JPH02180991A - Method for preventing formation of nickel hyposulfide in partial oxidation of heavy liquid and/or solid fuel - Google Patents

Abstract

PURPOSE: To prevent the formation of ash containing toxic Ni₂S₂ by partially oxidizing a specified fuel feed material in the presence of a material containing Cu and/or Co.

CONSTITUTION: To (i) a fuel feed material containing heavy hydrocarbon fuel containing S and/or solid carbonaceous fuel having ash containing Ni, V, Si is mixed with (ii) a material containing Cu and/or Co with a weight ratio of Cu and/or Co to Ni of 0.2-10 and a weight ratio of Cu and or Co to Si of 0.0001-0.04, the resulting mixture is reacted with (iv) an oxygen-containing gas in a down-flowing free-flow unobstructed vertical reaction zone with refectory lined walls of a partial oxidation gas generator (iii) in the presence of a temperature regulator and under 2-250 atmospheres and reductive atmosphere at 1800-2900°F to perform a partial oxidation, whereby a hot raw effluent gas substantially containing no Ni₂S₂ and containing H₂ and CO and a slag to be carried away is produced, and 90-99.9 wt.% in the component (i) is converted into carbon monooxide.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention provides a method for removing sulfur with ash containing nickel, vanadium and silicon, producing a gaseous mixture containing H2 and Co, leaving a molten slag. The present invention relates to a method of partially oxidizing a heavy liquid hydrocarbon-based or solid carbonaceous fuel contained therein. More particularly, the present invention relates to an additive system for preventing the formation of toxic Ni8S in the molten slag.

BACKGROUND OF THE INVENTION It is known to partially oxidize slurries of liquid hydrocarbon fuels such as petroleum products and solid carbonaceous fuels such as coal and petroleum coke. The foreseen trend in petroleum stocks is that the source crude oil produced becomes progressively heavier and of lower quality. To compensate for this trend, oil refiners must use more modified heavy fractions than ever before to provide the desired light product. The current industrial "incubator" for achieving such quality improvements is some type of (delayed or flowing) coking operation. A very large part of the current refinery development is coking. equipment installation and development, so coking will likely become a commonly used method for some time to come.

The major disadvantage of coking is the disposal of the coke produced. Appropriately clean coking equipment (coke machine)
By providing carbon, the coke produced has been substituted for applications requiring relatively high purity carbon, such as the production of electrodes. As the quality of the feedstock declines, a complex of factors that do not affect coke machine operation become a problem. The coke obtained from such raw materials is of very poor quality when the raw materials contain many impurities such as sulfur, metals (mainly vanadium, nickel and iron) and ash which is concentrated in the coke produced. , resulting in a product that is not available for many common uses. For example, the presence of toxic Ni8S in the coke ash significantly limits the use of coke. Furthermore, since the crude feedstock is heavier, i.e. contains more coke precursors, each feedstock of heavy liquid hydrocarbon fuels containing ash will produce less quality coke. Manufactured. The production of petroleum coke pellets by a delayed coking process is described in commonly assigned US Pat. No. 2,709,676.

Texaco's partial oxidation gasification process provides an alternative processing route for applications with heavy liquid hydrocarbon fuels containing coke or ash. For example, an aqueous slurry of petroleum coke is reacted by partial oxidation as described in commonly assigned US Pat. No. 3,607,157. Gasification method is a convenient means of processing coke.
often mentioned. The decision to utilize gasification as a means of processing coke is generally based on economics. With expected increases in energy costs and laws requiring the full use of the crude feedstock supplied, there will soon be an increased use of petroleum coke fed to partially oxidized gas generators. Heavy liquid hydrocarbon fuels pose some unforeseen operational problems because gasification is preceded and coking is delayed. For example, in slag produced from heavy liquid hydrocarbon fuels containing sulfur and/or petroleum coke, said fuels contain nickel.

Since it has an ash content containing vanadium and silicon,
Microscopic clusters of toxic nickel subsulfide (Ni8S) were observed. In addition, the ash is usually molten and discharged as slag from the gasifier, but it is discharged without being completely melted. Otherwise, ash will accumulate on internal walls such as fireproof ridge tiles. Nickel-containing impurities, under certain conditions, can produce nickel-carbonyl deposits downstream of the device. Co-Assigned Nine U.S. Patents 4,671,80
In No. 4, a large I iron-containing additive is used to avoid problems with nickel subsulfide. However, the amount of slag produced and the cost of slag treatment increase. Additionally, iron oxide contributes to increased formation of silicate crystals, which can have a detrimental effect on the flow properties of the slag. Co-Assigned U.S. Patent No. 4,654,
No. 164, all of the sulfur forms a copper oxysulfide detergent that collects at least a portion of the vanadium and other ashing components and carries them away from the reaction zone. In commonly assigned U.S. Pat. No. 4,732,700,
A slag separation chamber was provided after the gasifier collected on its side wall a portion of the slag carried away in the process gas flow.

The fuel is mixed with the reformed slag recirculation portion and copper-containing additives and fed to the gasifier. U.S. Pat. No. 1,799.885 utilized in the aforementioned methods and coal operations
No. 2,644,745 do not provide an answer to Applicant's problems involving troublesome nickel and sulfur.

As the subject invention proposes, by adding small amounts of copper- and cobalt-containing materials with the supply of fuel,
It was unexpectedly found that the chemical equilibrium shifts away from the Ni8S region. By this,
It makes it possible to operate partial oxidation gas generators without producing ash containing toxic nickel hyposulfide.
This is a technical improvement.

In the subject invention, the 10th) silicon-containing additive and the 2nd
of the copper- and/or cobalt-containing additive reacts with vanadium and nickel contained in the ash of the sulfur-containing liquid hydrocarbon-based fuel and/or solid carbonaceous fuel. The partial oxidation gasifier can be operated continuously because the slag does not accumulate on the walls of the gasifier, but falls naturally and is discharged from the bottom of the reaction zone.

[Ninth means to solve the problem]

In one embodiment, the present invention provides a heavy liquid hydrocarbon fuel containing sulfur and having an ash content that includes nickel, vanadium, and silicon; Partial oxidation of a solid carbonaceous fuel feedstock provides a method for producing a gaseous mixture containing H8 and CO. Further, the feedstock may contain at least about 0.2% by weight, such as about 1.5-6% by weight.
5% by weight of sulfur, and the feedstock contains at least 0.5 ppm (parts per million), such as about 2.0 ppm (parts per million).
~1'7 Kel of ~42OOOOppm, at least about 1.0
ppm, e.g., about 20 to 5,000 ppm vanadium, and at least about 5.0 ppm, e.g., about 5.0
Contains ~20,000 ppm silicon. The additive system eliminates the toxic nickel subsulfide (Ni8S,
) is prevented from being generated. The cost of the downstream gas purification system is thereby minimized.

