NL1027765C2 - Systems, methods and catalysts for producing a crude product. - Google Patents

Systems, methods and catalysts for producing a crude product. Download PDF

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Publication number
NL1027765C2
NL1027765C2 NL1027765A NL1027765A NL1027765C2 NL 1027765 C2 NL1027765 C2 NL 1027765C2 NL 1027765 A NL1027765 A NL 1027765A NL 1027765 A NL1027765 A NL 1027765A NL 1027765 C2 NL1027765 C2 NL 1027765C2
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crude
catalyst
product
feed
content
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NL1027765A
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Dutch (nl)
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NL1027765A1 (en
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Scott Lee Wellington
Opinder Kishan Bhan
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Shell Int Research
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20Vanadium, niobium or tantalum
    • B01J23/22Vanadium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • B01J35/1052Pore diameter
    • B01J35/10612-50 nm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/10Solids characterised by their surface properties or porosity
    • B01J35/108Pore distribution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0203Impregnation the impregnation liquid containing organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203Naphthenic acids, TAN
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/205Metal content

Abstract

Contact of a crude feed with one or more catalysts produces a total product that include a crude product. The crude product is a liquid mixture at 25°C and 0.101 MPa. One or more other properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed.

Description

- 1 -

SYSTEMS, METHODS AND CATALYSTS FOR PRODUCING A RAW-OIL PRODUCT

FIELD OF THE INVENTION

The present invention relates in a general sense to systems, methods and catalysts for treating crude feed and to 5 .com positions that can be produced with such systems, methods and catalysts. More specifically, certain embodiments described herein relate to systems, methods, and catalysts for converting a crude feed into a total product, wherein the total product includes a crude product containing at 25 ° C and 0.101. MPa is a liquid mixture and has one or more properties that are altered with respect to the respective property of the crude feed.

DESCRIPTION OF THE RELATED ART

Crude-containing raw materials that have one or more unsuitable properties that prevent crude-containing raw materials from being economically transported or processed with conventional facilities are commonly referred to as "disadvantaged crudes": crude-containing raw materials with adverse characteristics.

Disadvantaged crudes can include acid components that contribute to the total acid value ("TAN") of the crude feed. Disadvantaged crudes with a relatively high TAN can contribute to corrosion of metal components during 1027765 - 2 -

transport and / or processing of the disadvantaged crudes. I

The removal of acid components from disadvantaged crudes may include chemically neutralizing acid components with various bases. Corrosion-resistant metals can also be used in transport and / or processing equipment. The use of corrosion-resistant metal often involves considerable costs, so that the use of corrosion-resistant metal in existing equipment may not be desirable.

Another method of counteracting corrosion may include addition of corrosion inhibitors to disadvantaged crudes prior to transportation and / or processing of the disadvantaged crudes. The use of corrosion inhibitors can adversely affect equipment used for the processing of crude oil raw materials and / or on the quality of products produced from the crude oil raw materials.

Disadvantaged crudes often have relatively high residue levels. Such high residue levels are usually difficult and expensive to transport and / or process with conventional facilities

Disadvantaged crudes often contain organically bound heteroatoms (for example sulfur, oxygen and nitrogen). Organically bound heteroatoms can have an adverse effect on catalysts in some situations.

Disadvantaged crudes may include relatively large amounts of metal contaminants, such as, for example, nickel, vanadium and / or iron.

During the processing of such crude-containing raw materials, metal contaminants and / or compounds of metal contaminants may deposit on a surface of the catalyst or in the void volume of the catalyst. Such deposits may cause a decrease in the activity of the catalyst.

5 During the processing of disadvantaged crudes, coke can form and / or deposit rapidly on catalyst surfaces. Regenerating the catalytic activity of a coke-contaminated catalyst can be a costly affair. High temperatures used during regeneration can also reduce the activity of the catalyst and / or degrade the catalyst.

Disadvantaged crudes may include metals in metal salts of organic acids (e.g., calcium, potassium and / or sodium). Metals in metal salts of organic acids are usually not split off from disadvantaged crudes by conventional processes, for example desalination and / or acid washing.

Conventional processes often encounter processes when metals are present in metal salts of organic acids. Unlike nickel and vanadium, which are usually located near the outer surface of. When depositing the catalyst, metals in metal salts of organic acids can preferably deposit in empty volumes between catalyst particles, in particular at the top of the catalyst bed. Deposition of impurities, for example metals in metal salts of organic acids, at the top of the catalyst bed generally leads to an increase in pressure drop through the bed and can in fact clog the catalyst bed. In addition, the metals in metal salts of organic acids can cause rapid deactivation of catalysts.

1027765 - 4 -

Disadvantaged crudes can include organic oxygen compounds. Treatment facilities that process disadvantaged crudes with an oxygen content of at least 0.002 grams of oxygen per gram of disadvantaged crude may encounter problems during processing. Organic oxygen compounds, when heated during processing, may form higher oxidation compounds (e.g., ketones and / or acids formed by oxidation of alcohols and / or acids formed by oxidation of ethers) that are difficult to remove from the treated crude feedstock and / or that equipment may corrode / contaminate during processing and cause blockage in transport lines.

15 'Disadvantaged crudes can include low-hydrogen hydrocarbons. In the processing of low-hydrogen hydrocarbons, consistent amounts of hydrogen must generally be added, in particular when unsaturated fragments are produced that are the result of cracking processes. Hydrogenation during processing, which usually involves the use of an active hydrogenation catalyst, may be necessary to prevent coke formation through unsaturated fragments. Hydrogen is expensive to produce and / or transport to treatment facilities.

Disadvantaged crudes also tend to show instability during processing in conventional facilities. Instability of crude feedstock tends to result in phase separation of components during the processing and / or formation of undesirable by-products (e.g., hydrogen sulfide, water, and carbon dioxide).

1027765 - 5 -

Conventional processes often do not have the ability to change a selected trait of a disadvantaged crude without substantially changing other traits of the disadvantaged crude. For example, conventional processes often do not have the ability to significantly reduce the TAN of a disadvantaged crude and at the same time change the content of certain components (such as sulfur or metal contaminants) in the disadvantaged crude by only a desired degree.

Some processes to improve the quality of crude feedstock include adding a diluent to disadvantaged crudes to reduce the weight percentage of components that contribute to the adverse properties. However, the addition of diluent generally increases the handling costs of disadvantaged crudes because of the costs of the diluent and / or increases the physical handling costs of disadvantaged crudes. Addition of diluent to a disadvantaged crude can in some situations reduce the stability of such a crude-containing raw material.

U.S. Patent Nos. 6,547,957, to Sudhakar et al., 6,277,269, to Meyers et al., 6,063,266, to Grande et al., 5,928,502, to Bearden. et al., 5,914,030, to Bearden et al., 5,897,769, to Trachte et al .; 5,871,636, to Trachte et al., and 5,851,381, to Tanaka. et al., describe various processes, systems and catalysts for the processing of crude oil-containing raw materials. However, due to many of the technical problems set forth above, the processes, systems and catalysts described in these patents have limited applicability.

Taken together, disadvantaged crudes generally have undesirable properties (e.g., a relatively high TAN, a tendency to become unstable during treatment and / or a tendency to consume relatively large amounts of hydrogen during treatment). Other undesirable properties include relatively large amounts of unwanted components (for example residue, organically bound heteroatoms, metal contaminants, metals in metal salts of organic acids and / or organic oxygen compounds). Such properties tend to cause problems in conventional transport and / or treatment facilities, including increased corrosion, shorter catalyst life, process blocking and / or increased use of hydrogen during treatment. There is therefore 20. a significant economic and technical need for improved systems, methods and / or catalysts for converting disadvantaged crudes into crude-containing products with more desirable properties. There is also a considerable economic and technical need for systems, methods and / or catalysts that

selected properties of a disadvantaged crude can change and thereby only selectively change other properties of the disadvantaged crude. SUMMARY OF THE INVENTION

The inventions described herein generally relate to systems, methods, and catalysts for converting a crude-containing feed into a total product comprising a crude-containing product and, in some embodiments, non-condensable gas. The inventions described herein also relate in a general sense to compositions which have new component combinations therein. Such compositions can be obtained using the systems and methods described herein.

The invention provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to form a total product comprising, inter alia, the crude product, the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a TAN of at least .15 0.3 and wherein at least one of the catalysts is one.

pore size distribution with a median pore diameter in a range from 90 A to 180 A, with at least 60% of the total number of pores in the pore size distribution having a pore diameter within 45 A of the median pore diameter 20, pore size distribution being as determined by ASTM method D4282 ; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is such.

Determined by ASTM method D664.

The invention also provides a. a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to form a total product comprising inter alia the crude product, the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the crude feed having a TAN of at least 1027765 - 8 · - 0.3, at least one of the catalysts having a pore size distribution with a median pore diameter of at least 90 A has, as determined by ASTM method D4282, and wherein the catalyst with the pore size distribution per gram of catalyst has 0.0001 gram to 0.08 gram of: molybdenum, one or more molybdenum compounds, calculated as a weight of molybdenum, or mixtures thereof; And controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM method D664.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a TAN of at least 0.3, as determined with ASTM D664, wherein at least one of the catalysts has a pore size distribution with has a median pore diameter of at least 180 A, as determined by ASTM method D4282, and wherein the pore size distribution catalyst comprises one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of comprises the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM method D664.

The invention also provides a method for producing a crude oil-containing product, comprising: 1027765-9 contacting a crude-oil-containing feed with one or more catalysts to form a total product which inter alia comprises the crude oil-containing product wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the crude feed having a TAN of at least 0.3, as determined by ASTM method D664, and wherein at least one of the catalysts comprises: (a) one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and (b) one or more metals from Column 10 of the Periodic System, a. or more compounds of one or more metals from Column 10 of the Periodic System or mixtures thereof and wherein 15 a molar ratio of the total metal from i

Column 10 until the total metal from Column 6 is in a range of 1 to 10; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM method D664.

The invention also provides a method for producing a crude oil-containing product, comprising: contacting a crude-containing feed with one or more catalysts to form a total product which inter alia comprises the crude-containing product wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a TAN of at least 0.3 and wherein the one or more catalysts comprise: (a) a first catalyst, wherein the first catalyst per gram of first catalyst has 0.0001 to 0.06 gram of:. one or more metals from Column 6 of the Periodic 1027765 - 10 -

System, one or more compounds of one or more metals from Column 6 of the Periodic System, calculated as weight of metal, or mixtures thereof; and (b) a second catalyst, wherein the second catalyst has at least 0.02 grams per 5 grams of second catalyst of: one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic System, calculated as a weight of metal, or mixtures thereof; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM method D664.

The invention also provides a catalyst composition comprising: (a) one or more metals from Column 5 of the Periodic Table, one or more compounds of one or more metals from Column 5 of the Periodic Table or mixtures thereof; (b) a support material with a theta-alumina content of at least 0.1 gram of theta-alumina per gram of support material, as determined by X-ray diffraction; and wherein the catalyst has a pore size distribution with a median pore diameter of at least 230 A, as determined by ASTM method D4282.

The invention also provides a catalyst composition comprising: (a) one or more metals from

Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; (b) a support material with a theta-alumina content of at least 0.1 gram of theta-alumina per gram of support material. as determined by X-ray diffraction; and wherein the catalyst has a pore size distribution with a median pore diameter of at least 230 A, as determined by ASTM method D4282.

The invention also provides a catalyst composition comprising: (a) one or more metals from Column 5 of the Periodic Table, one or more compounds of one or more metals from Column 5 of the Periodic Table, one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; (b) a support material with a theta-alumina content of at least 0.1 gram of theta-alumina per gram of support material, as determined by X-ray diffraction; and wherein the catalyst has a pore size distribution with a median pore diameter of at least i.

Has 230 A, as determined by ASTM method D4282.

The invention also provides a method for producing a catalyst, comprising: combining a carrier with one or more metals to form a mixture of carrier and metal, the carrier comprising: theta alumina. and one or more of the metals comprising one or more metals from Column 5 of the Periodic Table, one or more compounds of one or more metals from Column 5 of the Periodic Table or mixtures thereof; thermally treating the mixture of theta-alumina support and metal at a temperature of at least 4 ° C; and forming the catalyst, wherein the catalyst has a pore size distribution with a median pore diameter of at least 230 A, as determined by ASTM method D4282.

The invention also provides a method for producing a catalyst, comprising: combining a support with one or more metals to form a mixture of support and metal, the support comprising: 1027761-12 support: theta alumina and a or more of the metals comprising one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; thermally treating the mixture of theta-alumina support and metal at a temperature of at least 400 ° C; and forming the catalyst, wherein the catalyst has a pore size distribution with a median pore diameter of at least 230 A, such as.

10 determined by ASTM method D4282.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the. crude feed has a TAN of at least 0.3, wherein at least one of the catalysts has a 2 pore size distribution with a median pore diameter of at least 180 A, as determined by ASTM method D4282, and wherein the catalyst with the pore size distribution theta alumina and one or more metals from Column 6 of the Periodic System, one or .25 more compounds of one or more. metals from Column 6 of the Periodic System or mixtures thereof; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein 30 'is TAN as determined by ASTM method D664.

The invention also provides a method for producing a crude product, comprising: contacting it in the presence of a hydrogen source

1 0 2 7 7 δ S

- introducing a crude-oiled feed with one or more catalysts to form a total product which includes the crude-oiled product, the crude-oiled product being a liquid mixture at 25 ° C and 0.0101 MPa wherein the crude feed has a TAN of at least 0.3, the crude feed having an oxygen content of at least ten. at least 0.0001 grams of oxygen per gram of crude feed and wherein at least one of the 10 catalysts has a pore size distribution with a median pore diameter of at least 90 A, as determined by ASTM method D4282; and controlling the contact conditions to lower the TAN such that the crude product has a TAN of at most 90% of the TAN of the crude feed and to lower an organic oxygen-containing content such that the crude product has an oxygen content of at most 90% of the oxygen content of the crude 20 'oil feed, wherein TAN is as determined by ASTM method D664 and oxygen content is as determined by ASTM method E385.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a TAN of at least 0.1 and at least one of the catalysts per gram of catalyst at least 0.001 gram has from: one or more metals from Column 6 of the Periodic System, a 1027765 -14-.

or more compounds of one or more metals from Column 6 of the Periodic System ,. calculated as a weight of metal, or mixtures thereof; and controlling the contact conditions such that a specific liquid transfer rate (LHSV) per hour in a contact zone is more than 10 h '1 and that the crude product has a TAN of at most 90% of the TAN of the crude oily food, wherein TAN is as determined. with ASTM-met.hode D664.

The invention also provides a method for producing a crude-containing product, comprising: contacting a crude-containing feed in the presence of a hydrogen source with one or more catalysts to form a total product comprising inter alia the crude oil-containing product, wherein the crude-oil product is a liquid mixture at 25 ° C and 0.101 MPa, wherein the crude-oil feed has a TAN of at least 0.1, wherein the crude-oil feed has a sulfur content of at least 0.0001 grams of sulfur per gram of crude feed and wherein at least one of the catalysts one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table System or mixtures thereof; and controlling the contact conditions such that the crude feed during contact absorbs molecular hydrogen at a selected rate to prevent phase separation of the crude feed during contact such that the specific liquid transfer rate per hour in one or more more contact zones is more than 10 h "1, that the crude product has a TAN of at most 90% of the TAN of the crude feed and that the crude product has a sulfur content of 70-130% of the sulfur content of the crude feed, where TAN is as determined by ASTM method D664 and sulfur content is as determined by ASTM method D4294.

The invention also provides a method for producing a crude product, comprising: contacting a crude feed in the presence of a hydrogen gas source with one or more 10 'catalysts to form a total product which includes the crude oil-containing product, wherein the crude-oil product is a liquid mixture at 25 ° C and 0.101 MPa; and controlling the contact conditions such that the crude feed 15. absorbs hydrogen at a selected rate during contact to prevent phase separation of the crude feed during contact.

The invention also provides a method for producing a crude product, comprising: contacting a crude feed with hydrogen in the presence of one or more catalysts to form a total product comprising inter alia the crude product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture; and controlling the contact conditions such that the crude feed is contacted with hydrogen under a first hydrogen uptake condition and then under a second hydrogen uptake condition, wherein the first hydrogen uptake condition is different from the second hydrogen uptake condition and wherein the net hydrogen uptake in the first hydrogen uptake condition is controlled to prevent the P-value of a 1027765 -16 mixture of crude oil-containing food and total product from falling below 1.5 and with one or more properties of the crude product compared to the respective one or more more properties of the raw. 5 change the oil-containing diet by at most 90%.

The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts at a first temperature, followed by contact at a second temperature to form a total product comprising inter alia the crude product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture and wherein the crude .15 feed has a TAN of at least 0.3; and it such

controlling the contact conditions that the first contact temperature is at least 30 ° C lower than the second contact temperature and that the crude product has a TAN of at most 90% with respect to the TAN of the crude feed, where TAN

is as determined by ASTM method D664.

The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to form a total product comprising inter alia the crude product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a TAN of at least 0.3, the crude feed having a sulfur content of at least 0, 0001 grams of sulfur per gram of crude feed and wherein at least one of the catalysts contains one or more metals from Column 6 of the 1027765 - 17 -

Periodic Table, one or. more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed and that the crude product has a sulfur content of 70-130% of the sulfur content of the crude feed, where TAN is as determined by ASTM method D664 and 10 is sulfur content as determined by ASTM method D4294.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.1, the crude oil feed having a residue content of at least 0.1 grams of residue per gram of crude feed and wherein at least one of the catalysts comprises one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed that the crude product has a residual content of 70-130%. of the residual content of the crude feed, where TAN is as determined by ASTM method D664 and residue is as determined by ASTM method D5307.

1027765 - 18 -

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, wherein the crude feed has a TAN of at least 0.1, wherein the crude feed has a VGO content of at least 0 , 1 gram of VGO per gram of crude feed and wherein at least one of the catalysts one or more metals from Column 6 of the Periodic System, one or more compounds of one or more. more metals from Column 6 of the Periodic System or 15. mixtures thereof; and controlling the contact conditions in such a way that the crude product has a TAN of at most 90% of the TAN of the crude feed, that the crude product has a VGO content of 70-130% of the VGO-20 content of the crude feed and wherein VGO content is as determined by ASTM method D5307.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a TAN of at least 0.30, and wherein at least one of the catalysts can be obtained by combining a support with one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof to produce a catalyst precursor; and forming the catalyst by heating the catalyst precursor in the presence of one or more sulfur-containing compounds at a temperature below 500 ° C; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a viscosity of at least 10 cSt at 37.8 ° C (100 ° F), the crude feed has an API density of at least 10 and wherein at least one of the catalysts 20 has one or more metals from Column 6 of the Periodic

System, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a viscosity at 37.8 ° C of at most 90% of the viscosity at 37.8 ° C of the crude feed and wherein the crude product has an API density of 70-130% of the API density of the crude feed, wherein API density is as determined by ASTM method D6822 and viscosity is as determined by ASTM method D2669.

