silicon in said fuel feedstock to vanadium fuel feedstock is in the range of about 2 to 10; and including in said mixture a second addi­tive comprising a material selected from a group consisting of a copper-containing material, a cobalt-containing material, and mixtures thereof; whereby the ratios of copper to nickel, cobalt to nickel, and copper + cobalt to nickel when said metals are present in said mixture are in range of about 0.5 to 20; and the weight ratio of said second addi­tive to ash in said fuel feedstock is in the range of about 0.01 to 1.5; (2) reacting said mixture from (1) by partial oxidation with a free-oxygen containing gas in a reducing atmosphere and in the presence of a temperature moderator including H2O at a pressure in the range of about 2 to
• % of a silicate phase selected from the group consisting of a copper silicate phase, a cobalt silicate phase, and mixtures thereof and containing an element from the group consisting of Cu, Co, and mixtures thereof in the range of about 0.01 to 3.0 wt. % of said silicate phase; (iii) from about 1.8 to 12 wt. % of a spinel phase in which the following are present in wt.
• the remainder of the slag comprises a fluid oxysulfide phase comprising at least one sulfide from the group consisting of Cu, Co, Fe, and mixtures thereof, and wherein said slag contains substantially no Ni3S3 and there is a reduction in the mole ratio H2S + COS/H2 + CO in the raw effluent gas stream over said mole ratio when said partial oxidation reaction takes place in the absence of said first and second additives; and (3) separating non-­ gaseous materials containing substantially no Ni3S2 from said hot raw effluent gas stream.
• the gas generator is not shut down for slag removal.
• the subject process it is not necessary to oxidize the slag on the walls of the reaction zone in order to reduce the fusion temperature and viscosity.
• the molten slag substantially free from Ni3S2, flows by gravity to the bottom of the gas generator.
• a mixture of sulfur-containing heavy liquid hydrocarbonaceous fuel with a nickel, vanadium and silicon-containing ash, and said copper and/or cobalt-containing material, or said silicon-containing material, and copper and/or cobalt-containing material is fed to a coker to produce a sulfur-containing petroleum coke with a nickel, vanadium, and silicon-containing ash.
• the copper and/or cobalt-containing material, or the silicon-containing material and the copper and/or cobalt-containing material is uniformly dispersed throughout said petroleum coke. This petroleum coke is then reacted in the partial oxidation gas generator to produce synthesis gas, reducing gas, or fuel gas.
• One embodiment of this process comprises the following: a process for the production of gaseous mixtures comprising H2 + CO by the partial oxidation of a fuel feedstock comprising sulfur-containing petroleum coke having an ash comprising nickel, vanadium, and silicon; and said feedstock includes a minimum of about 0.5 ppm nickel, a minimum of about 0.2 wt. % of sulfur, a minimum of about 1.0 ppm of vanadium, and a minimum of about 5.0 ppm of silicon; said process comprising:
• these feed­stocks include a minimum of about 0.2 wt. % of sulfur, such as in the range of about 0.2 to 6.5 wt. % a minimum of about 0.5 ppm of nickel, such as in the range of about 2.0 to 4000 ppm; a minimum of about 1.0 ppm vanadium, such as in the range of about 20 to 5,000 ppm; a minimum of about 5.0 ppm of silicon, such as in the range of about 5.0 to 20,000 ppm, or more.
• sulfur-containing heavy liquid hydrocarbonaceous material or fuel having a nickel, vanadium, and silicon-containing ash is a petroleum or coal derived fuel selected from the group consisting of virgin crude, residue from petroleum distillation and cracking, petroleum distillate, reduced crude, whole crude, asphalt, coal oil, coal derived oil, shale oil, tar sand oil, and mixtures thereof.
• sulfur-containing petroleum coke having a nickel, vanadium, and silicon-containing ash is petroleum coke made from sulfur-containing heavy liquid hydrocarbonaceous fuel having a nickel, vanadium, and silicon-containing ash by conventional coke methods such as by the delayed or fluid coking process, such as described in coassigned U.S. Patent No. 3,673,080, which is incorporated herein by reference.
