JPH06100871A - Improved hydrogenating and converting method - Google Patents

Abstract

PURPOSE: To improve a conversion ratio from heavy oil into light oil and a removing ratio of S, N and metals, to increase an H/C ratio of hydrocarbonaceous adhered substances and to obtain a solid heterogeneous catalyst having high accumulated pore volume and high performance by adopting specified conditions in a method for hydroconverting hydrocarbon oil catalytically.

CONSTITUTION: In a method for hydroconverting hydrocarbon oil catalytically, hydrocarbon oil contg. a substantial amount of compounds boiling higher than about 538°C (such as vacuum residual oil) is brought into contact with a solid heterogenous catalyst contg. hydrogenating metal (such as Ni and Mo) supported on a porous carrier (such as alumina) and an oil-miscible compd. (such as molybdenum naphthate) contg. a metallic compd. in an amount to improve an effective porosity at a conversion area, to convert a substantial part of high boiling compounds in hydrocarbon oil into compounds boiling lower than about 538°C in the presence of H₂ and mercaptans under converting conditions and to produce hydrocarbon oil contg. a substantial part of low boiling compounds.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

This invention relates to the hydroconversion of heavy hydrocarbon oils. More particularly, the present invention relates to hydrotreating catalyst systems having improved cumulative pore volume properties, as well as methods of making and using such materials.

[0002]

BACKGROUND OF THE INVENTION In petroleum refining, it is necessary to convert high boiling fractions of petroleum distillates such as vacuum resids to lower boiling fractions of higher value, easier handling and marketability. Often required. The following patents illustrate various methods to address this need.

US Pat. No. 4,579,646 describes partially coking a hydrocarbon feedstock, which coke is in the feedstock Group IV-B, Group V-B.
A visbreaking hydroconversion process for bottom oil is disclosed which is contacted with an oil-soluble compound of a Group III, Group VII-B or Group VIII metal to obtain a hydroconversion catalyst.

US Pat. No. 4,226,742 describes a catalyst for hydroconversion of heavy hydrocarbon oils formed in situ by heating an oil-soluble metal compound in the presence of hydrogen. Is disclosed. The oil-soluble metal compound is
It is added to the feedstock in an amount of 10 to 950 ppm, preferably 50 to 200 ppm. The mixture is converted to the solid, non-colloidal form by heating at 325-415 ° C in the presence of hydrogen gas. After performing the hydroconversion at 26-482 ° C, the catalyst solids are separated from the hydroconversion effluent.

US Pat. No. 4,564,441 describes metals (Cu, Zn, Group III-B, Group IV-B, Group VI).
-Group B, Group VII-B or Group VIII) degradable compounds in the presence of a mixture of hydrocarbon-containing feed stream and hydrofining is disclosed, the mixture then being described as "suitable" such as alumina. In contact with other refractory inorganic materials.

US Pat. No. 4,557,824 discloses decomposable compounds of Group VI-B, VII-B or VIII metals added to the feedstock, as well as Zr, Co.
Alternatively, demetalization in the presence of a heterogeneous catalyst containing Fe phosphate is disclosed.

US Pat. No. 4,134,825 discloses Group IV-B, Group V-B, Group V added to a feedstock.
Hydroconversion of heavy hydrocarbons in the presence of an oil-soluble compound of a VI-B, VII-B or VIII metal converted to a solid, non-colloidal form by heating in the presence of hydrogen. Is disclosed.

US Pat. No. 4,066,530 discloses that (i) an iron component and (ii) an oil-soluble metal compound are dissolved in an oil, and the metal compound in the oil is catalytically active. Discloses the hydroconversion in the presence of other catalytically active metal components, which is prepared by converting the metal component to.

EP-A-512778 discloses oil-soluble catalysts 10 to 10 under the operating conditions disclosed therein, for example, in particular in Examples II to IV and related Table II.
It teaches that by adding 200 ppm by weight to a heterogeneous catalyst, improvements in conversion and other factors can be achieved, for example. In particular, Example I shows that using 160 ppm by weight molybdenum additive can achieve much higher conversions.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a hydroconversion process in which the conversion rate of heavy hydrocarbon oil to light oil and the removal rate of sulfur, nitrogen and metal are large. Another object of the present invention is to provide a high performance solid heterogeneous catalyst in such a hydroconversion process having a hydrocarbon-based deposit with a higher hydrogen: carbon ratio and a greater cumulative pore volume. It is to provide a method of obtaining.

