JP3051566B2 - New hydroconversion process - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the conversion of heavy hydrocarbon oils. More specifically, the present invention relates to
The present invention relates to a hydrotreating catalyst system which makes it possible to obtain an increased conversion of the charged oil to a low-boiling product.

[0002]

BACKGROUND OF THE INVENTION As is well known to those skilled in the art, petroleum refiners can more easily handle and / or market higher boiling fractions, such as vacuum distillation bottoms. It wants to convert to a lower boiling fraction. The vast amount of prior art patent examples has led this problem to the following flow.

US Pat. No. 4,579,646 teaches that a hydrocarbon feed is partially coked and the coke is added to the feedstock in groups IVB, VB, VII of the periodic table.
A resid visbreaking hydroconversion process is disclosed which comprises contacting an oil-soluble metal compound of a Group B or Group VIII metal to obtain a hydroconversion catalyst.

US Pat. No. 4,724,069 teaches a supported catalyst of a Group VIB, VIIB or VIII metal of the Periodic Table supported on alumina, silica or silica-alumina. Discloses hydrofining. There, naphthenates of Co or Fe are introduced as additives along with the feedstock.

US Pat. No. 4,567,156 discloses that a water-soluble aliphatic polyhydroxy compound (eg, glycerin) is added to chromic acid in the presence of a chromium catalyst.
It discloses a hydroconversion process in which a hydrocarbon is added and the mixture is heated in the presence of hydrogen sulfide to obtain a slurry.

US Pat. No. 4,564,441 discloses metals (copper, zinc, groups IIIB, IVB, VIB, VIIB or VIIB) of a metal mixed with a hydrocarbon-containing feed stream.
Discloses hydrotreating in the presence of a decomposable compound of group III) and then contacting the mixture with a "suitable hardly soluble inorganic substance" such as alumina.

US Pat. No. 4,557,823 describes decomposable compounds of metals of group IVB of the periodic table and supported catalysts containing metals of groups VIB, VIIB and VIII of the periodic table. Discloses hydrorefining in the presence.

[0008] US Pat. No. 4,557,824 describes a group VIB, VI of the Periodic Table added to a feedstock and a heterogeneous catalyst containing a phosphate of Zr, Co or Fe.
Disclosed is demetallation of a Group IB or Group VIII metal in the presence of a decomposable compound.

[0009] US Patent No. 4,551,230 discloses a group IVB, VB, VB, or VB of the periodic table added to a feedstock and a heterogeneous catalyst containing NiAs _x on alumina.
Disclosed is demetallation of a Group VIB, VIIB or VIII metal in the presence of a decomposable compound.

[0010] US Patent No. 4,430,207 discloses a group VB, VIB of the Periodic Table added to a feedstock and a heterogeneous catalyst containing a phosphate of Zr or Cr. ,
Disclosed is demetallation of a Group VIIB or VIII metal in the presence of a decomposable compound.

US Pat. No. 4,389,301 teaches that a dispersed hydrogenation catalyst (typically ammonium molybdate) and porous contact particles (typically F
Hydrogen treatment in the presence of CC catalyst fines, alumina, or naturally occurring clay) is disclosed.

US Pat. No. 4,352,729 discloses a hydrotreatment in which a hydrocarbon feed is introduced in the presence of molybdenum blue in a polar solvent.

US Pat. No. 4,338,183 discloses liquefaction of coal in the presence of unsupported finely divided metal catalyst.

US Pat. No. 4,298,454 describes Periodic Tables Groups IVB, VB, VIB, VIIB.
Disclosed is the hydrocracking of a coal oil mixture in the presence of a Group VIII or Group VIII metal, preferably molybdenum.

US Pat. No. 4,134,825 describes the addition of raw materials to the Periodic Table of Groups IVB, VB,
Disclosed is a hydroconversion in which the compound is heated in the presence of hydrogen to convert it to a solid, non-colloidal form in the presence of an oil-soluble compound of a Group VIB or Group VIII metal.