The method includes: (1) mixing a material containing copper and/or cobalt with the fuel feedstock, and adjusting the weight ratio of copper and/or cobalt to nickel in the mixture to be in the range of about 0.2 to 10; , the steel and/or the cobalt to silicon weight ratio in the mixture is approximately 0.0001.
~004 process and (2) refractory lining in the partially oxidized gas generator! Step (1) in a downflow gravity vertical reaction zone having 1100 ft walls, in the presence of a temperature control agent at a pressure in the range of about 2 to 250 atmospheres, and at a temperature in the range of about 1800"F to below 2900"F. In the step of partially oxidizing the mixture obtained by reacting with a free oxygen-containing gas under a reducing atmosphere, the equilibrium oxygen concentration in the gas phase in the reaction zone is about 1.7 X 10 to 2.3 X 10
With a partial pressure in the range of atmospheric pressure, the equilibrium sulfur concentration in the gas phase in the reaction zone is approximately 2.53 x 10 to 8.1 x
10 atmospheres, the free 0/C atomic ratio is in the range of about 0.3 to 1.2, and the H30/liquid hydrocarbon fuel and/or solid carbonaceous fuel has a heavy j ratio of about 0
．． 1 to 5.0, thus producing in the reaction zone a hot feed gas stream consisting of H8 and CO and carried away molten slag, and approximately 90 to 5.0 of the carbon in the fuel feedstock. 99.9 wt. at least a portion, such as about 10
60-98.0% by weight of a slag deposited on the inner walls of the reaction zone, which slag contains the following phases: (1) about 0.1-10% by weight of a Cu-Ni alloy phase and/or (ii) a Co-Ni alloy phase in which the weight ratio of Cu and/or CO to Ni is in the range of 0.2 to 0.9; (ii) a copper silicate phase of about 5.0 to 85% by weight; or cobalt silicate phase, Cu and/or cobalt silicate phase.
or CO in the range of about 0.01-2.0 wt-i, (it) about 2.5-45 wt% spinel phase, 5-60 wt% V, 7-65 wt-i %F+1,0
．． 1 to 40% by weight of Al, 0.1 to 35% by weight of Mg,
0.01-42 wt% Cr and 0.1-10 wt%
and (iv) a fluid oxysulfide phase consisting of sulfides of Cu and/or Co and Fe. When said partial oxidation reaction takes place in the absence of said Cu and/or Co-containing substances, the molar ratio Has + cos / in the raw effluent gas stream.
(3) removing substantially [
The method is characterized in that it includes a step of separating a non-gaseous substance that does not contain Ni or S.

In one embodiment, after about 1 to 180 days of operation, the gas generator is shut down. The reducing atmosphere in the reaction zone is changed to an oxidizing atmosphere.

The slag on the inner wall of the reaction zone is oxidized so that the melting temperature and viscosity are reduced. The molten slag, substantially free of Ni8S, descends by gravity to the bottom of the gas generator.

In another aspect, the present invention provides a heavy liquid hydrocarbon fuel containing sulfur and having an ash containing nickel, vanadium and silicon and/or an ash containing sulfur and containing nickel, vanadium and silicon. The present invention provides a method for producing a gaseous mixture containing H3 and CO by partially oxidizing a fuel feedstock consisting of a solid carbonaceous fuel having a carbonaceous fuel of at least 0.2 % by weight, e.g. about 15-6.
511i and the feedstock contains at least about 0.5 ppm sulfur, such as from about 2.0 to 4.5 ppm. OOO
ppm of nickel, at least about 1.0 ppm, e.g., about 20-2.000 ppm vanadium, and at least about 5.0 ppm, e.g., about 5.0-10,00 ppm.
Contains 0 ppm silicon. The additive system includes a sulfur-containing gas, for example HllS-? This prevents the formation of toxic nickel subsulfide (Ni8S) in the slag produced during partial oxidation of the feedstock without increasing CO8 activity and pressure. The cost of the downstream gas purification system is thereby minimized. The method includes: (1) mixing a tenth additive comprising a silicon-containing material having about 25 to 65 weight percent silicon with the fuel feedstock; 10) total weight ratio of silicon to vanadium in the feedstock is in the range of about 2 to 10, and in said mixture there is a copper-containing material, a cobalt-containing material, and mixtures thereof. a second additive containing selected materials, whereby the weight ratio of copper to nickel, cobalt and copper to cobalt when the metal is present in the mixture is from about 0.5 to 20; (2) a refractory lined wall of a partially oxidized gas generator; In a vertical reaction zone under downward gravity flow with a
In the presence of a temperature regulator comprising a pressure Hρ in the range of atmospheric pressure,
The mixture obtained in step (1) is then reacted with a free oxygen-containing gas under a reducing atmosphere at a temperature ranging from about 1800 degrees Fahrenheit to below 2900 degrees Fahrenheit to perform partial oxidation to form free oxygen/carbon atoms. The ratio is in the range of about 0.4 to 1.2, and the weight ratio of H20/solid hydrocarbon fuel and/or solid carbonaceous fuel is in the range of about 0.1 to 3.0; producing a hot feed gas stream of slag nitrogen which is carried away with Hll and CO and converting about 90 to 99.9% by weight of the carbon in the fuel feedstock to carbon oxide; The second additive combines with at least a portion of the nickel, vanadium, silicon and sulfur components of the ash and other components to form a slag, the slag having the following phases: (1) Cu
-Ni alloy phase, Co-Ni alloy phase, C, u-Fe
About 0.0005 to 1.5% by weight of an alloy phase selected from the group consisting of an alloy phase and a mixture thereof, and when present in the alloy phase, the alloy phase is selected from the group consisting of Cu, Co, and Cu and Co relative to NiK. The weight ratio of each of the mixtures is about 1 to 20
(11) about 4 selected from the group consisting of a copper silicate phase, a cobalt silicate phase, and a mixed phase thereof;
5.0 to 977 amounts of silicate phase, Cu,
(ill) about 1.8 to 12% by weight of said silicate phase containing an element selected from the group consisting of Co and mixtures thereof in the range of about 0.01 to 3.0 1% by weight of said silicate phase;
spinel phase of 5 to 60 fjk% V, 7 to
65% by weight Fe.

0.1-40% by weight Al, 0.1-35% by weight -
containing 10.01-42ifi% Cr and 0.1-10% by weight of other elements, and (iv) C
u.

The remainder of the slag is composed of a fluid oxysulfide phase containing at least one sulfide selected from the group consisting of Co, Fe and mixtures thereof, the slag is substantially free of Ni8S, and the said portion When the brewing reaction takes place without the presence of said first and second additives, HsS + CO to said molar ratio in the feed effluent gas stream.
8/ A step in which a decrease in the molar ratio of Hs +Co occurs, and (3
) separating a non-gaseous material substantially free of Ni8S from the hot feed effluent gas stream.

With the method of the invention, it is possible to operate the gas generator without having to shut it down for slagging even after approximately 1 to 180 days of operation. If the method of the present invention is applied,
It is advantageous that it is not necessary to oxidize the slag on the inner walls of the reaction zone to reduce the melting temperature and viscosity. In the present invention, substantially Ni. The molten slag, free of S, flows down to the bottom of the gas generator by gravity.

In another embodiment, a sulfur-containing heavy liquid hydrocarbon fuel comprising ash comprising nickel, vanadium and silicon, said steel and/or cobalt-containing material, or said silicon-containing material, copper and/or A mixture with cobalt-containing materials is fed to a coking unit to produce nickel.

Produces sulfur-containing petroleum coke with ash containing vanadium and silicon. A substance containing copper and/or cobalt, or a substance containing silicon and a substance containing copper and/or cobalt are uniformly dispersed throughout the petroleum coke. This petroleum coke is then fff3
react in an oxidizing gas generator to produce synthesis gas, reducing gas, or fuel gas.

One embodiment of the method of the invention is as follows.

