CA1328737C

CA1328737C - Prevention of formation of nickel subsulfide in partial oxidation of heavy liquid and/or solid fuels

Info

Publication number: CA1328737C
Application number: CA000610907A
Authority: CA
Inventors: Mitri Salim Najjar
Original assignee: Texaco Development Corp
Current assignee: Texaco Development Corp
Priority date: 1988-09-12
Filing date: 1989-09-11
Publication date: 1994-04-26
Anticipated expiration: 2011-04-26
Also published as: EP0364074A1; JPH02180991A

Abstract

PREVENTION OF FORMATION OF NICKEL SUBSULFIDE IN PARTIAL
OXIDATION OF HEAVY LIQUID AND/OR SOLID FUELS
(D#79.140 -F) ABSTRACT

A sulfur-containing heavy liquid hydrocarbonaceous fuel and/or solid carbonaceous fuel with a nickel, vanadium, and silicon containing ash is mixed with a silicon-containing material, and a copper and/or cobalt-containing material.
The mixture is reacted by partial oxidation in a down-flow-ing free-flow unobstructed vertical reaction zone with refractory lined walls at a temperature in the range of about 1800°F to 2900°F. A raw effluent gas stream is produced comprising H2+CO and containing entrained slag comprising the following phases; (i) an alloy phase selected from the group consisting of Cu-Ni, Co-Ni, Cu-Fe, and mixtures thereof; (ii) a silicate phase selected from the group consisting of copper silicate, cobalt silicate, and mixtures thereof; (iii) a spinel phase; and (iv) a fluid oxysulfide phase comprising at least one sulfide from the group consisting of Cu, Co, Fe, and mixtures thereof. There is a reduction in the mole ratio H2S+COS/H2+CO in the raw effluent gas stream. Non-gaseous materials e.g. slag containing substantially no Ni3S2 are separated from the hot raw effluent gas stream from the gasifier.

Description

- 1 3 2 8 7 3 7 60~88-2833 PREVENTION OF FORMATION OF NICKEL SUBSULFIDE IN PARTIAL
- OXIDATION OF HEAVY_LI9UID AND/OR SOLID FUELS

FIELD OF THE INVENTION
Thls inventlon relates to a process for the partlal oxldatlon of a sulfur-contalnlng heavy liquid hydrocarbonaceous or solld carbonaceous fuel havlng a nlckel, vanadlum, and slllcon-contalning ash to produce gaseous mlxtures comprlslng H2 + CO and entralned molten slag. More partlcularly, lt pertalns to an addl-tlve system for preventlng the formatlon of toxlc N13S2 ln sald molten slag.
The partlal oxldatlon of llquld hydrocarbonaceous fuels such as petroleum products and slurries of solld carbonaceous . ~ , fuels such as coal and petroleum coke are well known processes.
The foreseeable trend of petroleum reserves ls that the produced crude wlll be lncreaslngly heavler and of poorer quallty. To compensate for thls trend, reflners must employ more "bottom of the barrel" upgradlng to provlde the deslred light products. The current lndustry workhouse to provlde thls upgradlng is some type . ., of coking operatlon (either delayed or fluld). A good deal of current reflnery expanslon lncludes the lnstallatlon or expanslon of coker unlts, and thls, coklng will be a process of general use for some time to come.
A ma~or drawback for coklng ls the dlsposal of the pro-- duct coke. Wlth a reasonably clean coker feed, the product coke has been substltuted for appllcatlons requiring relatively pure carbon, such as for electrode manufacture. Wlth the feed crudes becomlng poorer, there are compoundlng factors affectlng coker operatlons. Slnce the crudes contaln more contamlnants, l.e.
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, 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. Further, because the crudes are heavier, i.e, contain more coke precursors, more of this poorer quality coke is produced from each barrel of ash-containing heavy liquid hydrocarbonaceous fuel. The manufacture of petroleum coke pellets by a delayed coking process is described in co-assigned U.S. Patent No. 2,709,676.
The Texaco partial oxidation gasification process offers an alternative processing route for use of the coke or the ash-containing heavy liquid hydrocarbonaceous fuel.
For example, water slurries of petroleum coke are reacted by partial oxidation in coassigned U.S. Patent No. 3,607,157.
~asification 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 expect-ed rise in energy costs and legislation requiring total use of feed crude should shortly bring about a greater utiliza-tion of petroleum coke feeds to the partial oxidation gas generator.
Previous gasification runs with delayed coke and heavy liquid hydrocarbonaceous fuel gave rise to some unexpected ; 25 operating problems. For example, a very fine intergrowth of toxic nickel subsulfide (Ni3S2) was found in slag produced by the partial oxidation of sulfur-containing heavy liquid hydrocarbonaceous fuels and/or petroleum coke with said fuels having a nickel, vanadium and silicon-containing ash.
Further, the ash which normally melts and is discharged from the gasifier as a slag, was not melting completely and being discharged. Instead, it was building up on the walls of the refractory. Nickel impurities may under certain condition form troublesome nickel carbonyl deposits downstream in the system. In coassigned U.S. Patent No. 4,671,804, large amounts of iron-containing additives were used and problems .- '~ ' ' ' -~- 1328737 with nickel subsulfide were avoided. However, the amount of -~ slag produced and slag disposal costs were increased.
Further, iron oxide may contribute to the formation of increased amounts of silicate crystals that can have delet-erious effects on the slag flow properties. In coassigned u.s. Patent No . 4, 654 ,164, all of the sulfur forms a copper oxysulfide washing agent that collects and transports at ~east a portion of the vanadium and other ash components out of the reaction zone. In coassigned U.S. Patent No.
4,732,700, a slag separation chamber was provided after the gasifier for collecting on its walls a portion of the slag entrained in the process gas stream. 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.
In the subject invention, a first silicon-containing ` 20 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. It was - unexpectedly found that by the addition of the copper and/or cobalt-containing materials with the fuel feed, as provided by the subject invention, the equilibrium is shifted away from the Ni3S2 field. This is an improvement in the art since it permits operation of the partial oxidation gas generator without the production of ash containing toxic nickel subsulfide.

