DD140894A5 - METHOD FOR THE HYDROPREATMENT OF HEAVY HYDROCARBONSTRUCTURES - Google Patents

Description

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Process for the hydrotreatment of a heavy hydrocarbon troins

Field of application of the invention

The invention relates to the catalytic treatment of heavy hydrocarbon streams containing asphaltene material, metals, nitrogen compounds and sulfur compounds in the presence of hydrogen. "

Characteristic of the known technical solutions

It is well known that various organometailic compounds and asphaltenes are present in petroleum crude oils and other heavy petroleum hydrocarbon streams such as petroleum hydrocarbon bottoms, hydrocarbon streams derived from heavy oil sands, and hydrocarbon streams derived from coal. The most common found in such hydrocarbon streams Metals are nickel, vanadium and iron. Such metals are detrimental to various petroleum refining processes such as hydrocracking, hydrodesulfurization and catalytic cracking. The metals and asphaltenes lead to clogging of the catalyst bed and reduced catalyst life. The various metal deposits on the catalyst tend to poison or to catalyze the catalyst

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deactivate. Moreover, the asphaltenes tend to reduce the accessibility of the hydrocarbons to desulfurization. When a catalyst such as a desulfurization catalyst or cracking catalyst in the form of a fluidized bed or fluidized bed is exposed to a hydrocarbon fraction containing metals and asphaltenes, the catalyst is rapidly deactivated and subjected to premature removal from the particular reactor and replaced with a new catalyst.

Although methods of hydrotreating heavy hydrocarbon streams including but not limited to heavy crudes, reduced crudes and petroleum hydrocarbon residues are known, the use of fixed bed catalytic processes for converting such feeds without appreciable asphaltene segregation and reactor clogging to effectively remove metals and other impurities, such as sulfur compounds and nitrogen compounds, are not all that common. While once the heavy fractions of the hydrocarbon streams could be used as low quality fuel or as a source of asphalt type materials, today's policies and economics require that such material be hydrotreated to eliminate environmental degradation and more to obtain usable products from such feeds.

It is well known that petroleum hydrocarbon streams in the presence of a catalyst comprising a hydrogenation component and a suitable carrier material _s like an aluminum

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niumoxid, an alumina-silica, or silicon-alumina, hydrotreated, d. h, hydrodesulfurized, hydroenitrified and / or hydrocracked. The hydrogenation component comprises one or more metals from Group VI and / or Group VIII of the Periodic Table of the chemical elements, such as the periodic table on page 628 of Webster ¹ S Seventh Hew Collegiate Dictionary, 6 · C · Merriam Company, Springfield, Massachusetts, USA (1963).

Such combinations of metals such as cobalt and molybdenum, nickel and molybdenum, cobalt, nickel and molybdenum, and nickel and tungsten have been found to be useful. For example, US Pat. No. 3,340,180 teaches that heavy hydrocarbon streams containing sulfur, asphaltic materials and metal-containing compounds as impurities can be hydrotreated in the presence of a catalyst containing such metal combinations and an activated alumina less than 5 % of its weight Pore volume, which is in the form of pores with a radius of 0 angstrom units [a] (0 nm) to 300 A (30 nm), in pores with a radius greater than 100 A (10 nm), and less than 10% pore volume in pores with a radius of

o than 80 A (8 nm) is present.

US Pat. No. 4,016,067 discloses that heavy hydrocarbon streams can be demetallised and desulfurized in a two-component catalyst system wherein the first catalyst is a Group VI metal and a Group VIII metal, preferably molybdenum and cobalt, in conjunction with an alumina carrier with a considerable salary

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at 0- and / or Θ- »alumina, in which at least 60 % of its pore volume in pores having a diameter of about 100 A (10 nm) to 200 2 (20 nm) are present and at least about 5 % of its pore volume in Pores with a diameter

ο greater than 500 A (50 nm) and having a specific surface area of up to about 110 m / g and in which the second catalyst component comprises a similar hydrogenation component in combination with a refractory base, preferably alumina, and at least 50 % , Preferably, 60 % of the pore volume are formed by pores with a

Q O

Diameter of 30 A (3 nm) to 100 A (10 nm) and the specific surface is at least 150 m / g.

U.S. Patent No. 2,890,162 teaches that catalysts comprising alumina active catalytic components have a most common pore diameter of from 60Å (6nm) to 400Å (40nm) and pores having diameters greater than 1000Å (100Å) nm), are suitable for the desulfurization, hydrocracking, the hydroforming process of naphtha hydrocarbons, the alkylation, the reforming process of naphthas, the isomerization of paraffins u. Like., Hydrogenation, dehydrogenation and for various types of hydrofining and the hydrocracking of residues and other asphalt-containing materials. It is recommended that suitable active components and promoters include a metal or catalytic compound of various metals, with molybdenum and chromium being listed among 35 enumerated metals.

GB-PS 1 051 341 describes a process for the hydrodealkylation of certain aromatics which comprises a catalyst.

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which consists of oxides or sulfides of a group VI metal, coated on alumina with a porosity of 0.5 ml / g to 1.8 ml / g and a specific surface of

ρ Ο

138 m / g to 200 m / g, whereby at least 85 % of the total

total porosity is due to pores having a diameter of 150 Å (15 μm) to 550 Å (55 nm).

U.S. Patents 3,245,919 and 3,267,025 disclose hydrocarbon conversion processes such as the reforming process, hydrocracking, hydrodesulphurization, isomerization, hydrogenation and dehydrogenation, which is a catalyst of a catalytic amount of a metal component selected from metals Group VI and Group VIII, such as chromium, molybdenum, tungsten, iron, nickel, cobalt, and the platinum group metals, their compounds, and mixtures thereof, supported on an X- alumina obtained by drying and calcining a bimethylaluminum oxide product having a pore structure, in which a total of at least about 0.5 cc / g in pores greater than 80 Å (8 nm) in size.

U.S. Patent 3,630,888 teaches the treatment of residual hydrocarbon feedstocks in the presence of a catalyst comprising a promoter selected from the group consisting of Group VIB and Group VIII elements of the Periodic Table, their oxides and combinations thereof, and a particulate catalytic agent of silica, alumina and combinations thereof having a total pore volume of greater than 0.40 cnr / g, said pore volume comprising micropores and access channels, said access channels being interstitially spaced throughout the structure of said micropores, a first portion of said access channels being of diameter between about 100 A (10 nm) and about 1000 A

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(100 nm), which first part comprises 10 % to 40 % of the pore volume, a second part of the access channels has diameters greater than 1000 A (100 nm), the second part comprising 10 % to 40 % of the pore volume, the remaining Part of the Pore Volume Micropores with diameters less than 100 A (10 nm) include which remaining portion comprises 20 % to 80 % of the total pore volume.

U.S. Patent 3,114,701, while indicating that in hydrofining processes, nitrogen compounds are derived from petroleum hydrocarbons in the presence of various catalysts, which generally contain chromium and / or molybdenum oxides along with iron, cobalt and / or nickel oxides on a porous oxide support such as alumina or silica-alumina include, be removed, a Hydrodenitrifizierungsverfahren that uses a catalyst containing large concentrations of nickel and molybdenum on a predominantly alumina carrier to Kohlenwasserstoffßtröme which (at 82 ⁰ C 180 ⁰ P ) to about 566 ⁰ C (1050 ⁰ P), to be treated

US Pat. No. 2,843,552 discloses that a catalyst containing chromium oxide in substantial amount with alumina gives a catalyst with very good wear resistance, impregnated with molybdenum oxide and used for reforming, debindering and isomerization processes can be.