The invention also provides a method for producing a crude product, comprising: 1 02 7 7 65.

Contacting a crude-containing feed with one or more catalysts to form a total product comprising inter alia the crude-containing product, the crude-containing product being a liquid mixture at 25 ° C and 0.101 MPa wherein the crude feed has a TAN of at least 0.1 and wherein the one or more catalysts comprise: at least one catalyst comprising vanadium, one or more vanadium compounds or mixtures thereof; and an additional catalyst, wherein the additional catalyst comprises one or more metals from Column 6, one or more compounds of one or more metals from Column 6 or combinations thereof; and controlling the contact conditions such that the crude oil 15. product has a TAN of up to 90% of the TAN of the crude feed, where TAN is as determined by ASTM method D664.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture and wherein the 25. crude feed has a TAN of at least 0.1; generating hydrogen during the contact; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM method D664.

The invention also provides a method for producing a crude oil-containing product, comprising: contacting one or more catalysts with a crude-oil feed to form a total product which includes the crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the crude feed having a TAN of at least 0.1 and wherein at least one of the catalysts vanadium, one or more vanadium compounds or mixtures thereof; and controlling the contact conditions such that a contact temperature is at least 200 ° C and wherein the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as determined with ASTM method D664.

The invention also provides a method for producing a crude oil-containing product, comprising: contacting one or more catalysts. of a crude-containing feed to form a total product comprising inter alia the crude-containing product, wherein the crude-containing product is a liquid mixture at 25 ° C and 0.101 MPa, the crude-containing feed having a TAN of at least 0.1 and wherein at least one of the catalysts comprises vanadium, one or more vanadium compounds or mixtures thereof; providing a gas comprising a hydrogen source during contact, wherein the gas flow is provided in a direction opposite to the flow of the crude feed; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM method D664.

1027765 - 22 -

The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to form a total product which includes the crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the crude feed per gram of crude feed having a total Ni / V / Fe content of at least 10 ~ 0.00002 grams, wherein at least one of the catalysts comprises vanadium, one or more vanadium compounds or mixtures thereof, and wherein the vanadium catalyst has a pore size distribution with a median pore diameter of at least 180: and controlling the contact conditions such that the crude-containing product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed, wherein Ni / V / Fe content is as determined with AST M method D5708.

The invention also provides a method for producing a crude product, comprising: contacting one or more catalysts with a crude feed to form a total product which includes the crude product, wherein the crude product at ... 25 ° C and 0.101 MPa is a liquid mixture, wherein at least one of the catalysts comprises vanadium, one or more vanadium compounds or mixtures thereof, wherein the crude feed contains one or more alkali metal Salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof, and wherein the crude oil feed per gram of crude oil feed has a total content of alkali metal and alkaline earth metal in metal has salts of organic acids of at least 0.00001 grams; and controlling the contact conditions such that the crude product has a total content of alkali metal and alkaline earth metal in the metal salts of organic acids of at most 90% of the content of alkali metal and alkaline earth metal in metal salts of organic acids in the organic salts crude feed, wherein the content of alkali metal and alkaline earth metal in metal salts of organic acids is determined by ASTM method D1318.

The invention also provides a method for producing a crude product, comprising:. contacting a crude-containing feed with one or more catalysts to form a total product comprising inter alia the crude-containing product, wherein the crude-containing product at 25 ° C and 0.101 MPa is a liquid mixture, wherein the crude feed comprises one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof, wherein the crude feed contains a total content of per gram of crude feed alkali metal and alkaline earth metal in metal salts of 25 organic acids of at least 0.00001 grams and wherein at least one of the catalysts has a pore size distribution with a median pore diameter in a range of 90 A to 180 A, with at least 60% of the total number pores in the pore size distribution 30 has a pore diameter within 45 Å of the median pore diameter, with pore size distribution being s determined by ASTM method D4282; and controlling the contact conditions such that the crude product has a total alkali metal and alkaline earth metal content in metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in metal salts of 5 organic acids of the crude feed, wherein the content of alkali metal and alkaline earth metal in metal salts of organic acids is as determined by ASTM method D1318.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the crude feed having a total Ni / V / Fe content of at least 0.00002 grams per gram of crude feed and wherein at least one of the. catalysts has a pore size distribution with a median pore diameter in a range of 90 A to 180 A, wherein at least 60% of the total number of pores in the pore size distribution has a pore diameter within 45 A of the median pore diameter, wherein pore size distribution is as determined by ASTM method D4282; and controlling the contact conditions such that the crude product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed, wherein Ni / V / Fe content is as determined by ASTM method D5708.

The invention also provides a method for producing a crude-containing product, comprising: contacting a crude-containing feed with one or more catalysts to form a total product comprising, inter alia, the crude oil-containing product, wherein the crude-oil product is a liquid mixture at 25 ° C and 0.101 MPa, the crude-containing feed having a total content of 5 alkali metals and alkaline-earth metals in metal salts of organic acids of at least 0.00001 grams per grams of crude feed, wherein at least one of the catalysts has a pore size distribution with a median pore diameter of at least 180 A, as determined by ASTM method D4282, and wherein the catalyst with the pore size distribution has one or more metals from Column 6 of the Periodic Table, comprises one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at most 90% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the crude oil containing food wherein the alkali metal and alkaline earth metal content in metal salts of organic acids is as determined by ASTM method D133.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed being one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures 1027765 - 26 - thereof and wherein the crude feed has a total content of alkali metals and alkaline earth metals in metal salts of organic acids of at least 0.00001 grams per gram of crude feed, wherein at least one of the catalysts has a pore size distribution with has a median pore diameter of at least 230 A, as determined by ASTM method D4282, and wherein the catalyst with a pore size distribution comprises one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a total content of alkali metal and alkaline earth metal in metal salts of organic acids of at most 90% of the content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude feed , wherein the alkali metal and alkaline earth metal content. Metal salts of organic acids is as determined by ASTM method D1318.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a total Ni / V / Fe content of at least 0.00002 grams of Ni / V / Fe per gram of crude has an oil feed, wherein at least one of the catalysts has a pore size distribution with a median pore diameter of at least 230 A, as determined 1027765 - 27 - by ASTM method D4282, and wherein the catalyst with a pore size distribution has one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed, wherein Ni / V / Fe content is as determined by ASTM method D5708.

The invention also provides a method for producing a crude product, comprising:; contacting a crude-containing feed with one or more catalysts to form a total product which comprises, inter alia, the crude-containing oil product, wherein the crude-containing product is a liquid mixture at 25 ° C and 0.101 MPa, wherein the crude feed comprises one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof, wherein the crude feed contains a total content per gram of crude feed to alkali metal and. alkaline earth metal in metal salts of organic acids of at least 0.00001 grams, at least one of the catalysts having a pore size distribution. with a median pore diameter of at least 90 A, as determined by ASTM method D4282, and wherein the catalyst size distribution per gram of catalyst has a total molybdenum content of 0.0001 gram to 0.3 gram at: molybdenum, one or more molybdenum compounds, calculated as a weight of molybdenum, or mixtures thereof; and controlling the contact conditions such that the crude product has a total content of alkali metal and alkaline earth metal in metal salts of organic acids of up to 90% of the content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude feed, wherein the content of alkali metal and alkaline earth metal in metal salts of organic acids is as determined by ASTM method D1318.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° G and 0.101 MPa is a liquid mixture, the crude feed having a TAN of at least 0.3 and wherein the crude feed per gram of crude feed has a total Ni / V / Fe content of at least 0.00002 grams, wherein at least one of the catalysts has a pore size distribution with a median pore diameter of at least 90 A, as determined by ASTM method D4282, and wherein the catalyst has a total molybdenum content from 0.0001 grams to 0.3 grams has: molybdenum, one or more molybdenum compounds, calculated as a weight of molybdenum, or mixtures thereof; and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed and that the crude product has a total Ni / V / Fe content of at most Has 90% of the .Ni / V / Fe content of the crude feed, with Ni / V / Fe content being 1027765 - 29 - as determined by ASTM method D5708 and TAN as determined by ASTM method D64 4.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed being one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof and wherein the crude feed has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at least 0.00001 grams per gram of crude feed and wherein at least one of the catalysts comprises: (a) a or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and (b) one or more metals from Column 10 of the Periodic Table, one or more compounds of one or more metals from Column 10 of the Periodic Table or mixtures thereof, wherein a molar ratio of the total metal from Column 10 to the total metal from Column 6 is in a range of 1 to 10; and controlling the contact conditions such that the crude product has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at most 90% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the crude oil containing food, wherein the content of alkali metal and 1027765.

- alkaline earth metal in metal salts of organic acids is as determined by ASTM method D1318.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product which includes the crude oil-containing product, wherein the crude product at 25 ° C and 0.10.1 MPa is a liquid mixture, the crude feed having a total Ni / V / Fe content of at least 0.00002 grams of Ni / V / Fe per gram of crude has an oil feed and wherein at least one of the catalysts comprises: (a) one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof ; and (b) one or more metals from Column 10 of the Periodic Table, one or more compounds of one or more metals from Column 10 of the Periodic Table or mixtures thereof, wherein a molar ratio of the total metal from Column 10 to the total metal from Column 6 is in a range of 1 to 10; and controlling the contact conditions such that the crude product has a total Ni / V / Fe content of at most 90% of the 25 Ni / V / Fe content of the crude feed, wherein Ni / V / Fe content is as determined by ASTM method D5708.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product is a liquid mixture at 1027765 - 31 - 25 ° C and 0.101 MPa, the crude feed being one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof, wherein the crude feed has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at least 0.00001 grams per gram of crude feed and wherein the one or more catalysts comprise: (a) a first catalyst, wherein the first catalyst per gram of first catalyst has 0.0001 to 0.06 gram of: one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table, calculated as a weight of metal, or mixtures thereof; and (b) a second catalyst, wherein the second catalyst has at least 0.02 grams per gram of second catalyst of: one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic System, calculated as a weight of metal, or mixtures thereof; and controlling the contact conditions such that the crude product contains a total content of ... alkali metal and alkaline earth metal in metal salts of organic acids.

25 has a maximum of 90% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the crude feed, the content of alkali metal and alkaline earth metal in metal salts of organic acids being as determined by ASTM method D1318.

The invention also provides a method for producing a crude oil-containing product, comprising: contacting one or more catalysts. "| 1027765 - 32 -.

of a crude-containing feed to form a total product comprising inter alia the crude-containing product, wherein the crude-containing product is a liquid mixture at 25 ° C and 0.101 MPa, the crude-containing feed being one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof, wherein the crude feed per gram of crude feed contains a total content of alkali metal and alkaline earth metal in metal salts of organic has acids of at least 0.00001 grams and wherein at least one of the catalysts per gram of catalyst has at least 0.001 gram of: one or more metals from Column 6 of the Periodic System, one or more compounds of one or more metals from Column 6 of the Periodic System, calculated as a weight of metal, or mixtures thereof; and controlling the contact conditions such that the specific liquid transfer rate per hour in a contact zone is more than 10 h -1 and wherein the crude product has a total alkali metal and alkaline earth metal content in metal salts of organic acids of up to 90% of the content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude feed, the content of alkali metal and alkaline earth metal in metal salts of organic acids being as determined by ASTM method D1318.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product is a liquid mixture at 1027765 - 33 - 25 ° C and 0.101 MPa, the crude feed having a total Ni / V / Fe content of at least 0.0,0002 grams per crude feed wherein at least one of the catalysts 5 per gram of catalyst has at least 0.001 gram of: one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table, calculated as weight of metal, or mixtures thereof; and controlling the contact conditions such that the specific liquid transfer rate per hour in a contact zone is more than 10 h "1 and wherein the crude product contains a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed 15, wherein Ni / V / Fe content is as determined by ASTM method D5708.

The invention also provides a method for. producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude-oil product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having per gram of crude feed: an oxygen content of at least 0.0001 grams of oxygen and a sulfur content of at least 0.0001 grams of sulfur and wherein at least one of the catalysts one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has an oxygen content of at most 90% of the oxygen content of the crude feed and that the crude product has a sulfur content of 70-130% of has the sulfur content of the crude feed, wherein oxygen content is as determined by ASTM method E385 and sulfur content is as determined by ASTM method D4294.

The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to form a total product comprising inter alia the crude product, the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed per gram of crude feed having a total Ni / V / Fe content of at least 0.00002 grams and a sulfur content of has at least 0.0001 grams of sulfur and wherein at least one of the catalysts comprises one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed and that the crude feed product has a sulfur content of 70-130% of the sulfur content of the crude, oil-containing feed, where Ni / V / Fe content is as determined by ASTM method D5708 and sulfur content is as determined by ASTM method D4294.

The invention also provides a method for producing a crude-containing product, comprising: contacting a crude-containing feed with one or more catalysts to form a 1 0 2 7 7 6 5.

- 35 - total product which includes the crude oil. product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, wherein the crude feed contains one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof, wherein the crude feed has a total alkali metal and alkaline earth metal content in metal salts of 10 organic acids of at least 0.00001 grams and a residue content of at least 0.1 grams of residue per gram of crude oil feed and wherein at least one of the catalysts comprises one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the touch conditions such that the.

crude product containing a total content of alkali metal and alkaline earth metal in metal salts of j. ·.

organic acids has up to 90% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the crude feed and that the crude product has a residual content of 70-130% of the residual content of the.

has a crude feed, wherein the content of alkali metal and alkaline earth metal in metal salts of organic acids is as determined by ASTM method D1318 and residue content as determined by ASTM method D5307.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product is a liquid mixture at 1 0 2 7 7 6 5 - 36 - 25 ° C and 0.101 MPa, the crude feed per gram of crude feed having a residue content of at least 0.1 gram residue and has a total Ni / V / Fe content of at least 0.00002 grams and where at least one of the catalysts has one or more metals from Column 6 of the Periodic System, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed and that the crude oil-containing product has a residual content of 70-130% of the residual content of the crude feed, wherein Ni / V / Fe content is as determined by ASTM method D5708 and residue content is as determined by ASTM method D5307.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed being one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof, wherein the crude feed has a VGO content (vacuum gas oil) of at least 0.1 grams per gram of crude feed and a total alkali metal and alkaline earth metal content in metal salts of organic acids of 0.0001 grams and wherein at least one of the catalysts comprises one or more metals from Column 6 of the Periodic System, one or more compounds of one or more metal n from Column 6 of the Periodic System or mixtures thereof; and controlling the contact conditions such that the crude product has a total content of alkali metal and alkaline earth metal in metal salts of organic acids of up to 90% of the content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude oil feed and wherein the crude product has a VGO content of 70-130% of the VGO content of the crude food, wherein VGO content is as determined by ASTM method D5307 and the alkali metal and alkaline earth metal content in metal salts of organic acids is as determined by ASTM method D1318.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the crude feed per gram of crude feed having a total Ni / V / Fe content of at least 0.00002 25 grams and a VGO- content of at least 0.1 gram and wherein at least one of the catalysts comprises one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and controlling the contact conditions such that the crude product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed and that the crude feed 1027765 - 38 - product has a VGO content of 70-130% of the VGO content of the crude feed, where VGO content is as determined by ASTM method D5307 and Ni / V / Fe content is as determined with ASTM method D5708.

The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to form a. total product comprising inter alia the crude product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, wherein the crude feed contains one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof and wherein the crude-containing feed per gram of crude-containing feed has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at least 0.00001 grams and wherein at least one of the catalysts can be obtained by combining a support with one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof, to producing a catalyst precursor and forming the catalyst by heating a catalyst precursor in the presence of one or more sulfur-containing compounds at a temperature of less than 400 ° C; and controlling the contact conditions such that the crude product has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at most 90% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the crude oil 1027765 - 39 - Oil-based feed, the content of alkali metal and alkaline earth metal in metal salts of organic acids being determined by ASTM method D1318.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a gram of crude feed having a total Ni / V / Fe content of at least 0.00002 grams and wherein at least one of the catalysts can be obtained by combining a support 15 with one or more metals from Column 6 of the Periodic

System, one or more compounds of one or more metals from Column 6 of the Periodic System or mixtures thereof to produce a catalyst precursor and forming the catalyst by heating the catalyst precursor in the presence of one or more sulfur-containing compounds at a temperature lower than 400 ° C; and controlling the contact conditions such that the crude product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed, wherein Ni / V / Fe content is as determined by ASTM method D5708.

The invention also provides a crude-oil composition with per gram of crude-oil composition: at least 0.001 gram of hydrocarbons with a boiling range spread between 95 ° C and 260 ° C at 0.101 MPa; at least 0.001 gram of hydrocarbons with a boiling range spread between 260 ° C and 320 ° C at 0.101 MPa; at least 0.001. grams of hydrocarbons with a boiling range distribution between 1027765.

- 40 - 320 ° C and 650 ° C at 0.101 MPa and more than 0 grams but less than 0.01 grams of one or more catalysts per gram of crude product.

The invention also provides a crude oil composition with per gram composition: at least 0.01 grams of sulfur, as determined by ASTM method D4294; at least 0.2 grams of residue as determined by ASTM method D5307 and wherein the composition has a weight ratio of MCR to Cs asphaltenes content of at least 1.5, wherein MCR content is as determined by ASTM method D4530 and C5 asphaltenes content is as determined by ASTM method D2007.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product is condensable at 25 ° C and 0.101 MPa, the crude feed having an MCR content of at least 0.001 grams per gram of crude feed and wherein at least one of the catalysts is obtained by combining a support with one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof to produce a catalyst precursor and forming the catalyst by heating the catalyst precursor in the presence of one or more sulfur-containing compounds at a temperature below 500 ° C; and controlling the contact conditions such that the crude product has an MCR content of at most 90% of the MCR content of the crude feed 1027765 - 41 - wherein MCR content is as determined by ASTM method D4530.

The invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product comprising inter alia the crude-oil product, wherein the crude product is condensable at 25 ° C and 0.101 MPa, the crude oil feed having an MCR content of at least 0.001 grams per gram of crude oil feed and wherein at least one of the catalysts has a pore size distribution having a median pore diameter in a range of 70 Å to 180 Å, wherein at least 60% of the total number of pores in the pore size distribution has a pore diameter within 45 Å of the median pore diameter, wherein pore size distribution is as determined by ASTM method D4282; and controlling the contact conditions such that the crude product has an MCR of at most 90% of the MCR of the crude feed, wherein MCR is as determined by ASTM method D4530.

The invention also provides a crude oil composition with per gram composition: at most 0.004 grams of oxygen, as determined by ASTM method E385; not more than 0.003 grams of sulfur as determined by ASTM method D4294 and at least 0.3 grams of residue as determined by ASTM method D5307.

The invention also provides a crude oil composition with per gram composition: at most 0.004 grams of oxygen, as determined by ASTM method E385; not more than 0.003 grams of sulfur, as determined by ASTM method D4294; at most 0.04 grams of basic nitrogen, such as 1027765.

- 42 - determined by ASTM method D2896; at least 0.2 grams of residue as determined by ASTM method D5307; and wherein the composition has a TAN of at most 0.5, as determined by ASTM method D664.