That is, a method of producing a gaseous mixture comprising H8 and CO by partially oxidizing a fuel feedstock comprising sulfur-containing petroleum coke having an ash comprising nickel, vanadium and silicon, wherein said feedstock contains at least about o, s p p m nickel, at least about 0.2
% by weight of sulfur, at least about 1.0 ppm of vanadium and at least about 5.0 ppm of silicon; Mixing a substance containing copper and/or cobalt with the fuel,
The weight ratio of copper and/or cobalt to nickel in said mixture ranges from about 0.2 to 10, and the weight ratio of copper and/or cobalt to nickel in said mixture ranges from about 0.2 to 10. ! (2) coking the mixture obtained in step (1) to have an ash containing nickel, vanadium and silicon; (3) producing petroleum coke containing sulfur by dispersing the steel and/or cobalt-containing substance therein; and (3) converting the petroleum coke produced in step (2) to water, liquid hydrocarbons Gravity refractory lined 9 partial oxidation reaction zone as slurry petroleum coke that can be pumped in a fluid or a mixture thereof, or as substantially dry petroleum coke that can be transported in a gaseous transport means. (4) refractory lining of the partial oxidation gas generator; and (4) refractory lining of the partial oxidation gas generator. , and approximately 1800°F' to 290
In the step of partial oxidation by reacting the slurry petroleum coke obtained in step (3) with a free oxygen-containing gas at a temperature in the range below 0, the equilibrium oxygen concentration in the gas phase in the reaction zone is approximately 1.7 x 10
It has a partial pressure in the range of ~2.3X10 atmospheres,
The equilibrium sulfur concentration in the gas phase in the reaction zone is approximately 2.53
X10 ~8. It has a partial pressure in the range of I x 10 atmospheres and a free oxygen/carbon atomic ratio of about 0.3 to 1.
The weight ratio of H20/liquid hydrocarbon fuel and /1t is solid carbonaceous fuel is approximately 0.1 to 5.0.
range, thus producing a hot feed effluent gas stream consisting of H3 and CO and the carried away slag, and converting about 90-99,9% of the carbon in the fuel feedstock to carbon oxides. in the reaction zone, the steel and/or cobalt-containing material combines with at least a portion of the nickel, sulfur and silicon components in the fuel feedstock to form the slag;
- the slag is at least partially deposited on the inner walls of the reaction zone and comprises the following phases: (1) about 0.1 to 10% by weight;
Cu-Ni alloy phase and/or Co-Ni alloy phase, in which Cu and/or Ni are
or the weight ratio of Co is in the range of about 0.2 to 0.9; (ii) about 5.0 to 85% by weight of a copper silicate phase and a cobalt silicate phase; About 0.01 to 2.0% by weight of Cu and/or Co in
present in the range of about 2.5 to 45% by weight
in the spinel phase, this phase contains 5 to 60% by weight of v,
7-65% by weight F*, 0.1-40% by weight (7) A/
, containing 0.1-35% by weight of Mgeo, 01-42% by weight of Cr and 0.1-10% by weight of other elements, and (1) Cu and/or cobalt and F. The remainder of the slag consists of a fluid oxysulfide phase containing sulfides of Ni8
When the partial oxidation reaction takes place without the presence of Cu and/or Co-containing substances, H, S + , relative to the molar ratio in the feed gas stream
a step in which a decrease in the molar ratio of CO8/H2+CO occurs;
5) separating substantially Ni-, S-free, non-gaseous materials from the hot feed effluent gas stream.

Another embodiment of the method of the invention is as follows. A method of producing a gaseous mixture comprising H2 and Co by partially oxidizing a fuel feedstock comprising sulfur-containing petroleum coke having an ash content comprising nickel, vanadium and silicon, wherein the feedstock comprises a ，
000 ppm nickel, at least about 0.2 wt% sulfur, about 1.0-2.000 ppm vanadium, and about 5-10,000 ppm silicon;

10) an additive comprising a silicon-containing material having about 25 to 65 wt. The total weight ratio of silicon in the 10th) additive to vanadium in the feedstock and silicon in the fuel feedstock is in the range of about 2 to 10, and copper-containing substances, cobalt-containing substances, and a second additive containing a substance selected from the group consisting of a mixture of Cu/Ni, Cu/Ni,
Co/'Ni and Cu+Co/Ni ratios are approximately 0.5
20, wherein the ratio of the second additive to ash in the fuel feedstock is in the range of about 0.01 to 1.5; a step of coking the mixture to have an ash containing nickel, vanadium and silicon, and containing the silicon-containing substance and copper and/or cobalt-containing substance dispersed therein; 3) The petroleum coke produced in step (2) can be transported as a slurry of crushed petroleum coke that can be pumped in water, liquid hydrocarbon-based fluids or mixtures thereof, or as a substance that can be transported in gaseous transport means. (4) Introducing the partially dried crushed petroleum coke into a gravity-flow refractory-lined partial oxidation reaction zone; , in the presence of a temperature regulator containing HO at a pressure in the range of about 2 to 250 atmospheres, and about 1
The slurry petroleum coke produced in step (3) is reacted with a free oxygen-containing gas under a reducing atmosphere at temperatures ranging from 800°F to below 2900°C to achieve partial oxidation and to maintain equilibrium in the gas phase in the reaction zone. Oxygen concentration is approximately 1.2X
With a partial pressure in the range of 10 to 2.0 x 10-' atm, the equilibrium sulfur concentration in the gas phase in the reaction zone is approximately 1.7 x
10 ~1. It has a partial pressure in the range of lx10 atmospheres and a free oxygen/carbon atomic ratio in the range of approximately 0.4 to 1.2, with a , 0 fr weight ratio about 0.1-3.0
, thus producing a hot feed effluent gas stream consisting of H2 and CO and then slag, and converting about 90 to 99.9 i of the carbon in the fuel feed into carbon oxides. In the reaction zone, the silicon-containing substance and the copper and/or cobalt-containing substance are combined with at least a portion of the nickel, vanadium, silicon and sulfur components and other components of the ash. This slag has the following phases: (1) Cu/N 1 alloy phase, Co-
about 0.0005 to 1.5 selected from the group consisting of Ni alloy phase, Cu-Fe alloy phase, and mixtures thereof.
11rj% of the alloying phase, Cu, /'Nl when the metal is present in the former alloying phase.

the weight ratio of Co/NI+ and Cu+Co/Ni is in the range of about 1 to 10; (it) the silicate phase;
about 45.0 to 97% by weight of a silicate phase selected from the group consisting of a cobalt silicate phase, and mixtures thereof, the silicate phase being Cu, Co i? ! and mixtures thereof, in an amount of about 0.01 to 30
Contains in the range of weight-f1%, It) about 1.8 to 1
It is a double fl-chi spinel phase, and this phase contains 5 to 601
1F11%l7)V, 7-65 weight 31%OFe,
0.1-40% by weight Al, 0.1-35% by weight Mg
0.01-42 wt% Cr and 0.1-10 wt%
and (lv) Cu,
Co.

a fluid oxysulfide phase L containing at least one sulfide of an element selected from the group consisting of Fe and a mixture thereof;
9, said slag being substantially Nf
8S, and when said partial oxidation reaction occurs without the presence of said silicate-containing material and Cu and/or Co-containing material, relative to said molar ratio in the feed effluent gas stream. (5) separating non-gaseous material substantially free of Ni 8S from said hot feed effluent gas stream. It is something that

[Disclosure of the invention]

A method for partial oxidation of heavy liquid hydrocarbon fuels and petroleum coke is disclosed in co-assigned U.S. Pat. Nos. 4,411,670 and 3,607, which are incorporated by reference.
, No. 156, respectively. Also described in the above reference are suitable gravity gravity lined gas generators and burners for use in producing synthesis gas, reducing gas or fuel gas from these materials. The method of the present invention comprises a sulfur-containing heavy liquid hydrocarbon fuel having an ash content containing nickel, vanadium and silicon;
Alternatively, it is advantageous to use relatively inexpensive fuel feedstocks, including petroleum coke. As used herein, the expression “↓ and/or °゛” means either or both of the specified friend item or substance; and
These feedstocks contain at least about 0.2% sulfur by weight, such as from about 0.2 to 65% by weight, at least about 0.5% by weight.
ppm, e.g. 2.0-4000 ppm nickel, at least about 1.0 Ppm %, e.g. about 20-5.
000 ppm of vanadium, at least about 5.0 ppm.
0 ppm silicon, for example in the range of about 5.0 to 20.000 ppm.

The term sulfur-containing heavy liquid hydrocarbonaceous substances or fuels with an ash content containing nickel, vanadium and silicon are defined as unused raw materials9 residues of petroleum distillation and petroleum cranking2 petroleum distillates, reduced Raw materials, total raw materials, asphalt.

The fuel is a petroleum-based or coal-based fuel selected from the group consisting of coal tar, coal M1, shale oil, tar sands oil, and mixtures thereof.