• ashes derived from the partial oxidation, without an additive, of a feedstock comprising sulfur-containing heavy liquid hydrocarbonaceous fuels and/or solid carbonaceous fuel having nickel, vanadium, and silicon-containing ashes show that they are largely composed of oxide-and sulfide compounds of nickel, vanadium, and silicon along with some normally occurring mineral matter species.
• the total ash content of heavy liquid hydrocarbonaceous fuel or petroleum coke may be only about one-half to 5 weight percent (wt. %), whereas coal typically contains 10-20 wt. % ash.
• One embodiment of this invention provides an improved copper and/or cobalt-containing additive system to prevent the formation of toxic nickel subsulfide (Ni3S2) in slags generated during the partial oxidation of sulfur, nickel, vanadium, and silicon-containing heavy liquid hydrocarbonaceous and/or petroleum coke feedstocks.
• Ni3S2 toxic nickel subsulfide
• Another advantage of the subject invention is the reduction in the activity, pressure, and concentration of sulfur-bearing gases e.g. H2S and COS. For example, the concentration.
• H2S + COS in the raw product gas stream from the partial oxidation gas generator may be reduced in the range of about 1 to 20 %, such as about 5 to 10%, by the subject invention, in comparison with the concentration of H2S + COS in the raw product gas stream as produced without the copper and/or cobalt-containing material.
• the cost of downstream, gas purification is thereby minimized.
• a means of introducing the copper and/or cobalt-containing material into the system to give maximum effectiveness is provided.
• the copper and/or cobalt-containing material comprises compounds of copper and/or cobalt, and preferably the oxides of copper and/or cobalt.
• Sufficient copper and/or cobalt-­containing material is introduced to provide a wt. ratio of copper and/or cobalt to nickel in the range of about 0.2 to 10, such as about 1 to 3, and the weight ratio of copper and/or cobalt to silicon in said mixture is in the range of about 0.0001 to 0.04, such as about .005 to 0.02. This ratio may be also expressed as 0.02 parts by wt. of copper and/or cobalt per part by wt. of nickel in the fuel feedstock.
• the partial oxidation reaction takes place at a pressure in the range of about 2 to 250 atmospheres, such as about 15 to 200 atmospheres, in a down-flowing free-flow unobstructed vertical reaction zone with refractory lined walls.
• the fuel feed is reacted by partial oxidaiton with a free-oxygen containing gas in a reducing atmosphere and in the presence of a temperature moderator.
• the temperature in the reaction zone is in the range of about 1800°F to 2900°F, such as about 2250°F to 2500°F.
• An equilibrium oxygen con­ centration is provided in the gas phase in the reaction zone with a partial pressure in the range of about 1.7 x 10 ⁇ 15 to 2.3 x 10 ⁇ 8 atmospheres; and an equilibrium sulfur concen­tration is provided in the gas phase with a partial pressure in the range of about 2.53 x 10 ⁇ 7 to 8.1 x 10 ⁇ 2 atmospheres.
• the free O/C atomic ratio is in the range of about 0.3 to 1.2, such as about 0.8 to 0 92; and the H2O/liquid hydrocarbonaceous fuel and/or solid carbonaceous fuel weight ratio is in the range of about 0.1 to 5.0, such as about 0.15 to 2.
• a hot raw effluent gas stream leaves the reaction zone comprising H2 + CO and entrained molten slag. About 90 to 99.9 wt. % of the carbon in said fuel feedstock is converted into carbon oxides.
• the copper and/or cobalt-containing material combines with at least a portion, such as substantially all or a large fraction e.g. about 40 to 100 wt. %, say about 70 to 90 wt. % of nickel, vanadium, silicon, and sulfur constituents found in the feedstock to produce molten slag comprising the following phases: (i) from about 0.1 to 10 wt. % of a Cu-Ni alloy phase and/or Co-Ni alloy phase, wherein the weight ratio of Cu and/or Co to Ni is in the range of about 0.2 to 0.9; (ii) from about 5 to 85 wt.