US Pat. No. 4,125,455 discloses a hydrotreating treatment in the presence of a fatty acid salt of a Group VIB metal of the Periodic Table, typically molybdenum octoate.

US Pat. No. 4,077,867 describes a Periodic Table of Groups VB, VIB, VIIB or VI.
Disclosed is the hydroconversion of coal in the presence of a hydrogen donor solvent in addition to an oil-soluble compound of a Group II metal.

US Pat. No. 4,067,799 discloses hydroconversion in the presence of dispersed iron particles in addition to the metal phthalocyanine.

US Pat. No. 4,066,530 discloses that (i) an iron component; and (ii) an oil-soluble metal compound is dissolved in oil, and the metal compound in the oil is converted to a corresponding catalytically active metal component. Discloses hydroconversion in the presence of catalytically active metal components other than iron produced by the conversion.

[0020]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel hydroconversion process characterized in that particularly increased conversions are obtained. Other objectives will be apparent to those skilled in the art.

[0021]

SUMMARY OF THE INVENTION In accordance with some of the features of the present invention, the present invention provides a method for producing a hydrocarbon feedstock containing a significant amount of components having a boiling point above about 1,000 ° F.
(I) As a hydrotreating component, Periodic Table IVB on a carrier
A heterogeneous solid catalyst containing a Group IVB, VIB, VIB, VIIB or VIII metal; and (ii) as an oil-soluble catalyst, a group IVB, V B
Contacting with a compound of a Group VIB, Group VIIB or Group VIII metal; the raw hydrocarbon oil containing a substantial amount of a component having a boiling point of about °
A significant portion of components with boiling points above F are 1,000 °
Maintaining the conversion zone in the conversion conditions in the presence of hydrogen and sulfur containing compounds, such that the conversion to components having a boiling point of F or less;
Thereby forming a product containing a significant portion of components having a boiling point of less than about 1,000 ° F .; and forming the product containing a significant portion of components having a boiling point of less than about 1,000 ° F. Feed hydrocarbon oils containing a significant amount of components having a boiling point above about 1,000 ° F., including recovering material, to convert a significant portion thereof to components having a boiling point below 1,000 ° F. The conversion is directed to catalytic hydroconversion.

The feedstock treated in the process of the present invention typically includes high boiling hydrocarbons having an initial boiling point (ibp) of about 650 ° F. or higher. This method requires a considerable amount of about 1,0
It is particularly useful in the treatment of raw hydrocarbon oils containing components having a boiling point above 00 ° F. to convert a significant portion thereof to components having a boiling point below 1,000 ° F.

Typical examples of these feed oils are heavy crude oil, atmospheric distillation bottoms, vacuum distillation bottoms, asphaltenes, tars, coal liquors, and bottom oils of bis-breakers. Examples of these feedstocks are Alaska North Slope crude (59
% By volume), Arabia medium crude oil (5% by volume), Arabia heavy crude oil (27% by volume) and Bonny light crude oil (9% by volume). And have properties as listed in Table I.

[0024]

[Table 1]

The characteristics of these feed hydrocarbons are that they are nitrogen (up to 1% by weight, typically 0.2-0.8% by weight, for example about 0.52% by weight), sulfur (10% by weight). And typically up to 2-6% by weight, such as about 3.64% by weight, and metals including Ni, V, Fe, Cr, Na, etc. (up to 900% by weight, typically 40-40
0 ppm by weight (eg, about 198 ppm by weight). The undesired asphaltene content of the raw hydrocarbon is 22% by weight.
It may be as high as 8-16% by weight, for example 11.97% by weight (analyzed as n-heptane insoluble component).

The API specific gravity of the raw material may be as low as -5, typically from -5 to +35, for example about 5.8. The content of components having a boiling point above about 1,000 ° F. may be as high as 100% by weight, typically 50-98%.
+% By weight, for example 93.1% by weight. Alcoa MCR The carbon content may be as high as 30% by weight, typically 1%.
5 to 25% by weight, for example 19.86% by weight.