What is defined by the term sulfur-containing petroleum coke with an ash content containing nickel, vanadium and silicon is:
From a sulfur-containing heavy liquid hydrocarbon-based fuel with an ash content containing nickel, vanadium and silicon, commonly assigned U.S. Pat.
673, 080, such as delayed coking or fluid coking.

The ash obtained by partial oxidation without additives of feedstocks containing sulfur-containing heavy liquid hydrocarbon fuels and/or solid carbonaceous fuels with ash contents containing nickel, vanadium and silicon was investigated in more detail. It has been found that such ash consists mostly of nickel, vanadium and silicon oxides and sulfides, with some minerals of the commonly occurring types. As for the heavy liquid hydrocarbon fuel tN, the total ash content of petroleum coke is only about 0.5 to 5% by weight, whereas coal typically contains an ash content of 10 to 20% by weight. do.

The theory is that in heavy liquid hydrocarbon-based materials and petroleum coke-based materials, much of the ash material is isolated as material with a single molecular weight. This means that during vacuum distillation or coking, the raw material in the raw material, which usually exists as a porphyrin-type structure (metal atoms, their oxides, and ions trapped in an organic framework), is The method is such that the metallic material is incorporated into the collapsed carbon matrix.

One embodiment of the invention is sulfur, nickel.

Toxic nickel hyposulfide (Ni 8S) is present in the slag generated during the partial oxidation of heavy liquid hydrocarbon and/or petroleum coke feedstocks containing vanadium and silicon.
, ) to prevent the formation of improved copper and/or
Or to provide an additive system containing cobalt.

Without the present invention, in the slag there would be approximately 0.01 to 5.03i
J1% of toxic nickel subsulfide is produced.

Another advantage of the present invention is that it reduces the activity, pressure and concentration of sulfur-containing gases such as H8S and CO8.

For example, H in the raw product gas stream from a partial oxidation gas generator
, S and CO8, and according to the present invention, the concentration of the friend is:
Copper and /lj may range from about 1 to 20% by weight compared to the combined H2S and CO8 concentration in the raw product gas stream that would be produced in the absence of the cobalt-containing material, e.g.
It decreases by 1011ijF%.

The costs of downstream gas purification are thereby minimized. Additionally, means are provided for introducing steel and/or cobalt-containing materials into the reaction system for maximum effect.

Cobalt and/or cobalt-containing substances include copper and/or cobalt compounds, preferably copper and/or cobalt oxides. The weight ratio of copper and/or cobalt to nickel is approximately 0.2 to 1.
0 range, such as about 1 to 3.
or a cobalt-containing substance is introduced, wherein the weight ratio of copper and/or cobalt to silicon in said mixture ranges from about o,oooi to 0.04, e.g. from 0.005 to 0.
．． It is 02. This ratio may be expressed as 0.02 parts by weight of copper and/or cobalt to 1 part by weight of nickel in the fuel feedstock.

Pressures in the range of about 2 to 250 atmospheres, e.g.
At 200 atmospheres, a partial oxidation reaction takes place. The supplied fuel is partially oxidized by reacting with a gas containing free oxygen in a reducing atmosphere in the presence of a temperature control agent. The temperature of the reaction zone ranges from about 18,007 to below 2,900°C, such as about 22°C.
50°F to below 2500°F. The equilibrium oxygen concentration in the gas phase in the reaction zone is approximately 1.7 X 10 to 2.3 X 1
With a partial pressure in the range of 0 atm, the equilibrium sulfur concentration in the gas phase is about 2.53 x 10 to 8. It has a partial pressure in the range of 1×10 atmospheres. In the reaction zone, the free oxygen/carbon atomic ratio is about 0.3 to 1.2, e.g. about 0.
．． The weight ratio of H, 0 to liquid hydrocarbon fuel and/or solid carbonaceous fuel is in the range of about 0.1 to 5.0, for example about 0.15 to 2. be. A hot raw gas stream containing Hl and COL and transported molten slag exits the reaction zone. About 90-99.9% by weight of the carbon in the fuel feedstock is converted to carbon oxide.

In the reaction zone of the partial oxidation gas generator, the copper- and/or cobalt-containing material is present in at least a portion, e.g. substantially all or a majority, of the nickel, vanadium, silicon and sulfur components present in the feed, e.
0-100 wt%, perhaps 70-90 wt-fi%, to produce a molten slag containing the following phases: These phases are (1) about 0.1-10 wt% Cu-Ni alloy phase and/or Co-Ni alloy phase, with a weight ratio of copper and/or Co to Ni of about 0.2-0; ．．
(11) a silicate steel phase and/or a cobalt silicate phase with a weight of about 5 to 85 fl';
Co is present in the range of about 0.01 to 2.0 weight, (ill) it is a spinel phase with about 2.5 to 45 weight, and 5 to 607 weight. % V, 7-65 wt. % Fe.

0.1-40% Al by weight, 0.1-35% weight.

0.01~42! f% Cr and o, 1~1o1J-
those containing Ik% of other elements, and (Iv) Cu
0 to 5% by weight of the slag residue, for example, consisting of a fluid oxysulfide phase containing sulfides of CU and/or Co, and the partial oxidation reaction When occurring in its absence, the molar ratio of H, S + CO8/)I, + Co in the original gas stream is reduced by an amount of, for example, about 1 to 201 i, compared to said molar ratio. In this way, generation of significant Ni8S is prevented. According to the present invention, it is advantageous, etc.
Substantially no nickel subsulfide exists in the slag, for example, only about 0.001% by weight or less of nickel subsulfide exists. The potential for sulfur in the gas and the costs of downstream gas cleaning are reduced.

Another aspect of the invention is that copper and/or cobalt-containing materials are not only used to produce detergents and fluxes as described above, but are also selected based on selective catalytic properties. This is something that can be done. For example, this material acts to improve the properties of light products obtained by coking operations. This material also improves gasification by increasing the reaction rate and increasing the throughput of the gas generator, or by smoothing the conversion rate and thus improving the overall efficiency of the process. encourage However, furthermore, the invention is not based on the catalytic properties of cobalt- and/or cobalt-containing materials.

In yet another embodiment, the copper and/or cobalt containing material is mixed with a sulfur-containing heavy liquid hydrocarbon fuel having an ash containing nickel, vanadium and silicon. This mixture is then fed to a conventional coking unit to produce petroleum coke. In this way, the finely divided copper and/or cobalt containing material is homogeneously mixed throughout the petroleum coke product.

Finely powdered copper and/or cobalt-containing substances and finely powdered petroleum coke and mixtures thereof are approximately 425
ASTM E in the range μm to 28 μm or less
-110) The particle size is such that approximately 100% of the particles pass through a standard sieve grade sieve. The components of the mixture described above may be ground separately and then mixed. Otherwise, these ingredients may be mixed and dry milled or wet milled. In this way, homogeneous mixing of the solid materials is achieved, and the particle size of each solid material in the mixture is substantially equal. The dry grinding mixture is mixed with water and/or a liquid hydrocarbon-based material to produce approximately 50%
A pumpable slurry containing solids in the range of 65% by weight may be produced. Alternatively, the solid material may be wet milled with a liquid slurry medium. Alternatively, the particulate solid mixture may be transported in a gaseous medium and introduced into the gas generator. The gaseous transport medium is water vapor,
COB, N21 free oxygen containing gas, recycled syngas L and mixtures thereof. In one embodiment of this process, non-gaseous materials, such as particulate carbon and slag, are separated from the hot effluent gas stream from the partial oxidation reaction zone by contacting the gas stream with water or oil scrubbing means. be done. A portion of the sulfur in the feedstock, e.g. about 1-2011iJ1%, is
The Cu and /1 atoms are converted to Co and Fa oxysulfides and leave the reaction zone remaining in the slag.