`` 132~737 SUMMARY OF THE INVENTION
This is a process for the production of gaseous mix-tures 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 con-; ~ taining sulfur and having an ash comprising nickel, vanadium and silicon. Further, said feedstock includes a minimum of about 0.2 wt. % of sulfur, such as about 1.5 to 6.5 wt. %;
and 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 ; 25 feedstock to vanadium fuel feedstock is in the range of about 2 to 10; and including in said mixture a second addi-tive 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 addi-tive 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 3~ oxidation with a free-oxygen containing gas in a reducing atmosphere and in the presence of a temperature moderator '' ' :

including H20 at a pressure in the range of about 2 to 250 atmospheres in a down-flowing free-flow unobstructed verti-cal reaction zone with refractory lined walls of a partial -` oxidation gas generator and at a temperature in the range of about 1800~F to 2900F, the free 0/C atomic ratio is in the range of about 0.4 to 1.2, the H20/solid hydrocarbonaceous - fuel and/or solid carbonaceous fuel weight ratio is in the range of about 0.1 to 3.0; thereby producing a hot raw effluent gas stream comprising H2 + CO and entrained slag;
and converting about 90 to 99.9 wt. % of the carbon in said fuel feedstock into carbon oxides; and said first and second additives combine with at least a portion of said nickel, vanadium, silicon, and sulfur constituents, and other components of the ash to produce slag comprising the follow-; 15 ing phases in wt. %: (i) 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 to Ni, ;~ Co to Ni, and mixtures of Cu + C0 to Ni when present in said alloy phases are in the range of about 1 to 20; (ii) from about 45.0 to 97 wt. % 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 1.3 to 12 wt. % of a spinel phase in which the following are present in wt. %: V 5-60, Fe 7-65, Al 0.1-40, Mg 0.1-35, Cr 0.01-42, and others ~ 0.1-10; and (iv) the remainder of the slag comprises a fluid - 30 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 + C0 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-.