The invention also provides a crude oil composition with per gram composition: at least 0.001 gram of sulfur, as determined with. ASTM method D4294; at least 0.2 grams of residue as determined by ASTM method D5307; and . wherein the composition has a weight ratio MCR content 10 to Cs asphaltenes content of at least 1.5 and the composition has a TAN of at most 0.5, wherein TAN! is as determined by ASTM method D66.4, MCR weight is as determined by ASTM method D4530 and Cs asphaltenes; weight is as determined by ASTM method D2007.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, crude feed that: (a) has not been treated, distilled and / or fractionally distilled in a refinery; (b) has 20 components with a carbon number greater than 4 and wherein the crude feed has at least 0.5 grams of such components per gram of crude feed; (c) comprises hydrocarbons of which a part: a boiling range spread below 100 ° C at 0.101 MPa, a boiling range spread between 100 ° C and 200 ° C at 0.101 MPa, a boiling range spread between 200 ° C and 300 ° C at 0.101 MPa, a boiling range distribution between 300 ° C and 400 ° C at 0.101 MPa and has a boiling range spread between 400 ° C and 650 ° C at 0.101 MPa; (d) per gram of crude oil-containing feed at least: 0.001 gram of hydrocarbons with a boiling range spread below 100 ° C at 0.101 MPa, 0.001 gram of hydrocarbons with a boiling range spread between 100 ° C and 200 ° C at 0.101 MPa, 1027765 - 43 - 0.001 grams of hydrocarbons with a boiling range spread between 200 ° C and 300 ° C at 0.101 MPa, 0.001 grams of hydrocarbons with a boiling range spread between 300 ° C and 400 ° C at 0.111 MPa and 0.001 grams of 5 hydrocarbons with a boiling range spread between 400 ° C and 650 ° Has C at 0.101 MPa; (e) has a TAN of at least 0.1, at least 0.3 or in a range of 0.3 to 20, 0.4 to 10 or 0.5 to 5; (f) has an initial boiling point of at least 200 ° C at 0.101 MPa; (g) 10 comprises nickel, vanadium and iron; (h) has a total of at least 0.00002 grams of Ni / V / Fe per gram of crude feed; (i) comprises sulfur; (j) has at least 0.0001 grams or 0.05 grams of sulfur per gram of crude feed; (k) has at least 0.001 gram of VGO per gram of crude-oiled food; (1) has at least 0.1 grams of residue per gram of crude feed; (m) comprises oxygen-containing hydrocarbons; (n) one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof; (o) comprises at least one zinc salt of an organic acid; and / or (p) at least one arsenic salt of an organic acid.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, crude-containing feed that can be obtained by removing naphtha and compounds that are more volatile than naphtha from a crude-containing raw material.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method of contacting a crude feed with one or more catalysts to form a 1027765.

- 44 - total product comprising inter alia the crude-oil product, the crude-oil feed and the crude-oil product both having a Cj-asphaltenes content and an MCR content, and wherein: (a) a sum of 5 the Cs asphaltenes content in a crude oil feed and the MCR content in a crude oil feed is S, a sum of the Cs asphaltenes content in a crude oil product and the MCR content in a crude oil product S ' and wherein the touch conditions are controlled such that S 'is at most 99% of S; and / or (b) the contact conditions are controlled such that a weight ratio of an MCR content of the crude product to a Cs asphaltenes content of the crude product in a range of 1.2 to 2.0 or 1 , Is 3 to 1.9.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a hydrogen source, wherein the hydrogen source: (a) gaseous; (b) hydrogen. gas; (c) methane; (d) light hydrocarbons; (e) inert gas; and / or (f) mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method of contacting a crude-containing feed with one or more catalysts to form a total product comprising inter alia the crude-containing product, wherein the crude-containing feed is contacted in a contact zone that is located or coupled to an offshore facility.

In some embodiments, the invention also provides, in combination with one or more of the methods or 1027765.

- Compositions according to the invention, a method which comprises: contacting a crude-containing feed in the presence of a gas and / or a hydrogen source with one or more catalysts and controlling the contact conditions such that: (a a ratio of a hydrogen gas source to the crude-containing feed is in a range of 5-800 normally cubic meters of hydrogen gas source per cubic meter of crude-containing feed contacted with one or more of the catalysts; (b) the selected rate of net hydrogen uptake is controlled by varying a partial pressure of the hydrogen source; (c) it. hydrogen uptake rate is such that the crude product has a TAN of less than 0.3, but that the hydrogen uptake is less than an amount of hydrogen uptake that causes significant phase separation between the crude feed and the total product during contact ; (d) the selected hydrogen uptake rate is in a range of 1-30 or 1-80 normally cubic meters from the hydrogen source per cubic meter of crude feed; (e) the specific liquid flow rate per hour of gas and / or the hydrogen source at least 11 h'1, at least 15 h -1 or at least. maximum 20 h "is 1; (f) a partial pressure of the gas and / or the hydrogen source is controlled during the contact; (g) a contact temperature is in a range of 50-500 ° C, a total specific liquid transfer rate per hour of the gas and / or the hydrogen source is in a range of 0.1-30 h -1 and the total pressure of the gas and / or the hydrogen source is in a range of 1.0-20 MPa; (h) a flow of the gas and / or the hydrogen source is in a direction opposite to a flow of the crude feed; (i) the crude feed 1027765.

- product has an H / C of 70-130% of an H / C of the crude, oil-containing feed; (j) hydrogen uptake by the crude feed is at most 80 and / or is in a range of 1-80 or 1-50 normally cubic meters of hydrogen per cubic meter of crude feed; (k) the crude product has a total Ni / V / Fe content of at most 90%, at most 50% or at most 10% of the Ni / V / Fe content of the crude feed; (1) the crude product has a sulfur content of 70-130% or 80-120% of it! has the sulfur content of the crude feed; (m) the crude product has a VGO content of 70-130% or 90-110% of the VGO content of the crude feed; (n) the crude product has a residual content of 70-130% or 90-110% of the residual content of the crude feed; (o) the crude product has an oxygen content of at most 90%, at most 70%, at most 50%, at most 40% or at most 10% of the oxygen content of the crude feed; (p) the crude product has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at most 90%, at most 50% or at most 10% of the content of alkali metal and alkaline earth metal in metal salts of organic acids in the. crude food; (q) a P value of the crude feed during contact is at least 1.5; (r) the crude product has a viscosity at 37.8 ° G of at most 90%, at most 50% or at most 10% of the viscosity at 37.8 ° C of the crude feed; (s) the crude product has an API density of 70-130% of an API density of the crude feed; and / or 1 0 2 7 7 6 5 - ____ - 47 - (t) the crude product has a TAN of at most 90%, at most 50%, at most 30%, at most 20% or at most 10% of the TAN of the crude feed and / or a TAN in the range of 0.001 to 5 to 0.5, 0.01 to 0.2 or 0.05 to 0.1.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method which comprises contacting one or more catalysts with a crude feed and controlling the contact conditions for reduction of a content of organic oxygen-containing compounds wherein: (a) a content of selected organic oxygen-containing compounds is reduced such that the crude-containing product has an oxygen content of at most 90% of the oxygen content of the crude-containing feed; (b) at least one compound of the organic oxygen-containing compounds comprises a metal salt of a carboxylic acid; (c) at least one compound of the organic oxygen-containing compounds comprises an alkali metal salt of a carboxylic acid; (d) at least one compound of the organic oxygen-containing compounds comprises an alkaline earth metal salt of a carboxylic acid; (e) at least one compound of the organic oxygen-containing compounds comprises a metal salt of a carboxylic acid, the metal comprising one or more metals from Column 12 of the Periodic Table; (f) the crude product has a non-carboxyl-containing organic compound content of up to 90% of the non-carboxyl-containing organic compound content in the crude feed; and / or (g) at least one of the oxygen-containing compounds in the crude feed is from naphthenic acid or non-carboxyl-containing organic oxygen compounds.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method comprising contacting a crude feed with one or more catalysts wherein: (a) the crude oil feed is contacted at least with one of the 10 catalysts at a first temperature, followed by contact with a second temperature and the contact conditions are controlled such that the first contact temperature is at least 30 ° C lower than the second contact temperature; (b) the crude feed 15 is contacted with hydrogen under a first hydrogen uptake condition and then under a second hydrogen uptake condition and the temperature of the first uptake condition is at least 30 ° C lower than the temperature of the second uptake condition; (C) the crude feed is contacted with at least one of the catalysts at a first temperature, followed by contacting with a second temperature and wherein the contact conditions are controlled such that the first contact temperature is at most 200 ° C is lower than the second contact temperature; (d) hydrogen gas is generated during the contact; (e) hydrogen gas is generated during the contact and the contact conditions are also controlled such that the crude feed contains at least a portion of the generated hydrogen; (f) the crude feed is contacted with a first and second catalyst and wherein the contact of the crude feed with the first catalyst forms a first crude product and wherein the first crude feed product has a TAN of up to 90% of the TAN of the crude feed; and wherein the contact of the first crude product with the second catalyst forms a crude product and wherein the crude product has a TAN of at most 90% of the TAN of the first crude product; (g) the contact 10 is in a stacked bed reactor; (h) the contact occurs in a bubbling bed reactor; (i) the crude feed after contact with the one or more catalysts is contacted with an additional catalyst; (j) one or. more of the catalysts is a vanadium catalyst and the crude feed after contact with the vanadium catalyst is contacted with an additional catalyst in the presence of a hydrogen source; (k) hydrogen is generated at a rate in a range of 1-20 normally cubic meters per cubic meter of crude oil-containing feed; (1) during the contact hydrogen is generated, the crude feed is contacted with an additional catalyst in the presence of a gas and at least a part of the generated hydrogen and the contact conditions are also controlled such that a flow of the gas is in a direction opposite to the flow of the crude feed and a flow of the generated hydrogen; (M) the crude feed is contacted with a vanadium catalyst at a first temperature and then with an additional catalyst at a second temperature and wherein the contact conditions are controlled such that the first temperature is at least 30 ° C is lower than the second temperature; (n) during the contact hydrogen gas is generated, the crude feed is contacted with an additional catalyst and the contact conditions are controlled such that the additional catalyst absorbs at least a part of the generated hydrogen; and / or (o) the crude feed is then contacted with an additional catalyst at a second temperature and the contact conditions are controlled such that the second temperature is at least 180 ° C.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method comprising contacting a crude feed with one or more catalysts wherein: (a) the catalyst a supported catalyst and the support comprises alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide or mixtures thereof; (b) the catalyst is a supported catalyst and the support is porous; (c) the method further comprises an additional catalyst that has been thermally treated at a temperature above 400 ° C prior to sulfurization; (D) a service life of at least one of the catalysts is at least 0.5 years and / or (e) at least one of. the catalysts are in a fixed bed or as a slurry in the crude feed.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method comprising contacting a crude feed with one or more catalysts, wherein at least one 0 2 7 7 6 5 of the catalysts is a supported catalyst or a bulk metal catalyst and wherein the supported catalyst or bulk metal catalyst: (a) one or more metals from Columns 5-10 of the Periodic Table, one or more compounds of one or more metals from Columns 5-10 of the Periodic Table or mixtures thereof; (b) per gram of catalyst has at least 0.0001 gram, 0.0001-0.6 gram or 0.001-0.3 gram of: one or more metals from Columns 5-10 of the Periodic System, one or more compounds of one or more metals from Columns 5-10 of the Periodic Table or mixtures thereof; (c) comprises one or more metals from Columns 6-10 of the Periodic Table, one or more compounds of one or more metals from Columns 6-10 of the Periodic Table or mixtures thereof; (d) one or more metals from Columns 7-10 of the Periodic Table, one or more compounds of one or more metals from Columns 7-10 of the Periodic Table or mixtures thereof; (e) per gram of catalyst has 0.0001-0.6 grams or 0.001-0.3 grams of: one or more metals from Columns .7-10 of the Periodic

System, one or more compounds of one or more metals from Columns 7-10 of the Periodic Table or mixtures thereof; (f) one or more metals from Columns 5-6 of the Periodic Table, one or more compounds of one or more metals from Columns 5-6 of the Periodic Table or mixtures thereof; (g) one or more metals from Column 5 of the Periodic Table, one or more compounds of one or more metals from Column 5 of the Periodic Table or mixtures thereof; (h) per gram of catalyst has at least 0.0001 gram, 0.0001-0.6 gram, 0.001-0.3 gram, 0.005-0.1 gram or 0.01-0.08 gram of: one or more metals from Column 5 of the Periodic Table, one or more compounds of one or more metals from Column 5 of the Periodic Table or mixtures thereof; (i) one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; (j) per gram of catalyst has 0.0001-0.6 grams, 0.001-0.3 grams, 0.005-0.1 grams, 0.01-0.08 grams of one or more metals from Column 6 of the Periodic System , one or more compounds of one or more metals, from Column 6 of the Periodic System or mixtures thereof; (k) one or more metals from Column 10 of the Periodic Table, one or more compounds of one or more metals from Column 10 of the Periodic Table or mixtures thereof; (1) per gram of catalyst has 0.0001-0.6 grams or 0.001-0.3 grams of: 15. one or. more metals from Column 10 of the Periodic

System, one or more compounds of one or more metals from Column 10 of the Periodic System or mixtures thereof; (m) comprises vanadium, one or more vanadium compounds or mixtures thereof; (n) comprises nickel, one or more nickel compounds or mixtures thereof; (o) comprises cobalt, one or more cobalt compounds or mixtures thereof; (p) molybdenum, one or more molybdenum compounds or mixtures thereof; (g) per gram of catalyst has 0.001-0.3 grams or 0.005-0.1 grams of: molybdenum, one or more molybdenum compounds or mixtures thereof; (r) comprises tungsten, one or more tungsten compounds or mixtures thereof; (s) per gram of catalyst has 0.001-0.3 grams of: tungsten, one or more tungsten compounds or mixtures thereof; (t) one or more metals from Column 6 of the Periodic Table and one or more metals from Column 10 of the Periodic Table, wherein the molar ratio of the metal from Column 10 to the metal from Column 6 is 1 to 5; (u) one or more elements from Column 1027765.

53 - 15 of the Periodic Table, comprises one or more compounds of one or more elements from Column 15 of the Periodic Table or mixtures thereof; (v) per gram of catalyst has 0.00001-0.06 grams of: one or more elements from Column 15 of the Periodic Table, one or more compounds of one or more elements from Column 15 of the Periodic Table or mixtures thereof; (w). phosphorus, one or more phosphorus compounds or mixtures thereof; (x) has at most 0.1 gram of alpha alumina per gram of catalyst and / or (y) has at least 0.5 gram of theta alumina per gram of catalyst.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method of forming a catalyst, comprising combining a support with one or more metals to form a mixture of support and metal, the support comprising theta-alumina, thermally treating the mixture of theta-alumina support and metal at a temperature of at least 400 ° C and further comprising: (a) combining the mixture of support and metal with water to form a paste and extrude the paste; (b) obtaining theta alumina by heat treating alumina at a temperature of at least 800 ° C; And / or (c) sulfurizing the catalyst.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method comprising contacting a crude feed with one or more catalysts, the pore size distribution of at least one of the catalysts: (a) a median pore diameter of at least 60 A, at least 90 A, at least 180 A, at least 200 A, at least 1027765 - 54 -

at least 230 A, at least 300 A, at most 230 A, at most 500 A, or in a range of 90-180 A, 100-140 A, 120-130 A, 230-250 A, 180-500 A, 230-500 A; or 60-300 A; (b) wherein at least 60% of the total number of pores have a pore diameter within 45 A, 35 A or 25 A

of the median pore diameter; (c) an area of at least 60 m2 / g, at least 90 m2 / g, at least 100 m2 / g, at least 120 m2 / g, at least 150 m2 / g, at least 200 m2 / g or at least 220 m2 / g and / or (d) a total volume of all pores of at least 0.3 cm3 / g, at least 0.4 cm3 / g, at least 0.5 cm3 / g or at least 0 Has 7 cm 3 / g.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method comprising contacting a crude feed with one or more supported catalysts, wherein the support: ( a) comprises alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide or mixtures thereof and / or zeolite; (b) comprises gamma alumina and / or delta alumina; (c) has at least 0.5 grams of gamma-alumina per gram of carrier; (d) per gram of carrier has at least 0.3 grams or at least 0.5 grams of theta alumina; (e) alpha alumina, gamma alumina, delta alumina, theta alumina or a mixture thereof; (f) at most 0.1 gram alpha. alumina per gram of carrier.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a vanadium catalyst which: (a) has a pore size distribution with a median pore diameter of at least 60 A; (b) comprises a support, wherein the support comprises theta alumina and the vanadium catalyst has a pore size distribution 1027765 - 55 - with a median pore diameter of at least 60 A; (c) comprises one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof and / or (d) has at least 0.001 gram per gram of catalyst of: one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a crude product that has: (a) a TAN of at most 0.1, from 0.001 to 0.5 , from 0.01 to 0.2; or from 0.05 to 0.1; (b) at most 0.000009 grams of the alkali metal and alkaline earth metal in metal salts of organic acids per gram of crude product; (c) at most 0.00002 grams of Ni / V / Fe per gram of crude product; and / or (d) more than 0 grams, but less than 0.01 grams, of at least one of the catalysts per gram of crude product.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof wherein: (a) at least one of the alkali metals is lithium, sodium or potassium and / or (b) at least one of the alkaline earth metals is magnesium or calcium.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method comprising 1027765.