In embodiments, the coke is fed to the coke by mixing with a sulfur-containing heavy liquid hydrocarbon-based fuel having an ash content containing copper and/or cobalt, nickel, vanadium and silicon. Cobalt-containing material is introduced directly into the ash-containing petroleum liquid feed to the vacuum distillation column, which usually precedes the coke unit.

In either coking or distillation unit operations, substantially all copper and/or cobalt-containing materials should remain in the appropriate bottoms stream. In other words: It is highly unlikely, if any, that copper- and/or cobalt-containing material will be carried away with the lighter products. Nitrogen tower feed stream K,
An expected advantage to mixing additives is that the feed to the vacuum column will have a significantly lower viscosity than the bottoms from the vacuum column. This allows for more thorough mixing to be achieved effectively.

For example, high boiling liquid petroleum, i.e. nickel.

A mixture consisting of a sulfur-containing heavy liquid hydrocarbon fuel with an ash content containing vanadium and silicon and a material containing ground copper and/or cobalt is used, for example in reference 9, at a temperature below about 650 °C. The reactor is introduced into the delayed coking zone via line 33, shown and described in commonly assigned U.S. Pat. No. 3,673,080. At a temperature in the range of about 8007 to 895 T and a pressure in the range of about 20 to 60 psig, uncondensed hydrocarbon effluent steam and water vapor are removed above and the petroleum coke mixed with copper and/or cobalt containing materials is removed from the bottoms of the delayed coking zone.

In another embodiment, a sulfur-containing high boiling liquid petroleum having an ash content comprising nickel, vanadium and silicon;
A mixture of comminuted copper and/or cobalt-containing materials is applied at a temperature in the range from about 5,507 to below 750° C., for example, in US Pat.
709.676 to the fluidized bed coking zone via line 31 as illustrated and described in US Pat. No. 709.676. Temperatures ranging from about 1000°F to below 1200°F, about 10-20°C
At pressures in the psig range, uncondensed hydrocarbon effluent vapor and water vapor are removed above and the petroleum coke is removed from the coking zone bottoms. and,
Petroleum coke is crushed to fuel size as described above.

In some other embodiments, the present invention can be applied to similar other petroleum processing methods that produce streams suitable for gasification. To the extent that the bottoms or residue stream is not modified, the bottoms treatment process ultimately produces a residue stream.

Such flows pose similar problems for coke, whether it is liquid or normally solid but pumpable at high temperatures. that's why,
Inventions relating to the introduction of copper- and/cobalt-containing materials as part of petroleum processing prior to gasification, depending on the particular process, should produce feedstocks that do not have the gasification problems described above. Most of these methods utilize vacuum distillation as a pretreatment. Thus, as previously mentioned, the steel and cobalt-containing materials are mixed with the vacuum distillation feed having an ash content containing nickel, vanadium and silicon.The additives are then removed from the bottoms from the distillation column. It comes out in the flow.

The bottoms stream now becomes the feed stream for the reforming process. The incorporation of such copper- and/or cobalt-containing materials must not adversely affect these processes, and the additives must ultimately exit with the nickel-, vanadium-, and silicon-containing residue stream from the respective process. It is something that should come. In all steps, this residue stream must be suitable for gasification by partial oxidation.

In another embodiment, the partial oxidation gas generator is operated continuously for about 1 to 180 days, accumulating slag on the interior walls of the reaction zone. The reaction is stopped and the gas generator is opened to oxidize the slag on the inner wall of said gas generator. The melting temperature of the slag is reduced to about 20,007 or below and the viscosity is reduced. Substantially Ni 8S,
The molten slag, which does not contain l, flows down the inner wall of the reaction zone under the influence of gravity.

The hot molten slag is poured into quenching water contained in a quenching tank located at the bottom of the gas generator.

See co-assigned US Pat. No. 3,544,291, which is incorporated by reference. Otherwise, the molten slag is placed at the bottom of the slag gas generator and then passes through the central outlet. Reference is made to commonly assigned U.S. Pat. No. 4,312,637, which is incorporated by reference.

The main advantage of the process of the invention is that it produces a relatively small volume of slag with a relatively high vanadium content, for example about 2.0% V by weight.

Therefore, this slag has high commercial value for recycling companies.

Another embodiment of the invention improves slagging removal from gas generators during partial oxidation of heavy liquid hydrocarbon systems and/or petroleum coke feedstocks containing sulfur, nickel, panadium and silicon. The present invention provides an improved subsilicon-containing additive that prevents the formation of toxic nickel subsulfide (Ni8S2) in slag. If the present invention did not exist, approximately 0.
1-5.0% by weight of the troublesome toxic nickel subsulfide may be present. Another advantage of the present invention is that the activity, pressure and concentration of sulfur-containing gases such as H, S and COS are reduced. For example, the concentration of the mixture of H2S and CO8 in the raw product gas stream leaving the partial oxidation gas generator is, according to the invention, lower than the concentration of the raw product gas produced when no copper- and/or cobalt-containing substances are added. Compared to the concentration of the mixture of H, S and CO8 in the stream, approximately 1-2
0% by weight, for example in the range of about 5-10% by weight. The costs of downstream gas purification are thereby minimized.

Furthermore, it is equipped with means for introducing a substance containing silicon and a substance containing copper and/or cobalt into the reaction system to obtain maximum efficiency.

The silicon-containing additive is a material selected from the group consisting of silicon monoquartz, volcanic ash, and mixtures thereof. The silicon-containing material is at least about 25-65 frJI%
contains silicon. ,, the weight ratio of the total amount of silicon in the silicon-containing substance # and silicon in the feedstock to vanadium in the fuel feedstock is about 2 to 10.
Sufficient silicon-containing material is introduced into the reaction zone to provide a range of .

The substance containing copper and/or cobalt consists of a compound of copper and/or cobalt, preferably an oxide of copper and/or cobalt. Steel and/or nickel
Or the 11:heavy duty ratio of cobalt is about 0.5 to 20. For example, the weight ratio of copper and/or cobalt to ash in the fuel feedstock may range from about 0.01 to 1.
．． Sufficient copper- and/or cobalt-containing material is introduced into the reaction zone to bring the range to 5.5. The weight ratio of copper and/or cobalt to nickel is Cu/Ni,
It may be expressed as a weight ratio of Co/N I and Cu + Co/N i . When the metal is present in the mixture, the weight ratio ranges from about 0.5 to 20.

The partial oxidation reaction occurs at a pressure in the range of about 2 to 250 atmospheres, such as in the range of about 15 to 200 atmospheres, in a downflow gravity-flow vertical reaction zone with refractory lined walls. The fuel feed material, in the presence of a temperature regulator,
It is partially oxidized by reacting with a gas containing free oxygen in a reducing atmosphere. Typical temperature regulators are H, O, CO,...
N, selected from the group consisting of cooled and recirculated product gas, and mixtures thereof. Temperature regulators are usually
It contains H,0 as at least one form. The temperature of the reaction zone is in the range of about 18,007 to 2,900" F, such as about 2,250 to 2,500". The free oxygen/carbon atomic ratio is in the range of about 0.4 to 1.2, such as about The H100 weight ratio to liquid hydrocarbon fuel and/or solid carbonaceous fuel is in the range of about 0.1 to 3.0, for example about 0.15 to 2. The equilibrium oxygen concentration in the gas phase in the reaction zone is approximately 1.2
preferably having a partial pressure in the range of 10-'atmospheres;
The equilibrium sulfur concentration in the gas phase is approximately 1.7X10 to 1. lX
Preferably, it has a partial pressure in the range of 10″□4 atmospheres.

The hot raw gas stream leaves the reaction zone and includes molten slag transferred to the H8 and CO gases. About 90-99.9% by weight of the carbon in the fuel feedstock is converted to carbon oxide.