`~ `` 1328737 gaseous materials containing substantially no Ni3S3 from said hot raw effluent gas stream.
Unlike other partial oxidation processes, after from about 1-180 days of operating by the subject process, the gas generator is not shut down for slag removal. Advantage-ously, by 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. In the subject process, the molten slag, substantially free from Ni2S3, i 10 flows by gravity to the bottom of the gas generator.In another embodiment, a mixture of sulfur-containing heavy liquid hydrocarbonaceous fuel with a nickel, vanadium , and silicon-containing ash, and said (1) silicon-containing ; material, and (2) copper and/or cobalt-containing materialis fed to a coker to produce a sulfur-containing petroleum coke with a nickel, vanadium, and silicon-containing ash.
The silicon-containing material and the copper and/or ~- cobalt-containing material are uniformly dispersed through-~ out said petroleum coke. This petroleum coke is then ; 20 reacted in the partial oxidation gas generator to produce -~ synthesis gas, reducing gas, or fuel gas. 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 about 0.5 ppm to 4 ! ppm of nickel, a minimum of about 0.2 wt. % of sulfur, about 1.0 ppm to 2,000 ppm of vanadium, and about 5 ppm to 10,000 ppm of silicon;
said process comprising: (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 feed-stock in said is in the range of about 2 to 10; and includ-ing in said mixture a second additive comprising a material . ` . . '', ' ~`- 132~737 selected from the 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 ~ feedstcok is in the range of about .01 to 1.5; (2) coking said mixture from step (1) to produce sulfur-containing petroleum coke having a nickel, vanadium, and silicon-con-taining ash and having dispersed therein said silicon-con-taining material and copper and/or cobalt-containing mater-ial; (3) introducing the petroleum coke from step (2) into ` a free-flow refractory lined partial oxidation reaction zone as a pumpable slurry of pulverized petroleum coke in water, liquid hydrocarbonaceous fluid or mixtures thereof, or as substantially dry pulverized petroleum coke entrained in a : gaseous transport medium; (4) reacting said slurry of :~ petroleum coke from step (3) by partial oxidation with a free-oxygen containing gas in a reducing atmosphere and in the presence of a temperature moderator including H20 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 of a partial oxidation gas generator and at a temperature in the range of about 1800F
to 2sO0F, and 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 x10-9 atmospheres; an equilibrium sulfur concentration is provided in the gas phase in the reaction zone with a partial pressure in the range of about 1.7 x 1o-6 to 1.1 x 10-4 atmospheres, the free o/c atomic ratio is in the range of about 0.4 to 1.2, the H2O/liquid hydrocarbonaceous fuel and/or solid carbonaceous fuel weight ratio is in the range ; of about 0.1 to 3.0; thereby producing a hot raw effluent gas stream comprising H2 + C0 and entrained slag; and converting about 90 to 99.9 wt. % of the carbon in said fuel :
~ 1 3 2 ~ 7 3 7 60288-2833 feedstock lnto carbon oxldes; and where ln sald reactlon zone sald :'~
slllcon-contalnlng materlal and copper and/or cobalt-contalnlng materlal comblne with at least a portlon of sald nlckel, vanadlum, ; slllcon, and sulfur constltuents, and other components of the ash to produce slag comprlslng the followlng phases ln wt. %: (i) about 0.0005 to 1.5 wt. % of an alloy phase selected from the group conslstlng of a Cu-Nl alloy phase, a Co-Nl alloy phase, a , - Cu-Fe alloy phase, and mlxtures thereof, whereln the welght ratlo . . ' of Cu to Nl, Co to Nl, and mlxtures of Cu + Co to Nl when present ln sald alloy phases are ln the range of about 1 to 10; (11) from about 45.0 to 97 wt. % of a slllcate phase selected from the group conslstlng of a copper slllcate phase, a cobalt slllcate phase, and mlxtures thereof, and sald slllcate phase contalns an element from the group conslstlng of Cu, Co, and mlxtures thereof ln the amount ln the range of about 0.01 to 3.0 wt. % of sald slllcate phase; (111) from about 1.8 to 12 wt. % of a splnel phase ln whlch the followlng are present ln wt. %: V 5-60, Fe 7-65, Al 0.1-40, Mg 0.1-35, Cr 0.01-42, and others 0.1-10; and (lv) the remalnder of the slag comprlses a fluld oxysulfide phase comprlslng at least i 20 one sulflde from the group conslstlng of Cu, Co, Fe, and mlxtures - thereof; and whereln sald slag contalns substantlally no N13S2 and ,~ there ls a reductlon in the mole ratlo H2S + COS/H2 ~ CO ln the raw effluent gas stream over sald mole ratlo when sald partlal oxldatlon reactlon takes place in the absence of sald silicon-contalnlng material, and Cu and/or Co-contalnlng materlals; and (5) separatlng non-gaseous materlals contalnlng substantlally no N13S2 from sald hot raw effluent gas stream.