U.S. Patent 2,577,823 teaches that hydrodesulfurization of heavy hydrocarbon fractions containing 1 % to 6.5%

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Containing sulfur in the form of organic sulfur compounds, such as reduced crude oil, can be passed over a catalyst of chromium, molybdenum and aluminum oxides, this catalyst by simultaneously precipitating the oxides of chromium and molybdenum on a previously formed alumina slurry at a pH Value is formed from 6 to 8 ·

US Pat. No. 3,265,615 describes a method for preparing a supported catalyst in which a high specific surface area catalyst support such as alumina is impregnated with ammonium molybdate and then immersed in an aqueous solution of chromium sulfate and the treated support is dried overnight and then reduced by treatment with hydrogen at the following temperature sequences: 288 ⁰ C (550 ⁰ P) for 1/2 hour; 399 ^° C (750 ^° F) for 1/2 hour; and 510 ^° C (950 ^° F) for 1/2 hour. The reduced material is sulfided and a hydrofining process of heavy gas oil having a boiling point of 343 ⁰ C (650 ⁰ F) to 499 ⁰ C (930 ⁰ P) used.

US Pat. No. 3,956,105 discloses a process for hydrotreating petroleum hydrocarbon fractions, such as residual heating oils, using a catalyst comprising a Group VIB metal (chromium, molybdenum, tungsten), a Group VIII metal (nickel, cobalt) and a refractory inorganic oxide, which may be alumina, silica, zirconia, thoria, boria, chromia, magnesia and mixtures thereof. The catalyst is prepared by dry blending a finely divided Group VIB metal compound, a Group VIII metal compound, and a Group VIII metal compound

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refractory inorganic oxide, peptizing the mixture and forming an extrudable dough-like mass, extruding and calcining.

U.S. Patent 3,640,817 discloses a two-step process for treating asphaltene-containing hydrocarbons. Both catalysts in the process comprise one or more metallic components selected from the group consisting of molybdenum, tungsten, chromium, iron, cobalt, nickel, and the platinum group metals on a porous support material such as alumina, silica, zirconia, magnesia, titania and mixtures thereof, wherein in the first catalyst more than 50 % of its macropore volume is due to pores having a pore diameter greater than about

1000 A (100 nm) and in the second catalyst less than 50 % of its macropore volume is characterized by pores having a pore diameter greater than about 1000 A (100 nm).

US Pat. No. 3,957,622 teaches a two-stage hydration process for treating asphaltene-containing dark oils or black oils. The desulphurization takes place in the first stage over a catalyst in which less than 50 % of its pore volume is characterized by pores having a pore diameter of greater than about 1000 A (100 nm). The accelerated conversion and desulfurization of the asphaltenic moiety occurs at the second stage over a catalyst in which more than 50 % of its macropore volume is characterized by pores having a pore diameter greater than 1000 Å (100 nm). Each catalyst comprises one or more metallic components selected

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from the group consisting of molybdenum, tungsten, chromium, iron; Cobalt, nickel, the platinum group metals and mixtures thereof, on a support material of alumina, silica, zirconia, magnesia, titania, boria, strontia, hafnia or mixtures thereof.

PR Patent Publication 2 281 972 teaches the preparation of a catalyst comprising the oxides of cobalt, molybdenum and / or nickel on a base of alumina and 3 to 15% by weight of chromium oxide, and its use for the refining process of hydrocarbons. Fractions, preferably for Hydrodesulfurierung of fuel oils, obtained by vacuum distillation, or residual oils, obtained by distillation under atmospheric pressure. The base can be prepared by co-precipitation of compounds of chromium and aluminum.

U.S. Patent 3,162,596 teaches that in an integrated process, a residual hydrocarbon oil, the metal contaminant. ments (Meckel and Vanadin), first with either a hydrogen donor diluent or over a catalyst containing one or more hydrogenation-promoting metals supported on a solid support, exemplified by alumina or silica, is hydrogenated, and then vacuum distilled is to separate a heavy gas oil fraction containing reduced amounts of metals from a non-distilled residue boiling predominantly above about 593 ⁰ C (1100 ⁰ P) and contains asphalt-like material. The heavy gas oil fraction is then catalytically cracked.

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US Pat. No. 3,180,820 teaches that a heavy hydrocarbon feedstock can be upgraded in a two-zone hydrodesulfurization process in which each zone uses a solid hydrogenation catalyst containing one or more metals of Groups VB, VIB and VIII of the Periodic Table of Chemical Elements includes. Each catalyst may be supported or unattached. In a preferred embodiment, the first zone contains a non-supported catalyst-oil slurry, and the second zone contains a supported catalyst in a plague bed, slurry, or fluidized bed. The support supported catalyst is a porous, refractory inorganic oxide support comprising alumina, silica, zirconia, magnesia, titania, thoria, boria, strontia, hafnia, and complexes of two or more oxides such as silica-alumina, silica Zirconia, silica-magnesia, alumina-titania, and silica-magnesia-zirconia, among others. The patent provides that the supported catalyst suitable for use in the invention has a

2 2

specific surface area of about 50 m / g to 700 m / g, a pore diameter of about 20 A (2 nm) to 600 A (60 nm) and a pore volume of about 0.10 ml / g to 20 ml / g having.

US Pat. Nos. 3,977,961 and 3,985,684 describe methods of hydroconversion of heavy crude oils and residues using one or two catalysts, each of which is a Group VIB metal and / or a Group VIII metal on a refractory inorganic Oxide, such as alumina _f

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Silica, zirconia, magnesia, boria, phosphate, titania, ceria and thoria, may comprise a Group IVA metal such as germanium, has a very high specific surface area, and has an ultrahigh pore volume. In the first catalyst at least about 20 % of its total pore volume has an absolute

ο o

Diameters in the range of about 100 A (10 nm) to about 200 A (20 nm), if the catalyst has a particle size diameter up to 1/50 inch, have at least 15 % of its total pore volume an absolute diameter.

o o

about 150A (15nm) to about 250A (25nm) when the catalyst has a particle size diameter of about 1/50 inch (0.051 cm) to about 1/25 inch (0.102 cm) has at least about 15% of its total pore volume an absolute diameter in the range of about 175 A (17.5 nm) to about 275 A (27.5 nm) when the catalyst has an average particle size diameter in the range of about 0.252 cm (1/25 inch) to about 0.32 cm (1/8 inch), and the specific surface area is about

2 2

200 m / g to about 600 m / g and the pore volume of about 0.8 cm / g to about 3.0 cm / g. In the second catalyst, at least 55 % of its total pore volume has an absolute diameter in the range of about 100 Å (10 nm) to about 200 Å (20 nm), less than 10% of its pore volume pore diameter of 50 Å (5 nm). ), less than about 25 % of its total pore volume pore diameter of 300 A + (30 nm +),

the specific surface is about 200 m / g to about 600 m / g and the pore volume about 0.6 cm-Vg to about 1.5 cm / g. These patents also teach that the effluent from such processes can be fed to a catalytic cracking unit or hydrocracking units. "

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US Pat. No. 4,054,508 discloses a process for demetallization and desulfurization of residual oil fractions using two catalysts in three zones. The oil in the first zone is contacted with a major portion of a first catalyst comprising a Group VIB metal and an iron group metal oxide deposited on an alumina support, at least 60 % of its pore volume in pores in the first catalyst

oo

a diameter of 100 A (10 nm) to 200 A (20 nm) and at least about 5% of its pore volume in pores with a

having diameters greater than 500 A (50 nm), in the second zone contacted with the second catalyst comprising a Group VIB metal and an iron group metal oxide in association with an alumina support, the second catalyst having a specific surface area of at least 100 m / g and at least 50 % of its pore

o o

Volume in pores with diameters of 30 A (3 nm) to 100 A (10 nm) is present, and then brought into contact in a third zone with a smaller proportion of the first catalyst.

According to British Patent No. 1 367 243, a hydrodesulfurization catalyst is prepared by reacting a support material such as alumina, silica, zirconia, thoria, boria and the like with the precursor of at least one catalytically active metallic component selected from Groups VIB and VIII of the Periodic Table, and thereafter drying and calcining this composition in a special way, including two calcination steps. This British patent teaches that such a catalytic composition is useful for hydroentanation.

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Sulfurization of residual oil can be used * It does not contain an example of a special catalytic composition which simultaneously contains molybdenum and chromium. Obviously, it also fails to recognize the importance of the presence of both Group VIB metals in the same catalytic composition for the treatment of heavy metals Has hydrocarbon streams.