• a portion such as substantially all or a large fraction e.g. about 40 to 100 wt. %, say about 70 to 90 wt. % of nickel, vanadium, silicon, and sulfur constituents found in the feedstock to produce molten slag comprising the following phases: (i) from about 0.1 to 10 wt. % of a Cu-N
• the copper and/or cobalt-containing material may be selected on the basis of serendipitous catalytic properties in addition to its use in the generation of the washing and fluxing agent, as previously described. For example, it may act to produce more and/or a better quality of light products from the coker operation. It may also aid in the gasification reactions either by increasing the reaction rate and thus the throughput capacity of the gasifier or by increasing the conversion of the smooth and thus the overall efficiency of the process. Again, however, this invention does not depend on the catalytic properties of the copper and/or cobalt-containing material.
• the copper and/or cobalt-­containing material are mixed with the sulfur-containing heavy liquid hydrocarbonaceous material having a nickel, vanadium, and silicon-containing ash.
• the mixture is then fed into a conventional coking unit to produce petroleum coke.
• the finely ground copper and/or cobalt-containing material may be intimately mixed through­out the petroleum coke product.
• the comminuted copper and/or cobalt-containing material and the comminuted petroleum coke and mixtures thereof have a particle size so that 100% passes through a sieve of the size ASTM E-11 Standard Sieve Designation in the range of about 425 microns to 28 microns, or below.
• the ingredients of the aforesaid mixtures may be separately ground and then mixed together.
• the ingredients may be wet or dry ground together. Intimate mixing of the solid materials is thereby achieved, and the particle sizes of each of the solid materials in the mixture may be substantially the same.
• the dry ground mixture may be mixed with water or a liquid hydrocarbonaceous material or both to produce a pumpable slurry having a solids content in the range of about 50-65 wt. %.
• the solid materials may be wet ground with the liquid slurry medium.
• the mixture of particulate solids may be entrained in a gaseous medium and then introduced into the gas generator.
• the gas trans­port medium may be selected from the group consisting of steam, CO2, N2, free-oxygen containing gas, recycle synthesis gas, and mixtures thereof.
• the non-gaseous materials e.g. particulate carbon and slag may be separated from the hot effluent gas stream from the partial oxidation reaction zone by contact­ing the gas stream with water or an oil scrubbing medium.
• part of the sulfur in the feedstock e.g. about 1-20 wt. % may be converted into the oxysulfides of Cu and/or Co and Fe and leave the reaction zone in the slag.
• the copper and/or cobalt-containing material may be intro­duced directly into the ash-containing petroleum liquid feed to the vacuum distillation tower, which normally precedes the coker unit.
• substantially all of the copper and/or cobalt-containing material should stay behind in the desired bottoms streams. In other words there should be little, if any, carry over of the copper and/or cobalt-containing material with the lighter products.
• a possible advantage for mixing the additive with the vacuum tower feed stream in preference to the bottoms stream i. e. coker feed
• the feed to the vacuum tower is significantly less viscous than the bottoms from the vacuum tower. A more thorough mixing may be thereby effected.
• a mixture comprising a high boiling liquid petroleum i.e. sulfur-containing heavy liquid hydrocarbon­aceous fuel having a nickel, vanadium, and silicon-contain­ing ash and the comminuted copper and/or cobalt-containing material, at a temperature in the range of about 650°F is introduced into a delayed coking zone, for example by way of line 33, such as shown and described in coassigned U.S. Patent No. 3,673,080, which is incorporated herein be reference.
• uncondensed hydrocarbon effluent vapor and steam are removed overhead, and petroleum coke in admixture with copper and/or cobalt-containing material is removed from the bottom of said delayed coking zone.
• a mixture comprising a sulfur-­containing high boiling liquid petroleum having a nickel, vanadium, and silicon-containing ash and the comminuted copper and/or cobalt-containing material, at a temperature in the range of about 550°F to 750°F is introduced into a fluidized bed coking zone for example by way of line 31, such as shown and described in U.S. Patent No. 2,709,676, which is incorporated herein by reference.