' ` 1 3 2 8 7 3 7 60288-2833 DISCLOSURE OF THE INVENTION
Processes for the partlal oxldatlon of heavy llquld hydrocarbonaceous fuel and petroleum coke are descrlbed respect-lvely in coasslgned U.S. Patent Nos. 4,411,670 and 3,607,156.
Further, sultable free-flow refractory lined gas generators and burners that may be used in the sub~ect process for the productlon of synthesis gas, reduclng gas, or fuel gas from these materlals are also descrlbed ln the aforesald references. Advantageously, the sub~ect process uses relatlvely lnexpenslve fuel feedstocks comprlslng sulfur-contalnlng heavy llquld hydrocarbonaceous fuel and/or petroleum coke feedstocks wlth sald materlals havlng a nlckel, vanadlum, and slllcon-containlng ash. The expresslon "and~or" as used hereln means either one or both of the ltems or ma~erlals speclfled~ Further, these feedstocks lnclude a mlnlmum of about 0.2 wt. % of sulfur, such as ln the range of about 0.2 to 6.5 wt. ~; a mlnlmum of about 0.5 ppm of nlckel, such as ln the range of about 2.0 to 4000 ppm; a mlnimum of about 1.0 ppm van-adium, such as in the range of about 1.0 to 2,000 ppm; a mlnlmum of about 5.0 ppm of slllcon, such as ln the range of about 5.0 to ~ ~, 10,000 ppm.
By deflnltlon, the term sulfur-contalnlng heavy llquld hydrocarbonaceous materlal or fuel havlng a nlckel, vanadlum, and sllicon-containlng ash is a petroleum or coal derived fuel selec-ted from the group consisting of vlrgin crude, resldue from petro-leum dlstlllatlon and cracklng, petroleum dlstlllate, reduced crude, whole crude, asphalt, coal tar, coal derlved oll, shale oll, tar sand oll, and mlxtures thereof.

. ~y deflnltlon, the term sulfur-containlng petroleum coke havlng a nickel, vanadlum, and sillcon-contalnlng ash ls petroleum coke made from sulfur-containlng heavy llquld hydrocarbonaceous fuel havlng a nlckel, vanadlum, and slllcon-contalnlng ash by con-ventlonal coklng methods such as by the delayed or fluld coklng process, such as descrlbed ln coassigned U.S. Patent No.
3,673,080.
Closer study of the ashes derlved from the partlal oxldation, wlthout an addltlve, of a feedstock comprlslng sulfur-contalning heavy llquld hydrocarbonaceous fuels :