Contacting a crude-containing feed with one or more catalysts to form a total product which includes a crude-containing product, which method further comprises: (a) combining the crude-containing product with a crude-containing raw material, whether or not different from the crude-containing feed, to form a mixture suitable for transport; (b) combining it. crude-containing product with a crude-containing raw material, which may or may not be different from the crude-containing feed, forming a mixture suitable for treatment facilities; (c) fractionating the crude product; and / or (d) fractionating the crude product into one or more distillate fractions and producing transport fuel from at least one of the distillate fractions.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a supported catalyst composition which: (a) per gram of carrier is at least 0.3 'gram or at least 0.5 gram has theta alumina; (b) comprises delta alumina in the carrier; (c) has a maximum of 0.1 gram of alpha alumina per gram of carrier; (d) has a pore size distribution with a median pore diameter of at least 230 A; (e) has a pore volume of the pores of the pore size distribution of at least 0.3 cm 3 / g or at least 0.7 cm 3 / g; (f) has an area of at least 60 m2 / g or at least 90 m2 / g; (g) one or more metals from Columns 7-10 of the Periodic Table, one or more compounds of one or more metals from Columns 7-10 of the Periodic Table or mixtures thereof; (h) one or more metals from Column 5 of 1027765 - 57 - comprises the Periodic Table, one or more compounds of one or more metals from Column 5 of the Periodic Table or mixtures thereof; (i) per gram of catalyst has 0.0001-0.6 grams or 0.001-0.3 grams of: one or more metals 5 from Column 5, one or more compounds of metals from

Column 5 or mixtures thereof; (j) one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; (k) per gram of catalyst has 0.0001-0.6 grams or 0.001-0.3 grams of: one or more metals from Column 6, one or more compounds of metals from Column 6 or mixtures thereof; (1) vanadium, one or more vanadium compounds or mixtures thereof; (m) molybdenum, one or more molybdenum compounds or mixtures thereof; (n) comprises tungsten, one or more tungsten compounds or mixtures thereof; (o) comprises cobalt, one or more cobalt compounds or mixtures thereof and / or (p) comprises nickel, one or more nickel compounds or mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a crude oil composition that: (a) a TAN of at most 1, at most 0.5, at most 0 Has 3 or a maximum of 0.1; (B) per gram of composition at least 0.001 gram of hydrocarbons with a boiling range spread between 95 ° C and 260 ° C at 0.101 MPa, at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between 260 ° C C and 320 ° C at 0.111 MPa and at least 0.001 gram of hydrocarbons with a boiling range spread. between 320 ° C and 650 ° C at 0.101 MPa; (c) has at least 0.0005 grams of basic nitrogen per gram of composition; (d) per gram of composition has a total of 1 0 2 7 7 6 5, - 58 - at least 0.001 gram or at least 0.01 gram of nitrogen and / or (e) in total at most 0.00005 gram of nickel and vanadium per gram of composition.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a crude composition comprising, inter alia, one or more catalysts, wherein at least one of the catalysts: (a) a pore size distribution with a median pore diameter of 10 has at least 180 A, at most 500 A and / or is in a range of 90-180 A, 100-140 A, 120-130 A; (b) has a median pore diameter of at least 90 A, wherein more than 60% of the total number of pores in the pore size distribution has a pore diameter within 45 A, 35 A 15 or 25 A of the median pore diameter; (c) has an area of at least 100 m2 / g, at least 120 m2 / g or at least 220 m2 / g; (d) a support, wherein the support comprises alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, zeolite and / or mixtures thereof; (e) one or more metals from

Comprises Columns 5-10 of the Periodic Table, one or more compounds of one or more metals from Columns 5-10 of the Periodic Table or mixtures thereof; (f) one or more metals from Column 5 of the Periodic Table, one or more compounds of one or more metals from Column 5 of the Periodic Table or mixtures thereof; (g) has at least 0.0001 grams per gram of catalyst of: one or more metals from Column 5, one or more compounds of metals from Column 5 or mixtures thereof; 30 (h) one or more metals from Column 6 of the Periodic

System, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; (i) per gram of catalyst at least 0.0001 gram 102776? - 59 - has: one or more metals from Column 6, one or more compounds of metals from Column 6 or mixtures thereof; (j) one or more metals from Column 10 of the Periodic Table, one or more compounds of one or more metals 5 from Column 10 of the Periodic Table or mixtures thereof and / or (k) one or more elements from Column 15 of the Periodic Table, one or more compounds of one or more elements from Column 15 of the Periodic Table or mixtures thereof.

In further embodiments, features of specific embodiments of the invention can be combined with features of other embodiments of the invention. For example, features of an embodiment of the invention can be combined with features of any of the other embodiments.

In further embodiments, crude-containing products can be obtained by any of the methods and systems described herein.

In further embodiments, additional features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of the present invention will be apparent to those skilled in the art from the following detailed description and with reference to the accompanying drawings, in which:

FIG. 1 is a schematic representation of an embodiment of a touch system.

FIG. 2A and 2B are schematic representations of embodiments of touch systems that include two touch zones.

1027765 - 60 -

FIG. 3A and 3B are schematic representations of embodiments of touch systems that include three touch zones.

FIG. Chem is a schematic representation of an embodiment of a separation zone in combination with a touch system.

FIG. 5 is a schematic representation of an embodiment of a mixing zone in combination with a touch system.

FIG. 6 is a schematic representation of an embodiment with a combination of a separation zone, a touch system and a mixing zone.

FIG. 7 is a table of representative properties of crude feed and crude product for an embodiment in which the crude feed is contacted with three catalysts.

FIG. 8 is a graphical representation of the weighted average bed temperature, plotted against the process run time, for an embodiment where the crude feed is contacted with one or more catalysts.

FIG. 9 is a table of representative properties of crude feed and crude product for an embodiment in which the crude feed is contacted with two catalysts.

FIG. 10 is another table of representative properties of crude feed and crude product for an embodiment in which the crude feed is contacted with two catalysts.

j 1027765 - 61 -

FIG. 11 is a table of crude feed and crude products for embodiments where crude feed is contacted with four different catalyst systems.

FIG. 12 is a graphical representation of the P value of crude oil products, plotted against the process run time, for embodiments involving crude oil. feeds are contacted with four different catalyst systems.

FIG. 13 is a graphical representation of the net hydrogen uptake by crude oil feeds, plotted against the process run time, for embodiments where crude oil feeds are contacted with four different catalyst systems.

FIG. 14 is a graphical representation of the residue content, expressed as a percentage by weight, of crude oil products, plotted against the process run time, for embodiments where crude oil feeds are contacted with four different catalyst systems.

FIG. 15 is a graphical representation of a change in the API density of crude products, plotted against the process run time, for embodiments where the crude feed is contacted with four different catalyst systems.

FIG. 16 is a graphical representation of the oxygen content, expressed as a percentage by weight, of crude oil products, plotted against the process run time, for embodiments where crude oil feeds are contacted with four different catalyst systems.

FIG. 17 is a table of representative properties of crude oil feed and crude oil products for embodiments where the crude oil feed is contacted with catalyst systems that include varying amounts of a molybdenum catalyst and a vanadium catalyst with a catalyst system that includes a vanadium catalyst and a molybdenum / vanadium catalyst and glass beads.

FIG. 18 is a table of crude-oil feed properties and crude-oil products for embodiments where crude-oil feed is contacted with one or more catalysts at varying specific liquid throughput rates per hour.

FIG. 19 is a table of properties of crude oil feeds and crude oil products 2Ö for embodiments in which crude oil feeds are contacted at various contact temperatures.

Although the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale. It is to be understood that the drawings and the detailed description are not thereby intended to limit the invention to the specifically stated form. Rather, the intention is to cover all modifications, equivalents, and alternatives that fall within the spirit and scope of the present invention, as defined by the appended claims.

DETAILED DESCRIPTION

Certain embodiments of the inventions 5 are further described herein. Expressions used herein are defined as follows.

"ASTM" refers to American Standard Testing and Materials.

"API density" refers to the API-10 density at 15.5 ° C (60 ° F). The API density is as determined by ASTM method D6822.

Hydrogen atom percentage and carbon atom percentage of the crude feed and crude product are as determined by ASTM method D5291.

Boiling range spread for the crude feed, the total product and / or the crude oil product are as determined by ASTM method D5307, unless otherwise stated.

"C5 asphaltenes" refers to asphaltenes that are insoluble in pentane. The Cs asphaltenes content is as determined by ASTM method D2007.

"Metal / (metals) from Column X" refers to one or more metals from Column X of the Periodic Table and / or one or more compounds of one or more metals from Column X of the Periodic Table, where X with a column number (for example, 1-12) of the Periodic System. For example, "metal / (metals) from Column 6" refers to one or more metals from Column 6 of the Periodic Table and / or one or more compounds of one or more metals from Column 6 of the Periodic Table

System.

"Element (s) from Column X" refers to one or more elements from Column X of the Periodic Table 1 0-27 7 65.

And / or one or more compounds of one or more elements from Column X of the Periodic Table, where X corresponds to a column number (for example, 13-18) of the Periodic Table. For example, "element (s) from 5 Column 15" refers to one or more elements from

Column 15 of the Periodic Table and / or one or more compounds of one or more elements from Column 15 of the Periodic Table.

Within the scope of this application, weight of a metal from the Periodic Table, weight of a connection of a metal from the Periodic Table, weight of an element from the Periodic Table or weight of a connection of an element from the Periodic Table as the weight of metal or the weight of element. For example, if 0.1 gram of MO3 is used per gram of catalyst, the calculated weight of the molybdenum metal in the catalyst is 0.067 gram per gram of catalyst.

"Content" refers to the weight of a component in a substrate (e.g., a crude-containing feed, a total product or a crude-containing product), expressed as a weight fraction or percentage by weight based on the total weight of the substrate. "Wtppm" refers to parts by weight of 25 per million.

"Mixture of crude feed and total product" refers to the mixture that comes into contact with the catalyst during processing.

"Distillate" refers to hydrocarbons with a boiling range spread between 204 ° C (400 ° F) and 343 ° C (650 ° F) at 0.101 MPa. Distillate content is as determined by ASTM method D5307.

1027765 - 65 - "Heteroatoms" refers to oxygen, nitrogen, and / or sulfur in the molecular structure of a hydrocarbon. The content of heteroatoms is as determined by ASTM methods E385 for oxygen, D5762 for total nitrogen and D4294 for sulfur. "Total basic nitrogen" refers to nitrogen compounds that have a pKa of less than 40. Basic nitrogen ("bn") is as determined by ASTM method D2896.

"Hydrogen source" refers to hydrogen and / or a compound and / or compounds which are present in the presence of a crude feed. catalyst and thereby provide hydrogen to compound (s) in the crude feed. A hydrogen source may include, but is not limited to, hydrocarbons (e.g., C 1-4 hydrocarbons such as methane, ethane, propane, butane), water, or mixtures thereof. A mass balance can be made to evaluate the net amount of hydrogen provided to the compound (s) in the crude feed.

"Flat plate breaking strength" refers to the compressive force required to break a catalyst. Flat plate breaking strength is as determined by ASTM method D4179.

"LHSV" refers to a volumetric fluid supply rate per total catalyst volume and is expressed in hours (h-1). The total volume of catalyst is calculated by adding all the catalyst volumes in the contact zones, as described herein.

"Liquid mixture" refers to a composition that includes one or more compounds that are liquid at standard temperature and pressure (25 ° C, 0.101 MPa, 1027765 - 66 - hereinafter referred to as "STP") or a composition that inter alia comprises a combination of one or more compounds that are liquid in STP and one or more compounds that are solid in STP.

5 "Periodic Table" refers to the

Periodic Table as specified by the International Union of Pure and Applied Chemistry (IUPAC), November 2003.

"Metals in metal salts of organic acids" refers to alkali metals, alkaline earth metals, zinc, arsenic, chromium or combinations thereof. A metal content in metal salts of organic acids is as determined by ASTM method D1318.

"Micro carbon residue" ("MCR") refers to an amount of carbon residue that remains after evaporation and pyrolysis of a substrate. MCR content is as determined by ASTM method D4530.

"Naphtha" refers to hydrocarbon components with a boiling range spread between 38 ° C (100 ° F) and 200 ° C (392 ° F) at 0.101 MPa. Naphtha content is as determined by ASTM method D5307.

"Ni / V / Fe" refers to nickel, vanadium, iron or combinations thereof.

"Ni / V / Fe content" refers to the content of nickel, vanadium, iron or combinations thereof. It

Ni / V / Fe content is as determined by ASTM method D5708.

"Nm3 / m3" refers to normal cubic meters of gas. per cubic meter of crude oil-containing food.

"Non-carboxyl-containing organic oxygen compounds" refers to organic oxygen compounds that do not have a carboxyl group (-CC> 2 group). Non-carboxyl-containing organic oxygen compounds include, but are not limited to, ethers, cyclic ethers, alcohols, aromatic alcohols, ketones, aldehydes, or combinations thereof that do not have a carboxyl group.

"Non-condensable gas" refers to 5 components and / or mixtures of components included with STP

are gases.

"P (eptization) value", or "P value", refers to a numerical value that represents the flocculation of asphaltenes in the crude feed. The determination of the P value is described by J. J. Heithaus in "Measurement and Significance of Asphaltene Peptization", Journal of Institute of Petroleum, Vol. 48, Number 458, February 1962, pp. 45-53.

"Pore diameter", "median pore diameter" and "pore volume" refer to pore diameter, median pore diameter and pore volume as determined by ASTM method D4284 (mercury porosimetry at a contact angle equal to 140 °). To determine these values, a 20 micromeritics® A9220 instrument (Micromeritics Ine.,

Norcross, Georgia, U.S.A.) are used.

"Residue" refers to components that have a boiling range spread above 538 ° C (1000 ° F), as determined by ASTM method D5307.

"SCFB" refers to Standard cubic feet of gas per barrel of crude feed.

"Surface" of a catalyst is as determined by ASTM method D3663.

"TAN" refers to total acid number, expressed as milligrams. ("Mg") KOH per gram ("g") sample. The TAN is as determined by ASTM method D664.

"VGO" refers to hydrocarbons with a boiling range distribution between 343 ° C (650 ° F) and 538 ° C

1027765 - 68 - (1000 ° F) at -0.101 MPa. The VGO content is as determined by ASTM method D5307.

"Viscosity" refers to kinematic viscosity at 37.8 ° C (100 ° F). The viscosity is as determined by ASTM method D445.

Within the context of this application, it is to be understood that if the value obtained for a particular property of the tested substrate falls outside the limits of the testing method, the testing method can be modified and / or re-calibrated to still test that property.

Crude oil-containing raw materials can be produced and / or distilled from hydrocarbon-containing formations and then stabilized. Crude oil-containing raw materials may include crude oil. Crude oil-containing raw materials are generally solid, semi-solid and / or liquid. Stabilization may include, but is not limited to, removal of non-condensable gases, water, salts or combinations thereof from the crude feedstock to form a stabilized crude feedstock. Such stabilization can often take place at or near the production and / or degradation location.

Stabilized crude-containing raw materials are usually not distilled in a treatment facility and / or fractionally distilled to produce multiple components with a specific boiling range spread (for example, naphtha, distillates, VGO and / or lubricating oils). Distillation includes, but is not limited to, atmospheric distillation methods and / or vacuum distillation methods. Non-distilled and / or unfractionated, stabilized crude oil raw materials may include components that have a carbon number higher than 4 in amounts of at least 0.5 grams of components per gram of crude-containing raw material. Examples of stabilized crude oil raw materials include crude oil raw materials as a whole, topped crude oil raw materials, desalinated crude oil raw materials, desalinated topped crude oil raw materials or combinations thereof. "Capped" refers to a crude-containing raw material that has been treated such that at least some of the components that have a boiling point below 35 ° C at 0.101 MPa (95 ° F at 1 atm) are removed raw materials usually have a content of at most 0.1 gram, at most 0.05 gram or at most 0.02 gram of such components per gram of capped raw material.

Some stabilized crude-containing raw materials have properties that make it possible to transport the stabilized crude-containing raw materials with conventional transport facilities with pipelines (for example, pipelines, trucks or ships). Other crude-containing raw materials have one or more unsuitable properties that disadvantage them. "create (give adverse properties).

Such "disadvantaged crudes" may be unacceptable for a means of transport and / or a treatment facility, which gives the disadvantaged crude a low economic value. The economic value can be such that a reservoir that includes, among other things, the disadvantaged crude 30 is considered too expensive to produce, transport and / or treat.

Characteristics of disadvantaged crudes can include, but are not limited to: a) a TAN of at least 1027765 - 70 - at least 0.1, at least 0.3; b) a viscosity of at least 10 cSt; c) an API density of at most 19; d) a total Ni / V / Fe content of at least 0.00002 grams or at least 0 ^ 0001 grams of Ni / V / Fe per gram of crude-containing raw material; e) a total heteroatom content of at least 0.005 grams of heteroatoms per gram of crude feedstock; f) a residue level of at least 0.01 grams of residue per gram of crude-containing raw material; g) a C5 asphaltenes content of at least 0.04 grams of Cs asphaltenes per gram of crude feedstock; h) an MCR content of at least 0.002 grams of MCR per gram of crude feedstock; i) a metal content in metal salts of organic acids of at least 0.00001 grams of metals per gram of crude-containing raw material, or j) combinations thereof. In some embodiments, disadvantaged crude per gram of disadvantaged crude may include at least 0.2 grams of residue, at least 0.3 grams of residue, at least 0.5 grams of residue, or at least 0.9 grams of residue. In some embodiments, the disadvantaged crude can have a TAN in a range of 0.1 or 0.3 to 20, 0.3 or 0.5 to 10 or 0.4 or 0.5 to 5. In certain forms, disadvantaged crudes per gram of disadvantaged crude can have a sulfur content of at least 0.005 grams, at least 0.01 grams or at least 0.02 grams.

In some forms, disadvantaged crudes have features including, but not limited to: a) a TAN of at least 0.5; b) an oxygen content of at least 0.005 grams of oxygen per gram of crude feed; c) a C5 asphaltenes content of at least 0.04 grams of C5 asphaltenes per gram of crude feed; d) a higher viscosity than desired (e.g.> 10 cSt for a crude feed with an API density of 1027765 - 71 - of at least 10); e) a metal content in metal salts of organic acids of at least 0.00001 grams of metals per gram of crude feedstock or f) combinations thereof.

Disadvantaged crudes may include, but are not limited to, per gram of disadvantaged crude: at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between 95 ° C and 200 ° C at 0.101 MPa; at least 0.01 gram, at least 0.005 gram or at least 0.001 gram of hydrocarbons with a boiling range spread between 200 ° C and 300 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between 300 ° C and 400 ° C at 0.101 MPa and at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between 400 ° C and 650 ° C at 0.101 MPa.

Disadvantaged crudes may include, but are not limited to, per gram of disadvantaged crude: at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread of at most 100 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between 100 ° C and 200 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between 200 ° C and 300 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between 300 ° C and 400 ° C at 0.101 MPa and at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between 400 ° C and 650 ° C at 0.101 MPa.

1027765 - 72 -

Some disadvantaged crudes can, in addition to higher boiling components, comprise per gram of disadvantaged crude among others at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread of at most 100 ° C at 0.101 MPa.

The disadvantaged crude usually has a content of such hydrocarbons of at most 0.2 gram or at most 0.1 gram per disadvantaged crude.

Some disadvantaged crudes can include per gram of disadvantaged crude, inter alia, at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread of at least 200 ° C at 0.101 MPa.

Some disadvantaged crudes can include per gram of disadvantaged crude inter alia at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread of at least 650 ° C.

Examples of disadvantaged crudes that can be treated using the processes described herein include, but are not limited to, ... crude oil resources from the following regions of the world: the US Gulf Coast and Southern California , the Canadian tar sands, the Brazilian

Santos and Campos basins, the Egyptian Gulf of Suez, Chad, the British sector of the North Sea, the Angolan Offshore, the Chinese Bohai Bay, the Venezuelan Zulia region, Malaysia and Sumatra.

Treatment of disadvantaged crudes can improve the properties of the disadvantaged crudes such that the crude-containing raw materials are acceptable for transport and / or handling.