US Pat. No. 4,066,574 relates to a process for the hydrodesulfurization of a hydrocarbon feed containing at least 10 ppm metals, such as residue feeds; in this process, the feed is contacted with a catalyst prepared by impregnating an alumina-containing support with a Group VIB metal and a Group VIII metal or metal compounds, the carrier having at least 70% by volume of its pore volume pores having a diameter from

ο ο 80 A to 150 A and less than 3% by volume of its pore

volume has pores with a diameter above 1000 A. Only hydrogenation metal combinations of cobalt or nickel and molybdenum are given, and only catalysts with cobalt and molybdenum are used in the examples. This patent gives no indication of catalysts which simultaneously have chromium and molybdenum in their composition.

Object of the invention

The object of the invention is to provide a simple and economical process for hydrotreating a heavy hydrocarbon stream to remove or substantially remove

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reduction of the impurities contained in it, metals, asphaltenes, sulfur and nitrogen.

Explanation of the essence of the invention

The invention has for its object to find a suitable catalyst for the hydrotreatment.

Now, a process for hydrotreating a heavy hydrocarbon stream comprising metals, asphaltenes, nitrogen compounds and sulfur compounds has been found and developed, which process uses a catalyst having specific physical properties and a hydrogenation component comprising molybdenum and chromium and optionally cobalt *

Generally speaking, according to the present invention, there is provided a process for hydrotreating a heavy hydrocarbon stream comprising metals, asphaltenes, nitrogen compounds and sulfur compounds, which process comprises contacting the stream under suitable conditions and in the presence of hydrogen with a catalyst, which comprises a hydrogenation component comprising molybdenum and chromium, their oxides, their sulfides and mixtures thereof on a large pore, catalytically active alumina. The molybdenum may be present in an amount of about 5% to _e * ca 15% by weight, calculated as MooO, based on the total catalyst weight, are present, and the chromium may be in an amount of about 5% to about, 20% by weight, calculated as CrpO ,, based on the total catalyst weight, are present. The catalyst has a pore volume in the range of 0.4 cnr / g to about 0.8 cnr / g, a specific

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2 2

Surface in the range of about 150 m / g to about 300 m / g and an average pore diameter in the range of about

ο o

100 A (10 nm) to about 200 A (20 nm).

The catalyst may additionally contain cobalt and / or its oxide and / or its sulphide. If cobalt is present, it is present in an amount of about 0.1% by weight to about 5 % by weight , calculated as CoO, based on the total catalyst weight.

The catalyst used in the process of the present invention can be prepared by calcining the alumina (pseudo-boehmite) in air at a temperature of from about 427 ^° C (800 ^° F) to about 760 ^° C (1400 ^° F) for a period of about 1/2 hour to about 2 hours to form an ^ -alumina and then impregnating the If-alumina with one or more aqueous solutions containing heat-decomposable salts of molybdenum and chromium.

In the catalyst used in the process of the invention about 0 % to about 10% of its pore volume in pores having diameters less than 50 A (5 nm), about 30 % to about 80 % of its pore volume in pores with diameters of about 50 A (5 nm) to about 100 A (10 nm), about 10 % to about 50 % of its pore volume in pores with diameters of about 100 A (10 nm) to about 150 A (15 nm) and about 0 % to about 10 % of its pore volume in pores with diameters of larger

above 150 A (15 nm).

The process according to the invention is carried out at a hydrogen partial pressure in the range of about 6.9 MPa (1000 psia) to about

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20.7 MPa (3000 psia), an average catalyst bed temperature of about 371 ⁰ C (700 ⁰ P) to about 438 ⁰ G (820 ⁰ P), an hourly liquid-space velocity (LHSV) of about Volume of hydrocarbon per hour per volume of catalyst to about 3 volumes of hydrocarbon per hour per volume of catalyst and a hydrogen recycle rate or hydrogen addition rate of about 356 nr / nr [2000 standard cubic feet of hydrogen per barrel of hydrocarbon (SCPB)] to approx 2672 nrVm ³ (1.5 000 SCPB).

The invention relates to a novel process for the hydrotreating of heavy hydrocarbon feeds. Such feeds include asphaltenes, metals, nitrogen compounds and sulfur compounds. It will be understood that the feeds to be treated by the process of the present invention contain a small amount of nickel and vanadium, ζ. Β _{β contains} less than 40 ppm up to more than 100 ppm of nickel and vanadium (a combined total of nickel and vanadium) and up to about 25% by weight of asphaltenes. If the feed contains either a combined amount of nickel and vanadium which is too large, or an amount of asphaltenes which is excessively large, then the feed may be subjected to a preliminary treatment to reduce the excess amount of the particular impurity. Such prior treatment comprises a suitable hydrogenation treatment to remove metals from the feed and / or conversion of asphaltenes in the feed to reduce the impurities to satisfactory levels, such treatment using any suitable, relatively inexpensive catalyst. The impurities mentioned above adversely affect the

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closing processes of such feeds if they have not been reduced to acceptable levels.

Typical feeds which can be satisfactorily treated by the process of the present invention often contain a substantial amount of components boiling above 538 ^° C (1000 ^° F). Examples of typical feeds include crude oils, topped crude oils, petroleum hydrocarbon residues, both atmospheric and vacuum residues, oils derived from heavy oil sands and residuals derived from heavy oil sands, and coal-derived hydrocarbon streams. Such hydrocarbon streams contain organometallic contaminants that cause detrimental effects in various refining processes that use catalysts in the conversion of the particular hydrocarbon stream to be treated. The metallic contaminants found in such feeds include, but are not limited to, iron, vanadium and hickel.

Hiekel exists in the form of soluble organometallic compounds in most crude oils and residue fractions. The presence of nickel-porphyrin complexes and other hickel-organometallic complexes causes serious difficulties in the refining process and in the recovery of heavy hydrocarbon streams, even when the concentration of such complexes is relatively low. It is known that a cracking catalyst is rapidly destroyed and its selectivity changes when in the presence of a significant amount of organometallic

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Nickel compounds is worked. A considerable amount of such organometallic nickel compounds in coatings to be hydrotreated or hydrocracked seriously affect such processes. The catalyst is deactivated and clogging or increase in pressure drop in a fixed bed reactor results from the deposition of wrap compounds in the interstices between the catalyst particles.

Iron-containing compounds and vanadium-containing compounds are present in virtually all of the crude oils accompanied by the asphaltic and / or asphaltenic portion of the high Conradson carbon crude. Of course, such metals are concentrated in the remaining floors, when a crude oil for the removal of such fractions boiling below about 232 ⁰ C (450 ⁰ P) to 316 ⁰ C (600 ⁰ F), is topped. When such residue is treated by further processes, the presence of such metals adversely affects the catalyst in such processes. It should be emphasized that nickel-containing compounds adversely affect cracking catalysts to a greater extent than iron-containing compounds. When such oil-containing oil is used as fuel, the metals result in poor fuel oil performance in industrial furnaces as they corrode the metal surfaces of the furnaces.

While metallic impurities, such as vanadium, nickel and iron, are often present in fairly small amounts in various hydrocarbon streams, they are often present in concentrations greater than 40 to 50 ppm, by weight of the product.

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often found in excess of 1000 ppm. Of course, other metals are present in a special hydrocarbon stream. Such metals exist as oxides or sulfides of the particular metal, or are present as the soluble salt of the particular metal or as high molecular weight organometallic compounds including metal naphthenates and metalloporphyrins and their derivatives. For each pass, the feed stream for demetallization may be treated prior to use in the process of the invention if the total amount of nickel and vanadium is excessively high.