• 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 effluent vapor and steam are removed overhead and said petroleum coke is removed from the bottom of said coking zone.
• the petroleum coke may be then ground to fuel size as previously described.
• this invention may be applied to other similar petroleum processes that produce a stream suitable for gasification. Any "bottom of the barrel" process that does not upgrade the bottoms or residue stream to extinction must ultimately produce such a stream. These streams, either liquid or normally solid but pumpable at elevated temperature, will produce the same gasification problems as discussed for coke.
• the invention of introducing copper and/or cobalt-containing material as part of the petroleum processing prior to gasification should, depending on the specific process, produce a feedstock that will be free of the gasification problems mentioned above.
• Most of these processes employ vacuum distillation as pretreatment. Accordingly, as described above, the copper and/or cobalt-containing material may be mixed with the vacuum distillation feed having a nickel, vanadium, and silicon ash.
• the bottoms stream is the feed stream for the upgrading process.
• This incorporation of the copper and/or cobalt-containing material should not adversely affect these process, and the addition agents should ultimately emerge with the nickel, vanadium, and silicon-containing residue stream from each respective process. In all of the processes, this residue stream should be suitable for gasification by partial oxidation.
• the partial oxidation gas generator is operated continuously for about 1 to 180 days while, accumulating slag on the walls of the reaction zone.
• the reaction is stopped and the gas generator is opened thereby oxidizing the slag on the walls of said gasifier.
• the fusion temperature of the slag is reduced to about 2000°F or below, and the viscosity is reduced.
• Molten slag containing substantially no Ni3S2 flows by gravity down the inside walls of the reaction zone.
• the hot molten slag may fall into quench water contained in a quench tank located in the bottom of the gas generator. See coassigned U.S. Patent 3,544,291, which is incorporated herein by reference.
• the molten slag may pass through a central outlet located in the bottom of the slag gas generator. See coassigned U.S. Patent 4,312,637, which is incorporated herein by reference.
• a major benefit of the subject process is to produce a smaller volume of slag, with a higher vanadium content e.g. in excess of about 2.0 wt. % of V. Accordingly, the slag is more attractive for sale to a reclaimer.
• Another embodiment of this invention provides an improved silicon-containing additive for improved slag removal from the gasifier plus a copper and/or cobalt-containing additive system to prevent the formation of toxic nickel subsulfide (Ni3S2) in slags generated during the partial oxidation of sulfur, nickel, vanadium, and silicon-containing heavy liquid hydrocarbonaceous and/or petroleum coke feedstocks.
• Ni3S2 toxic nickel subsulfide
• Another advantage of the subject invention is the reduction in the activity, pressure, and concentration of sulfur-bearing gases e.g. H2S and COS.
• the concentration of H2S + COS in the raw product gas stream from the partial oxidation gas generator may be reduced in the range of about 1 to 20%, such as about 5 to 10%, by the subject invention, in comparison with the concentration of H2S + COS in the raw product gas stream as produced without the copper and/or cobalt-containing material.
• the cost of downstream, gas purification is thereby minimized.
• a means of introducing the silicon-containing material and the copper and/or cobalt-containing material into the system to give maximum effectiveness is provided.
• the silicon-containing additive is a material selected from the group consisting of silicon, quartz, volcanic ash, and mixtures thereof.
• the silicon-containing material comprises at least from about 25 to 65 wt. % of silicon.
• Sufficient silicon-containing material is introduced into the reaction zone to provide a wt. ratio of silicon in said silicon-containing material plus the silicon in the feed­stock to vanadium in said fuel feedstock in the range of about 2 to 10.
• the copper and/or cobalt-containing material comprises compounds of copper and/or cobalt, and preferably the oxides of copper and/or cobalt.
• Sufficient copper and/or cobalt-­containing material is introduced in the reaction zone to provide a wt. ratio of copper and/or cobalt to nickel in the range of about 0.5 to 20, such as about 1 to 3, and the weight ratio of copper and/or cobalt to ash in said fuel feedstock is in the range of about 0.01 to 1.5.