In practicing the process of the present invention, the feed hydrocarbon oil is passed through a hydroconversion operation, where it comprises about 500
~ 5,000 psig, preferably about 1,500 ~ 2,500
Under a hydrogen partial pressure of 0 psig, for example 2,000 psig, 70
The conversion reaction occurs in the liquid phase at conversion conditions that include temperatures of 0-850 ° F, preferably about 750-810 ° F, for example 800 ° F.

A feature of the process of the present invention is that the feedstock hydrocarbon oil (preferably prior to hydroconversion) is provided with a catalytically effective amount of an oil-miscible, preferably oil-soluble, periodic table. Group IVB, group VB, group VIB, group VIIB or VI
The addition of a Group II metal catalyst compound.

When the metal is a Group IV metal, it can be titanium (Ti), zirconium (Zr) or hafnium (H
f). When the metal is a Group V metal, it can be vanadium (V), niobium (Nb) or tantalum (Ta).
It may be. When the metal is a Group VI metal, it can be chromium (Cr), molybdenum (Mo) or tungsten (W)
It may be. When the metal is a Group VII metal, it may be manganese (Mn) or rhenium (Re).

When the metal is a Group VIII metal, it may be iron (F
e), a non-noble metal such as cobalt (Co) or nickel (Ni), or ruthenium (R
Noble metals such as u), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) or platinum (Pt).

Preferably, the metal is a Group VI metal, most preferably molybdenum (Mo).

The metal compound is an oil-soluble compound represented by the following. (I) Aliphatic metal carboxylate: molybdenum stearate, molybdenum palmitate, molybdenum myristate, molybdenum octoate (ii) Naphthenic metal carboxylate: cobalt naphthenate, iron naphthenate, molybdenum naphthenate (iii) A) Alicyclic carboxylic acid metal salt: molybdenum cyclohexanecarboxylate (iv) Aromatic carboxylic acid metal salt: cobalt benzoate, o
-Cobalt methyl benzoate, cobalt m-methyl benzoate, cobalt phthalate, molybdenum p-methyl benzoate (v) Metal salt of sulfonic acid: molybdenum benzene sulfonate, cobalt p-toluene sulfonate, iron xylene sulfonate (vi) Sulfinic acid metal salt: molybdenum benzenesulfinate, iron benzenesulfinate (vii) Phosphonic acid metal salt: molybdenum phenylphosphonate (viii) Sulfur-containing compound metal salt: iron octyl mercaptide,
Cobalt hexyl mercaptide (ix) Phenol metal salt: cobalt phenolate, iron phenolate (x) Metal salt of polyhydroxy aromatic compound: iron catecholate, molybdenum resorcinate (xi) Organometallic compound: molybdenum hexacarbonyl,
Iron hexacarbonyl, cyclopentadiene molybdenum tricarbonyl (xii) Metal chelate: ethylenediaminetetracarboxylic acid diiron salt (xiii) Organic amine metal salt: pyrrole cobalt salt

Preferred compounds are cobalt naphthenate,
Molybdenum hexacarbonyl, cobalt naphthenate and cobalt octenoate.

The effect of using oil-soluble compounds has been found to be increased by using compounds of two or more metals. By way of example, it has been found that if molybdenum is used (eg, as a naphthenate), it is preferable to add an additional amount of cobalt (eg, as a naphthenate). Such a combination has a positive synergistic promoting effect on catalytic desulfurization and demetallization. Typically, 0.2 to 2 moles per mole of molybdenum, for example 0.4
Molar cobalt may be added.

The metal compound used can be mixed with oil, and is preferably oil-soluble. That is, they have a solubility in the feed hydrocarbon oil of at least 0.01 g / 100 g, typically 0.025-0.25 g / 100 g, such as about 0.1 g / 100 g, or alternatively , They are easily dispersed, at least in their amounts, in the raw hydrocarbon oil. These metal compounds, when activated as described below, can also be mixed with the hydrocarbon oil when the activated compound is contacted during the process of the present invention. It is a feature.