Generally speaking, according to the present invention, there is provided a method of hydrotreating a heavy hydrocarbon stream comprising metals, asphaltenes, nitrogen compounds and sulfur compounds to reduce the content of metals, asphaltenes, nitrogen compounds and sulfur compounds in that stream by passing this catalyst under suitable conditions and in the presence of hydrogen, characterized in that the catalyst comprises a hydrogenation component comprising the metals of molybdenum and chromium, their oxides, their sulfides or mixtures thereof on a large pore, catalytically active alumina, wherein the molybdenum in an amount of about 5% by weight to about 15% by weight, calculated as MoOo and based on the total catalyst weight, wherein the chromium is present in an amount of about 5% by weight to about 20% by weight. calculated as CrpO-a and based on the total catalyst weight, and wherein this catalyst has a pore volume in the range of ca, 0.4 cnr / g to ca, 0.8 cnr / g, a specific

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2 2

Surface in the range of about 150 m / g to about 300 m / g and an average pore diameter in the range of about 100 S (10 nm) to about 200 A (20 nm) has.

The process according to the invention is further characterized in that the hydrogenation component of the catalyst comprises the metal cobalt, its oxide, its sulphide or mixtures thereof, the cobalt being present in an amount of from about 0.1% to about 5% by weight, calculated as CoO and based on the total weight of the catalyst.

It will be understood that in the present case, all of the fourth indicated for the specific surface area are those obtained by the BET nitrogen adsorption method. All values given for pore volume are those obtained by nitrogen adsorption. All values given for the average pore diameter are those given by the relationship:

4 x PV χ 10 ⁴ "APD =

S.A.

 be calculated,

where A.P * D. = average pore diameter in A PeV, = pore volume in cnr / g and

ο S.Ä «= specific surface area in m / g.

Furthermore, the pore size distributions are those that

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using a Digisorb 2500 instrument using nitrogen desorption techniques.

In the process of the present invention, the catalyst provides good demetallization activity, moderate desulfurization activity and good deactivating stability when used at high temperature and / or moderate pressure, such as about 1200 psig (8.37 MPa).

The hydrogenation component of the catalyst used in the process of the invention is a specific molybdenum and chromium-containing component.

In one embodiment of the process according to the invention, the hydrogenation component of the catalyst consists essentially of molybdenum and chromium, their oxides, their sulphides or mixtures thereof. According to this embodiment, there is provided a process for hydrotreating a hydrocarbon stream containing metals, asphaltenes, nitrogen compounds and sulfur compounds to reduce the content of metals, asphaltenes, nitrogen compounds and sulfur compounds in that stream, which stream is reacted with the catalyst under suitable conditions and conditions in the presence of hydrogen, characterized in that the catalyst comprises a hydrogenating component consisting essentially of metals of molybdenum and chromium, their oxides, their sulphides or mixtures thereof on a large pore, catalytically active alumina, the Molybdenum is present in an amount of about 5% to about 15% by weight, calculated as MoO 2 and based on the total catalyst weight,

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the chromium is present in an amount of about 5% by weight to about 20% by weight, calculated as Cr ₂ O-, and based on the total catalyst weight, and the catalyst has a pore volume of about 0.4 cnrVg to approx 0.8 cm / g, a specific surface area of about 150 m / g to about 300 m / g and

ο has an average pore diameter of about 100 A (10 nm) to about 200 A (20 mn).

Optionally, the hydrogenation component of the catalyst used in the process of the invention may also contain cobalt. The molybdenum and chromium and cobalt, if present, are present in elemental form, in the form of oxides of the metals, as sulfides of the metals or mixtures thereof. The molybdenum is present in an amount of about 5% by weight to about 15% by weight, calculated as MoO 2 and based on the total weight of the catalyst. The chromium is present in an amount of about 5% to about 20% by weight, calculated as Cr ₂ Oo and based on the total weight of the catalyst. The cobalt, if present, is present in an amount of from 0.1% to about 5% by weight, calculated as CoO and based on the total weight of the catalyst. Preferably, the molybdenum is present in an amount of from about 7% to about 13% by weight, calculated as MoO 2 and based on the total weight of the catalyst, of the chromium in an amount of about 6% by weight to about 15% by weight, calculated as Cr ₂ O ^ and based on the total weight of the catalyst, and is the cobalt in an amount of about 1% by weight to about 3% by weight, calculated as CoO, based on the total catalyst weight, present.

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Accordingly, there is provided a method of hydrotreating a heavy hydrocarbon stream comprising metals, asphaltenes, nitrogen compounds and sulfur compounds to reduce the content of metals, asphaltenes, nitrogen compounds and sulfur compounds in that stream, wherein the stream is treated with a catalyst under suitable conditions and conditions Presence of hydrogen is brought into contact, which is characterized in that the catalyst comprises a hydrogenation component comprising molybdenum, chromium and cobalt, their oxides, their sulfides and mixtures thereof on a large pore, catalytically active alumina, wherein the molybdenum in an amount from approx

 5% by weight to about 15% by weight, calculated as MoOo and based on the total weight of the catalyst, the chromium in an amount of about 5% by weight to about 20% by weight, calculated as C ^ O is present, and based on the total weight of the catalyst, the cobalt in an amount of about 0% by weight to about 5% by weight, calculated as CoO and based on the total weight of the catalyst, and the catalyst has a pore volume in Section

about 0.4 cnr / g to about 0.8 cur / g, a specific surface area

2 2

in the range of about 15Om / g to about 300 m / g and a

ο average pore diameter in the range of about 100 A

(10 nm) to about 200 A (20 μm).

Suitable catalytically active, large pore aluminas are used in the catalyst used in the process of the present invention. A typical example of such an alumina is Aero-100 alumina manufactured by the American Cyanamid Company. The alumina should have a pore volume greater than 0.4 cm / g,

Berlin, July 19, 1979 AP C 10 G / 210 059 GZ 54 802 18

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2 have a specific surface area of more than 150 m / g and an average pore diameter of more than 100 A (10 nm).

Significantly, the catalytic composition used in the process of the present invention can be prepared by impregnation with various metals on the appropriate catalytically active, large pore alumina. Such impregnation may be effected with one or more solutions of the heat-decomposable compounds of the appropriate metals. The impregnation may be a C impregnation if a single solution of the metals is used. Alternatively, the impregnation may be accomplished by the stepwise impregnation with various metals from two or more solutions of the heat decomposable compounds of the appropriate metals. The impregnated support is dried at a temperature of at least 121 ⁰ C (250 P) for a period of at least 1 hour and in air at a temperature of at least 538 C (1000 ⁰ P) for at least calcined for 2 hours. Preferably, the catalyst used in the process of the invention is prepared by first pseudo-boehmite in static air at a temperature of 427 ⁰ C (800 ⁰ P) to about 760 (1400 ⁰ P) for about 1/2 hour to about 2 hours calcined to form T-alumina. This f- alumina is then impregnated with the aqueous solution or solutions containing the heat-decomposable salts of cobalt, if present, and molybdenum and chromium.

The finished catalyst which is used in the

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has a pore volume of about 0.4 cnr / g to ca · 0.8 cm / g, a specific surface area

ρ Ο

from about 150 m / g to about 300 m / g and an average pore diameter in the range of about * 100 X (10 nm) to about 200 A (20 nm). Preferably, the catalyst has a pore volume in the range of ca, 0.5 cm / g to about 0.7 cm / g,

a specific surface area in the range of about * 150 m / g to about 250 m / g and an average pore diameter

ο o

in the range of about 110 A (11 nm) to about 150 A (15 nm).

The catalyst used in the process according to the invention should be about 0 % to about 10% of its pore volume in po

have diameters smaller than 50 A (5 nm), about 30 % to about 80 % of its pore volume in pores

O Q

with diameters in the range of about 50 A (5 nm) to about 100 A (10 nm), about 10% to about 50 of its pore volume in pores with diameters from 100 A (10 nm) to about 150 A ( 15 nm) and about 0 % to about 10 % of its pore volume in pores with throughput

o blades larger than 150 A (15 nm).