' .
;~

, ~, ' ' , ~ ~32~737 and/or solid carbonaceous fuel having nickel, vanadium, and silicon-containing ashes shows that they are largely com-posed 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.
It is theorized that in the heavy liquid hydrocarbon-aceous material and petroleum coke systems, a good deal of the ash material is liberated as individual molecular species. This is because upon vacuum distillation or coking, the metallic species in the crude, which are gener-ally presented as porphyrin type structures (metal atoms, oxides or ions thereof confined in an organic framework), are entrapped within the collapsed carbon matrix.
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 hydrocarbon-; aceous and/or petroleum coke feedstocks. Without the subject invention, there may be about 0.1 to 5.0 wt. % of troublesome toxic nickel subsulfide in the slag. 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 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. Further, a means of introducing the silicon-containing material and the copper - 1~2~7~7 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,5¦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 feed-; 10 stock 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.
,j 20 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 pres-sure 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 tempera-ture moderators are selected from the group consisting of H20, C02, 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 1800F to 2900F, such as about 2250F
to 2500F. 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 tha range of about 0.1 to 3.0, such as about 0.15 to 2. Preferably, an equilibrium oxygen concen-~ 5 tration 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 concen-- tration 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.
In the reaction zone of the partial oxidation gas generator, the first additive comprising the silicon-con-taining 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.
; 20 % 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 O.OOOS 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 follow-ing are present in wt. %: V 5-60, Fe 7-65, Al 0.1-40, Mg 0.1-35, Cr 0.01-42, and others 0.1-10; and (iv) the remaind-er 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 + C0 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. Advantageously, by the subject invention there is substantially no e.g. less than about 0.001 wt. ~ of nickel subsulfide in the slag. Non~gaseous materials containing substantially no Ni3S2 are separated by conven-tional 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 per-cent: H2 10 to 70, C0 15 to 57, C02 0.1 to 25, H20 0.1 to 20, CH4 nil to 60, H2S nil to 3, COS nil to 0.1 N2 nil to 60, and Ar nil to 2Ø 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). Depending on the composition after removal of the entrained particulate carbon and ash by quench cooling and/or scrubbing with water or an oil scrubbing medium, and with or without dewatering, the gas stream may be employed -~ as synthesis gas, reducing gas or fuel gas.
Another aspect of this invention is that 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 genera-tion 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 in-creasing 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.
It was unexpectedly found that 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 i mixtures thereof. In another embodiment 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 com-pounds 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; (3) concentrated copper ore comprising a mixture of the sulfides of copper, copper-iron, and iron with a small amount of gangue minerals; (4) copper sulfide and/or copper oxide minerals; (5) copper sulfide minerals selected from the groups consisting of bornite, chalcopyrite, tetrahed-rite, tennentite, chalcocite, covellite, digenite and mixtures thereof; and (6) copper oxide minerals selected ; 30 from the group consisting of cuprite, tenorite, malachite, azurite, brochantite, atacamite, chrysocolla and mixtures thereof.
In the preferred embodiment of the subject invention, 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 ,~ ' ' ' , ' - 1~28737 sulfur-containing solid carbonaceous fuel having a nickel, vanadium, and silicon-containing ash, and the silicon-con-taining material, and the copper and/or cobalt-containing material are introduced into the partial oxidation gasifier.
In another embodiment, the fuel feedstock to the subject process comprises a pumpable slurry of petroleum coke in - water, liquid hydrocarbon fuel, or mixtures thereof.
In still another embodiment, the silicon-containing ;- material, and the copper and/or cobalt-containing material are mixed with the sulfur-containing heavy liquid hydrocar-bonaceous material having a nickel, vanadium, and silicon-containing ash. The mixture is then fed into a conventional coking unit to produce petroleum coke. By this means, 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-con-taining 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 Desig-B nation in the range of about 425 microns to ~ 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. %. Alternatively, the solid materials may be wet ground with the liquid slurry medium.
Alternatively, 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.

,. ' ~. .

In one embodlment of this proces , the non-gaseous materlals e.g.
partlculate carbon and slag may be separated from the hot effluent gas stream from the partlal oxldatlon reactlon zone by contactlng the gas stream wlth water or an oll scrubblng medlum.
Advantageously, part of the sulfur ln the feedstock e.g. about 1-20 wt. % may be converted lnto the oxysulfldes of Cu and/or Co and Fe and leave the reactlon zone in the slag.
In the embodlment whereln ground slllcon-contalnlng materlal, and the copper and/or cobalt-contalnlng materlal 19 mlxed wlth the sulfur-contalnlng heavy llquld hydrocarbonaceous fuel havlng a nickel, vanadlum, and slllcon-contalnlng ash and fed - lnto a coker, the slllcon-contalnlng materlal, and the copper and/or cobalt-contalnlng materlal may be lntroduced dlrectly lnto the ash-contalnlng petroleum llquld feed to the vacuum dlstlllatlon tower, whlch normally precedes the coker unlt. In elther unlt operatlon ~coklng or dlstlllatlon), substantlally all of the sllicon-contalnlng materlal, and the copper and/or cobalt-contalnlng materlal should stay behlnd ln the deslred bottom streams. In other words there should be llttle, lf any, carry over of the sllicon-contalnlng materlal, and the copper and/or cobalt-contalnlng materlal wlth the llghter products. A posslble advantage for mlxlng the addltlve wlth the vacuum tower feed ~tream ln preferene to the bottoms stream (l.e. coker feed) is that the feed to the vacuum tower ls slgnlflcantly less vlscous than the bottom from the vacuum tower. A more thorough mlxlng may be thereby effected.

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-In another embodlment, the fuel feedstock contalns about 0.2 to 6.5 wt. % of sulfur and about 10.0 to 5,000 ppm of slllcon or more, and the molten ~lag produced ln step ~2) comprl~es ln wt.

% about 0 to 5 wt. % of sald oxysulflde phase, and at least about 0.1 to 1.0 wt % of sald Cu-Nl alloy phase.