By carrying out the method of the present invention, the periodic table IV
Activation of oil-miscible compounds derived from Group B, VB, VIB, VIIB or VIII metals can be accomplished by pretreatment (prior to hydroconversion) or in situ (hydrogen conversion). (During conversion). In order to obtain a highly dispersible catalyst type, it is preferred to carry out the activation in situ in the presence of a hydrogenation catalyst.

Activation by the preferred method is 60-30.
At 0 ° F, for example 200 ° F, 10-
It is carried out by adding 200 ppm by weight, for example 30 ppm by weight, of a metal compound. 500-5,000psi
g, typically 1,000 to 3,000 psig, for example 2,000 psig of hydrogen and a partial pressure of 5 to 500 psig, typically 10 to 300 psig, for example 50 psig of the gaseous sulfur-containing compound. Activate the mixture by heating to 400-835 ° F, typically 500-700 ° F, for example 600 ° F. Total pressure is 500 ~ 5
500 psig, typically 1,000-3,300 psig,
For example, it may be 2,050 psig. Usually the gas is 4
It may contain 0-99% by volume, typically 90-99% by volume, for example 98% by volume of hydrogen and 1-10% by volume, for example 2% by volume of sulfur-containing compounds, for example hydrogen sulfide.
The activation time may be 1 to 12 hours, typically 2 to 6 hours, for example 3 hours.

It is noted that in this embodiment, the activation occurs at a temperature below the conversion temperature.

The sulfur-containing compound used may include hydrogen sulfide; aliphatic mercaptans represented by methyl mercaptan, lauryl mercaptan, etc .; aromatic mercaptans; dimethyl disulfide; carbon disulfate.

These sulfur compounds apparently decompose during the activation process. Activity can occur as a result of forming metal sulfide during processing.

When the sulfur content of the feed hydrocarbon is above about 2%, no sulfur-containing compound needs to be added during activation.
That is, desulfurization of the feedstock provides sufficient sulfur-containing compounds that can be mixed with the oil and adequately activate the decomposable catalyst (ie, form sulfides).

In an alternative activation procedure, an oil-miscible metal compound is activated in the presence of an oil that is compatible with the base oil, ie, another portion of the base oil or an oil that is different from the base oil. You may. In this alternative, the oil-miscible metal compound can be added in significantly greater amounts (eg, 2 to 20 times) than if the compound were activated in the presence of the feedstock. After activation (under the same conditions that are effective when activated in the feedstock), a compatible oil containing the activated metal is added to the required amount of the activated oil-miscible metal compound. It is added to the raw material feed in an amount sufficient to give it.

In yet another embodiment, the activation is carried out in the presence of a sulfur-containing compound, but in the absence of a heterogeneous hydroconversion catalyst, with the starting hydrocarbon oil containing the oil-miscible metal compound. , About 500-5,000 psig, preferably about 1,
At a hydrogen partial pressure of 500-2,000 psig, for example 2,000 psig, 700-850 ° F, preferably about 750-
It can be carried out by subjecting to hydroconversion conditions involving a temperature of 810 ° F, for example 800 ° F.

In a preferred embodiment, the activation can be carried out during hydroconversion, ie in the presence of a heterogeneous hydroconversion catalyst, hydrogen and a sulfur-containing compound.

The hydroconversion is carried out on a support which is typically carbon or an oxide of aluminum, silicon, titanium, magnesium or zirconium.
It is carried out in the presence of a solid heterogeneous catalyst containing a Group B, VB, VIB, VIIB or VIII metal as hydrogenation component. Preferably, the catalyst may contain Group VIB and Group VIII metals, typically nickel and molybdenum.