In the reaction zone of the partial oxidation gas generator, a 10) additive consisting of a substance containing silicon and a second additive consisting of a substance containing copper and/or cobalt are used to reduce the ash content of nickel, vanadium, silicon and sulfur. component and at least a portion of the other components, e.g. substantially all or most, e.g.
0% by weight to produce a slag containing the following phases:

This slag consists of (1) Cu-Ni alloy phase, Co-Ni
about 0.0005 to 1.5% by weight of an alloy phase selected from the group consisting of an alloy phase, a Cu-F alloy phase, and mixtures thereof, and when these metals are present as an alloy phase, K is The weight ratio of Cu and/or cobalt to Ni is in the range of about 1-10, (It)Cu,
about 45 to 97% containing about 0.01 to 3.0% by weight of an element selected from the group consisting of Co and mixtures thereof
wt% silicate phase, (il+) about 1.8-12 wt%
is a spinel phase containing the following elements, namely 5 to 6
0 wt% V, 7-65 wt% Fe, 0.1-4
0% weight) Al, 0.1~3513#% Mg,
0.01 to 42 Cr and 0.1 to 10 J
1% of other elements, and (iv) the remainder of the slag, e.g. about 0-5% by weight, including Cu, Co, F.
s and mixtures thereof, and the partial oxidation reaction occurs without the presence of the first and second additives. , H, S + in the raw gas stream
The molar ratio Lv of CO8/H,+Co is also about 1 to
This is a decrease of 20 inches. In addition, the formation of toxic Ni8S is also prevented.

Advantageously, according to the invention, substantially no nickel subsulfide is present in the slag, for example about 0.001% by weight.
Only the following nickel subsulfides exist: Practically Ni!
]S, is separated from the hot raw gas stream by conventional means.

The potential for sulfur in the gas and the costs of downstream gas cleaning are reduced.

In all of the aforementioned embodiments of the invention, the composition of the hot raw gas stream directly emerging from the reaction zone of the gravity flow partial oxidation gas generator, expressed in mole percentages (4), is as follows: H310 ~70. C015~57, Co, 0.1
~25, H,OO,1~20. CH, O~60. H
2So~3, cos o~0.1. N, 10-60
and Ar O~2.0° granular carbon is about 0.2~20
present in a range of % by weight (based on the carbon content of the feed material). Ash is present in the range of about 0.5-5.0% by weight, such as about 1.0-3.0% by weight (based on the total weight of the fuel feedstock). Depending on the composition of the gas, the gas stream is transferred to the gas to remove particulate carbon and ash by means of water quenching and/or water or oil scrubbing, in some cases also with dehydration. , used as reducing gas or fuel gas.

Another aspect of the present invention is that silicon-containing materials and copper- and/or cobalt-containing materials are used to produce detergents and fluxes for vanadium and nickel with selective catalytic properties. selected based on. For example, these substances act to improve the properties of the light products obtained in coking operations. These materials aid the gasification reaction either by increasing the reaction rate and increasing the throughput of the gas generator or by increasing the overall efficiency of the process. However, the present invention is not based on the catalytic properties of silicon-containing materials and copper- and/or cobalt-containing materials.

For all the above embodiments of the invention, nickel,
Preferred copper- and/or cobalt-containing materials to be mixed with sulfur-containing heavy liquid hydrocarbonaceous materials having ash contents containing vanadium and silicon or sulfur-containing solid carbonaceous fuels having ash contents containing nickel, vanadium and silicon. , oxides, sulfides, sulfates, carbonates, cyanides.

Chlorides, nitrates, hydroxides, ferrocyanides.

In another embodiment, the copper and/or cobalt compound is selected from the group consisting of ferricyanide, phosphate groups and mixtures thereof. Substances containing cobalt include naphthenate, oxalate, acetate, quartate, benzoate, oleate, tartrate,
An organic substance selected from the group consisting of butyrates, formates and mixtures thereof. The substance containing copper and/or cobalt contains about 30% of copper and/or cobalt compounds.
．． It may be contained in an amount of 0 to 100% by weight. The substance containing copper and/or cobalt to be added includes any of the following substances. (11 Copper inorganic compounds TFC are organic compounds, (2) concentrated copper minerals containing at least 20% by weight copper, (3) copper, copper-iron and iron sulfides with multi-mouth gangue. (4) Minerals consisting of copper sulfides and/or copper oxides (5) 7d copperite, chalcopyrite, tetrahedrite.

a copper sulfide mineral selected from the group consisting of arsenite, chalcocite, copper indigo, digenite and mixtures thereof, and (6
) red copperite, acopperite, kujiyakuite, blue copperite.

It is a copper oxide mineral selected from Proshan copperite, glaurite copperite, dillite, and a mixture of these.

Preferably with respect to all of the foregoing embodiments of the subject invention, a sulfur-containing heavy liquid hydrocarbon fuel having an ash content comprising nickel, vanadium and silicon and/or comprising nickel, vanadium and silicon. A sulfur-containing solid carbonaceous fuel having an ash content and a silicon-containing material and/or a cobalt-containing material are introduced into a partially oxidized gas generator.

In another embodiment, a fuel feedstock suitable for the subject method is a pumpable slurry of petroleum coke in water, liquid hydrocarbon fuel, or mixtures thereof.

In yet another embodiment, a silicon-containing material and a steel and/or cobalt-containing material are mixed with a sulfur-containing heavy liquid hydrocarbonaceous material having an ash content comprising nickel, vanadium, and silicon. This mixture is then fed to a conventional coking unit to produce petroleum coke. In this manner, the finely divided silicon-containing material and copper and/or cobalt-containing material are homogeneously mixed throughout the petroleum coke product.

The crushed nine silicon-containing materials and copper and/or cobalt-containing materials, and the crushed petroleum coke and mixtures thereof, are passed through ASTM E-110) standard sieve grade mesh sieves ranging from approximately 425 μm to 28 μm or less. The particle size is large enough to allow approximately 100% of the particles to pass through. The components of the foregoing mixtures may be ground separately and then mixed.

Otherwise, the ingredients may be wet-milled or dry-milled together. In this way, homogeneous mixing of the solid substances is achieved, and the particle size of each solid substance in the mixture is substantially the same. The dry milled mixture is mixed with water and/or liquid hydrocarbon-based material for about 50 minutes.
A pumpable gas slurry is produced having a solids concentration ranging from 0 to 65% by weight.

Alternatively, the solid material may be wet milled with liquid slurry means. Alternatively, the mixture of particulate solid substances is transported in a gaseous medium and introduced into a gas generator. The gas transport medium is water vapor, CO,.

N8. selected from the group consisting of free oxygen containing gas, recycled syngas and mixtures thereof.

In one embodiment of the process of the invention, non-gaseous substances, such as particulate carbon and slag, are separated from the hot effluent gas stream from the partial oxidation reaction by contacting the gas stream with water or oil scrubbing means. be done. A portion of the sulfur in the feedstock, for example 1 to 20% by weight, is Cu and/or C.

and F. are advantageously converted to oxysulfides which leave the reaction zone and remain in the slag.

The crushed silicon-containing material and the steel and/or cobalt-containing material are mixed with a sulfur-containing heavy liquid hydrocarbon fuel having an ash content containing nickel, vanadium and silicon and fed to a coke machine! ? ! At 11, the silicon-containing material and the copper and/or cobalt-containing material are introduced directly into the ash-containing petroleum liquid feed to the vacuum distillation column, which typically precedes the coking unit. In either coking or distillation unit operations,
Substantially the silicon-containing material and the copper- and/or cobalt-containing material in the pan remain in the desired bottom stream.

In other words, even if there is a problem, it is highly unlikely that the silicon-containing material and the copper and/or cobalt-containing material will be carried away together with the light products. The expected advantage to mixing additives into the vacuum column feed stream is that the feed to the vacuum column has a significantly lower viscosity than the vacuum column feed (coker feed). Yes, this friend can effectively achieve more thorough mixing.

For example, high boiling liquid petroleum, i.e. nickel.