For example, a mlxture comprl~lng a hlgh bolllng llquld .
petroleum l.e. sulfur-contalnlng heavy llquld hydrocarbonaceous fuel havlng a nlckel, vanadlum, and slllcon-contalnlng ash and the commlnuted sillcon-containing materlal, and the copper and/or cobalt-contalnlng materlal, at a temperature ln the range of about 650F to 930F ls lntroduced lnto a delayed coklng zone, for example by way of llne 33, such as shown and descrlbed ln ~ coasslgned U.S. Patent No. 3,673,080, :`

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1 3 2 8 7 3 7 60288-28~3 At a temperature ln the range of about 800F to 895F and a pressure ln the range of about 20 to 60 pslg, uncondensed hydrocarbon effluent vapor and steam are removed overhead, and petroleum coke in admlxture wlti.
the slllcon-contalnlng materlal, and the copper and/or cobalt-~ contalnlng materlal are removed from the bottom of sald delayed ; coklng zone.
In another embodlment, a mlxture comprlslng a sulfur-contalnlng hlgh bolllng llquld petroleum havlng a nlckel, van-` 10 adlum, and slllcon-contalnlng ash and the commlnuted slllcon-contalnlng materlal, and the copper and/or cobalt-contalnlng ~; materlal, at a temperature ln the range of about 550F to 750F ls ,~
introduced into a fluidlzed bed coking zone for example by way of line 31, such as shown and described in U.S. Patent No. 2,709,676.
At a temperature ln the range of about 1000F to 1200F. and a pressure ln the range of about 10 to 20 pslg, uncondensed hydro-carbon effluent vapor and steam are removed overhead and sald petroleum coke ls removed from the bottom of sald coklng zone.
The petroleum coke may be then ground to fuel slze as prevlously descrlbed.
In other embodlments, thls lnventlon may be applled to other slmllar petroleum processes that produce a stream sultable for gaslflcatlon. Any "bottom of the barrel" process that does not upgrade the bottoms or resldue stream to extlnctlon must ultl-mately produce such a stream. These streams, elther llquid or normally solld but pumpable at elevated temperature, wlll produce the same gaslflcatlon problems as dlscussed for coke. Thus, the .,, ~
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~ 3 2 8 7 3 7 60288-2833 lnventlon of introducing the slllcon-contalning material, and the copper and/or cobalt-contalnlng material as part of the petroleum processlng prlor to gasification should, depending on the speclfic process, produce a feedstock that wlll be free of the gaslflcation problems mentloned above. Most of these processes employ vacuum dl:tll~Eltlon a~ pretreatment.

.

., '', '' i.l : ~ ~ 17a 132~37 .-Accordingly, as described above, 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. In turn, 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 pro-cesses, this residue stream should be suitable for gasifica-tion 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.
- Various modifications of the invention as herein before set forth may be made without departing from the spirit and scope thereof, and therefore, only such limitations should be made as are indicated in the appended claims.

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Claims

1. A process for the production of gaseous mixtures com-prising H2 + CO by the partial oxidation of a fuel feedstock comprising sulfur-containing heavy liquid hydrocarbonaceous fuel and/or solid carbonaceous fuel, and said fuels having nickel, vanadium and silicon-containing ashes, and said feedstock includes a minimum of about 0.5 ppm to 4,000 ppm of nickel, a minimum of about 0.2 wt. % of sulfur, about 1.0 ppm to 2000 ppm of vanadium, and about 5 ppm to 10,000 ppm silicon; said process comprising:

(1) mixing together with said fuel feedstock a first addi-tive comprising 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 in said fuel feedstock in said mixture is in the range of about 2 to 10; and including in said mixture a second additive comprising a material selected from the 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 .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 250 atmospheres in a down-flowing free-flow unobstructed vertical reaction zone with refractory lined walls of a partial oxidation gas generator and at a temperature in the range of about 1800°F
to 2900°F, the free O/C atomic ratio is in the range of about 0.4 to 1.2, the H2O/solid hydrocarbonaceous fuel and/or solid carbonaceous fuel weight ratio is in the range of about 0.1 to 3.0; thereby producing a hot raw effluent gas stream comprising H2 + CO and entrained slag; and converting about 90 to 99.9 wt. % of the carbon in said fuel feedstock into carbon oxides; and said first and second additives combine with at least a portion of said nickel, vanadium, silicon, and sulfur constituents, and other components of the ash to produce slag comprising the follow-ing phases in wt. %: (i) 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 to Ni, Co to Ni, and mixtures of Cu + CO to Ni when present in said alloy phases are in the range of about -1 to 20; (ii) from about 45.0 to 97 wt. % of a silicate phase selected from the group consisting of a copper silicate phase, a cobalt silicate phase, and mixtures thereof 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 w. % of a spinel phase in which the following are present in wt. %: V 5-60, Fe 7-65, Al 0.1-40, Mg 0.1-35, Cr 0.01-42, and others 0.1-10: and (iv) 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 substantial-ly no Ni3S3 from said hot raw effluent gas stream.