When the metal is a Group IVB metal, it can be titanium (Ti), zirconium (Zr) or hafnium (H
f). When the metal is a Group VB metal, it can be vanadium (V), niobium (Nb) or tantalum (T
a). When a metal Group VIB metal, it may be chromium (Cr), molybdenum (Mo) or tungsten (W). When the metal is a Group VIIB metal, it may be manganese (Mn) or rhenium (Re).

When the metal is a Group VIII metal, it may be iron (F
e), a non-noble metal such as cobalt (Co) or nickel (Ni), or ruthenium (R
u), a noble metal such as rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) or platinum (Pt).

[0048] The solid heterogeneous catalyst may also include
It may contain a metal of Group IA, IB, IIA, IIB or VA of the periodic table.

When the promoter is a Group IA metal, it may preferably be sodium (Na) or potassium (K). When the promoter is a Group IB metal, it may preferably be copper (Cu). When the promoter is a Group IIA metal, it can be beryllium (Be), magnesium (M
g), calcium (Ca), strontium (Sr),
It may be barium (Ba) or radium (Ra). When the promoter is a Group IIB metal, it may be zinc (Z
n), cadmium (Cd) or mercury (Hg). When the promoter is a Group VA metal, it is preferably arsenic (As), antimony (Sb) or bismuth (B
i).

The metal for hydrogenation is prepared by adding a carrier for the catalyst to a solution (for example, a solution of ammonium heptamolybdate).
Soak for 24 hours, for example 24 hours, then 60-30
Dry at 0 ° F, for example 200 ° F for 1 to 24 hours, for example 3 hours, and 570 to 1,100 ° F, for example 75
Calcination at 0 ° F. for 1 to 12 hours, for example 3 hours, can be supported as a solid heterogeneous catalyst.

The promoter metal is deposited on a catalyst support, preferably a calcined metal for hydrogenation-even if added simultaneously or otherwise. (Bismuth nitrate solution) for 2 to 24 hours, for example, 24 hours, and then dried at 60 to 300 ° F., for example, 200 ° F. for 1 to 24 hours, for example, 3 hours.
70-1100 ° F, for example 1-12 at 750 ° F
By calcining for a period of time, for example, 3 hours, the catalyst can be supported as a solid heterogeneous catalyst.

[0052] Solid heterogeneous catalysts used in the process of the present invention, 0.2~1.2ml / g, for example the total pore volume of ^{0.77ml / g; 50~500m 2 / g} , for example 280 meters ² / g surface area; and the pore size distribution described below.

[0053]

[Table 2]

In another embodiment, it may have the following pore size distribution.

[0055]

[Table 3]

Solid heterogeneous catalysts are typically from 4 to 30
% By weight, for example 9.5% by weight molybdenum; 0 to 6% by weight, for example 3.1% by weight of nickel; and 0 to 6% by weight, for example 3.1% by weight of a promoter metal, for example bismuth May be. LHS of hydroconversion reactor
V may be 1-2, for example 0.7. Preferably, the heterogeneous catalyst can be used in the form of an extrudate having a diameter of 0.7 to 6.5 mm, for example 1 mm; a length of 0.2 to 25 mm, for example 5 mm.

The hydroconversion can be carried out in a fixed, moving, fluidized or preferably ebullated bed.

A feature of the process of the present invention is that hydroconversion can be carried out on one or more catalyst beds. The active form of the catalyst is formed or aggregates in the first of several reactors, so that increased conversion and heteroatom removal activity appears to occur in the first of some reactors Was found.

[0059]

The effluent of the hydroconversion reaction is typically characterized by an increase in the content of liquids having a boiling point below 1,000 ° F. Typically, materials having a boiling point above 1,000 ° F. have a conversion of 30-90% by weight, for example 67%.
%, Which is typically 5 to 25% by weight, for example 12%, better than obtained in the prior art.