[0011]

SUMMARY OF THE INVENTION The present invention is directed to a process for catalytically hydroconverting hydrocarbon oils which comprises three essential steps. Step (a) comprises a hydrocarbon oil containing a substantial amount of high boiling compounds boiling above about 538 ° C. and (1) a hydrotreating metal supported on a porous support in the conversion zone. Contacting with a solid heterogeneous catalyst, and (2) an oil-miscible compound containing an effective porosity improving amount of a metal compound. Step (b) converts a significant portion of the high boiling compounds in the hydrocarbon oil to low boiling compounds boiling below about 538 ° C. in the presence of hydrogen and mercaptans under conversion conditions to convert the low boiling compounds to low boiling compounds. Producing a hydrocarbon oil containing a substantial portion.
Here, the mercaptans include organic mercaptans, as well as gaseous or low-boiling liquid sulfur compounds such as hydrogen sulfide, dimethyl disulfide and carbon disulfide. Step (c) comprises (1) a hydrocarbon-based deposit with a higher hydrogen: carbon ratio and (2) a larger cumulative pore volume than the equivalent produced in the absence of the oil-miscible compound. Producing a solid heterogeneous catalyst having.

Also provided is a process comprising such steps for enhancing the effective porosity of an in situ solid heterogeneous catalyst during catalytic hydroconversion of hydrocarbon oils. .

Feedstocks that can be treated by the process of the present invention include high boiling hydrocarbons, typically about 34
Some have an initial boiling point (ibp) above 3 ° C. The process treats a feed hydrocarbon containing a substantial amount of components that boil at temperatures above about 538 ° C, with a substantial portion of 538
It is particularly useful for converting to components that boil below ° C.

Typical hydrocarbon oils include, among other things, one or several of the following: That is,
Examples include heavy crude oil, atmospheric distillation crude oil, atmospheric distillation residual oil, vacuum residual oil, asphaltene, tar, coal liquid, visbreaking residual oil, and the like. Typical of such feedstocks are Alaska North Slope crude oil (59% by volume), Arabian
The properties shown in the following table are obtained by blending vacuum residual oil fractions obtained from medium crude oil (5% by volume), Arabian heavy crude oil (27% by volume) and Bonny light crude oil (9% by volume). The vacuum residual oil which it has can be mentioned.

[0015]

[Table 1]

Hydrocarbon oils generally contain up to about 1% by weight of undesired constituents, such as nitrogen, usually from about 0.2%.
0.8 wt%, for example 0.52 wt%; up to about 10 wt% sulfur, usually about 2-6 wt%, for example 3.64 wt%; and metals such as Ni, V, Fe, Cr, Na
Etc. up to about 900 ppm by weight, usually about 40 to 400 ppm by weight, for example 198 ppm by weight. The undesired asphaltene content of hydrocarbon oils can be as high as about 22% by weight, usually about 8-16% by weight, for example 11.97% by weight, when analyzed as an insoluble component in n-heptane. .

The API gravity of the feedstock can be as low as about -5, usually about -5 to 35, for example 5.8. The content of components boiling above about 538 ° C. can be as high as 100% by weight, usually about 50-98 +% by weight, for example 93.1% by weight. Alcor MC
The R carbon content can be as high as about 30% by weight, usually about 15-25% by weight, for example 19.86% by weight.

The feed hydrocarbon oil may be subjected to a hydroconversion operation in which conversion occurs in the liquid phase, with effective conversion conditions including known ones. Typical operating conditions are temperatures of about 371-454 ° C., preferably about 398-432 ° C., eg 427 ° C., and about 107-1,038 MPa.
, Preferably about 314-521 MPa, for example 417 MPa
Including hydrogen partial pressure of.