1027765 - 73 -

A crude oil raw material to be treated and / or disadvantaged crude is referred to herein as a "crude oil feed." The crude feed may be topped as described herein. The crude-oil product obtained from treatment of the crude feed, as described herein, is generally suitable for transport and / or handling. Properties of the crude oil product produced as described herein are closer to the corresponding properties of West Texas

Intermediate oil than that of the crude feed or closer to the corresponding properties of Brent crude than that of the crude feed, which increases the economic value of the crude feed. Such a crude-containing product can be refined with less or no pre-treatment, which increases the refining efficiency. Pre-treatment may include desulfurization, demetallization, and / or atmospheric distillation to remove impurities.

Treatment of a crude feed according to the inventions described herein may include contacting the crude feed with the catalyst (s) in a touch zone and / or combinations of two or more touch zones. In a contact zone, at least one property of a crude feed can be changed by contacting the crude feed with one or more catalysts relative to the same property of the crude feed. In some embodiments, the contact occurs in the presence of a hydrogen source. In some embodiments, the hydrogen source is one or more hydrocarbons that react under certain contact conditions and thereby provide relatively small amounts of hydrogen to one or more compounds in the crude feed.

FIG. 1 is a schematic representation of touch system 100, which includes touch zone 102A.

Crude oil-containing feed enters touch zone 102 via line 104. A contact zone can be a reactor, a part of a reactor, multiple parts of a reactor or combinations thereof. Examples of a contact zone include a stacked bed reactor, a fixed bed reactor, a bubbling bed reactor, a continuously stirred tank reactor ("CSTR"), a fluidized bed reactor, a spray reactor and a liquid / liquid contactor. In certain embodiments, the touch system is located at an offshore facility or is coupled thereto. The contact of the crude feed with the catalyst (s) in contact system 100 can be a continuous process or a batch process.

The contact zone may include one or more catalysts (for example, two catalysts).

In some embodiments, contacting the crude feed with a first catalyst of the two catalysts can lower the TAN of the crude feed. Subsequent contact of the crude feed with reduced TAN with the second catalyst lowers heteroatoms content and increases API density. In other embodiments, TAN, viscosity, Ni / V / Fe content, hetero atom content, residue content, API density or combinations of these properties of the crude product change by at least 10% relative to the same properties of the crude oil feed 1027765 - 75 - after contacting the crude oil feed with one or more catalysts.

In certain embodiments, a catalyst volume in the touch zone is in a range of 10-60 vol%, 20-50 vol% or 30-40 vol% of a total volume of crude feed in the touch zone. In some embodiments, a slurry of catalyst and crude-containing feed in the contact zone may include 0.001-10 grams, 0.005-5 grams or 0.01-3 grams of catalyst per 100 grams of crude feed.

The contact conditions in the contact zone may include, but are not limited to: temperature, pressure, flow of the hydrogen source, flow of the crude feed or combinations thereof. In some embodiments, the contact conditions are controlled to produce a crude product with specific properties. The temperature in the touch zone can range from 50-500 ° C, 60-440 ° C, 70-430 ° C or 80-420 ° C. The pressure in a touch zone can range from 0.1-20 MPa, 1-12 MPa, 4-10 MPa or 6-8 MPa. The LHSV of the crude feed will generally range from 0.1-30 h '1, 0.5-25 h'1, 1-20 h'1, 1.5-15 h_1 or 2-10 h "1. In some embodiments, the LHSV is at least 5 h '1, at least 11 h "1, at least 15 h-1 or at least 20 h" 1.

In embodiments where the hydrogen source is supplied as a gas (e.g., hydrogen gas), a ratio of the hydrogen gas source to the crude feed that is contacted with the catalyst (s) usually ranges from 0.1-100,000 Nm 3 / m3 0.5-10,000 Nm3 / m3, 1-8,000 Nm3 / m3, 2-5,000 NirrVm3, 5-3,000 Nm3 / m3 or 10-800 Nm3 / m3. In some embodiments, the hydrogen source is combined with carrier gas (s) and recirculated through the touch zone. Carrier gas can be, for example, nitrogen, helium and / or argon. The carrier gas can promote the flow of the crude feed and / or the flow of the hydrogen source in the contact zones (s). The carrier gas can also enhance the mixing in the contact zone (s). In some embodiments, a hydrogen source (e.g., hydrogen, methane, or ethane) can be used as carrier gas and recirculated through the touch zone 10.

The hydrogen source may enter contact zone 102 in direct current with the crude feed into line 104 or separately through line 106. In contact zone 102, contacting the crude feed with a catalyst yields a total product which includes a crude product and, in some embodiments, gas. In some embodiments, a carrier gas is combined with the crude feed and / or the hydrogen source in line 106. The total product can leave touch zone 102 and enter separation zone 108 via line 110.

In separation zone 108, the crude product and the gas can be separated from the total product using well-known separation techniques, for example gas-liquid separation. The crude-containing product can leave separation zone 108 via line 112 and then be transported to transport means, pipelines, storage vessels, refineries, other processing zones or a combination thereof. The gas may include gas formed during processing (e.g. hydrogen sulfide, carbon dioxide and / or carbon monoxide), excess hydrogen 1027765.

- 77 - gas source and / or carrier gas. The excess gas can be recirculated to touch system 100, purified and transported to other processing zones, storage vessels or combinations thereof.

In some embodiments, the contact of the crude feed with the catalyst (s) takes place to form a total product in two or more contact zones. The total product can be split off, forming the crude product and gas (s).

FIG. 2-3 are schematic representations of embodiments of touch system 100, which includes two or three touch zones. In FIG. 2A and 2B include touch system 100 including touch zones 102 and 114. FIG. 3A and 3B include, inter alia, touch zones 102, 114, 116. In FIG. 2A and 3A, touch zones 102, 114, 116 are depicted as separate touch zones in a reactor. The crude-containing feed enters into contact zone 102 via line 104.

In some embodiments, the carrier gas is combined with the hydrogen source in line 106 and introduced into the contact zones as a mixture. In certain embodiments, as disclosed in FIG. 1, 3A and 3B, the hydrogen source and / or the carrier gas may enter one or more contact zones, while the crude feeder enters separately via line 106 and / or in a direction opposite to the flow of the crude feeder via, for example, line 106 '. Addition of the hydrogen source and / or the carrier gas 30 in opposite flow from that of the crude-containing feed can promote the mixing and / or contact of the crude-containing feed with the catalyst.

1 0 2 7 7 6 5 - 78 -

The contact of the crude feed with catalyst (s) in contact zone 102 forms a feed stream. The feed current flows from touch zone 102 to touch zone 114. In FIG. 3A and 3B, the feed current flows from touch zone 114 to touch zone 116.

Touch zones 102, 114, 116 may include one or more catalysts. As shown in FIG. 2B, leaves the feed stream touch zone 102 via line 118 and enters touch zone 114.

As shown in FIG. 3B, leaves the feed stream touch zone 114 via line 118 and enters touch zone 116.

The feed stream in contact zone 114 and / or contact zone 116 may be contacted with additional catalyst (s) to form the total product. The total product leaves touch zone 114 and / or touch zone 116 and enters separation zone 108 via line 110. The crude product 20 and / or gas is / are separated from the total product. The crude oil-containing product leaves separation zone 108 via line 112.

FIG. 4 is a schematic representation of an embodiment of a separation zone upstream of touch system 100. The (whether or not capped) disadvantaged crude enters separation zone 120 via line 122. In separation zone 120, at least a portion of the disadvantaged crude is cleaved using techniques known in the art (e.g. spraying, membrane separation, pressure reduction) to produce the crude feed. For example, water can be split off at least partially from the disadvantaged crude. In another example, 1 02 7 7 65.

- Components that have a boiling range spread below 95 ° C or below 100 ° C are at least partially split off from the disadvantaged crude to produce the crude feed. In some embodiments, at least a portion of naphtha and compounds that are more volatile than naphtha are split off from the disadvantaged crude. In some embodiments, at least a portion of the spliced components leaves separation zone 120 via conduit 124.

In some embodiments, the crude-oil feed obtained from separation zone 120 includes a mixture of components with a boiling range spread of at least 100 ° C or, in some embodiments, a boiling range spread of at least 120 ° C. Typically, the cleaved crude feed contains a mixture of components with a boiling range spread between 100-1000 ° C, 120-900 ° C or 200-800 ° C. At least a portion of the crude feed leaves separation zone 120 and enters touch system 100 via line 126 (see, e.g., touch zones in Figs. 1-3) to be further processed to form a crude product. In some embodiments, separation zone 120 may be located upstream or downstream of a desalination unit. After processing, the crude product leaves touch system 100 via line 112.

In some embodiments, the crude oil product is mixed with a crude oil raw material that may or may not be the same as the crude oil feed. For example, the crude-oil product can be combined with a crude-oil raw material with a different viscosity, yielding a 1027765 - 80 - mixed product with a viscosity that is between the viscosity of the crude-oil product and the viscosity of the crude-oil raw material. In another example, the crude product 5 can be mixed with crude raw material that has a TAN that is different, yielding a product that has a TAN between the TAN of the crude product and that of the crude product. oil-containing raw material. The mixed product can be suitable for transport and / or handling.

As shown in FIG. 5, in certain embodiments, crude feed enters touch system 100 through line 104 and leaves at least a portion of the crude product touch system 100 through line 128 and is introduced into mixing zone 130. In mixing zone 130, at least a portion of the crude oil-containing product is combined with one or more process streams (e.g., a hydrocarbon stream such as naphtha produced by separation of one or more crude-containing feeds), a crude-containing raw material, a crude-oiled feed or mixtures thereof, to form a mixed product. The process streams, crude feed, crude feed or mixtures thereof are directly introduced into mixing zone 130 or upstream of such a mixing zone via line 132. A mixing system may be located in or near mixing zone 130. The mixed product can meet product specifications set by refineries and / or transporters. Product specifications include, but are not limited to, an area or limit of the API density, TAN, viscosity, or combinations thereof. The mixed product 1027765 - 81 - leaves mixing zone 130 via line 134 to be transported or processed.

In FIG. 6, the disadvantaged crude enters separation zone 120 through conduit 122 and the disadvantaged crude is split off as previously described, forming the crude feed. The crude feed then enters through touch 126 touch system 100. At least some components of the disadvantaged crude leave separation zone 120 via line 124. At least a portion of the crude product leaves contact system 100 and enters mixing zone 130 through line 128. Other process streams and / or crude oil-containing raw materials enter mixing zone 130 directly or via line 132 and 15. are combined with the crude-containing product to form a mixed product. The mixed product leaves mixing zone 130 via line 134.

In some embodiments, the crude oil-containing product and / or the mixed product is / are transported to a refinery and / or a treatment facility. The crude oil-containing product and / or the mixed product can / can be processed to produce commercial products such as transport fuel, fuel fuel, lubricants or chemical products.

Processing may include distillation and / or fractional distillation of the crude product and / or mixed product, with formation of one or more distillate fractions. In some embodiments, the crude product, the blended product, and / or the one or more distillate fractions may be treated with hydrogenation.

In some forms, the crude product has a TAN of at most 90%, at most 1027765 - 82 - at most 50%, at most 30% or at most 10% of the TAN of the crude feed. In some forms, the crude product has a TAN in a range of 1-80%, 20-70%, 30-60% or 40-50% of the TAN of the crude feed. In certain forms, the crude product has a TAN of at most 1, at most 0.5, at most 0.3, at most 0.2, at most 0.1 or at most 0.05. The TAN of the crude product will often be at least 0.0001 and more often at least 0.001. In some forms, the TAN of the crude product may be in the range of 0.001 'to 0.5, 0.01 to 0.2 or 0.05 to 0.1.

In some forms the crude oil-containing product has a total Ni / V / Fe content of at most 90%, at most 50%, at most 10%, at most 5% or at most 3% of the Ni / V / Fe content of the crude feed. The crude product has a total 20 Ni / V / Fe content in some forms in a range of 1-80%, 10-70%, 20-60% or 30-50% of the Ni / V / Fe content of the crude feed. In certain forms, the crude oil-containing product has a total Ni / V / Fe content per gram of crude product in a range of 1 x 25 10 "7 grams to 5 x 10 ~ 5 grams, 3 x 10 ~ 7 grams to 2 x 10 "5 grams or 1 x 10" 6 grams to 1 x 10 "5 grams. In certain forms, the crude-containing raw material has a maximum of 2 x 10 5 grams of Ni / V / Fe. In some forms, the total Ni / V / Fe content of the crude product is 70-130%, 80-120% or 90-110% of the Ni / V / Fe content of the crude feed.

In some forms, the crude product has a total metal content in $ 102776 - metal salts of organic acids of up to 90%, up to 50%, up to 10% or up to 5% of the total metal content in metal salts of organic acids in the crude feed. In certain forms, the crude product has a total metal content in metal salts of organic acids in a range of 1-80%, 10-70%, 20-60% or 30-50% of the total metal content in metal salts of organic acids in the crude feed. Organic acids that generally form metal salts include, but are not limited to, carboxylic acids, thiols, imides, sulfonic acids, and sulfonates. Examples of carboxylic acids include, but are not limited to, naphthenic acids, phenanthrene acids and benzoic acid. The metal part of the metal salts may include alkali metals (e.g. lithium, sodium and potassium), alkaline earth metals (e.g. magnesium, calcium and barium), metals from Column 12 (e.g. zinc and cadmium), metals from Column 15 (e.g. arsenic), 20 metals from Column 6 (e.g. chromium) or mixtures thereof.

In certain forms, the crude, oil-containing product has a total metal content in metal salts of organic acids per gram of crude-oil product in a range of 0.0000001 grams to 0.00005 grams, 0.0000003 grams to 0.00002 grams or 0.000001 grams to 0.00001 grams of metals in metal salts of organic acids per gram of crude product. In some forms, a total metal content of metal salts of organic acids of the crude product is 70-130%, 80-120% or 90-110% of the total metal content of metal salts of organic acids in the crude product. oil-based food.

1027765 - 84 -

In certain forms, the API density of the crude product produced by contact with the contact conditions of the crude feed with catalyst is 70-130%, 80-120%, 90-110% or 100-130% of the API density of the crude feed. In certain forms, the API density of the crude product is 14-40, 15-30 or 16-25.

In certain forms, the crude product has a viscosity of at most 90%, at most 80% or at most 70% of the viscosity of the crude feed. In some forms the crude product has a viscosity in a range of 10-60%, 20-50% or 30-40% of the viscosity of the crude feed. In some forms, the viscosity of the crude product is at most 90% of the viscosity of the crude feed, while the API density of the crude product is 70-130%, 80-120% or 90- Is 110% of the API density of the crude feed.

In some forms, the crude product has a total heteroatom content of at most 90%, at most 50%, at most 10% or at most 5% of the total content of heteroatoms in the crude feed. In certain forms, the crude product has a total heteroatom content of at least 1%, at least 30%, at least 80% or at least 99% of the total heteroatoms content in the crude feed.

In some forms, the sulfur content of the crude product may be at most 90%, at most 50%, at most 10%, or at most 5% of the sulfur content of the crude product. In certain forms, the crude product has a sulfur content of at least 1%, at least 30%, at least 80%, or at least 99% of the sulfur content of the crude feed. In some forms, the sulfur content of the crude product is 70-130%, 80-120% or 90-110% of the sulfur content of the crude feed.

In some forms, the total nitrogen content of the crude product may be at most 90%, at most 80%, at most 10% or at most 5% of a total nitrogen content of the crude feed. In certain forms, the crude product has a total nitrogen content of at least 1%, at least 30%, at least 80% or at least 99% of the total nitrogen content of the crude feed.

In some forms, the basic nitrogen content of the crude product may be at most 95%, at most 90%, at most 50%, at most 10% or at most 5% of the basic nitrogen content of the crude feed. In certain forms, the crude product has a basic nitrogen content of at least 1%, at least 30%, at least 80% or at least 99% of the basic nitrogen content of the crude feed.

In some forms, it may be oxygen The crude oil content may not exceed 90%, up to 50%, up to 30%, up to 10% or up to 5% of the oxygen content of the crude feed. In certain forms, the crude product has an oxygen content of at least 1%, at least 30%, at least 80%, or at least 99% of the oxygen content of the crude product. nutrition. In some forms, the oxygen content of the crude product is in a range of 1-80%, 10-70%, 20-60% or 30-50% of the oxygen content of the crude feed. In some forms, the total carboxylic acid compound content of the crude product may be at most 90%, at most 50%, at most 10%, at most 5% of the content of the carboxylic acid compounds in the crude feed. In certain forms, the crude product has a total content of carboxylic acid compounds of at least 1%, at least 30%, at least 80% or at least 99% of the total content of carboxylic acid compounds in the crude feed.

In some embodiments, selected organic oxygen compounds can be lowered in the crude feed. In some embodiments, carboxylic acids and / or metal salts of carboxylic acids can be chemically reduced prior to non-carboxyl-containing organic oxygen compounds.

Carboxylic acids and non-carboxyl-containing organic oxygen compounds in a crude-containing product can be differentiated by analysis of the crude-containing product using well-known spectroscopy methods (e.g., infrared analysis, mass spectrometry and / or gas chromatography).

The crude product in certain forms has an oxygen content of at most 90%, at most 80%, at most 70% or at most 50% of the oxygen content of the crude feed and the TAN of the crude product is at most 1027765 - 87 - at most 90%, at most 70%, at most 50% or at most 40% of the TAN of the crude feed. In certain forms, the crude product has an oxygen content of at least 1%, at least 30%, at least 80% or at least 99% of the oxygen content of the crude feed and the crude product has a TAN of at least 1%, at least 30%, at least 80% or at least 99% of the TAN of the crude feed.

In addition, the crude product may have a carboxylic acid and / or metal salts of carboxylic acids of up to 90%, up to 70%, up to 50% or up to 40% of the crude feed and a non-oil content -carboxyl-containing organic oxygen compounds within 70-130%, 80-120% or 90-110% of the non-carboxyl-containing organic oxygen compounds in the crude feed.

In some forms, the crude product in its molecular structures comprises, among others, 0.05-0.15 grams or 0.09-0.13 grams of hydrogen per gram of crude product. The crude product may include in its molecular structure 0.8-0.9 grams or 0.82-0.88 grams of carbon per gram of crude product. A ratio of atomic hydrogen to atomic carbon (H / C) of the crude product can be within 7.0-130%, 80-120% or .90-110% of the H / C atomic ratio of the crude nutrition. An H / C atomic ratio of the crude oil-containing product that is within 10-30% of the H / C atomic ratio of the crude-oil-containing feed indicates that uptake and / or consumption of hydrogen in the process is relatively low and / or that hydrogen is produced in situ.

1027765 - 88 -

The crude-containing product includes components with various boiling points. In some forms, the crude product comprises per gram of crude product, inter alia: at least 0.001 gram or 0.001 to 0.5 gram of hydrocarbons with a boiling range spread of at most 100 ° C at 0.101 MPa; at least 0.001 gram or 0.001-0.5 gram of hydrocarbons with a boiling range spread between 100 ° C and 200 ° C at 0.101 MPa; at least 0.001 gram or 0.001-0.5 gram of hydrocarbons with a boiling range spread between 200 ° C and 300 ° C at 0.101 MPa; at least 0.001 grams or 0.001-0.5 grams of hydrocarbons with a boiling range spread between 300 ° C and 400 ° C at 0.101 MPa and at least 0.001 grams or 0.001 to 0.5 grams of hydrocarbons with a boiling range spread between 400 ° C and 538 ° C at 0.101 MPa.