It is a feature of the present invention that improved sulfur removal (H
DS conversion); removal of nitrogen (HDN conversion) and removal of metal (HDNi and HDV conversion) can be achieved. HDS conversion is typically 30-90%, for example 65%, which is 1-10%, for example 4%, higher than in comparative experiments. HDN conversion is typically 20-6.
0%, for example 45%, which is 1 to
10%, for example 4% higher. The sum of the HDNi conversion and the HDV conversion is typically 70 to 99%, for example, 90%.
Which is 5-20% from the comparative experiment, for example 13
%high.

[0061]

The practice of the method of the invention will be apparent to those skilled in the art from the following examples. Here, all parts are parts by weight unless otherwise stated in this specification. An asterisk (*) represents a comparative example.

Example I This example illustrates the best known mode of implementing the method of the present invention. The raw material hydrocarbon is Alaska Nor
th Slope (59% by volume), Arabia medium (5% by volume), Ar
abia Heavy (27% by volume) and Bonny light (9% by volume) a mixture of vacuum resid from each crude.

The solid heterogeneous catalyst used was a commercially available hydrotreating catalyst (Criterion Catalyst, H
DS-1433B catalyst).
It contains 2.83% by weight nickel and 8.75% by weight molybdenum on alumina. This catalyst has a diameter of 1/3
Extruded 2 inches, 5mm long, surface area 285.2m ²
/ g, the total pore volume is 0.78 ml / g. The pore size distribution is>
250% at 0.28 ml / g,> 500% at 0.21 ml / g;
> 1,500 / is 0.19 ml / g;> 4,000Å is 0.19 ml / g.
It is 11 ml / g.

In this example, 160%
Molybdenum naphthenate was added in an amount to give ppm metal molybdenum. During the hydroconversion of the catalyst, in place,
Activated at 785 ° F under 2,000 psig hydrogen partial pressure. The flow rate of hydrogen was 6,300 SCFB. Raw material L
HSV was 0.4-1 h ^-1 .

The results are shown in Table II. Table II shows that 1,000
Conversion of components with boiling points above ° F, HDS conversion, H
The DV conversion, HDNi conversion and cyclohexane-insoluble matter are shown, all expressed in% by weight.

EXAMPLES II-V ^{* In} this series of examples, Example I was repeated except that the molybdenum concentration (ppm) was changed. The operating temperature was determined in Examples I to
785 ° F. over V ^* .

[0067]

[Table 4]

From Table II, the following results could be derived. (I) In all cases of Examples I to IV carried out by the method of the present invention, conversion of components having a boiling point of 1,000 ° F. or higher, hydrodesulfurization (HDS) conversion, hydrodevanadium ( HDV) conversion, hydrodenickelization (HDN)
i) shows the improvement in conversion and coke content as measured by cyclohexane insolubles. (Ii) The present invention exhibits a 10-30% improvement in conversion of components having a boiling point above 1,000 ° F. (Iii) The present invention exhibits an improvement in HDS conversion of 5-17%. (Iv) The present invention exhibits an improvement in HDV conversion of 6-14%. (V) The present invention shows an improvement in HDNi conversion of 20-47%. (Vi) The present invention exhibits about a 20-50% reduction in coke content.

EXAMPLES VI ^* -VII In this series of experiments, the procedure of Examples IV was followed, with the following exceptions. (I) The operating temperature is 800 ° F. (Ii) In Example VII, an amount of cobalt naphthenate was added to give 160 ppm of metallic cobalt. Note that molybdenum naphthenate was not added. (Iii) In Example VI ^* , Example V ^* was repeated except for the operating temperature. The results are shown in Table III.

[0070]

[Table 5]

From Table III, it appears that cobalt naphthenate appears to be less preferred than molybdenum, but is effective as an effective oil-miscible catalytic metal.

Example VIII In this example, molybdenum naphthenate was added at 100 ppm
Molybdenum hexacarbonyl such that the resulting molybdenum metal was obtained. The operating temperature was 800 ° F. The results are shown in Table IV in comparison with Example VI ^* .