A catalytically effective amount, usually IV-of the Periodic Table.
Group B, Group V-B, Group VI-B, Group VII-B or Group
An oil-miscible, preferably oil-soluble compound of a Group VIII metal is added to the feed hydrocarbon oil, preferably prior to hydroconversion. When the metal is a Group IV-B metal, it is titanium (Ti), zirconium (Zr) or hafnium (H
f). If the metal is a Group V-B metal, it can be vanadium (V), niobium (Nb) or tantalum (Ta). VI-
If a Group B metal, it can be chromium (Cr), molybdenum (Mo) or tungsten (W). If the metal is a Group VII-B metal, it can be manganese (Mn) or rhenium (Re). If the metal is a Group VIII metal, it may be iron (Fe), cobalt (Co) or nickel (Ni).
Non-noble metals such as; or ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (O
s), a noble metal such as iridium (Ir) or platinum (Pt). The metal is preferably VI
-Group B metal, most preferably molybdenum (Mo)
Is.

Typical oil-miscible or oil-soluble compounds include, inter alia, one or a mixture of the following: That is, metal salts of aliphatic carboxylic acids such as molybdenum stearate, molybdenum palmitate, molybdenum myristate and molybdenum octoate; metal salts of naphthenic carboxylic acids such as cobalt naphthenate, iron naphthenate and molybdenum naphthenate; alicyclic Metal salts of formula carboxylic acids, such as molybdenum cyclohexanecarboxylic acid; Metal salts of aromatic carboxylic acids, such as cobalt benzoate, cobalt o-methylbenzoate, cobalt m-methylbenzoate, cobalt phthalate and molybdenum p-methylbenzoate. Metal salts of sulphonic acids such as molybdenum benzene sulphonate, cobalt p-toluene sulphonate and iron xylene sulphonate; metal salts of sulphinic acid such as molybdenum benzenesulphinate and iron benzenesulphinate; Metal salts of acids such as molybdenum phenyl phosphate; metal salts of mercaptans such as iron octyl mercaptide and cobalt hexyl mercaptide; metal salts of phenols such as cobalt phenolate and iron phenolate; metal salts of polyhydroxyaromatic compounds such as Iron catecholates and molybdenum resorcinates; organometallic compounds such as molybdenum hexacarbonyl, iron hexacarbonyl and cyclopentadienyl molybdenum tricarbonyl; metal chelates such as ethylenediaminetetracarboxylic acid diiron salt; and metal salts of organic amines such as pyrrole. Is a cobalt salt. Preferred compounds include cobalt naphthenate, molybdenum hexacarbonyl, molybdenum naphthenate, molybdenum octoate and molybdenum hexanoate.

The metal compound used is at least 0.01 g, usually 0.025 g per 100 g feed hydrocarbon oil.
It is oil-miscible, preferably oil-soluble, in that it is readily dispersible, preferably soluble, in an amount of ˜0.25 g, for example about 0.1 g. The metal compound also becomes miscible in the hydrocarbon oil during the hydroconversion process when activated as described below.

Oil-miscible metal compounds are generally present in small amounts,
Normally, unexpected results can be reached when the metal is present in an amount up to about 60 ppm by weight, for example 10 to 60 ppm by weight, based on the hydrocarbon oil undergoing hydroconversion. It has been unexpectedly found that if the above amount is 15-60 ppm by weight, preferably 15-45 ppm by weight, most preferably 15 ppm by weight, the cumulative pore volume of the catalyst is improved. Specifically, the cumulative pore volume is generally increased by at least about 1%, preferably by about 5-50% or more, for example 31%, compared to the reference pore volume in the absence of the oil-miscible compound.

The conversion is calculated by subtracting the percentage of 538 ° C + substance in the product from the percentage of 538 ° C + substance in the feed and dividing that value by the percentage of 538 ° C + substance in the feed.

The level of miscible metal used, which is in the range of 15-60 ppm by weight, depends on the particular feedstock fed to the ebullated bed and the cumulative pore volume desired for the catalyst.
In either case, economic studies can readily determine the desired level of metal to use.

The oil-miscible compound can be added by any effective method, for example as a solution or mixture with a heavy aromatic oil. Highly aromatic heavy oils that can be used, typically heavy circulating gas oils (HCG
Heavy oils containing sulfur such as O) have the following characteristics.

[0026]

[Table 2]

Typical heavy oils having high aromaticity that can be used include the following.