• the wt. ratios copper and/or cobalt to nickel may be expressed as the ratios of copper to nickel, cobalt to nickel, and copper + cobalt to nickel. When said metals are present in said mixture said ratios are in the range of about 0.5 to 20.
• the partial oxidation reaction takes place at a pres­sure in the range of about 2 to 250 atmospheres, such as about 15 to 200 atmospheres, in a down-flowing free-flow unobstructed vertical reaction zone with refractory lined walls.
• the fuel feed is reacted by partial oxidaiton with a free-oxygen containing gas in a reducing atmosphere and in the presence of a temperature moderator.
• Typical tempera­ture moderators are selected from the group consisting of H2O, CO2, N2, cooled recycled product gas, and mixtures thereof.
• the temperature moderator usually includes H2O in a least one form.
• the temperature in the reaction zone is in the range of about 1800°F to 2900°F, such as about 2250°F to 2500°F.
• the free O/C atomic ratio is in the range of about 0.4. to 1.2, such as about 0.8 to 0.96, and the H2O/-­liquid hydrocarbonaceous fuel and/or solid carbonaceous fuel weight ratio is in the range of about 0.1 to 3.0, such as about 0.15 to 2.
• an equilibrium oxygen concen­tration is provided in the gas phase in the reaction zone with a partial pressure in the range of about 1.2 x 10 ⁇ 16 to 2.0 x 10 ⁇ 9 atmospheres; and an equilibrium sulfur concen­tration is provided in the gas phase with a partial pressure in the range of about 1.7 x 10 ⁇ 6 to 1.1 x 10 ⁇ 4 atmospheres.
• a hot raw effluent gas stream leaves the reaction zone comprising H2 + CO and entrained molten slag. About 90 to 99.9 wt. % of the carbon in said fuel feedstock is converted into carbon oxides.
• the first additive comprising the silicon-con­taining material and the second additive comprising the copper and/or cobalt-containing material combine with at least a portion, such as substantially all or a large fraction e.g. about 40 to 100 wt. %, say about 70 to 90 wt. % of the nickel, vanadium, silicon, and sulfur constituents and other components of the ash to produce slag comprising the following phases in wt. %: (i) from about 0.0005 to 1.5 wt.
• % of an alloy phase selected from the group consisting of a Cu-Ni alloy phase, a Co-Ni alloy phase, a Cu-Fe alloy phase, and mixtures thereof and wherein the weight ratios of Cu and/or Co to Ni when present in the alloy phase are in the range of about 1 to 10; (ii) from about 45 to 97 wt. % of a silicate phase containing an element from the group consisting of Cu, Co, and mixtures thereof in the range of about 0.01 to 3.0 wt. % of said silicate phase; (iii) from about 1.8 to 12 wt. % of a spinel phase in which the follow­ing are present in wt.
• the remaind­er of the slag e.g. about 0 to 5 wt. % comprises a fluid oxysulfide phase comprising at least one sulfide from the group consisting of Cu, Co, Fe, and mixtures thereof; and wherein there is a reduction e.g. about 1 to 20 % in the mole ratio H2S + COS/H2 + CO in the raw effluent gas stream over said mole ratio when said partial oxidation reaction takes place in the absence of said first and second addition agents. Further, the formation of toxic Ni3S2 is thereby prevented.
• Non-gaseous materials containing substantially no Ni3S2 are separated by conven­tional means from the hot raw effluent gas stream. The sulfur potential in the gas, and the downstream gas cleaning costs may be reduced.
• the composition of the hot, raw effluent gas stream directly leaving the reaction zone of the free-flow partial oxidation gas generator is about as follows, in mole per­cent: H2 10 to 70, CO 15 to 57, CO2 0.1 to 25, H2O 0.1 to 20, CH4 nil to 60, H2S nil to 3, COS nil to 0.1 H2 nil to 60, and Ar nil to 2.0.
• Particulate carbon is present in the range of about 0.2 to 20 weight % (basis carbon content in the feed).
