Note: Descriptions are shown in the official language in which they were submitted.
- 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
1328737 60288-2833
becomlng poorer, there are compoundlng factors affectlng coker
operatlons. Slnce the crudes contaln more contamlnants, l.e.
~.
sulfur, metals (predomlnately vanadlum, nickel, and lron~, and ash
whlch are
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28737
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
2--
.- '~ ' ' '
-~- 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
'' ' :
---- 1328737
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-
--5--
.
`~ `` 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
--7--
:
~ 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.
- 1 3 2 8 7 3 7 60288-2833
. ~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
--10--
- 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
--11--
:
1328737
.
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
-12-
.
''
.
1328737
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
-13-
1328737
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
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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.
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60288-2833
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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1 3 2 8 7 3 7 60288-2833
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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;. 16a
~; . ~, .
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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
17
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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.
.
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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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