In some forms the crude product comprises per gram of crude product, inter alia, at least 0.001 gram of hydrocarbons with a boiling range spread of at most 100 ° C at 0.101 MPa and / or at least 0.001 gram of hydrocarbons with a boiling range spread between 100 ° C and 200 ° C at 0.101 MPa.

In some forms, the crude product may have at least 0.001 grams or at least 0.01 grams of naphtha per gram of crude product.

In other forms, the crude product may have a naphtha content of at most 0.6 grams or at most 0.8 grams of naphtha per gram of crude product.

In some forms, the crude product has a distillate content of 70-130%, 80-120% or 90-110% of the distillate content of the crude feed. The distillate content per gram of the crude product of the crude product may be in the range of 0.00001-0.5 grams, 0.001-0.3 grams, or 0.002-0.2 grams.

In certain forms, the crude oil product has a VGO content of 70-130%, 80-120% or 90-110% of the VGO content of the crude feed. In some forms, the crude product has a VGO content per gram of crude product in a range of 0.00001-0.8 grams, 0.001-0.5 grams, 0.002-0.4 grams or 0.001-0 , 3 grams.

In some forms, the crude product has a residual content of 70-130%, 80-120% or 90-110% of the residual content of the crude feed. The crude product may contain 15 per gram of crude product a residue in a range of 0.00001-0.8 grams, 0.0001-0.5 grams, 0.0005-0.4 grams, 0.001-0, 3 grams, 0.005-0.2 grams or 0.01-0.1 grams.

In certain forms, the crude product has an MCR content of 70-130%, 80-120% or 90-110% of the MCR content of the crude feed, while the crude product has a C5 has asphaltenes content of at most 90%, at most 80% or at most 50% of the Cs asphaltenes content of the crude feed. In certain embodiments, the Cs asphaltenes content of the crude feed is at least 10%, at least 60% or at least 70% of the Cs asphaltenes content of the crude feed, while the MCR content of the crude oil -30 containing product is within 10-30% of the MCR content of the crude feed. In some embodiments, lowering the C5 asphaltenes content of the crude feed while maintaining a relatively stable MCR content can increase the stability of the crude feed / overall product mixture.

In some embodiments, the C5 asphaltenes content and the MCR content can be combined to produce a mathematical relationship between the highly viscous components in the crude oil product and the highly viscous components in the crude oil feed. For example, a sum of a C5 asphaltenes content in a crude feed and a MCR content in a crude feedstock can be represented as S. A sum of a Cs asphaltenes content in a crude product and an MCR content in a crude product can be represented as S '.

The sums can be compared with each other (S 'with S) to assess the net reduction in highly viscous components in the crude feed. S 'of the crude product may be in a range of 1-99%, 10-90% or 20-80% of S. In some embodiments, a ratio of the MCR content of the crude oil is 20. containing product up to the C5 asphaltenes content in a range of 1.0-3.0, 1.2-2.0 or 1.3-1.9.

In certain forms, the crude product has an MCR content that is at most 90%, at most 80%, at most 50% or at most 10% of the MCR content of the crude feed. In some forms, the crude product has an MCR content in a range of 1-80%, 10-70%, 20-60% or 30-50% of the MCR content of the crude feed. In some embodiments, the crude product has 0.0001-0.1 grams, 0.005-0.08 grams, or 0.01-0.05 grams of MCR per gram of crude product.

1027765 - 91 -

In some forms, the crude product includes, among other things, more than 0 grams but less than 0.01 grams, 0.000001-0.001 grams or 0.00001-00001 grams of total catalyst per gram of crude product . The catalyst can help stabilize the crude oil-containing product during transport and / or handling. The catalyst can prevent corrosion, prevent friction, and / or increase water separation capabilities of the crude product. Methods described herein can be configured to add one or more catalysts described herein to the crude product during treatment.

The crude-oil product produced from touch system 100 has other properties than the properties of the crude-oil feed.

Such properties may include, but are not limited to: (a) reduced TAN; b) reduced viscosity; c) reduced total Ni / V / Fe content; d) reduced sulfur, oxygen, nitrogen or .20 combinations thereof; e) reduced residue level; f) reduced Cs asphaltenes content; g) reduced MCR content; h) increased API density; (i) reduced metal content in metal salts of organic acids or. j) combinations thereof. In some embodiments, one or more properties of the crude-oil product can be selectively altered with respect to the crude-oil feed while other properties are not changed so strongly or substantially do not change. For example, it may be desirable to only selectively reduce TAN in a crude feed without also significantly changing the amount of other components (e.g., sulfur, residue, Ni / V / Fe or VGO). In this way, hydrogen uptake during the 1027765 - 92 contact can be "concentrated" on TAN reduction and not on reduction of other components. Thus, the TAN of the crude feed can be reduced while less hydrogen is used, since less of such hydrogen is also used to reduce other components in the crude feed. For example, if a disadvantaged crude has a high TAN but a sulfur content acceptable to meet handling and / or transportation specifications, then such a crude feed can be treated more efficiently to lower TAN without also lowering sulfur .

Catalysts used in one or more embodiments of the inventions may include one or more bulk metals and / or one or more metals on a support. The metals can be in elemental form or in the form of a metal compound. The catalysts described herein can be introduced as a precursor into the contact zone and subsequently become active as a catalyst in the contact zone (for example when sulfur and / or a sulfur-containing crude feed is contacted with the precursor). The catalyst or combination of catalysts used as described herein can be commercially available or non-commercially available catalysts.

Examples of commercially available catalysts contemplated for use as described herein include HDS3, HDS22, HDN60, C234, C311, C344, C411, C424, C344, C444, C447, C454, C448, C524 , C534, DN110, DN120, DN130, DN140, DN190, DN200, DN 8 0 0, DN 2118, DN2318, DN3100, DN3110, DN3300, DN3310, RC400, RC410, RN412, RN400, RN420, RN440, RN450, RN650, RN52 , RN5610, RN5650, RM430, RM5030, Z603, Z623, Z673, Z703, Z713, Z723, Z753 and Z763 available from CRI International, Ine. (Houston, Texas, U.S.A.).

In some embodiments, catalysts used to change properties of the crude feed include one or more metals from Column 5-10 on a support. Metal (s) from Column 5-10 include, but are not limited to, vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum or mixtures thereof. The catalyst can have a total metal / (metal) content from Column 5-10 of at least 0.0001 gram, at least 0.001 gram, at least 0.01 gram or in a range of 0.0001-0 per gram of catalyst, 6 grams, 0.005-15 0.3 grams, 0.001-0.1 grams or 0.01-0.08 grams. In some embodiments, in addition to the metal (s) from Column 5-10, the catalyst includes element (s) from Column 15. An example of elements from Column 15 includes phosphorus. The catalyst can produce a total element content per 20 grams of catalyst

Column 15 in the range of 0.000001-0.1 gram, 0.00001-0.06 gram, 0.00005-0.03 gram or 0.0001-0.001 gram.

In certain embodiments, a catalyst comprises, inter alia, metal / (metals) from Column 6. The catalyst 25 may have a total metal / (metal) content from Column 6 of at least 0.0001 grams, at least 0.01 grams per column of catalyst. , at least 0.02 grams and / or in a range of 0.0001-0.6 grams, 0.001-0.3 grams, 0.005-0.1 grams or 0.01-0.08 grams. In some embodiments, the catalyst includes, among others, 0.0001-0.06 grams of metal / (metals) from Column 6 per gram of catalyst. In some embodiments, the catalyst comprises in addition to 1027765.

- 94 - the metal (s) from Column 6, including element (s) from Column 15.

In some embodiments, the catalyst includes a combination of metal / (metals) from Column 5 with one or more metals from Column 5 and / or

Columns 7-10, wherein a molar ratio of metal from Column 6 to metal from Column 5 can be in a range of 0.1-20, 1-10 or 2-5. A molar ratio of metal from Column 6 to metal from Columns 7-10 can be in a range of 0.1-20, 1-10 or 2-5. In some embodiments, the catalyst comprises, in addition to the combination of metal (s) from Column 6 with one or more metals from Column 5 and / or 7-10, inter alia element (s) from Column 15. In other embodiments the catalyst comprises, inter alia, metal / (metals) from

Column 6 and metal / (metals) from Column 10. A molar ratio of the total metal from Column 10 to the. total metal from Column 6 in the catalyst can be in a range of 1-10 or 2-5. In certain embodiments, the catalyst comprises, inter alia, metal / (metals) from Column 5 and metal / (metals) from Column 10. A molar ratio of the total metal from Column 10 to the total metal from Column 5 in the catalyst can lie in a range of 1-10 or 2-5.

In some embodiments, metal (s) from Column 5-10 is / are incorporated in or deposited on a support to form the catalyst. In certain embodiments, metal (s) from Column 5-10 in combination with element (s) from Column 15 is / are incorporated in or deposited on the support to form the catalyst. In embodiments where metal (s) and / or 1027765 - 95 element (s) are supported, the weight of the catalyst comprises the entire support, all metal (s) and all element (s). The support may be porous and may include heat-resistant oxides, carbon-based porous materials, zeolites or combinations thereof.

Heat-resistant oxides may include, but are not limited to, alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof. Carriers can be obtained from a commercial manufacturer, such as Criterion Catalysts and Technologies LP

(Houston, Texas, U.S.A.). Porous materials based on carbon include, but are not limited to, activated carbon and / or porous graphite. Examples of zeolites include Y zeolites, beta zeolites, mordenite zeolites, ZSM-5 zeolites, and ferrierite zeolites. Zeolites can be obtained from a commercial manufacturer, such as Zeolyst (Valley Forge, Pennsylvania, U.S.A.).

In some embodiments, the support is prepared such that the support has an average pore diameter of at least 150 A, at least 170 A, or at least 180 A. In certain embodiments, a carrier is prepared by forming an aqueous paste from the carrier material. In some embodiments, an acid is added to the paste to facilitate extrusion of the paste. The water and the dilute acid are added in such amounts and by such methods as are necessary to give the extrudable paste a desired consistency. Examples of acids include, but are not limited to, nitric acid, acetic acid, sulfuric acid and hydrochloric acid.

To form extrudates, the paste can be utilized by well-known catalyst extrusion methods 1027765.

96 and catalyst cutting methods are extruded and cut. The extrudates can be thermally treated at a temperature in a range of 5-260 ° C or 85-235 ° C for a certain period of time (e.g. 5 for 0.5-8 hours) and / or until the moisture content of the extrudate is a desired has reached this level. The thermally treated extrudate can further be thermally treated at a temperature in a range of 800-1200 ° C or 900-1100 ° C to form the support with an average pore diameter of at least 150 A.

In certain embodiments, the carrier includes gamma alumina, theta alumina, delta alumina, alpha alumina, or combinations thereof. The amount of gamma alumina, delta alumina, alpha alumina or combinations thereof can be per gram of catalyst support in a range of 0.0001-0.99 grams, 0.001-0.5 grams, 0.01-0.1 grams or not more than 0.1 gram, as determined by X-ray diffraction. In some embodiments, the carrier itself or in combination with other forms of alumina has a theta alumina content in a range of 0.1-0.99 grams, 0.5-0.9 grams, or 0.6-0 per 20 grams of carrier. , 8 grams, as determined by X-ray diffraction. In some embodiments, the carrier may have at least 0.1 grams, at least 0.3 grams, at least 0.5 grams, or at least 0.8 grams of theta alumina, as determined by X-ray diffraction.

Supported catalysts can be prepared by well-known catalyst preparation techniques.

Examples of catalyst preparations are described in U.S. Patent Nos. 6,218,333 to Gabrielov et al., 6,290: 841 to Gabrielov et al. And 5,744,025 to Boon et al. And U.S. Pat. 97 - patent application with Publication no. 20030111391, to Bhan.

In some embodiments, the support can be impregnated with metal to form a catalyst. In certain embodiments, prior to impregnation with a metal, the support is thermally treated at temperatures in the range of 400-1200 ° C, 450-1000 ° C, or 600-900 ° C. In some embodiments, impregnation aids can be used during the preparation of the catalyst.

Examples of impregnation aids include a citric acid component, ethylenediaminetetraacetic acid (EDTA), ammonia or mixtures thereof.

In certain embodiments, a catalyst may be formed by adding or incorporating the metal (s) from Column 5-10 to thermally treated, molded mixture carriers ("overlaying"). Overlaying a metal on the thermally treated, shaped support with a substantially or relatively uniform metal concentration often confers the catalyst. favorable catalytic properties. Thermal treatment of a shaped support after each metal overlay tends to improve the catalytic activity of the catalyst. Methods to prepare a catalyst using overlay methods are described in

U.S. Patent Application Publication No.

20030111391, to Bhan.

The metal (s) from Column 5-10 and the support can be mixed with suitable mixing equipment to form a metal / metal mix from

Column 5-10 and carrier. The metal / (metal) mixture from Column 5-10 and support can be mixed using suitable mixing equipment. Examples of suitable mixing equipment include tumbler equipment, stationary trays or troughs, Muller mixers (e.g. batch type or continuous type), impact mixers and any other well-known mixer or device that suitably mixes the mixture. of metal / (metals) from Column 5-10 and support provided. In certain embodiments, the materials are blended until the metal (s) from Column 5-10 is / are substantially homogeneously dispersed in the support.

In some embodiments, after combining the support with the metal, the catalyst is thermally treated at temperatures of 150-750 ° C, 200-740 ° C, or 400-730 ° C.

In some embodiments, the catalyst can be thermally treated in the presence of hot air and / or oxygen-rich air at a temperature in a range between 400 ° C and 1000 ° C to remove volatiles so that at least a portion of the metals from Column 20 5-10 is converted to the corresponding metal oxide.

In other embodiments, however, the catalyst may be thermally treated in the presence of air for a period in a range of 1-3 hours at temperatures in a range of 35-500 ° C (e.g. below 300 ° C, below 400 ° C or below 500 ° C) to remove the majority of the volatile components without converting the metals from Column 5-10 to the metal oxide. Catalysts prepared by such a method are generally referred to as "non-annealed" catalysts. When catalysts are prepared in this way in combination with a sulfidation method, the active metals can be substantially dispersed in the support. Preparations of such catalysts are described in U.S. Patent Nos.

6,218,333 to Gabrielov et al. And 6,290,841 to Gabrielov et al.

In certain embodiments, a theta-alumina support may be combined with metals from Column 5-10 to form a mixture of theta-alumina support and metals from Column 5-10. The mixture of theta-alumina support and metals from Column 5-10 can be thermally treated at a temperature of at least 400 ° C, forming the catalyst with a pore size distribution with a median pore diameter of at least 230 A. Typically, such a heat treatment carried out at temperatures of at most 1200 ° C.

In some embodiments, the support (a commercial support or a support prepared as described herein) may be combined with a supported catalyst and / or a bulk metal catalyst. In some embodiments, the supported catalyst may include metal / (metals) from Column 15. For example, the supported catalyst and / or the bulk metal catalyst can be crushed into a powder with an average particle size of 1-50 microns, 2-45 microns or 5-25 microns. The powder can be combined with carrier to form an embedded metal catalyst. In some embodiments, the powder may be combined with the support and then extruded using standard techniques to form a catalyst with a pore size distribution with a median pore diameter in a range of 80-200 A or 90-180 A or 120-130 A.

102778 * - 100 -

By combining the catalyst with the support, in some embodiments, at least a portion of the metal may remain below the surface of the embedded metal catalyst (e.g., embedded in the support), leading to less metal at the surface than otherwise in the non-embedded metal catalyst would be the case. In some embodiments, having less metal on the catalyst surface extends the service life and / or catalytic activity of the catalyst by allowing at least a portion of the metal to go to the catalyst surface during use. The metals can be eroded by the catalyst surface during the contact of the; catalyst with a crude oil feed to the 15 catalyst surface. !

In some embodiments, intercalation and / or mixing of the components of the catalysts changes the structure arrangement of the metal from Column 6 into the crystal structure of the oxide from Column 6 into a virtually random arrangement of metal from Column 6 into the crystal structure of the embedded catalyst. The arrangement of the metal from Column 6 can be determined using powder X-ray diffraction methods.

The arrangement of elemental metal in the catalyst relative to the arrangement of elemental metal in the metal oxide can be determined by comparing the peak order of the metal from Column 6 in an X-ray diffraction spectrum of the oxide from Column 6 'with the peak order of the metal from Column 6 in an X-ray diffraction spectrum of the catalyst. From widening and / or lack of patterns associated with column 6 metal in an X-ray diffraction spectrum, it is possible to estimate that the metal (s) from Column 6 02 n 6 5 - 101 - virtually random in the crystal structure is / are ordered.

For example, molybdenum trioxide and the alumina support with a median pore diameter of at least 180 A can be combined with each other to form a mixture of alumina and molybdenum trioxide. The molybdenum trioxide has a fixed pattern (e.g. solid Doo1, Doo2 ~ and / or Doo3 peaks). The mixture of alumina and trioxide. Column 6 can be thermally treated at a temperature of at least 538 ° C (1000 ° F) to produce a catalyst that exhibits no pattern for molybdenum dioxide in an X-ray diffraction spectrum (e.g. absence of the Thaw peak).

In some embodiments, catalysts can be characterized by pore structure. Various pore structure parameters include, but are not limited to, pore diameter, pore volume, surfaces or combinations thereof. The catalyst may have a distribution of total amount of pore sizes relative to 20. pore diameters. The median pore diameter of the pore size distribution can be in a range of 30-1000 A, 50-500 A or 60-300 A. In some embodiments, catalysts that include at least 0.5 grams of gamma alumina per gram of catalyst have a pore size distribution with a median pore diameter in a range of 60-200 Å; 90-180 A, 100-140 A or 120-130 A. In other embodiments, catalysts which include at least 0.1 grams of theta alumina per gram of catalyst have a pore size distribution with a median pore diameter in a range of 180-500 A, 200-300 A or 230-250 A. In some embodiments, the median pore diameter of the pore size distribution is at least 120 A, at least 150 A, at least 180 A, at 1027765.

- 102 - at least 200 A, at least 220 A, at least 230 A or at least 300 A. Such median pore diameters are usually at most 1000 A.

The catalyst can have a pore size distribution with a median pore diameter of at least 60 A or at least 90 A. In some embodiments, the catalyst has a pore size distribution with a median pore diameter in a range of 90-180 Å 100-140 Å or 120-130 Å, with at least 60% of a total number of pores in the pore size distribution having a pore diameter within 45 Å, 35 A or 25 A of the median pore diameter. In certain embodiments, the catalyst has a pore size distribution with a median pore diameter in a range of 70-180 Å, with at least 60% of a | 15 total number of pores in the pore size distribution and a pore diameter within 45 A, 35 A or 25 A of the median; has a pore diameter.