The present process is particularly suitable for hydrotreating heavy hydrocarbon streams, such as petroleum residues, both atmospheric and vacuum residues, heavy oil sands, heavy oil sands residues, and coal derived liquids. In addition, the process can be used to satisfactorily hydrotreat petroleum hydrocarbon distillates such as gas oils, recirculating stocks and fuel oils. If the amount of nickel and vanadium is excessive or if the concentration of asphaltenes is too high, then the feed of a previous treatment should reduce the excess amount or amounts

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be subjected to more acceptable levels before the feed is used in the process according to the invention

Operating conditions for hydrotreating heavy hydrocarbon streams, such as petroleum hydrocarbon residues and the like, include a hydrogen partial pressure ranging from about 1000 psia to about 3000 psia ca · 371 ⁰ C (700 ⁰ P) to ca · 438 ⁰ C (820 ⁰ F), an LHSV in the range of about 0.1 volume of hydrocarbon per hour per volume of catalyst to about 3 volumes of hydrocarbon per hour per volume of catalyst and a hydrogen recycle rate or hydrogen addition rate ranging from about 356 m ³ / m ² (2,000 SCFB) to about 2672 mr / mr (15,000 SCFB). Preferably, the operating conditions include a hydrogen partial pressure in the range of about 8,27 MPa (1,200 SCFB) psia) to ca, 13.8 MPa (2000 psia), an average catalyst bed temperature in the range of about 388 ⁰ C (730 ⁰ F) to about 432 ⁰ C (810 ⁰ F), an LHSV in the range of approx 0.4 to about 1 and one water Offrezyklisierungsrate or Wasserstoffzugaberate in the range of about 890 m ³ / m ³ (5000 SCFB) to about 1780 m ³ / m ³ (10,000 SCFB).

When the process of the invention was used to treat hydrocarbon distillates, the operating conditions became a hydrogen partial pressure in the range of about 1.4 MPa (200 psia) to about 20.7 MPa (3000 psia), an average catalyst bed temperature in the range from about 316 ⁰ C (600 ⁰ F) to about 427 ⁰ C (800 ⁰ F), an LHSV in the range of about «0.4 volume of hydrocarbon per hour each

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Volume catalyst to about 6 volumes of hydrocarbon per hour per volume of catalyst and a Wasserstofffrezyklisierungsrate or Wasserstoffzugaberate in the range of about 178 m ³ / m ³ (1000 SCPB) to about 1780 m ³ / m ³ (10,000 SCFB) include. Preferred operating conditions for the hydrotreating of hydrocarbon distillates comprise a hydrogen partial pressure in the range of about "1.4 MPa (200 psia) to about 8.27 MPa (1200 psia), an average catalyst bed temperature in the range of about 316 ⁰ C (600 ⁰ F) to about 399 ° C (750 ⁰ P), an LHSV in the range of about 0.5 volume of hydrocarbon per hour per volume of catalyst to about 4 volumes of hydrocarbon per hour per volume of catalyst and a Wasserstofffrezyklisierungsrate or Wasserstoffzugaberate in the range of about 178 nr / nr (1000 SCPB) to about 1069 m ³ / m ³ (6000 SCPB).

embodiment

The invention will be explained in more detail using an exemplary embodiment.

The attached drawing shows a preferred embodiment of the method according to the invention in the form of a simplified flow diagram and not various parts of auxiliary devices such as pumps, compressors, heat exchangers and valves. Since the skilled person can easily recognize the necessity and attachment of such auxiliary devices, their omission is appropriate and facilitated the simplification of the figure. This process scheme is intended to be illustrative only and not limiting of the invention.

With reference to the figure, a vacuum residue of a

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Arabian light vacuum resid, which contains about 4% by weight of sulfur, less than 0.5% by weight of nitrogen and less than 100 ppm of wound and vanadium, from a supply source 10 via line 11 to the pump 12 withdrawn, being pumped through line 13. A hydrogen-containing recycle gas stream, which will be discussed below, is passed through line 14 in line 13 to be mixed with the hydrocarbon feed stream to form a mixed hydrogen-hydrocarbon stream. The mixed hydrogen-hydrocarbon stream is then transferred from line 13 to the furnace 15, where it is heated to a temperature of about 404 ⁰ C (760 ⁰ P) to about 416 ⁰ C (780 ⁰ P). The heated stream is then transferred through line 16 into the reaction zone 17.

The reaction zone 17 comprises one or more reactors, each containing one or more fixed catalyst beds. The catalyst comprises a hydrogenation component which calculates about 5% to about 15% by weight of molybdenum, calculated as MoO and based on the total catalyst weight, and about 5% to about 20% by weight of chromium as CrpO, and based on the total catalyst weight, on a large pore, catalytically active alumina. The molybdenum and the chromium are both present in elemental form, as oxides of the metals, as sulfides of the metals or as mixtures thereof. The catalyst has a pore volume of ca, 0.4 cnr / g to ca, 0.8 cnr / g, a specific upper

2 2

surface area of approx. 150 m / g to approx. 300 m / g.

average pore diameter from about 100 A (10 nm) to about

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200 A (20 nm) and a pore size distribution, according to about 0 % to about 10 % of the pore volume pores with diameters

O Q

from about 0 A (O nm) to about 50 A (5 nm), about 30 % to about 80 % of the pore volume pore diameter of about 50 A (5 nm) to about 100 A (10 nm), about 10 to about 50 % of the pore volume

ο o

Pore diameter of about 100 A (10 nm) to about 150 A (15 nm) and about 0 % to about 10% of the pore volume pore diameter greater than 150 A (15 nm) have.

The operating conditions used in this scheme include a hydrogen partial pressure of about 8.27 MPa (1200 psia) to about 11.0 MPa (1600 psia), an average catalyst bed temperature in the range of about 404 ⁰ C (760 F) to about 416 ⁰ C (780 ⁰ P), an LHSV in the range of about 0.4 volume of hydrocarbon per hour per volume of catalyst to ca, 0.8 volume of hydrocarbon per hour per volume of catalyst and a hydrogen recycle rate of about m ³ / m ³ (5000 SCI ¹ B) to about 1425 m ³ / m ³ (8000 SCFB).

The effluent from the reaction zone 17 is passed through line 18 into a high temperature door / high pressure / gas-liquid separator 19, which at the reactor pressure and at a temperature of about 404 ° C (760 ⁰ F) to about 416 ⁰ C. (780 ⁰ F) is operated. In the separator 19, a hydrogen-containing gas is separated from the rest of the effluent. The hydrogen-containing gas is passed from the separator 19 through line 20. It is cooled and introduced into a light hydrocarbon separator 21 in which the condensed light hydrocarbons are separated from the hydrogen-containing gas and withdrawn via line 22

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become. The hydrogen-containing gas is removed via line 23 and passed into a scrubber 24 where hydrogen sulfide is removed and scrubbed out of the gas. The hydrogen sulfide is removed from the system via line 25. The scrubbed hydrogen-containing gas is then passed through line 14, where it is combined with top-up hydrogen, if necessary, via line 26. The hydrogen-containing gas stream is then added to the hydrocarbon feed stream in line 13 as described above.

The liquid portion of the effluent is directed from the high temperature / high pressure / gas-liquid separator 19 via line 27 to the high temperature relaxation chamber or drum 28. In the flash chamber 28, the pressure is reduced to atmospheric pressure, and the temperature of the material is in the range of about 371 ⁰ C (700 ⁰ F) to about 427 ⁰ C (800 ⁰ F). In the expansion chamber 28, the light hydrocarbons which contain not only naphtha but also those distillates which boil up to a temperature of about 288 ⁰ C (550 ⁰ F) to 316 ⁰ C (600 ⁰ F), such as fuel oils, stripped from the rest of the product and removed from the system via line 29. Such light hydrocarbons containing from about 1% to about 4% by weight C. material, from about 2% to about 5% by weight of naphtha [c ^ to bis-182 ^° C. (C ₅ ) bis-36O ⁰ F) -Material] and about 10% to about 15% by weight of 182 ⁰ C - 343 C (360 ⁰ F -650 ⁰ F) material, based on the hydrocarbon feed, contained in their various components are separated and fed to the reservoir or other process units.