[0028]

[Table 3]

The oil-miscible compound is present in an amount to form a solution or mixture with the heavy oil, usually about 0.01 to 0.0.
It can be added in an amount of 4% by weight, preferably about 0.01 to 0.03% by weight, for example 0.02% by weight. The compounds may be added to heavy oils and stored and used in such form. When this is added to the feed hydrocarbon oil that is subjected to hydrotreating, the amount added is about 5 to 20 weight percent of the solution or mixture providing 10 to 60 ppm by weight of the metal desired to achieve the above results. %, Preferably about 15% by weight, for example 13% by weight. Usually the oil-miscible compound is added continuously, as is the case for feed hydrocarbons.
The oil-miscible compound may be added at any stage of the hydroconversion reaction, but is preferably added during the first stage of a multi-stage reaction such as a two-stage reaction.

Activation of the oil-miscible compound can either be carried out by pretreatment before hydroconversion or in situ during hydroconversion. It is preferred to carry out in situ activation in the presence of a hydrogenation catalyst to obtain highly dispersible catalyst species.

Activation by the preferred method is about 16-1.
It can be carried out at 49 ° C., for example 93 ° C., by adding the metal compound to the feed hydrocarbon in an amount to obtain the desired metal content. Add this mixture to about 25-21
8MPa, usually about 210-624MPa, for example 417MPa
hydrogen partial pressure of a and about 4 to 107 MPa, usually about 5 to 6
At a partial pressure of gaseous mercaptans of 7 MPa, for example 13 MPa, about 204-446 ° C, usually about 260-371 ° C,
For example, it is activated by heating at 316 ° C. The total pressure is about 107-1,142 MPa, usually about 210-
It can be 686 MPa, for example 552 MPa. Generally, the gas will contain about 40-99% by volume hydrogen, usually about 9%.
0 to 99% by volume, for example 98% by volume, and may contain about 1 to 10% by volume, for example 2% by volume, of mercaptans such as hydrogen sulphide. The time for carrying out the activation can be about 1 to 12 hours, usually about 2 to 6 hours, for example 3 hours. Activation can occur below the temperature of conversion.

The mercaptans that can be used include
Among other things, there is one or more of the following: That is, hydrogen sulfide; aliphatic mercaptans such as methyl mercaptan and lauryl mercaptan; aromatic mercaptans; dimethyl disulfide; carbon disulfide and the like. It is clear that these mercaptans decompose during the activation process. It is not clear why this treatment activates the metal compounds. The metal sulphides may be formed during the treatment, resulting in activity.

When the sulfur content of the feed hydrocarbon is greater than about 2% by weight, the hydrodesulfurization of the feedstock is sufficient to form sulfides from the oil-miscible degradable compounds for proper activation. It may be unnecessary to add mercaptans during activation, since different mercaptans can be provided.

The oil-miscible metal compound can be activated in solution or mixture with a heavy aromatic oil. Activation can be carried out under the same conditions used when carried out in the feedstock. A compatible oil containing freshly activated metal can be added to the feedstock in an amount sufficient to obtain the desired amount of the activated oil-miscible metal compound in the feedstock.

In yet another embodiment, about 371.
~ 454 ° C, preferably about 399-432 ° C, for example 4
The oil-miscible compound at a temperature of 27 ° C. and a hydrogen partial pressure of about 107-1,038 MPa, preferably about 317-417 MPa, for example 417 MPa, in the presence of mercaptans and in the absence of a heterogeneous hydroconversion catalyst. Activation can be carried out by hydroconverting the feed hydrocarbon oil containing.

In a preferred embodiment, the activation is
It can be carried out during the hydroconversion in the presence of a heterogeneous hydroconversion catalyst, hydrogen and mercaptans.

The hydroconversion is generally a Group IV-B, supported on a porous support which can contain carbon or metal oxides such as oxides of aluminum, silicon, titanium, magnesium, zirconium, etc. V-B group, No.
It is carried out in the presence of a solid heterogeneous catalyst containing a Group VI-B, VII-B or Group VIII metal as the hydrogenation component. Preferably, the catalyst may contain Group VI-B and Group VIII metals, usually nickel and molybdenum. When the metal is a Group IV-B metal, it is
It can be titanium (Ti) or zirconium (Zr). When the metal is a Group V-B metal, it is
Vanadium (V), niobium (Nb) or tantalum (T
It can be a). If the metal is a Group VI-B metal, it can be chromium (Cr), molybdenum (Mo) or tungsten (W). When the metal is a Group VII-B metal, it is manganese (Mn).
Or it can be rhenium (Re). Metal is first
When it is a Group VIII metal, it is a non-noble metal such as iron (Fe), cobalt (Co) or nickel (Ni);
Or ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (I
r) or a noble metal such as platinum (Pt).