In embodiments where the median pore diameter of the pore size distribution is at least 180 A, at least 20 200 A or at least 230 A, more than 60% of a total number of pores in the pore size distribution have a pore diameter within 50 A, 70 A or 90 A of the median pore diameter. In some embodiments, the catalyst has a pore size distribution with a median pore diameter in a range of 180-500 A, 200-400 A, or 230-300 A, with at least 60% of a total number of pores in the pore size distribution having a pore diameter within 50 A, 70 A or 90 A of the median pore diameter.

In some embodiments, the pore volume of pores can be at least 0.03 cm 3 / g, at least 0.7 cm 3 / g or at least 0.9 cm 3 / g. In certain embodiments, the pore volume of pores can range from 0.3-0.99 cm 3 / g, 0.4-0.8 cm 3 / g or 0.5-0.7 cm 3 / g.

The catalyst having a pore size distribution with a median pore diameter in a range of 90-180 Å can in some embodiments have an area of at least 100 m2 / g, at least 120 m2 / g, at least 170 m2 / g, at least 220 or at least 270 m2 / g. Such an area can be in a range of 100-300 m2 / g, 120-270 m2 / g, 130-250 m2 / g or 170-220 m2 / g.

In certain embodiments, the catalyst having a pore size distribution with a median pore diameter in a range of 180-300 Å can have an area of at least 60 m2 / g, at least 90 m2 / g, at least 100 m2 / g, at least 120 m2 / g or at least 270 m2 / g. Such an area can be in a range of 60-300 m2 / g, 90-280 m2 / g, 100-270 m2 / g or 120-250 m2 / g.

In certain embodiments, the catalyst exists in shaped shapes, for example granules, cylinders and / or extrudates. The catalyst usually has a flat plate breaking strength in a range of 50-500 N / cm, 60-400 N / cm, 100-350 N / cm, 200-300 N / cm or 220-280 N / cm.

. . In some embodiments, the catalyst and / or the catalyst precursor (prior to use) is sulfidated using techniques known in the art (e.g., the ACTICAT ™ process, CRI International, Ine.) To form metal sulfides. In some embodiments, the catalyst can be dried and then sulfided. Alternatively, the catalyst can be sulfided in situ by contacting the catalyst with a crude feed containing, inter alia, sulfur-containing compounds. In situ sulfurization, use can be made of gaseous hydrogen sulfide in the presence of hydrogen or of liquid phase sulfurizing agents such as organic sulfur compounds (including alkyl sulfides, polysulfides, thiols, and sulfoxides). Ex-situ sulfurization processes are described in U.S. Patent Nos.

5,468,372 to Seamans et al. And 5,688,736 to Seamans et al.

In certain embodiments, a first type of catalyst ("first catalyst") includes, among others, metal / 10 (metals) from Column 5-10 in combination with a support and has a pore size distribution with a median pore diameter in a range of 150-250 Å The first catalyst can have an area of at least 100 m2 / g. The pore volume of the first catalyst can be at least 0.5 cm 3 / g. The first catalyst can have a gamma alumina content of at least 0.5 grams of gamma alumina and usually at most 0.999 grams of gamma alumina per gram of first catalyst. In some embodiments, the first catalyst has a total metal / (metals) content per gram of catalyst

Column 6 in a range of 0.0001 to 0.1 grams. The first catalyst can remove a portion of the Ni / V / Fe from a crude feed, remove a portion of the components that contribute to the TAN of a crude feed, at least a portion of the

Remove Cs-asphaltenes from a crude-containing feed, at least part of the metals in metal salts of organic acids in the crude-containing. remove food or combinations thereof. Other properties (for example sulfur content, VGO content, API density, residue content or combinations thereof) can show relatively small changes when the crude feed with the first catalyst in

1 0 11 7 SI

- 105 - has been brought into contact. By being able to selectively change the properties of a crude-containing feed while other properties are only changed in relatively small quantities, the crude-containing raw material can be treated more efficiently. In some embodiments, one or more first catalysts can be used in any order.

In certain embodiments, the second type of catalyst ("second catalyst") includes, among others, metal / 10 (metals) from Column 5-10 in combination with a support and has a pore size distribution with a median pore diameter in a range of 90 A to 180 A. At least 60% of the total number of pores in the pore size distribution of the second catalyst has a pore diameter within 45 Å of the median pore diameter.

Touching the crude feed with the second catalyst under suitable contact conditions can yield a crude product that has selected properties (e.g., TAN) that are substantially altered from the same properties of the crude feed, while other properties can only be changed to a small extent. In some embodiments, a water source may be present during contact.

The second catalyst can reduce at least a portion of the components that contribute to the TAN of the crude feed, reduce at least a portion of the components that contribute to a relatively high viscosity and at least a portion of the 30 Ni / Reduce V / Fe content of the crude product. In addition, contact of crude feed with the second catalyst can yield a crude feed with a relatively minor change in the sulfur content relative to the sulfur content of the crude feed. For example, the crude product can have a sulfur content of 70%.

130% of the sulfur content of the crude feed. The crude product can also show relatively small changes in the distillate content, VGO content and residue content compared to the crude feed.

In some embodiments, the crude oil-containing feed can handle a relatively low content

Ni / V / Fe (for example, at most 50 wtppm) but have a relatively high TAN, asphaltene content or metal content in metal salts of organic acids. A relatively high TAN (for example, a TAN of at least 0.3) can make the crude feed unacceptable for transport and / or refining. A disadvantaged crude with a relatively high Cs asphaltenes content may exhibit less stability compared to | during processing other crude-containing raw materials with a relatively low C5 asphaltenes content. Touching the crude feed with the second catalysts can remove acidic components and / or Cs asphaltenes from the crude feed that contribute to TAN.

In some embodiments, lowering of C5-25 asphaltenes and / or components that contribute to TAN can reduce the viscosity of the crude-feed and total-product mixture relative to the viscosity of the crude-feed. In certain

embodiments may include one or more combinations of I

30 second catalysts, when used to treat crude feed as described herein, improve the stability of the total product and crude product mixture, extend the life of the 1027765 - 107 - catalyst, minimal net hydrogen uptake by the crude feed enable nutrition or achieve combinations thereof.

In some embodiments, a third type of catalyst ("third catalyst") can be obtained by

combining a support with metal / (metals) from Column 6 to produce a catalyst precursor. The catalyst precursor can be heated in the presence of one or more sulfur-containing compounds for a relatively short period of time at a temperature below 500 ° C.

(e.g. below 482 ° C) to form the non-annealed third catalyst. The catalyst precursor is usually heated to at least 100 ° C for 2 hours. In certain embodiments, the third catalyst may have an element content from Column 15 in a range of 0.001-0.03 grams, 0.005-0.02 grams, or 0.008-0.01 grams per column of catalyst. The third catalyst can exhibit considerable activity and stability when it is used to treat the crude feed as described herein. In some embodiments, the catalyst precursor is heated in the presence of one or more sulfur compounds at temperatures below 500 ° C.

The third catalyst can reduce at least a portion of the components that contribute to the TAN of the crude feed, reduce at least a portion of the metals in metal salts of organic acids, a Ni / V / Fe content of the crude reduce oil-containing product and lower the viscosity of the crude-oil-containing product. In addition, contact of crude-oil feeds with the third catalyst can be a crude-oil product with a relatively small change in the sulfur content relative to 1027765.

- 108 - yield sulfur content of the crude feed and with relatively minimal net hydrogen uptake by the crude feed. For example, a crude product may have a sulfur content of 70% -130% of the sulfur content of the crude feed. The crude oil-containing product produced using the third catalyst may also exhibit relatively minor changes in API density, distillate content, VGO content and residue content relative to the crude feed. By being able to lower the TAN, the metals in metal salts of organic salts, the Ni / V / Fe content and the viscosity of the crude product, while API density, distillate content, VGO content and residue content only to a small extent compared to the crude oil feed, the crude oil product can be used by a range of treatment facilities.

The third catalyst can, in some embodiments, reduce at least a portion of the MCR content of the crude feed while maintaining the stability of crude feed / total product. In certain embodiments, the third catalyst may have a metal / (metal) content from Column 6 per gram of catalyst in a range of 0.0001-0.1 grams, 0.005-0.05 grams or 0.001-0.01 grams and a content of metal / (metals) from Column 10 in a range of 0.0001-0.05 grams, 0.005-0.03 grams or 0.001-0.01 grams. A metal / (metal) 30 catalyst from Columns 6 and 10 can be operated at temperatures in the range of 300-500 ° C or 350-450 ° C and pressure values in the range of 0.1-10 MPa, 1-8 MPa or 2-5 MPa reduction 1027765 - 109 - promoting at least a portion of the components that contribute to the MCR in the crude feed.

In certain embodiments, a fourth type of catalyst ("fourth catalyst") includes, among others, metal / 5 (metals) from Column 5 in combination with a theta-alumina support. The fourth catalyst has a pore size distribution with a median pore diameter of at least 180 A. In some embodiments, the median pore diameter of the fourth catalyst can be at least 10 220 A, at least 230 A, at least 250 A, or at least 300 A. The carrier may include at least 0.1 grams, at least 0.5 grams, at least 0.8 grams, or at least 0.9 grams of theta alumina per gram of carrier. The fourth catalyst in some embodiments may include at most 0.1 grams of metal / (metals) from Column 5 per gram of catalyst and at least 0.0001 grams of metal / (metals) from Column 5 per gram of catalyst. In certain embodiments, the metal from Column 5 is vanadium.

In some embodiments, the crude feed after contact with the fourth catalyst may be contacted with an additional catalyst. The additional catalyst may be one or more of the following: the first catalyst, the second catalyst, the third catalyst, the fifth catalyst, the sixth catalyst, the seventh catalyst, commercially available catalysts as described herein or combinations thereof.

In some embodiments, hydrogen may be generated during the contact of the crude feed with the fourth catalyst at a temperature in a range of 300-400 ° C, 320-380 ° C or 330-370 ° C. The crude-oil product produced from such contact 1027765-110 may have a TAN of at most 90%, at most 80%, at most 50% or at most 10% of the TAN of the crude feed. The hydrogen generation can be in a range of 1-50 Nm3 / m3, 10-40 Nm3 / m3 or 15-25 Nm3 / m3. The crude product can have a total Ni / V / Fe content of at most 90%, at most 80%, at most 70%, at most 50%, at most 10% or at least 1% of the total Ni / V V / Fe content of the crude feed 10.

In certain embodiments, a fifth type of catalyst ("fifth catalyst") includes, among others, metal / (metals) from Column 6 in combination with a theta-alumina support. The fifth catalyst has a pore size distribution with a median pore diameter of at least 180 A, at least 220 A, at least 230 A, at least 250 A, at least 300 A or at most 500 A. The support may include at least 0, 1 gram, at least 0.5 gram or at most 0.999 gram of theta alumina per gram of carrier. In some embodiments, the carrier has an alpha alumina content of less than 0.1 grams of alpha alumina per gram of catalyst. In some embodiments, the catalyst comprises, inter alia, at most 0.1 gram of metal / (metals) from Column 6 per gram of catalyst and at least 0.0001 gram of metal / (metals) from Column 6 per gram of catalyst. In some embodiments, the / (the) metal is / (metals) from Column 6 is molybdenum and / or tungsten.

In certain embodiments, the net hydrogen uptake by the crude feed may be relatively low (e.g., 0.01-100 Nm3 / m3, 1-80 Nm3 / m3, 5-50 Nm3 / m3 or 10-30 Nm3 / m3) when the crude feed is contacted with the fifth catalyst at a temperature in a range 1027761 - 111 - of 310-400 ° C, 320-370 ° C or 33Ö-360 ° C. The net hydrogen uptake by the crude feed may in some embodiments be in a range of 1-20 5 · Nm3 / m3, 2-15 Nm3 / m3 or 3-10 Nm3 / m3. The crude oil product produced by contacting the crude feed with the fifth catalyst can have a TAN of at most 90%, at most 80%, at most 50% or at most 10% of the TAN of the crude feed 10 have. The TAN of the crude product may be in a range of 0.01-0.1, 0.03-0.05 or 0.02-0.03.

! In certain embodiments, a sixth type of catalyst ("sixth catalyst") includes, among others, metal / (metals) from Column 5 and metal / (metals) from Column 6 in combination with the theta-alumina support. The sixth

catalyst has a pore size distribution with a median pore diameter of at least 180 A. In some embodiments, the median pore size of the pore size distribution can be at least 220 A, at least 230 A, at least 250 A, at least 300 A, or at most 500 A

to be. The carrier may include at least 0.1 grams, at least 0.5 grams, at least 0.8 grams, at least 0.9 grams, or at most 0.99 grams of theta alumina per gram of carrier. The catalyst can, inter alia, in some embodiments, produce a total of metal / (metals)

Column 5 and metal / (metals) from Column 6 of at most 0.1 gram per gram of catalyst and at least 0.0001 gram of metal / (metals) from Column 5 and metal / (metals) from Column 6 per gram of catalyst. In some embodiments, the molar ratio of total metal from Column 6 to total metal from Column 5 may be in a range of 0.1-20, 1-10 or 2-5. In certain embodiments, the metal from Column 5 is vanadium and / or the metal (s) from Column 6 is molybdenum and / or tungsten.

When the crude feed is contacted with the sixth catalyst at a temperature in the range of 310-400 ° C, 320-370 ° C or 330-360 ° C, the net hydrogen uptake by the crude feed can lie in a range from -10 Nm3 / m3 to 20 Nm3 / m3, -7 Nm3 / m3 to 10 Nm3 / m3 or -5 Nm3 / m3 to 5 Nm3 / m3. Negative net hydrogen uptake is an indication that hydrogen is generated in situ. The crude product produced from contacting the crude feed with the sixth catalyst may have a TAN of at most 90%, at most 80%, at most 50%, at most 10% or at least 1% of the TAN of have the crude oil-containing feed. The TAN of the crude product may be in a range of 0.01-0.1, 0.02-0.05 or 0.03-0.04.

Low net hydrogen uptake during the contact of the crude feed with the fourth, fifth or sixth catalyst reduces the overall need for hydrogen during processing while producing a crude oil containing product that is acceptable for transport and / or handling . Since producing and / or transporting hydrogen is expensive, minimizing the use of hydrogen in a process lowers the overall processing costs.

In certain embodiments, a seventh type of catalyst ("seventh catalyst") has a total content of metal / (metals) from Column 6 in a range of 0.0001-0.06 grams of metal / (metals) from Column 6 per gram

catalyst. The metal from Column 6 is molybdenum and / or tungsten. The seventh catalyst is conducive to producing a crude product that is a TAN

1027765 - 113 - has at most 90% of the TAN of the crude feed.

Other embodiments of the first, second, third, fourth, fifth, sixth and seventh catalysts can also be made and / or used as described elsewhere herein.

Selection of the catalyst (s) according to this application and control of the operating conditions may allow a crude product to be produced that has a TAN and / or selected properties that have changed compared to the crude feed while others properties of. the crude oil. nutrition have not changed significantly. The crude-oil-containing product thus obtained may have improved properties over the crude-oil feed and thus be more acceptable for transport and / or refining.

Arrangement of two or more catalysts in a selected order may allow control of the order of property improvements of the crude feed. For example TAN, API density, at least a portion of. the C5 asphaltenes, at least a part of the iron, at least a part of it. nickel and / or at least a portion of the vanadium in the crude feed may be lowered before at least a portion of the heteroatoms in the crude feed are lowered.

Arrangement and / or selection of the catalysts may, in some embodiments, extend the service life of the catalyst. catalysts and / or improve the stability of the crude feed and total product mixture. Improving the life of the catalyst and / or the stability of the mixture of crude oil-based feed and total product during processing may allow a contact system for at least 3 months, at least 6 months or at least operated in the touch zone for at least 1 year without replacement of the catalyst.

Combinations of selected catalysts in the crude feed may allow for reduction of at least a portion of the Ni / V / Fe, at least a portion of the Cs asphaltenes, at least a portion of the metals in metal salts of organic acids, at least a part of the components that contribute to the TAN, at least a part of the residue or combinations thereof, before other properties of the crude feed are changed, while the stability of the crude oil blend feed and total product is maintained during processing (e.g., maintaining a P value of the crude feed above 1.5). Alternatively, C5 asphaltenes, TAN and / or API density can be reduced further and further by contacting the crude feed with selected catalysts. The ability to further and / or selectively change properties of the crude-oil feed can make it possible to maintain the stability of the mixture of crude-oil feed and total product during processing.

In some embodiments, the (described above) first catalyst may be arranged upstream of a series of catalysts. Such positioning of the first catalyst can allow removal of high molecular weight impurities, metal impurities and / or metals in metal salts of organic acids, while maintaining the stability of the crude-feed and total product mixture. is being held.

The first catalyst in some embodiments involves removal of at least a portion of Ni / V / Fe, removal of acidic components, removal of components that contribute to shortening the life of other catalysts in the system or combinations thereof from the crude feeding possible. For example, lowering at least a portion of the Cs asphaltenes in the crude-feed and total-product mixture relative to the crude-feeding feed inhibits clogging of other downstream catalysts and thus extends the length of time during which the touch system can be operated without catalyst replacement.

Removal of at least a portion of the Ni / V / Fe from the crude feed may, in some embodiments, extend the life of one or more catalysts disposed after the first catalyst.

The second catalyst (s) and / or the third catalyst (s) may be arranged downstream of the first catalyst. Further contact of the mixture of crude feed and total product with the second catalyst (s) and / or third catalyst (s) can further decrease the TAN, lower the Ni / V / Fe content, lower the sulfur content, reduce oxygen content and / or reduce metals content in metal salts of organic acids.

In some embodiments, contact of the crude feed with the second catalyst (s) and / or the third catalyst (s) can produce a mixture of crude feed and total product that has a reduced TAN, a reduced sulfur content, a reduced 1027765 Has an oxygen content, a reduced metal content in metal salts of organic acids, a reduced asphaltenes content, a reduced viscosity or combinations thereof relative to the respective properties of the crude feed while maintaining the stability of the crude oil blend nutrition and total product is maintained during processing. The second catalyst can be arranged in series, with the second catalyst upstream of the third catalyst or vice versa.

The ability to deliver hydrogen to specified touch zones tends to minimize the use of hydrogen during contact. Combinations of catalysts that promote hydrogen generation during the contact and catalysts that absorb a relatively low amount of hydrogen during the contact can be used to compare selected properties of a crude product with respect to the same properties of the crude oil containing change power supply. For example, the fourth catalyst can be used in combination with the first catalyst (s), second catalyst (s), third catalyst (s), fifth catalyst (s), sixth catalyst (s) and / or seventh catalyst (s) to change selected properties of a crude oil feed, while other properties of the crude oil feed are changed only to a selected extent and / or while maintaining the stability of crude oil feed / total product. The order and / or number of the catalysts can be selected to minimize the net hydrogen uptake while maintaining the stability of crude feed / total product 1027765 '- 117 -. Minimum net hydrogen uptake allows residual content, VGO content, distillate content, API density or combinations thereof of the crude feed to be kept within 20% of the respective properties of the crude feed while the TAN and / or the viscosity of the crude product is at most 90% of the TAN and / or the viscosity of the crude feed.