2. The process of Claim 1 wherein 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 in the reaction zone with a partial pressure in the range of about 1.7 x 10-6 to 1.1 x 10-4 atmospheres.

3. The process of Claim 1 where in (2) said reduction in the mole ratio of H2S + COS/H2 is in the range of about 1 to 20 wt. %.

4. The process of Claim 1 wherein said silicon-containing material is selected from the group consisting of silica, quartz, volcanic ash, and mixtures thereof.

5. The process of Claim 1 wherein said silicon-containing material comprises from about 25 to 65 wt. % of silicon.

6. The process of Claim 1 wherein the wt. ratio of silicon in said first additive plus the silicon in said fuel feedstock to vanadium in said fuel feedstock is in the range of about 2 to 10.

7. The process of Claim 1 wherein said copper and/or cobalt-containing material 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.

8. The process of Claim 1 wherein said 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.

21a

9. The process of Claim 1 wherein said supplemental copper and/or cobalt-containing material in (1) comprises inorganic or organic compounds of copper.

10. The process of Claim 1 wherein said copper and/or cobalt-containing material in (1) comprises concentrated copper ore comprising at least 20 weight % of copper.

11. The process of Claim 10 wherein said concentrated copper ore is a mixture of the sulfides of copper, copper-iron and iron with a small amount of gangue minerals.

12. The process of Claim 1 wherein said copper and/or cobalt-containing material comprises copper sulfide and/or copper oxide minerals.

13. The process of Claim 1 wherein said copper and/or cobalt-containing material conprises copper sulfide minerals selected from the group consisting of bornite, chalcopyrite, tetrahedrite, tennentite, chalcocite, covellite, digenite and mixtures thereof.

14. The process of Claim 1 wherein said copper and/or cobalt-containing material comprises copper oxide minerals selected from the group consisting of cuprite, tenorite, malachite, azurite, brochantite, atacamite, chrysocolla and mixtures thereof.

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

16. The process of Claim 1 wherein said sulfur-containing heavy hydrocarbonaceous fuel having a nickel, vanadium, and silicon-containing ash is a pumpable slurry of petroleum coke in water, liquid hydrocarbon fuel or mixtures thereof.

17. The process of Claim 1 where in step (1) said copper and/or cobalt-containing material is introduced into the feed to or the bottoms from a vacuum distillation unit.

18. The process of Claim 1 wherein said mixture of silicon-containing copper and/or cobalt-containing material and feedstock from step (1) has a particle size so that about 100% passes through a sieve of the size ASTM E-11 Standard Sieve Designation in the range of about 425 microns to 38 microns, or below.

19. The process of Claim 1 wherein substantially all of the sulfur in said feedstock is converted into the fluid oxysulfide phase in (2) (iv) and leaves the reaction zone in the slag.

20. The process of Claim 1 wherein said fuel feedstock contains about 0.2 to 6.5 wt. % of sulfur and about 10.0 to 5,000 ppm of silicon or more, and the molten slag produced in step (2) comprises in wt. % about 0 to 5 wt. % of said oxysulfide phase, and at least about 0.1 to 1.0 wt. % of said Cu-Ni alloy phase.

21. The process of Claim 1 wherein the molten slag is produced in step (2) with a reduced viscosity in comparison with molten slag produced by the same partial oxidation process but without the addition of said silicon-containing material and copper and/or cobalt-containing material.