• Ash is present in the range of about 0.5 to 5.0 wt. %, such as about 1.0 to 3.0 wt. % (basis total weight of fuel feed).
• the gas stream may be employed as synthesis gas, reducing gas or fuel gas.
• the silicon-­containing material, and the copper and/or cobalt-containing materials may be selected on the basis of serendipitous catalytic properties in addition to their use in the genera­tion of washing and fluxing agents, for vanadium and nickel. For example, they may act to produce more and/or a better quality of light products from the coker operation. They may also aid in the gasification reactions either by in­creasing the reaction rate and thus the throughput capacity of the gasifier or by increasing the overall efficiency of the process. Again, however, this invention does not depend on the catalytic properties of the silicon-containing material, and the copper and/or cobalt-containing material.
• a preferred copper and/or cobalt-containing material for mixing with the sulfur-containing heavy liquid hydrocarbonaceous material having a nickel, vanadium, and silicon-containing ash or sulfur-containing solid carbonaceous fuel having a nickel, vanadium, and silicon-containing ash comprises compounds of copper and/or cobalt selected from the group consisting of oxides, sulfide, sulfate, carbonate, cyanide, chloride, nitrate, hydroxide, ferro or ferri cyanide, phosphate and mixtures thereof.
• the copper and/or cobalt-containing material is an organic compound selected from the group consisting of naphthenate, oxalate, acetate, citrate, benzoate, oleate, tartrate, butyrate, formate and mixtures thereof.
• the copper and/or cobalt-containing material may comprise about 30.0 to 100 wt. % of the compounds of copper and/or cobalt.
• the supplemental copper and/or cobalt-containing material may comprise any of the following: (1) inorganic or organic compounds of copper; (2) concentrated copper ore comprising at least 20 wt.
• % of copper % of copper
• concentrated copper ore comprising a mixture of the sulfides of copper, copper-iron, and iron and with a small amount of gangue minerals
• copper sulfide and/or copper oxide minerals (5) copper sulfide minerals selected from the groups consisting of bornite, chalcopyrite, tetrahedrite, tennentite, chalcocite, covellite, digenite and mixtures thereof; and (6) copper oxide minerals selected from the group consisting of cuprite, tenorite, malachite, azurite, brochantite, atacamite, chrysocolla and mixtures thereof.
• a mixture comprising the aforesaid fuel feedstock comprising sulfur-containing heavy liquid hydrocarbonaceous fuel having a nickel, vanadium and silicon-containing ash and/or the sulfur-containing solid carbonaceous fuel having a nickel, vanadium, and silicon-containing ash, and the silicon-con­taining material, and the copper and/or cobalt-containing material are introduced into the partial oxidation gasifier.
• the fuel feedstock to the subject process comprises a pumpable slurry of petroleum coke in water, liquid hydrocarbon fuel, or mixtures thereof.
• the silicon-containing material, and the copper and/or cobalt-containing material are mixed with the sulfur-containing heavy liquid hydrocar­bonaceous material having a nickel, vanadium, and silicon-­containing ash.
• the mixture is then fed into a conventional coking unit to produce petroleum coke.
• the finely ground silicon-containing material, and the copper and/or cobalt-containing material may be intimately mixed throughout the petroleum coke product.
• the comminuted silicon-containing material, and copper and/or cobalt-con­taining material and the comminuted petroleum coke and mixtures thereof have a particle size so that 100% passes through a sieve of the size ASTM E-11 Standard Sieve Desig­nation in the range of about 425 microns to 28 microns, or below.
• the ingredients of the aforesaid mixtures may be separately ground and then mixed together. Alternatively, the ingredients may be wet or dry ground together. Intimate mixing of the solid materials is thereby achieved, and the particle sizes of each of the solid materials in the mixture may be substantially the same.
• the dry ground mixture may be mixed with water or a liquid hydrocarbonaceous material or both to produce a pumpable slurry having a solids content in the range of about 50-65 wt. %.
• the solid materials may be wet ground with the liquid slurry medium.
• the mixture of particulate solids may be entrained in a gaseous medium and then introduced into the gas generator.