The solid heterogeneous catalyst also contains a Group IA, IB, II-A, II-B or VA metal as a promoter. You can When the co-catalyst is a Group IA metal, it is sodium (N
It is preferably a) or potassium (K). When the co-catalyst is a Group IB metal, it is copper (Cu).
Is preferred. When the co-catalyst is a Group II-A metal, it is beryllium (Be), magnesium (Mg), calcium (Ca), strontium (S).
r), barium (Ba) or radium (Ra). When the cocatalyst is a Group II-B metal,
It can be zinc (Zn), cadmium (Cd) or mercury (Hg). If the co-catalyst is a Group IV-B metal, it can be titanium (Ti), zirconium (Zr) or hafnium (Hf). When the cocatalyst is a Group VA metal, it is arsenic (As), antimony (Sb) or bismuth (B).
i) can be.

The metal for hydrogenation may be applied by any effective technique, including those known in the art, for example, after soaking the catalyst support in a solution such as ammonium heptamolybdate for about 2 to 24 hours, for example 24 hours, and then about 16 to 149. A solid heterogeneous catalyst by drying at 0 ° C., for example 93 ° C., for about 1-24 hours, for example 8 hours and calcining at about 399-593 ° C., for example 499 ° C., for about 1-24 hours, for example 3 hours Can be supported on the substrate.

The cocatalyst metal may be added by any effective technique, including those known in the art, for example, a catalyst support loaded with a metal for hydrogenation, preferably calcined (either simultaneously or in any order). Is immersed in a solution of bismuth nitrate for about 2 to 24 hours, for example 24 hours, and then at about 16 to 149 ° C., for example at 93 ° C. for about 1 to 24 hours.
The solid heterogeneous catalyst can be supported by drying for 3 hours, for example, and calcining at about 299 to 593 ° C., for example, 399 ° C. for about 1 to 12 hours, for example 3 hours.

The fresh solid heterogeneous catalyst used in the process of the present invention is about 0.2 to 1.2 ml / g, eg 0.77.
Total pore volume of ml / g, about 50-500 m ² / g, eg 280
It can be characterized by a surface area of m ² / g and a pore size distribution such as:

[0042]

[Table 4]

In another embodiment, the pore size distribution may be as follows.

[0044]

[Table 5]

Solid heterogeneous catalysts usually contain about 4 Mo.
˜30 wt%, eg 9.5 wt%; Ni about 0 to 6 wt%, eg 3.1 wt%; and cocatalyst metal, eg bismuth, about 0 to 6 wt%, eg 3.1 wt%. be able to. Liquid hourly space velocity in the hydroconversion reactor (LH
The SV) can be about 0.1-2, for example 0.7. Preferably, the heterogeneous catalyst has a diameter of 0.7-6.
It can be used in the form of extrudates of 5 mm, for example 1 mm; length of 0.2-25 mm, for example 5 mm.

Although the hydroconversion can be carried out in a fixed bed, moving bed, fluidized bed or well stirred reactor, the advantages of the present invention are most apparent when the hydroconversion is carried out in the boiling bed. It was found that The hydroconversion can be carried out in one or more catalyst beds. The activated form of the catalyst is
Increased activity of conversion and heteroatom removal, whether formed or accumulated in the first of some reactors, can occur predominantly in the first of some reactors. Was found.

[0047]

The effluent from the hydroconversion is usually 53
It is characterized by an increased content of liquid boiling below 8 ° C. Generally, the conversion by weight percentage of materials boiling above 538 ° C is about 30-90%, for example 67%, which is typically about 5-25, more than the conversion achieved by the prior art. %, For example 12%.

A feature of the invention is the removal of sulfur (HDS conversion), nitrogen removal (HDN conversion) and metal removal (H
DNi and HDV conversion). H
The DS conversion can typically be about 30-90%, for example 65%, which is about 1-10 more than the control experiment.
%, For example 4% higher. HDN conversion is usually about 20-6
It can be 0%, for example 45%, which is about 1-10%, for example 4% higher than the control experiment. HDNi
And HDV conversion is usually about 70-99%, eg 9
It can be 0%, which is about 5-20% higher, for example 13%, than the control experiment.