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The heavier material that is separated from the light hydrocarbon, ie material which, at a temperature above about 316 ⁰ C (600 ⁰ P) and boiling in an amount of about 60 wt% to about 90% by weight based on the hydrocarbon feed, is removed from the flash chamber 28 via line 30 for use as feeds to other processes or as a heavy, low sulfur industrial fuel. Such liquid material contains from about .6% by weight to about 5% by weight. 1.2 weight percent sulfur, about 1.0 weight percent to about 3.0 weight percent asphaltenes, and about 5 ppm to about 15 ppm nickel and vanadium. Furthermore, more than 50% of the 538 ⁰ C + (1000 ^O P +) material is converted to 538 ⁰ C (1000 ^O P -) material.

This liquid effluent is passed via line 31 into the furnace 32 or other suitable heating means for heating to a temperature of as high as 427 ⁰ C (800 ⁰ P).

The heated stream from the furnace 32 is passed via line 33 to a vacuum tower 34 where vacuum gas oil (VGO) is separated from a low sulfur fuel residue. The VGO is supplied from the vacuum tower 34 via line 35 to a reservoir or conventional catalytic cracking unit (not shown). The low sulfur fuel residue is supplied from the vacuum tower 34 via line 36 to a storage vessel or other process units where it can be used as an energy source.

Alternatively, the above 316 ⁰ C (600 ⁰ P) boiling material which corresponds from the flash chamber 28 via line 30 can

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is supplied via line 37 of a catalytic cracking unit for residues (not shown).

The following examples are intended to facilitate the understanding of the invention and to explain the invention in more detail.

example 1

A catalyst, hereinafter referred to as Catalyst A, having a content of 8.3% by weight of MoO.sub.2 and 8.3% by weight of C.sub.2 O.sub.3, based on the total catalyst weight, was prepared on a large-pore, catalytically active alumina , A 40.8 g sample of Aero-100 alumina, obtained from American Cyanamid Company, was impregnated with a solution containing ammonium dichromate and ammonium molybdate. The Aero-100 alumina was in the form of a material having a mesh size from 0.83 to 1.17 mm (14 to 20 mesh) before and v? Ar previously on at a temperature of about 649 ⁰ C (1200 ⁰ F) Air was calcined for 2 hours.

The solution used for the impregnation was prepared by dissolving 6.8 g of ammonium dichromate and 5.3 g of ammonium molybdate in 40 ml of distilled water.

The impregnated alumina was dried under a heat lamp in static air over water to remove excess water. The dried material was then calcined in static air at a temperature of 538 ^° C. (1000 ^° F.) for 2 hours. The finished catalyst, catalyst A, represents an embodiment of the catalyst,

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used in the method according to the invention

Example 2

For comparative purposes, a commercially available catalyst obtained from the American Cyanamid Company was used. This commercially available catalyst was designated HDS-2A and specified by the American Cyanamid Company containing 3% by weight CoO and 13% by weight MoO- on an alumina carrier. This catalyst is hereinafter referred to as Catalyst B.

Example 3

The catalyst was obtained from NaIco Chemical Company. The catalyst referred to below as Catalyst C was specified to contain 3% by weight of CoO and 13% by weight of MoO.sup. On an alumina carrier. The properties of catalysts A, B and C are given in Table I below *

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210 059

Table I A B 3 C 3 - D catalyst properties 13 catalyst 13 Hydrierungskompoiienten, - 284 - Gev / ichts-% 8.3 330 0.61 - CoO 8.3 0.61 - Cr ₂ O ₃ 86 MoO ₃ 208 73 8.6 222 Physical Properties 0.60 7.3 0.73 epez. Surface, m / g Pore volume, cm / g 116 131 avg. Porendurch- 11.6 13.1 O knife, A nm

% Pore volume in:

0-50 X. (0-5 nm) pores 6.3 26.7 H.2 1.4 50-100 A (5-10 nm) pores 69.5 58.8 76.3 56.7

100-150 2 (10-15 nm) -

Pores 23.1 4.3 2.1 36.6

150-200 A (15-20 nm) -

Pores 0.4 1.6 0.7 1 # 6 ο 200-300 A (20-30 nm) -

Pores 0.3 2.1 1.1 1.4

300-400 A (30-40 nm) -

Pores 0.1 0.8 0.8 0.4

400 2+ (40 nm +) pores 0.3 5.7 4.8 1.9

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Table I (PortSetzung)

Catalyst iron machinations % Pore volume in: e P G catalyst O 0-50 A (0-5nm) pores hydrogenation, ο 50-100 A (5-10 nm) pores % by weight 100-150 1 (10-15 nm) pores - - - CoO 150-200 A (15-20 nm) pores - 5.2 15.4 Cr ₂ Oo 200-300 A (20-30 nm) pores 9 8.6 7.7 MoO ₃ 300-400 A (30-40 nm) pores Physical Properties 400 A + (40 nm +) pores 201 197 198 ßpez. Surface, m / g 0.66 0.60 12:59 Pore volume, cnr / g avg. Pore diameter, 130 122 119 1 13.0 12.2 11.9 nm 3.1 2.2 2.7 68.0 64.8 65.8 27.8 30.6 30.2 0.2 0.8 0.2 0.3 0.7 0.3 0.1 0.2 0.1 0.5 0.6 0.5

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In addition, Table I gives the physical properties of the alumina used as support material for Catalyst A. This carrier material is referred to as catalyst D. The incorporation of the metals into the alumina did not appreciably affect the pore size distribution, pore volume, specific surface area or average pore diameter of the alumina.

Example 4

Three additional catalysts were prepared to demonstrate the effect of various concentrations of chromium oxide on the catalyst comprising about 9 weight% molybdenum oxide and an aero-100A alumina support. These catalysts were prepared according to the preparation method outlined in Example 1 above , However, only the appropriate amounts of the metals were used to give the desired compositions of the finished catalysts. These three catalysts are hereinafter referred to as Catalysts E, F and G and were prepared with the same Aero-100 alumina type used in the preparation of Catalyst A. Their chemical compositions and physical properties are also given in Table I above. Again, it will be appreciated that incorporation of the metals onto and into the alumina does not appreciably affect the physical properties of the alumina.

Example 5

Each of the above-discussed catalysts was examined for suitability for the conversion of a

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Vacuum residue of a light arabic hydrocarbon (Arabian light vacuum resid). Suitable properties of this feed are given in Table II below.

Table II feed properties

Carbon,% by weight 84.91

Hydrogen, weight% 10.61 H / C (atomic). 1,499 nitrogen, weight% 0.34

Sulfur, weight% 4.07

Wraps, ppm 17.5

Vanadin 51.1

538 ⁰ C (1000 ^O F -) fraction 13.6

Ramsbottom carbon,% by weight 15.2

Heavy, ⁰ API 8,8

Density at 15 ⁰ C, g / cm ³ 1.0080

Asphaltene, weight% 8.0

Oils, weight% 39.2

Resins,% by weight 52.8

Resins / Asphaltenes 6,6

Each test was performed in a test bench test unit with automatic controls for pressure, reactant flow and temperature. The reactor was a 0.95 cm (3/8 inch) inside diameter thick-walled stainless steel tube. A 0.32 cm (1/8 inch) outer diameter thermocouple extended through the center.

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up the reactor. The reactor was heated by an electrically heated steel block. The hydrocarbon feed was fed to the unit by means of a Ruska pump, a positive exchange pump. The catalyst material having a particle size of 0.83 to 1.17 mm (14 to 20 mesh) was applied to alundum particles (refractory alumina) having a particle size of 2.00 to 2.38 mm (8 mesh). About 20 cnr of catalyst was used as the catalyst bed in each test. This amount of catalyst gave a catalyst bed length of about 25.4 cm (10 inches) to about 30.5 cm (12 inches). A 25.4 cm (10-inch) layer of 2.00 to 2.38 mm (8-10 mesh) alundum particles was placed over the catalyst bed in the reactor for each test. The catalyst used was placed in the annular space between the thermocouple and the inner wall of the 0.95 cm (3/8 inch) inside diameter reactor.

Prior to its use, each catalyst was calcined for 1 hour in still air at a temperature of about 538 ⁰ C (1000 ⁰ P). It was then cooled in a desiccator and placed in the appropriate reactor.