23a

22. A process for the production of gaseous mixtures com-prising H2 + CO by the partial oxidation of a fuel feedstock comprising sulfur-containing petroleum coke including additives to be further described, said fuel feedstock having an ash comprising nickel, vanadium and silicon; and said fuel feedstock includes about 0.5 ppm to 4,000 ppm of nickel, a minimum of about 0.2 wt. % of sulfur, about 1.0 ppm to 2,000 ppm of vanadium, and about 5 ppm to 10,000 ppm of silicon; said process comprising:

(1) mixing together with said fuel feedstock a first addi-tive comprising 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 in said fuel feedstock in said fuel mixture is in the range of about 2 to 10; and including in said mixture a second additive comprising a material select-ed from the group consisting of a copper-containing mater-ial, 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 .01 to 1.5;

(2) coking said mixture from step (1) to produce sulfur-containing petroleum coke having a nickel, vanadium, and silicon-containing ash and having dispersed therein said silicon-containing material and copper and/or cobalt-con-taining material;

(3) introducing the petroleum coke from step (2) into a free-flow refractory lined partial oxidation reaction zone as a pumpable slurry of pulverized petroleum coke in water, liquid hydrocarbonaceous fluid or mixtures thereof, or as substantially dry pulverized petroleum coke entrained in a gaseous transport medium;

(4) reacting said slurry of petroleum coke from step (3) 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 250 atmospheres in a down-flowing free-flow unobstruct-ed vertical reaction zone with refractory lined walls of a partial oxidation gas generator and at a temperature in the range of about 1800°F to 2900°F, and 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; an equilibrium sulfur concentration is provided in the gas phase in the reaction zone with a partial pressure in the range of about 1.7 x 10-6 to 1.1 x 10-4 atmospheres, the free O/C atomic ratio is in the range of about 0.4 to 1.2, the H2O/liquid hydro-carbonaceous fuel and/or solid carbonaceous fuel weight ratio is in the range of about 0.1 to 3.0; thereby producing a hot raw effluent gas stream comprising H2 + CO and en-trained slag; and converting about 90 to 99.9 wt. % of the carbon in said fuel feedstock into carbon oxides; and where in said reaction zone said silicon-containing material and copper and/or cobalt-containing material combine with at least a portion of said nickel, vanadium, silicon, and sulfur constituents, and other components of the ash to produce slag comprising the following phases in wt. %: (i) 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, wherein the weight ratio of Cu to Ni, Co to Ni, and mixtures of Cu +
Co to Ni when present in said alloy phases are in the range of about 1 to 10; (ii) from about 45.0 to 97 wt. % of a silicate phase selected from the group consisting of a copper silicate phase, a cobalt silicate phase, and mixtures thereof, and said silicate phase contains an element from the group consisting of Cu, Co, and mixtures thereof in the amount 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. %: V 5-60, Fe 7-65, Al 0.1-40, Mg 0.1-35, Cr 0.01-42, and others 0.1-10; and (iv) 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 Ni3S2 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 silicon-containing material, and Cu and/or Co-contain-ing materials; and (5) separating non-gaseous materials containing substantial-ly no Ni3S2 from said hot raw effluent gas stream.

23. The process of Claim 22 wherein said silicon-containing material is selected from the group consisting of silica, quartz, volcanic ash, and mixtures thereof.

24. The process of Claim 21 wherein said copper and/or cobalt-containing material comprises copper and/or copper compounds selected from the group consisting of oxides, sulfide, sulfate, carbonate, cyanide, chloride, nitrate and mixtures thereof.

25. The process of Claim 22 wherein said mixture of sil-icon-containing material, and copper and/or cobalt-contain-ing material and feedstock from step (1) has a particle size so that 100% passes through a sieve of the size ASTM E-11 Standard Designation in the range of about 425 microns to 38 microns or below.

26. The process of Claim 22 wherein said copper and/or cobalt-containing material includes an inorganic or organic compound of copper and/or cobalt.

27. The process of Claim 22 wherein said sulfur-containing heavy liquid hydrocarbonaceous fuel having a nickel, vanad-ium, and silicon-containing ash is a high boiling liquid petroleum feed to or the bottoms from a vacuum tower or a fractionator.

28. The process of Claim 22 where in step (2) the mixture from step (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 sulfur-containing petroleum coke having a nickel, vanadium, and silicon-containing ash and having uniformly dispersed therein said silicon-containing materials, and copper and/or cobalt-containing material is removed from the bottom.

29. The process of Claim 22 where in step (2) the mixture from step (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 effluent vapor and steam are removed overhead and said petroleum coke is removed from the bottom.

30. The process of Claim 22 where in step (5) said non-gaseous materials are separated from said hot effluent gas stream by contacting the gas stream from step (4) with a water or an oil scrubbing medium.