A mixture of a sulfur-containing heavy liquid hydrocarbon fuel having an ash content containing vanadium and silicon, and a pulverized material containing silicon and a material containing copper and/or cobalt is heated at about 650°F, e.g. Co-produced U.S. Patent No. 3,673,08 cited in
No. 0 is introduced into the delayed coking zone via line 33, as shown and described in No. 0. Approximately 800°F
Temperatures in the range of ~895°F, approximately 20-60 psig
At pressures in the range of , uncondensed hydrocarbon effluent steam and water vapor are removed above, mixed with silicon-containing materials and copper- and/or cobalt-containing materials, and petroleum coke is removed from the bottoms of the delayed coking zone. be done.

In another embodiment, the mixture of sulfur-containing high boiling liquid petroleum having an ash content comprising nickel, nocunadium and silicon, a ground silicon-containing material, and a copper and/or cobalt-containing material comprises about 550 At temperatures ranging from °F to 750 °F, e.g.
It is introduced into the fluidized bed coking zone via line 31 as illustrated and described in U.S. Pat. Approximately 1000"F ~ 1200
At temperatures in the lower range and pressures in the range of about 10 to 20 paig, uncondensed hydrocarbon effluent vapor and water vapor are removed above and the petroleum coke is removed from the coking zone bottoms. The petroleum coke is then crushed to fuel size as described above.

In some other embodiments, the present invention can be applied to similar other petroleum processing methods that produce streams suitable for gasification. Unless the bottoms or residue stream is modified to eliminate it, the bottoms treatment process will ultimately produce a residue stream.

Such a stream, whether it is liquid or usually solid but pumpable at high temperatures,
It raises the same gasification issues discussed for coke. Thus, inventions relating to the introduction of silicon-containing materials and copper- and/or cobalt-containing materials as part of oil processing prior to gasification vary depending on the individual method.
Feedstocks must be produced that do not have the gasification problems mentioned above. Most of these methods utilize vacuum distillation as a pretreatment.

Therefore, as mentioned above, the substance containing silicon and the substance containing copper and/or cobalt are nickel.

It is mixed with a vacuum distillation feed having an ash content containing vanadium and silicon. The additives then emerge from the distillation column highly dispersed in the bottoms stream. The bottoms stream now becomes the feed stream for the reforming process. The mixing of silicon-containing substances with copper and/or cobalt-containing substances must not have an adverse effect on these processes;
The additives should ultimately come out with the nickel-, vanadium-, and silicon-containing residue stream from each process. In all steps, this residue stream must be suitable for gasification by partial oxidation.

A major advantage of the process of the present invention is that it produces a relatively small volume of slag with a relatively high vanadium content, eg, greater than or equal to about 2.0% V by weight. Be friends,
This slag has high commercial value for recycling companies.

Various modifications of the invention described above are possible without departing from the spirit and scope of the invention, and accordingly, no limitations should be made other than as set forth in the appended claims. do not have.

Claims (23)