The catalyst was then subjected to the following pretreatment. The reactor was introduced into the reactor block at a temperature of 149 ⁰ C (300 ⁰ P). A gas mixture containing 8 lbs. Of hydrogen sulfide in hydrogen was injected at a rate of 28.3 l / hr at a pressure of 3 * 5 MPa (500 psig) and at a temperature of approx 149 ⁰ C (300 ⁰ P) passed over the catalyst. After 10 to 15 minutes one

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such treatment, the temperature of the block was raised to 204 ⁰ C (400 ⁰ F). After at least one additional hour had passed, and at least 28.3 1 had been (1 standard cubic foot) of gas mixture passed through the system, the temperature of the block was raised to 371 ⁰ C (700 ⁰ P). Thereafter, the gas mixture was passed through the catalyst bed for at least another hour in an amount of at least 28.3 L (1 standard cubic foot). At this time, the gas mixture was discontinued, hydrogen was introduced into the unit at a pressure of 8.37 MPa (1200 psig), a hydrogen flow was set at a rate of about 17 l / hr (0.6 SCFH), and the temperature increased to give an average catalyst bed temperature of 4o4 ⁰ C (760 ⁰ F). Subsequently, a hydrogen flow was adjusted at a rate such that an LHSV of 0.59 volume of hydrocarbon per hour per volume of catalyst was achieved. The effluent from the reaction zone was collected in a liquid product receiver while the formed gas was passed through the product receiver to a pressure control valve and then fed through a humidity tester to a suitable port.

After a period of 1 to 3 days, the average catalyst bed temperature was increased to 416 ⁰ C (780 ⁰ F) After a further period of time, for. B. about 3 to 5 days, the K was increased.

increased catalyst bed temperature to 416 ⁰ C (780 ⁰ F).

up to 5 days, the catalyst bed temperature to about 427 ⁰ C (800 ⁰ F)

Collected samples were taken from the product receptacle and analyzed for their pertinent information.

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mation. The test results are given in Table III below. These data were obtained from samples during the fifth to ninth day of the procedure at a IHSV of 0.59 volume of hydrocarbon per hour per volume of catalyst, at a temperature of 427 ⁰ C (800 ⁰ P) and at a pressure of 8,37 MPa (1,200 psig) unless otherwise stated

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Table III test results

Approach Hr. 12 3

Catalyst A B C E

Temperature, (F) Pressure, (psig) LHSV (800) (800) (780) (780) ⁰ o MPa % Sulfur removal 427 427 416 416 % Mckelentfernung (1,200) (1,200) (1,200) (1,200) % Vanadium removal 8:37 8.37 8:37 8:37 % Asphaltene conversion 12:59 12:59 12:59 12:59 Liquid density, ⁰ API 65.4 77.4 85 59 Density at 15 ⁰ C, g / cm ³ 85 43 48 40 % Conversion of 92.5 94.9 57 79 538 ⁰ C + (1000 ⁰ F +) - Mate 70 68.8 54 67.5 rial 20.1 19.9 20.4 17.5 Days under flow 0.9328 0.9341 0.9310 0.9491 59.1 47 · 3 40 - 6 7 7-18 ^ '5

Composite sample of the material obtained from day 7 to day 18.

Table III (continued)

test results

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Approach Hr. catalyst

Temperature, (P) ⁰ C pressure, (psig)

MPa LHSV

% Sulfur removal% nickel removal% Vanadinentfernung% asphaltenes conversion

Liquid density, ⁰ API density at 15 ⁰ C, g / cm ³

% Conversion of

538 ⁰ C + (1000 ⁰ P +) - material days under flow

(800) (800) (800) 427 427 427 1,200 1,200 1,200 8.37 8:37 8:37 12:59 12:59 12:59 60.5 60 69.6 64 64 78 81 87 90.6 66 70 71 19.3 17.6 21.1 0.9378 0.9485 0.9267 53 60.6 58.6 9 10 7

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The results given in Table III show that the approach mater use of catalyst A, d. h, an embodiment of the method according to the invention, was superior to the two tests using other catalysts. The data show that the inventive method a better Mckelentfernung, an approximately equally good Vanadinentfernung, better asphaltenes conversion, a better conversion of 538 ⁰ C + (1000 ⁰ F +) - yielded material, but a lower sulfur removal than the process, the other Catalysts used. Thus, the process of the present invention is a suitable process for demetallization, desulfurization, asphaltene conversion, and conversion of 538 ⁰ C + (1000 ^O P +) material when treating a heavy hydrocarbon stream. Moreover, the data of Runs 1, 4, 5 and 6 show that the presence of in the catalyst improved metal removal, sulfur removal, asphaltene conversion and conversion of 538 C + (1000 ^O F +) material to 538 ⁰ C (1000 ^ohm) F -) material.

Example 6

A catalyst, hereinafter referred to as Catalyst H, was added at a level of 1.1 wt% CoO, 8.2 wt% MoO _2, and 8.2 wt% Cr ₂ O, based on the total weight of the catalyst Catalyst prepared on a large pore, catalytically active alumina. A 63 »8 g sample of Aer0-100 alumina, obtained from American Cyanamid Company, was impregnated with a solution containing ammonium dichromate and ammonium molybdate. The Aero-100 alumina was in the form of a 0.83 to 1.17 mm (14 to 20 mesh) material and was previously at a temperature of

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about 649 ⁰ G (1200 ⁰ F) was calcined in air for 2 hours.

The solution used for the impregnation was prepared by dissolving 10.6 g of ammonium dichromate and 8.3 g of ammonium molybdate in 80 ml of distilled water. The alumina to be impregnated was added to the solution, and the resultant mixture was allowed to stand overnight.

The impregnated alumina was then dried under a heat lamp of static air for about 2 hours to remove excess water. The dried material was then calcined in static air at a temperature of 538 ^° C. (1000 ^° F.) for 2 hours.

One half of the calcined material was impregnated with a cobalt nitrate solution. This solution was prepared by dissolving 1.2 g of Co (NO ₂ ) ₂ .6H ₂ O in 40 ml of distilled water. The mixture of calcined material and solution was allowed to stand overnight.

The material was then dried under a heat lamp in static air for about 2 hours. The dried material was calcined in static air at a temperature of 538 ^° C. (1000 ^° F.) for 2 hours. The finished catalyst, Catalyst H, represents a preferred embodiment of the catalyst used in the process of the present invention. Its properties are shown in Table IV below.

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Example 7

A second catalyst, hereinafter referred to as Catalyst I, was added at a level of 3% to 1% by weight CoO, 8.1% by weight MoO ₂ , and 8.1% by weight Cr ₂ CU based on total catalyst weight. made on an aero-100 alumina carrier. This catalyst was prepared according to the preparation method outlined above in Example 6, but suitable amounts of the metals were used to give the desired composition. This catalyst, catalyst I, represents another embodiment of the catalyst used in the process according to the invention. Its properties are given below in Table IV.

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Table IV test results

Catalyst H I

Hydrogenation components,% by weight

CoO

Cr ₂ O ₃

MoO ₃

Physical properties specific surface area, m / g pore volume, cm / g average Pore diameter,

% Pore volume in: 0-50 2 (0-5 nm) pores 50-100 Χ (5-10 nm) pores 100-150 Ϊ (10-15 μm) pores I5O-2OO A (15-20 nm) Pores 200-300 A (20-30 nm) pores 300-400 A (30-40 nm) pores 400-600 A (40-60 nm) pores

1.1 3.1 8.2 8.1 8.2 8.1 176 186 12:55 12:56 125 120 12.5 12.0 3.9 4.7 66.3 65.4 28.9 29.1 0.3 0.3 0.3 0.3 0.1 0.1 0.2 0.1

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Example 8

Catalyst H and Catalyst I were each tested for their suitability for the conversion of a vacuum residue of a light hydrocarbon from Arabia, described above in Table II.

Each test was performed as described above in Example 5.

The results of these tests are given in Table V below. Table V also reproduces the test results of Batches 1, 2 and 3 "given above in Table III.