[0073]

[Table 6]

From Table IV, the following is noted. (I) Example VIII performed by the method of the present invention comprises:
11. Conversion of components having a boiling point above 1,000 ° F.
It showed a significant improvement of 4%. (Ii) Removal of vanadium and nickel should be performed using HDV and HDN.
i, which are 5.2% and 7.9, respectively.
% Improvement. (Iii) Coke formation dropped from 6.3% to 3.7%, as evidenced by cyclohexane insolubles, to 41%
Was reduced.

Example IX ^{* In} this Example IX ^* , the supported catalyst (Ni / M
o / alumina), neither Ni nor Mo adheres,
Example I was followed except that it was simply uncatalyzed alumina. The results are shown in Table V in comparison with Example III.

[0076]

[Table 7]

From Table V it is clear that the presence of the catalytic metal on the solid catalyst is necessary to obtain improved results.

Example X In Example X, the procedure of Example II was repeated except that 13 ppm of cobalt was used in an amount of cobalt naphthenate mixed with 60 ppm of molybdenum to obtain molybdenum.
I followed. The results are shown in Table VI together with Examples V ^* and III.

[0079]

[Table 8]

The following conclusions can be drawn from Table VI. (I) Adding a small amount of cobalt to the preferred molybdenum removes heteroatoms (HDS, HDV, HDNi)
Have a synergistic effect on (Ii) The addition of cobalt further reduces the coke content.

Although the invention has been described with reference to specific embodiments, it will be apparent to those skilled in the art that various raw materials may be used and modifications which are expressly within the scope of the invention.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (72) Inventor Ajito Kumar Bhattachala United States, New York 12533, Hopewell Junction, Sarah Lane 5 (72) Inventor Mahendra Somabuhai Patel United States, New York 12533, Hopewell Junction, Country Club Road 6 (72) Inventor Dennis Joseph Lao United States, New York 12533, Hopewell Junction And Elizabeth Drive 15 (56) References JP-A-60-120791 (JP, A) JP-A-60-123391 (JP, A) JP-A-63-113096 (JP, A) (58) Field (Int.Cl. ^7, DB name) C10G 49/02 B01J 23/28 B01J 31/20 C10G 45/04 C10G 47/02

Claims (4)

(57) [Claims] 1. A raw material hydrocarbon oil containing 50 to 98% by weight of a component having a boiling point of 538 ° C. ( 1,000 ° F. ) or more, as (i) a hydrotreating component, a component of the periodic table on a carrier.
As well as (ii) an oil-soluble catalyst, is contacted with a molybdenum compound and a cobalt compound;; IVB Group, Group V B, Group VIB, the VII B group or solid heterogeneous catalyst containing group VIII metals the the raw material hydrocarbon oil, 30 to 90 wt% of the component having a boiling point above the 538 ℃ (1,000 ° F) is 538 ° C.
Maintaining the conversion zone in the presence of hydrogen and sulfur-containing compounds at conversion conditions such that the components have a boiling point of less than ( 1,000 ° F. ) ; and recovering the converted oil. A raw hydrocarbon oil containing 50 to 98% by weight of a component having a boiling point of 538 ° C. ( 1,000 ° F. ) or more.
A catalytic hydroconversion method in which 30 to 90% by weight is converted to a component having a boiling point of 538 ° C. ( 1,000 ° F. ) or less. Wherein oil-soluble catalyst contains molybdenum naphthenate and cobalt naphthenate, who <br/> method of claim 1. Wherein oil-soluble catalyst is activated prior to entering the shift conversion zone, according to claim 1 or claim 2 method towards description. 4. The method according to claim 1 , wherein the activation is carried out in the presence of a sulfur-containing compound.
3.5 to 34.5MP in the presence of oil which can be mixed with the charge oil
In hydrogen partial pressure of a (500~5,000psig), 204
～446 carried out by heating the ℃ (400~835 ° F), methods who claim 3.