• the gas transport medium may be selected from the group consisting of steam, CO2, N2, free-oxygen containing gas, recycle synthesis gas, and mixtures thereof.
• the non-gaseous materials e.g.
• particulate carbon and slag may be separated from the hot effluent gas stream from the partial oxidation reaction zone by contacting the gas stream with water or an oil scrubbing medium.
• part of the sulfur in the feedstock e.g. about 1-20 wt. % may be converted into the oxysulfides of Cu and/or Co and Fe and leave the reaction zone in the slag.
• the silicon-containing material, and the copper and/or cobalt-containing material may be introduced directly into the ash-containing petroleum liquid feed to the vacuum distillation tower, which normally precedes the coker unit. In either unit operation (coking or distillation), substantially all of the silicon-contain­ing material, and the copper and/or cobalt-containing material should stay behind in the desired bottoms streams.
• a possible advantage for mixing the additive with the vacuum tower feed stream in preference to the bottoms stream is that the feed to the vacuum tower is signifi­cantly less viscous than the bottoms from the vacuum tower. A more thorough mixing may be thereby effected.
• a mixture comprising a high boiling liquid petroleum i.e. sulfur-containing heavy liquid hydrocarbon­aceous fuel having a nickel, vanadium, and silicon-contain­ing ash and the comminuted silicon-containing material, and the copper and/or cobalt-containing material, at a tempera­ture in the range of about 650°F is introduced into a delayed coking zone, for example by way of line 33, such as shown and described in coassigned U.S. Patent Ho. 3,673,080, which is incorporated herein be reference.
• uncondensed hydrocarbon effluent vapor and steam are removed overhead, and petroleum coke in admixture with the silicon-containing material, and the copper and/or cobalt-containing material are removed from the bottom of said delayed coking zone.
• a mixture comprising a sulfur-­containing high boiling liquid petroleum having a nickel, vanadium, and silicon-containing ash and the comminuted silicon-containing material, and the copper and/or cobalt-­containing material, at a temperature in the range of about 550°F to 750°F is introduced into a fluidized bed coking zone for example by way of line 31, such as shown and described in U.S. Patent No. 2,709,676, which is incorpor­ated herein by reference.
• 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 effluent vapor and steam are removed overhead and said petroleum coke is removed from the bottom of said coking zone.
• the petroleum coke may be then ground to fuel size as previously describ­ed.
• this invention may be applied to other similar petroleum processes that produce a stream suitable for gasification. Any "bottom of the barrel” process that does not upgrade the bottoms or residue stream to extinction must ultimately produce such a stream. These streams, either liquid or normally solid but pumpable at elevated temperature, will produce the same gasification problems as discussed for coke.
• the invention of introducing the silicon-containing material, and the copper and/or cobalt-containing material as part of the petroleum processing prior to gasification should, depending on the specific process, produce a feedstock that will be free of the gasification problems mentioned above. Most of these processes employ vacuum distillation as pretreatment.
• the silicon-containing material, and the copper and/or cobalt-containing material may be mixed with the vacuum distillation feed having a nickel; vanadium, and silicon ash.
• the additives will than emerge from the distillation column highly dispersed in the bottoms stream.
• the bottoms stream is the feed stream for the upgrading process.
• This incorporation of the silicon-containing material, and the copper and/or cobalt-­containing material should not adversely affect these processes and the addition agents should ultimately emerge with the nickel, vanadium, and silicon-containing residue stream from each respective process. In all of the pro­cesses, this residue stream should be suitable for gasifica­tion by partial oxidation.
• a major benefit of the subject process is to produce a smaller volume of slag, with a higher vanadium content e.g. in excess of about 2.0 wt. % of V. Accordingly, the slag is more attractive for sale to a reclaimer.

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• 1989
  • 1989-07-19 EP EP89307334A patent/EP0364074A1/fr not_active Withdrawn
  • 1989-09-11 CA CA000610907A patent/CA1328737C/fr not_active Expired - Fee Related
  • 1989-09-12 JP JP23484489A patent/JPH02180991A/ja active Pending

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