• T VL. ? 3 "T

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Table V test results

Approach Ur. , 7 8

Catalyst H I

Operationally Ingen

Temperature, ( ⁰ P) (800) (800)

⁰ C 427 427

Pressure, (psig) 1,200 1,200

MPa 8.37 8.37

LHSV 0.59 0.59

Sample from> day 9 9

% Sulfur removal 75 83

% Nickel removal 79 73

% Vanadium removal 93 96

% Asphaltene conversion 79 75 % conversion of

538 ⁰ C + (1000 ⁰ P +) - material 66 50

Liquid density, ⁰ API 20.9 20.7

Density at 15 ⁰ C, g / cm ³ 0.9280 9292 O _e

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Table V (port setting) Iesterp; ebniss_e

Approach Ur

 catalyst

Operating Conditions Temperature, ( ⁰ P) ⁰ C Pressure, (psig)

MPa LHSY sample of the day

% Sulfur removal% nickel removal% Vanadinentfernung% asphaltenes conversion% conversion of

538 ⁰ C + (1000 ⁰ P +) - material, liquid density, ⁰ API

Density at 15 ⁰ C, g / cm ³ 0.9328 0.9341 0.9310

'' Composite sample of the material obtained from day 7 to day 18.

1 2 3 A B 0 (800) (800) (780) 427 427 416 (1,200) (1,200) di 200) 8 _# 37 8:37 8:37 12:59 12:59 12:59 6 7 7-18 ⁽¹ > 65 77 85 85 43 48 93 95 57 70 69 54 59 47 40 20.1 19.9 20.4

Berlin, July 19, 1979

GZ 54 802 18

AP C 10 G / 210 059

.so. 210 059

These results show that approach-Hr ,. Figure 7, which illustrates a preferred embodiment of the process of the invention and uses a preferred embodiment of the catalyst used in the process of the present invention, always gives superior performance over the other approaches. Br leads to a good desulfurization, good Hickelentfernung, good Vanadinentfernung, superior asphaltenes conversion and superior conversion of 538 C + (1000 ⁰ J +?) - material to 538 ⁰ C (1000 ⁰ P -) - Material /

The approach Ur. Figure 8, which illustrates another embodiment of the process of the present invention, employs a catalyst that uses more cobalt (3.1 weight percent CoO) than catalyst A (1.1 weight percent CoO), but this larger amount still falls within the broad range Range from 0.1% to 5% by weight of CoO reported above for a catalyst which can be used in the process of the present invention. The increased amount of cobalt improves desulfurization activity, somewhat lowers metal removal, asphaltene conversion and conversion of 538 ⁰ C + (1000 ^O F +) material to 538 ⁰ C (1000 ^O F -) material of the catalyst.

Approach # 1 uses a catalyst containing chromium and molybdenum but no cobalt in its hydrogenation component. The absence of cobalt results in less sulfur removal, slightly improved metal removal, lower asphaltene conversion, and lower conversion of 538 ⁰ C + (1000 ^O F +) material.

The approaches 2 and 3 represent comparative experiments that

Berlin, July 19, 1979 AP C 10 G / 210 059 GZ 54 802 18

- ⁵¹ - 2 1 0 059

Use state-of-the-art ionizers. These two approaches gave essentially the same amount of desulfurization as the process of this invention. However, they showed a lower metals removal, AsphaItene conversion, and conversion of 538 538 ⁰ C (1000 ⁰ P -) - material.

conversion and conversion of 538 ⁰ C + (1000 ° P +) - material to

In view of the foregoing, the process of the present invention represents a novel process for hydrotreating heavy hydrocarbon streams. The use of a small amount of cobalt in the catalyst in conjunction with the Group VIB metals of the Periodic Table of the Chemical Elements, namely chromium and molybdenum, is unexpected This method using such a catalyst provides a very effective method of treating such heavy hydrocarbons.

Claims (6)

-52- 210 059 invention claim A method of hydrotreating a heavy hydrocarbon stream containing metals, asphaltenes, nitrogen compounds and sulfur compounds to reduce the content of metals, asphaltenes, nitrogen compounds and sulfur compounds in that stream, which stream is treated with a catalyst under suitable conditions and in the presence of is contacted by hydrogen, characterized in that the catalyst comprises a hydrogenation component comprising the metals of molybdenum and chromium, their oxides, their sulfides or mixtures thereof on a large pore, catalytically active alumina, wherein the molybdenum in an amount in the range from about 5% by weight to about 15% by weight, calculated as MoCU, based on the total catalyst weight, the chromium is present in an amount in the range from about 5% by weight to about 20% by weight. -%, calculated as CrgO ^ »based on the total catalyst weight, is present and wherein the catalyst has a pore volume in Be ranging from about 0.4 cc / g to ca, 0.8 cc / g, a specific surface area 2 2 in the range of about 150 m / g to about 300 m / g and an average pore diameter in the range of ca _# ο o 100 A (10 nm) to about 200 A (20 nm). 2. The method according to item 1, characterized in that the catalyst is prepared by calcining a pseudoboehmite in static air at a temperature of about 427 ⁰ C (800 ⁰ P) to about 760 ⁰ C (I400 ⁰ P) during about half an hour to about 2 hours to prepare an X-alumina, followed by impregnation Berlin, July 19, 1979 AP C 10 G / 210 059 GZ 54 802 18 - 53 - 210 059 this (f-aluminum oxide with one or more aqueous solutions of heat-decomposable compounds of these metals Method according to item 1, characterized in that the catalyst has about 0 % to about 10% of its pore volume in pores with diameters less than 50 A (5 nm), about 30 % to about 80 % % of its pore volume in pores has diameters of about 50 S (5 nm) to about 100 A (10 nm), about 10 to about 50% of its pore volume in pores with diameters of about 100 A ( 10 nm) to about 150 A (15 nm) and about 0% to about 10% of its pore volume in pores, with diameters larger than 150 A (15 nm). 4. The method according to item 1, characterized in that the hydrogenation component of this catalyst, the metal, cobalt, its oxide, its sulfide or mixtures thereof, wherein the cobalt in an amount of about 0.1 wt .-% to about 5% by weight , calculated as CoO, based on the total catalyst mixture. 5. The method according to item 2, characterized in that the. Catalyst about 0 % to about 10% of its pore volume present in pores has diameters smaller than 50 % (5 nm), about 30 % to about 80 % of its pore volume present in pores with diameters of ο o about 50 A (5 nm) to about 100 A (10 nm), about 10 % to about, 50 % of its pore volume is present in pores with ο o Diameters of about 100 A (10 nm) to about 150 A (15 nm) and about 0 % to about 10% of its pore volume in pores - 54 - 2 1 O 059 has diameters larger than 150 A (15 ma). 6. The method according to item 4, characterized in that the catalyst is prepared by calcining pseudoboehmite in static air at a temperature of about 427 ⁰ C (800 ⁰ P) to about 760 ⁰ C (1400 ⁰ F) during about
half an hour to about 2 hours to form " -alumina, and impregnating this fr- alumina with one or more aqueous solutions containing low-decomposable molybdenum and chromium salts. Process according to item 4, characterized in that the catalyst has about 0% to about 10% of its pore volume in pores having diameters less than 50 Å (5 nm), about 30 % to about 80 % % of its pore volume is present in pores with diameters of about 50 oo
A (5 mn) to approx. 100 A (10 ma), approx. 10 % to approx. 50% of its pore volume in pores has with diameter o o from about 100 A (10 nm) to about 150 A (15 nm) and ca. 0 % to about 10% of its pore volume in pores ο
has diameters larger than 150 A (15 nm). 8. The method according to item 6, characterized in that the catalyst is present in pores from about 0 % to about 10 % of its pore volume with diameters smaller than 50 A (5 nm), about 30 % to about 80 % of its pore volume is present in pores with diameters of about 50 1 (5 nm) to about 100 A (10 nm), about 10 % to about 50 %
of its pore volume in pores has with diameter o ° from ca, 100 A (10 nm) to about 150 A (15 nm) and about 0 % to about 10% of its pore volume is present in pores having diameters larger than 150 Å
(15 nm).