The present invention is (1) a hydrocarbon-based deposit having a higher hydrogen: carbon ratio than that produced when operating outside the conditions of the present invention, and (2) correspondingly,
Provided is an improved solid heterogeneous catalyst having a greater cumulative pore volume. Addition of oil-miscible compounds to hydrocarbon oils can result in hydrocarbonaceous deposits featuring hydrogen: carbon ratios that are typically up to about 30% greater than those obtained in the absence of oil-miscible compounds. Usually, the hydrogen: carbon ratio is about 0.088 from the reference ratio of about 0.062.
It can be increased to experimental ratios as high as five.

Increasing the total pore volume increases the activity of the in-situ aged catalyst due to the increased number of pores compared to the reference catalyst. This increase in the number of pores enhances the catalyst's ability to carry out hydrogenation reactions, such as sulfur removal.

[0051]

The following examples illustrate some of the embodiments of the present invention and are not intended to limit its scope. Unless stated otherwise, the percentages and amounts stated in the disclosure and the claims are by weight.

Examples 1C-5 In these examples, the oil-miscible compound is molybdenum naphthenate, which is added to the feedstock to the equipment at 15%.
It was added in an amount such that ~ 60 ppm by weight molybdenum was obtained. The feedstock has the following characteristics obtained by blending (i) reduced pressure residual oil, (ii) visbreaker residual oil, (iii) reduced pressure distillation residual oil recirculating oil, and (iv) heavy circulating light oil. It was a thing.

[0053]

[Table 6]

A mixture of feedstock and heavy cycle gas oil containing oil-soluble molybdenum naphthenate was introduced by a LHSV of 0.39 at 416-421 ° C and 521 MPa. 92% of hydrogen is 725 Nm ³ / m ³ (4,300
Supplied by SCFB).

The ebullated bed supported catalyst has a surface area of 285.2 m ² / g, a total pore volume of 0.78 ml / g and a pore size>
250Å pores 0.28 ml / g,> 500Å 0.21
ml / g,> 1,550Å is 0.19 ml / g,> 4,000Å
Supported on alumina showing a pore size distribution of 0.11 ml / g, nickel 2.83% by weight and molybdenum 8.75.
Cylindrical version of a commercial catalyst containing 0.5% by weight (diameter 0.
8 mm and length 5 mm). The catalyst was activated in situ during hydroconversion.

A baseline hydrogen: carbon weight ratio in the hydrocarbon-based deposit prior to addition of the oil-miscible compound and catalyst porosity in the total pore volume was analyzed in Example 1C to determine the oil-miscible compound. Similar measurements were performed after each addition. The results are shown in Tables 1-5.

Example 1C A baseline experiment was conducted to determine the product quality and solid catalyst properties prior to the addition of the liquid molybdenum compound. The standard condition is 0.39 LH based on all raw materials.
Reactor temperature 416 for SV, first stage and second stage respectively
C. and 421.degree. C., and system pressure 521 MPa. The catalyst was withdrawn daily to maintain the stored catalyst in the required aging condition. After 5 test periods, each 24 hours apart, a portion of the recovered catalyst was subjected to analysis to measure pore volume, carbon, hydrogen, sulfur and other qualities for comparison purposes. I found the reference point. Reference data show that the equilibrated solid heterogeneous catalyst has an H / C ratio of 0.062 in the first stage reactor and an H / C ratio of 0.0574 in the second stage reactor. Indicated. The surface area of the standard case was about 95 m ² / g.

Example 2 Molybdenum naphthenate was mixed with heavy cycle gas oil in an amount to give 15 ppm molybdenum in the fresh feed fed to the reactor. The feedstock consisted of a blend of vacuum residual oil, residual oil after visbreaking, and vacuum residual recirculating oil. Molybdenum naphthenate for 9 consecutive days,
Supplied during processing. The catalyst was collected daily. The catalyst recovered on day 9 was submitted for analysis. A comparison of the analytical results on day 9 with the reference values showed that when molybdenum was introduced, the amount of carbon, molybdenum, vanadium and sulfur adhering to the surface of the catalyst increased. Comparison of the hydrogen: carbon ratio of the reference catalyst with the catalyst recovered from the first stage showed an increase of 29.9% over the reference ratio. The hydrogen: carbon weight ratio in the second stage was increased by 7.7%. This indicates that the coke formed on the catalyst contains a higher amount of hydrogen than that of the standard. The HDS MAT activity test showed an increase in sulfur removal for the catalyst recovered when introducing 15 ppm in any stage.