[Claims] (1) A method for producing a gaseous mixture containing H_2 and CO by partial oxidation of a fuel feedstock containing a sulfur-containing heavy liquid hydrocarbon fuel and/or a solid carbonaceous fuel, comprising: has an ash containing nickel, vanadium, and silicon, and the feedstock has at least about 0.5 ppm nickel, at least about 0.2 wt% sulfur, at least about 1.0 ppm vanadium, and at least about 5.0 ppm silicon. The method includes:
(1) A substance containing copper and/or cobalt is mixed with the fuel feedstock, and C is mixed with respect to Ni in the mixture.
The weight ratio of u and/or Co is in the range of about 0.2 to 10, and the weight ratio of Cu and/or Co to Si in the mixture is
or (2) a downward gravity gravity vertical reaction zone with a refractory lined wall of a partial oxidation gas generator;
The mixture obtained in step (1) is heated under a reducing atmosphere containing oxygen in the presence of a temperature control agent at a pressure in the range of about 2 to 250 atmospheres and at a temperature in the range of about 1800°F to 2900°F. In the process of performing partial oxidation by reacting with a gas, the equilibrium oxygen concentration in the gas phase in the reaction region is in the range of about 1.7 x 10^-^1^5 to 2.3 x 10^-^8 atm. The equilibrium sulfur concentration in the gas phase in the reaction zone is approximately 2.53 x 10^-^7~8.1 x
It has a partial pressure in the range of 10^-^2 atm and a free oxygen/carbon atomic ratio in the range of approximately 0.3 to 1.2, with liquid hydrocarbon fuels and/or solid carbon. The weight ratio of H_2O to fuel feedstock is approximately 0.1 to 5.0, thus producing a hot feed effluent gas stream containing H_2 and CO and slag carried away, and carbon in the fuel feedstock. in the reaction zone, the copper and/or cobalt-containing material converts at least one of the nickel, sulfur and silicon components in the fuel feedstock. to form a slag at least partially deposited on the inner walls of the reaction zone, the slag comprising the following phases: (i) about 0.1-10% by weight of a Cu-Ni alloy phase; and/or a Co-Ni alloy phase in which the weight ratio of Cu and/or Co to Ni is in the range of 0.2 to 0.9; (ii) about 5.0 to 85% by weight of copper silicate; (iii) a cobalt silicate phase with Cu and/or Co in the range of about 0.01 to 2.0% by weight; (iii) a spinel phase of about 2.5 to 45% by weight; 5-60 wt% V, 7-65 wt% Fe, 0
．． 1 to 40% by weight Al, 0.1 to 35% by weight Mg,
0.01-42 wt% Cr and 0.1-10 wt%
and (iv) the remainder of a slag consisting of a fluidized oxyfluid phase containing sulfides of Cu and/or Co and Fe, said slag being substantially free of Ni_8S_2. (3) when the partial oxidation reaction occurs without the presence of the Cu and/or Co-containing substance, the molar ratio of H_2S+COS/H_2+CO is reduced relative to the molar ratio in the feedstock effluent gas stream; separating a non-gaseous material substantially free of Ni_8S_2 from said hot feed effluent gas stream. (2) A method for producing a gaseous mixture containing H_2 and CO by partial oxidation of a fuel feedstock containing a sulfur-containing heavy liquid hydrocarbon fuel and/or a solid carbonaceous fuel, comprising: has an ash content comprising nickel, vanadium and silicon, and the feedstock has an ash content of at least about 0.5 to 4,000 ppm nickel, at least about 0
．． 2% by weight sulfur, about 1.0 to 2000 ppm vanadium, and about 5 to 10,000 ppm silicon; a first additive comprising: a total amount of silicon in the first additive and silicon in the fuel feedstock, by weight relative to vanadium in the fuel feedstock in the mixture; the ratio is in the range of about 1 to 7, and the mixture includes a second additive containing a material selected from the group consisting of a copper-containing material, a cobalt-containing material, and mixtures thereof. This allows for Cu/Ni, Co/Ni and Cu+Co when the metal is present in the mixture.
/Ni in the range of about 0.5 to 20, and the weight ratio of the second additive to ash in the fuel feedstock is in the range of about 0.01 to 1.5. , (2) in a downflow gravity vertical reaction zone with refractory-lined walls of a partial oxidation gas generator in the presence of a temperature regulator comprising H_2O at a pressure in the range of about 2 to 250 atmospheres; At temperatures ranging from °F to 2900 °F,
The mixture obtained in step (1) is partially oxidized by reacting with a free oxygen-containing gas in a reducing atmosphere, and the free oxygen/carbon atomic ratio is in the range of about 0.4 to 1.2. , the weight ratio of H_2O to solid hydrocarbonaceous fuel and/or solid carbonaceous fuel is in the range of approximately 0.1 to 3.0, thus reducing the hot effluent containing H_2 and CO and the slag carried away. producing a feedstock gas stream and converting about 90 to 99.9% by weight of the carbon in the fuel feedstock to carbon oxide, wherein the first and second additives reduce the ash content of the nickel, vanadium , silicon and sulfur to form a slag, which contains the following phases: (i) Cu-Ni alloy phase, Co-Ni alloy phase, Cu-Fe alloy phase; about 0.0005 to 1.5 selected from the group consisting of mixtures;
% by weight of the alloy phase, and when present in said alloy phase, C
u/Ni, Co/Ni and Cu+Co/Ni weight ratios in the range of about 1 to 10; (ii) copper silicate phase;
about 45.0 to 97% by weight of a silicate phase selected from the group consisting of a cobalt silicate phase and mixtures thereof, the silicate phase containing an element selected from the group consisting of Cu, Co and mixtures thereof; Approximately 0.01-3.0% by weight of the acid salt phase
(iii) about 1.8 to 12
% by weight of spinel phase, 5-60% by weight of V, 7
~65 wt% Fe, 0.1-40 wt% Al, 0.
A group consisting of 1 to 35% by weight of Mg, 0.01 to 42% by weight of Cr and 0.1 to 10% by weight of other elements, and (iv) Cu, Co, Fe and mixtures thereof. The slag includes a residual slag containing a fluid oxysulfide phase consisting of a sulfide of at least one element selected from the following: the slag substantially does not contain Ni_8S_2, and the partial oxidation reaction and the second
H_2S+COS/H_2S+COS/H_
Production of a gaseous mixture, characterized in that it comprises a step in which a reduction in the molar ratio of 2+CO takes place; and (3) separating a non-gaseous material substantially free of Ni_8S_2 from said hot feed effluent gas stream. Law. (3) stopping the partial oxidation reaction after about 1 to 180 days;
substantially free of Ni_8S_2 by changing the atmosphere in the reaction zone from a reducing atmosphere to an oxidizing atmosphere, thereby oxidizing the slag on the inner wall of the reaction zone and lowering the melting temperature and viscosity of the slag. 2. The method of claim 1, further comprising the step of allowing the molten slag to flow down the inner walls of the reaction zone by gravity. (4) Claim 2, wherein the silicon-containing material contains about 25 to 65% by weight of silicon.
Section method. (5) A weight ratio of the total amount of silicon in the first additive and silicon in the fuel feedstock to vanadium in the fuel feedstock is in the range of about 2 to 10. The method according to claim 2 or 5. (6) The method according to any one of claims 2, 4, and 5, wherein the silicon-containing substance is selected from the group consisting of silica, quartz, volcanic ash, and mixtures thereof. . (7) The fuel feedstock is a sulfur-containing heavy liquid hydrocarbon fuel having an ash content containing nickel, vanadium, and silicon, and step (1) further includes coking the mixture to produce nickel, vanadium, and silicon. producing a sulfur-containing petroleum coke having an ash content containing said copper and/or cobalt-containing substance dispersed therein; or as substantially dry crushed petroleum coke transported in a gaseous transport means, into the gravity-flow refractory-lined partial oxidation reaction zone. 7. A method according to any one of claims 1 to 6, characterized in that: (8) The equilibrium oxygen concentration in the gas phase in the reaction region is approximately 1
．． It has a partial pressure in the range of 2 × 10^-^1^6 to 2.0 × 10^-^9 atmospheres, and the equilibrium sulfur concentration in the gas phase in the reaction zone is approximately 1.7 × 10^-^6 ~1.1×10^-^
8. A method according to any one of claims 1 to 7, characterized in that the partial pressure is in the range of 4 atmospheres. (9) A patent characterized in that the sulfur-containing heavy liquid hydrocarbon fuel having an ash content containing nickel, vanadium, and silicon is a high-boiling liquid petroleum feedstock or a residual liquid from a vacuum column or a rectification column. A method according to claim 7 or 8. (10) In step (1), the mixture at a temperature in the range of about 650°F to 930°F is heated to a temperature in the range of about 800°F to
In the range of 895°F and pressure approximately 20-60 psig
The uncondensed hydrocarbon effluent steam and water vapor are removed above and the nickel,
The sulfur-containing petroleum coke having an ash content containing vanadium and silicon and containing the substance containing copper and/or cobalt uniformly dispersed therein is removed from the residual liquor. Range 7th to 1st
Any method in item 0. (11) In step (1), the mixture at a temperature ranging from about 550°F to 750°F is mixed at a temperature ranging from about 1000°F to 1
in the range of 200°F with a pressure of approximately 10-20 psig
, wherein the uncondensed hydrocarbon effluent steam and water vapor are removed above, and the petroleum coke is removed from the bottom liquid. Any method of Section 10. (12) in step (3) said non-gaseous substances are separated from said hot effluent gas stream by contacting the gas stream obtained from step (2) with water or oil scrubbing means; Claim 7 characterized by
The method according to any one of Items 1 to 11. (13) The substance containing copper and/or cobalt,
Copper and/or cobalt compounds selected from oxides, sulfides, sulfates, carbonates, cyanides, chlorides, nitrates, hydroxides, ferrocyanides, ferricyanides, phosphates and mixtures thereof A method according to any one of claims 1 to 12, characterized in that the method comprises: (14) The substance containing copper and/or cobalt,
characterized in that it is an organic compound selected from the group consisting of naphthenates, oxalates, acetates, citrates, benzoates, oleates, tartrates, butyrates, formates and mixtures thereof. Claims 1 to 12
Either way. (15) Claims 1 to 12, characterized in that the substance containing copper and/or cobalt added in step (1) consists of an inorganic compound or an organic compound of copper and/or cobalt. Either way. (16) Claims 1 to 12, characterized in that the substance containing copper and/or cobalt in step (1) consists of a concentrated copper mineral containing at least 20% by weight of copper. Either way. 17. The method of claim 16, wherein the concentrated copper mineral is a mixture of copper, copper-iron, and iron sulfides with a small amount of gangue. (18) The substance containing copper and/or cobalt,
Consists of copper sulfide minerals selected from the group consisting of bornite, sulfurite, tetrahedrite, arsenotetra, chalcocite, copper indigo, digenite, and mixtures thereof, or cuprite, chalcopyrite, kujiite. Claims 1 to 12 are characterized in that the copper oxide mineral is selected from the group consisting of , blue copperite, Prussian copperite, glaurite copperite, diatomaceous stone, and mixtures thereof. Either way. (19) Said sulfur-containing heavy liquid hydrocarbon-based fuel having an ash feedstock containing nickel, vanadium and silicon comprises virgin crude feedstock, crude feedstock residues of petroleum distillation and petroleum cracking process operations, petroleum distillates, reduced Claims 1 to 8 and 8 are selected from the group consisting of crude raw materials, total crude raw materials, asphalt, coal tar, coal-based oils, shale oils, tar sands oils, and mixtures thereof. The method according to any one of Items 10 to 18. (20) In step (1), the substance containing copper and/or cobalt is introduced from a vacuum distillation unit into the supply path or the residual liquid. Either way. (21) Substances and processes containing copper and/or cobalt (
The mixture with the feedstock of 1) has a diameter of 424 μm to 38 μm.
Claims 1 to 20, characterized in that the particles have a particle size such that approximately 100% of the particles pass through a sieve having a standard sieve grade of ASTM E-11 in the range of 1000 m or less. Either way. (22) Substantially all of the sulfur in the feedstock is present in the step (
22. A process according to any one of claims 1 to 21, characterized in that the fluidized oxyfluid phase according to (iv) of 2) is converted into a fluidized oxyfluid phase which leaves the reaction zone and remains in the slag. (23) The fuel feedstock is about 0.2 to 6.5% by weight
of sulfur and about 5.0 to 20,000 ppm or more of silicon, and the molten slag produced in step (2) contains about 0 to 5% by weight of said fluid oxysulfide and at least about 0.1 to 20,000 ppm or more of silicon. Claims 1 to 2 contain 10% by weight of the Cu-Ni alloy phase.
Either method in Section 2.