Example 3 Molybdenum naphthenate was mixed with heavy cycle gas oil in an amount to give 30 ppm molybdenum in the fresh feed fed to the reactor. The feedstock consisted of a blend of vacuum residual oil, residual oil after visbreaking, and vacuum residual oil recirculating oil. Molybdenum naphthenate was fed continuously during the process for 8 days. The catalyst was collected daily. The catalyst recovered on day 8 was submitted for analysis. The comparison between the analysis results of the 8th day and the standard value is that when molybdenum is introduced,
It was shown that the amount of carbon, molybdenum and sulfur adhering to the surface of the catalyst was increased. The hydrogen: carbon weight ratios in the first and second stages are each 18.8% of the standard ratio.
And 2.9% higher. This indicates that the hydrogenation amount in the coke formed on the catalyst was increased. The HDS MAT activity test showed a reduction in sulfur removal when compared to the MAT activity of Example 2.

Example 4 Molybdenum naphthenate was mixed with heavy cycle gas oil in an amount to give 45 ppm of molybdenum in the fresh feed fed to the reactor. The feedstock consisted of a blend of vacuum residual oil, residual oil after visbreaking, and vacuum residual oil recirculating oil. Molybdenum naphthenate was fed continuously during the treatment for 4 days. The catalyst was collected daily. The catalyst recovered on day 8 was submitted for analysis. Comparison of the analytical results on day 4 with the reference values showed an increase in the amount of carbon, molybdenum, vanadium and sulfur adhering to the surface during the period of introduction of molybdenum. The hydrogen: carbon weight ratios in the first and second stages were 20.7% and 2.9% above the reference ratio, respectively. This indicates an increased level of hydrogen in the coke formed on the catalyst.

Example 5 Molybdenum naphthenate was mixed with heavy cycle gas oil in an amount to give 60 ppm of molybdenum in the fresh feed fed to the reactor. The feedstock consisted of a blend of vacuum residual oil, residual oil after visbreaking, and vacuum residual oil recirculating oil. Molybdenum naphthenate was fed continuously during the treatment for 11 days. The catalyst was collected daily. The catalyst recovered on day 11 was submitted for analysis. Comparison of the analytical results on day 11 with the reference values showed that during the period when molybdenum was introduced, the amount of carbon, molybdenum, vanadium and sulfur adhering to the surface increased. The hydrogen: carbon weight ratio in the first step was 4.4% lower than the reference value. The hydrogen: carbon weight ratio in the second stage was actually 10% above the standard value. The coke formed in the first stage during the period of introducing 60 ppm is
It appears to be of the same type as that normally formed during residual oil hydroconversion. Since the molybdenum was only introduced in the first stage, the second stage catalyst may have been less affected.

[0062]

[Table 7]

[0063]

[Table 8]

[0064]

[Table 9]

[0065]

[Table 10]

[0066]

[Table 11]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10G 47/12 2115-4H 49/02 2115-4H 49/12 2115-4H (72) Inventor Glenn Allen Crosen, 77277, Texas, USA, Nederland, Apartments 225, 27th Street 1516

Claims (2)

[Claims] 1. A method for catalytically hydroconverting a hydrocarbon oil, comprising: (a) a hydrocarbon oil containing a substantial amount of a high-boiling compound boiling above about 538 ° C. in the conversion zone.
(1) contacting with a solid heterogeneous catalyst containing a hydrotreating metal supported on a porous carrier, and (2) an oil-miscible compound containing an amount of a metal compound that improves effective porosity; ) Converting a substantial portion of the high boiling compounds in the hydrocarbon oil to a low boiling compound boiling below about 538 ° C. under a conversion condition in the presence of hydrogen and mercaptans to contain a substantial portion of the low boiling compounds. Producing a hydrocarbon oil; (c) a hydrocarbon-based deposit having a hydrogen: carbon ratio higher than (1) compared to the equivalent produced in the absence of an oil-miscible compound, and (2) a total greater than A method of producing a solid heterogeneous catalyst having a pore volume. 2. A method for increasing the effective porosity of a solid heterogeneous catalyst in situ during catalytic hydroconversion of hydrocarbon oils, the method of claim 1. A method characterized by.