Reduction of the net hydrogen uptake by the crude feed may yield a crude product that has a boiling range spread that is nearly equal to the boiling point distribution of the crude feed and that relative to the TAN of the crude feed reduced TAN. The H / C-15 atomic ratio of the crude oil-containing product can also change with only relatively small amounts, compared to the H / C-atomic ratio of the crude-containing feed.

Hydrogen generation in specific touch zones may allow selective addition of hydrogen to other touch zones and / or selective reduction of the properties of the crude feed. In some embodiments, a fourth catalyst (s) may be upstream, downstream or between additional catalyst (s) described herein.

are drawn up. Hydrogen can be generated during the contact of the crude feed with the fourth catalyst (s) and hydrogen can be supplied to the contact zones which include additional catalyst (s). The hydrogen can be supplied in countercurrent to the flow of the crude feed. In some embodiments, the supply of the hydrogen may be in direct current with the flow of the crude feed.

For example, in a stacked configuration (see, for example, Fig. 2B), hydrogen may enter into a touch zone (e.g., touch zone 102) during contact 5

FIG. 2B) and hydrogen can be supplied to an additional touch zone (e.g., touch zone 114 in Fig. 2B) in a direction opposite to the flow of the crude feed. In some embodiments, the hydrogen flow may be in direct current with the flow of the crude feed. Alternatively, hydrogen in a stacked configuration (see, e.g., Fig. 3B) can be generated during contact in a touch zone (e.g., touch zone 102 in Fig. 3B). A hydrogen source can be supplied to a first additional touch zone in a direction opposite to the flow of the crude feed (e.g., addition of hydrogen through line 106 'to touch zone 114, in Fig. 3B) and to a second additional touch zone in a direction that is in direct current with the flow, of the crude feed (e.g., addition of hydrogen through line 106 'to contact zone 116, in Fig. 3B).

In some embodiments, the fourth catalyst and the sixth catalyst are used in series, with the fourth catalyst upstream of the sixth catalyst or vice versa. The combination of the fourth catalyst with one or more additional catalysts can lower the TAN, lower the Ni / V / Fe content and / or lower a metal content in metal salts of organic acids, with a low net hydrogen uptake by the crude oil-based food. With a low net hydrogen uptake, it is possible to change other properties of the crude oil product only slightly compared to the same properties of the crude oil feed.

In some embodiments, two different seventh catalysts can be used in combination. The seventh catalyst used upstream of the downstream seventh catalyst may have a total content of 10 metal / (metals) from Column 6 in a range of 0.0001-0.06 grams per gram of catalyst. The downstream seventh catalyst can have, per gram of downstream seventh catalyst, a total content of metals from Column 6 that is equal to or greater than the total content of metal / (metals) from Column 6 in upstream seventh catalyst or at least least 0.02 grams of metal / (metals) from Column 6 per gram of catalyst. In some embodiments, the position of the upstream seventh catalyst and the downstream seventh catalyst may be reversed. The ability to use a relatively small amount of catalytically active metal in the downstream seventh catalyst makes it possible to change other properties of the crude-containing product only slightly compared to the same properties of the crude product. oil-containing feed (for example a relatively small change in heteroatom content, API density, residue content, VGO content or combinations thereof).

Contact of the crude feed with the upstream and downstream seventh catalysts can yield a crude product that has a TAN of at most 90%, at most 80%, at least 2%. at most 50%, at most 10% or at least 1% of the TAN of the crude feed. In some embodiments, the TAN of the crude feed may be further reduced stepwise by contacting the upstream and downstream seventh catalysts (e.g., contacting the crude feed with a catalyst to form a first crude-containing product with modified properties relative to the crude feed and then contacting the first crude product with an additional catalyst to form the crude product with modified properties relative to the first crude product). The ability to handle the TAN | | Further decreasing, maintenance of the stability during the processing of the mixture of i i

promote crude-oil foods and total products. I

In some embodiments, catalyst selection and / or order of catalysts in combination with control of the contact conditions (for example, temperature and / or flow rate of the crude feed) may be conducive to reducing hydrogen uptake by the crude feed, maintaining the stability of the mixture of crude-oil feed and total product during the processing and modification of one or more properties of the crude-oil product relative to the respective properties of the crude-oil feed. The stability of the crude-feed and total product mixture can be affected by various phases that separate from the crude-feed and total product mixture. Phase separation may be caused, for example, by the insolubility of the crude-oil feed and / or the crude-oil product in the crude-oil feed and total product mixture, flocculation of asphaltenes from the crude-oil feed and total product mixture precipitation of components from the crude-oil-feed mixture and total product or combinations thereof.

i! At certain times during the touch period! j can change the concentration of crude feed and / or total product in the mixture of crude feed and total product. As the concentration of the total product in the mixture of crude oil feed and total product changes due to the formation of the crude oil product, the solubility of the components of the crude oil feed and / or components of the total product in the mixture also has mixture of crude-oiled food and total product tends to change. The crude feed may, for example, contain components that are insoluble in the crude feed at the start of processing. As properties of the crude feed change (e.g., TAN, MCR, Cs asphaltenes, P value or combinations thereof), the components may tend to become less insoluble in the crude feed and total product mixture. In some cases, the crude feed and the total product can form two phases and / or become insoluble in each other. Changes in solubility can also cause the crude-oil-feed and total-product mixture to form two or more phases. Formation of two phases by flocculation of asphaltenes, change in the concentration of crude oil feed and total product and / or precipitation of components tends to shorten the life of one or more of the catalysts. Moreover, it can reduce the efficiency of the process.

For example, repeated treatment of the mixture of crude-oil feed and total product may be necessary to produce a crude-oil product with desired properties.

During processing, the P value of the crude-oil feed and total product mixture can be monitored and the stability of the process, the crude-oil feed and / or the crude-oil feed and total product mixture can be assessed .

A P value that is at most 1.5 indicates that flocculation of asphaltenes from the crude feed generally occurs. If the P-value is initially at least 1.5 and that P-value increases or is relatively stable during the contact, this indicates that the crude feed is relatively stable during the contact. The stability of the crude feed and total product mixture, as judged by the P value, can be controlled by control of the contact conditions, by selection of catalysts, by selective sequencing of catalysts or combinations thereof. Such control of the contact conditions may include control of LHSV, temperature, pressure, hydrogen uptake, flow of the crude feed or combinations thereof.

In some embodiments, the contact temperatures are controlled such that Cs asphaltenes and / or other asphaltenes are removed while maintaining the MCR content of the crude feed containing 1 0 2 7 7 6 5 - 123. Reduction of the MCR content due to hydrogen uptake and / or higher contact temperatures can lead to the formation of two phases that can improve the stability of the crude-feed and total product mixture 5 and / or the service life of one or more of the catalysts Reduce. Control of contact temperature and hydrogen uptake in combination with the catalysts described herein makes it possible to reduce the Cs asphaltenes while the MCR content of the crude feed changes only to a relatively small extent

In some embodiments, the touch conditions are controlled such that the temperatures in one or more touch zones may be different. Operating at different temperatures makes selective 15. modification of the properties of the crude-oil feed is possible while maintaining the stability of the mixture of crude-oil feed and total product. The crude-containing feed enters a first contact zone 20 at the start of a process. A first contact temperature is the temperature in the first touch zone. Other contact temperatures (for example, second temperature, third temperature, fourth temperature, etc.) are the temperatures in touch zones arranged after the first touch zone. A first contact temperature can be in a range of 100-420 ° C and a second contact temperature can be in a range that is 20-100 ° C, 30-90 ° C or 40-60 ° C different from the first contact temperature. In some embodiments, the second contact temperature is higher than the first contact temperature. Having different contact temperatures can lower the TAN and / or the C5 asphaltenes content in a crude product more strongly compared to the TAN and / or the C5 asphaltenes content of the crude feed than the extent of any TAN and / or C.5 asphaltene reduction that is obtained when the first and second contact temperatures are the same or within 10 ° C of each other.

For example, a first touch zone may include one or more first catalysts and / or one or more fourth catalysts, and a second touch zone may include other catalyst (s) described herein. The first contact temperature can be 350 ° C and the second contact temperature can be 300 ° C. Touching the crude feed with the first catalyst and / or fourth catalyst at the higher temperature in the first contact zone prior to contact with the other catalyst (s) in the second

touch zone can produce a greater reduction of the TAN and / or Cs asphaltenes in the crude-containing feed than the reduction of the TAN and / or Cs-asphaltenes in the same crude-containing feed when the first and second contact temperatures are within 10 ° C

from each other.

EXAMPLES

In the following, non-limiting examples of support preparation, catalyst preparations, and systems with a selected catalyst arrangement and controlled touch conditions are set forth.

Example 1, Preparation of a catalyst support. A support was prepared by crushing 576 grams of alumina (Criterion Catalysts and Technologies LP, Michigan City, Michigan, 30 U.S.A.) for 35 minutes with 585 grams of water and 8 grams of ice nitric acid. The finely rubbed mixture thus obtained was extruded through a 1.3 Trilobe ™ die plate, dried between 90-125 ° C and subsequently annealed at 918 ° C, yielding 650 grams of an annealed support with a median pore diameter of 182 A. The annealed support was placed in a Lindberg stove. The furnace temperature was raised to 1000-1100 ° C in 1.5 hours and was then kept in that area for 2 hours to produce the support. The carrier included 0.0003 grams of gamma-alumina, 0.0008 grams of alpha-alumina, 0.0208 grams of delta-alumina and 0.9781 grams of theta-alumina, as determined by X-ray diffraction, per gram of support. The support had an area of 110 m 2 / g and a total pore volume of 0.821 cm 3 / g. The support had a pore size distribution with a median pore diameter of 232 A, with 66.7% of the total number of pores in the pore size distribution having a pore diameter within 85 A of the median pore diameter.

This example demonstrates the preparation of a carrier that has a pore size distribution of at least 180 Å and includes at least 0.1 grams of theta alumina.

Example 2 Preparation of a vanadium catalyst with a pore size distribution with a median pore diameter of at least 230 A. The vanadium catalyst was prepared in the following manner. The alumina carrier, prepared by the method described in Example 1, was impregnated with a vanadium impregnation solution prepared by combining 7.69 grams of V0 SO4 with 82 grams of deionized water. A pH of the solution was 2.27.

The alumina support (100 g) was impregnated with the vanadium impregnation solution, aged for 2 hours with occasional stirring, dried for a few hours at 125 ° C and then calcined at 480 ° C for 2 hours. The catalyst thus obtained contained 0.04 102 77 65 - 126 grams of vanadium per gram of catalyst, with the remainder being supported. The vanadium catalyst had a pore size distribution with a median pore diameter of 350 A, a pore volume of 0.69 cm 3 / g and an area of 5 110 m 2 / g. In addition, 66.7% of the total number of pores in the pore size distribution of the vanadium catalyst had a pore diameter within 70 Å of the median pore diameter.

This example demonstrates the preparation of a Column 5 catalyst that has a pore size distribution with a median pore diameter of at least 230 A.

Example 3 Preparation of a molybdenum catalyst with a pore size distribution with a median pore diameter of at least 230 A. The molybdenum catalyst was prepared in the following manner. The alumina support prepared by the method described in Example 1 was impregnated with a molybdenum impregnation solution. The molybdenum impregnation solution was prepared by combining 4.26 grams of (NH 4) 2 MO 2 O 7, 6.38 grams of MO 3, 1.12 grams of 30% H 2 O 2, 0.27 grams of monoethanolamine (MEA) and 6.51 grams of deionized water forming a slurry. The slurry was heated to 65 ° G until the solids were dissolved. The heated solution was cooled to room temperature. The pH of the solution was 5.36. The volume of the solution was adjusted to 82 ml with deionized water.

. The alumina carrier (100 grams) was impregnated with the molybdenum impregnation solution, aged for 2 hours with occasional stirring, dried at 125 ° C for a few hours and then calcined at 480 ° C for 2 hours. The catalyst thus obtained contained 0.04 grams of molybdenum per gram of catalyst, with the remainder being supported. The molybdenum catalyst had a pore size distribution with a median pore diameter of 250 A ', a pore volume of 0.77 cm 3 / g and an area of 116 m 2 / g. In addition, 67.7% of the total number of pores in the pore size distribution of the molybdenum catalyst had a pore diameter within 86 Å of the median pore diameter.

This example demonstrates the preparation of a column 6 metal catalyst having a pore size distribution with a median pore diameter of at least 230 A.

Example 4. Preparation of a molybdenum / vanadium catalyst having a pore size distribution with a median pore diameter of at least 230 A. The molybdenum / vanadium catalyst was prepared in the following manner. The alumina support prepared by the method described in Example 1 was impregnated with a molybdenum / vanadium impregnation solution prepared as follows. A first solution was made by 2.14 grams of (NH 4) 2 MO 2 O 7, 3.21 grams of MO 3, 0.56 grams of 30% hydrogen peroxide (H 2 O 2), 0.14 grams of monoethanolamine (MEA) and 3.28 grams combine ionized water with one another to form a slurry. The slurry was heated to 65 ° C until the solids were dissolved. The heated solution was cooled to room temperature.

A second solution was made by combining 3.57 grams of VOSO4 with 40 grams of deionized water. The first and the second solution were combined with one another and sufficient deionized water was added to bring the volume of the combined solution to 82 ml, yielding the molybdenum / vanadium impregnation solution. The alumina was impregnated with the molybdenum / vanadium impregnation solution, aged for 2 hours with occasional stirring, dried for a few hours at 125 ° C and then annealed for 2 hours at 480 ° C. The catalyst thus obtained contained 0.02 grams of vanadium and 0.02 grams of molybdenum per gram of catalyst, with the remainder being supported. The molybdenum / vanadium catalyst had a pore size distribution with a median pore diameter of 300 A.

This example demonstrates the preparation of a catalyst from metal from Column 6 and a metal from

Column 5 having a pore size distribution with a median pore diameter of at least 230 A.

Example 5. Touch of a crude oil feed with three catalysts. A tubular reactor with a centrally positioned thermometer tube was equipped with thermocouples to measure temperatures throughout an entire catalyst bed. The catalyst bed was formed by filling the space between the thermometer tube and an inner wall of the reactor with catalysts and silicon carbide (20-grid, Stanford Materials; Aliso Viejo, CA).

It is believed that such silicon carbide has low, if not any, catalytic properties under the process conditions described herein. All catalysts were mixed with an equal volume amount of silicon carbide before placing the mixture in the touch zone portions of the reactor.

The flow of the crude feed to the reactor was from the top of the reactor to the reactor bottom. Silicon carbide 30 was placed at the bottom of the reactor to serve as the lower support. A lower mixture of catalyst and silicon carbide (42 cm 3) was placed on top of the silicon carbide to form a lower touch zone. The lower catalyst had a pore size distribution with a median pore diameter of 77 A, with 66.7% of the total number of pores in the pore size distribution having a pore diameter within 20 A of the median pore diameter. The lower catalyst contained 0.095 grams of molybdenum and 0.025 grams of nickel per gram of catalyst, with the remainder of an alumina carrier.

A middle mixture of catalyst and silicon carbide (56 cm 3) was placed on top of the lower touch zone to form a middle touch zone. The middle catalyst had a pore size distribution with a median pore diameter of 98 Å, with 66.7% of the total number of pores in the pore size distribution having a pore diameter within 24 Å of the median pore diameter. The middle catalyst contained 0.02 grams of nickel and 0.08 grams of molybdenum per gram of catalyst, with an alumina support for the rest.

On top of the middle touch zone, an upper mixture of catalyst and silicon carbide (42 cm 3) was placed to form an upper touch zone.

The upper catalyst had a pore size distribution with a median pore diameter of 192 A. It contained 0.04 grams of molybdenum per gram of catalyst, the remainder being essentially a gamma alumina carrier.

Silicon-Carbide was placed on top of the upper touch zone to fill up empty space and to serve as a preheating zone. The catalyst bed was loaded into a Lindberg stove which included five heating zones corresponding to the preheating zone, the upper, middle and lower touch zones and the lower support.

The catalysts were sulfided by introducing into the contact zones a gaseous mixture of 5 vol% hydrogen sulfide and 95 vol% hydrogen gas at a rate of 1.52765 - 130 g of 1.5 liter gaseous mixture per volume (ml) of total catalyst (silicon carbide was not counted as part of the catalyst volume). The temperatures of the touch zories were gradually increased in 5 hours from 5 to 204 ° C (400 ° F) and kept at 204 ° C for 2 hours.

After this holding at 204 ° C, the temperatures of the touch zones were gradually increased further at a rate of 10 ° C (50 ° F) per hour to 316 ° C (600 ° F). The contact zones were kept at 316 ° C for one hour, after which the temperature was gradually raised to 370 ° C (700 ° F) in 1 hour and kept at 370 ° C for two hours. The "touch zones" were allowed to cool to ambient temperature.

Crude oil crude from the Mars platform in the Gulf of Mexico was filtered, then heated in an oven for 12-24 hours at a temperature of 93 ° C (200 ° F) to form the crude oil feed with the in Table 1, FIG. 7 summarized properties. The crude feed was fed to the top of the reactor. The crude feed passed through the pre-heating zone, the upper touch zone, the middle touch zone, the lower touch zone, and the lower support of the reactor. The crude feed was contacted with each of the catalysts in the presence of hydrogen gas. The contact conditions were as follows: the ratio of hydrogen gas to the crude feed fed to the reactor was 328 Nm3 / m3 (2000 SCFB), the LHSV was 1 h -1 and the pressure was 6.9 MPa (1014.7 psi) . The three touch zones were heated to 370 ° C (700 ° F) and held at 370 ° C for 500 hours. The temperatures of the three touch zones were then raised and maintained in the following order: 379 ° C (715 ° F) for 1027765 - 131 - 500 hours and then 388 ° C (730 ° F) for 500 hours, then 390 ° C ( 734 ° F) for 1800 hours and then 394 ° C (742 ° F) for 2400 hours.

The total product (i.e., the crude product and the gas) left the catalyst bed. The total product was in a gas-liquid phase. separator. In the gas-liquid separator, the total product was split into the crude product and gas. The gas input into the system was measured with a mass flow controller. Gas that left the system was measured with a "wet test" meter. The crude product was analyzed periodically to determine a weight percentage of components of the crude product. The results mentioned are averages of the determined weight percentages of components. The properties of the crude product are summarized in Table 1 of FIG. 7.

As shown in Table 1, the crude product had per gram of crude product a sulfur content of 0.0075 grams, a residue content of 0.255 grams and an oxygen content of 0.0007 grams. The crude product had a MCR content to Cs asphaltenes content of 1.9 and a TAN of 0.09. The total nickel and vanadium was 22.4 wtppm.

The service life of the catalysts was determined by. measurement of a weighted average bed temperature ("WABT") with respect to the duration of the process of the crude feed. The service life of the catalysts can be correlated to the temperature of the catalyst bed. It is believed that as the life of the catalyst decreases, a WABT increases. FIG. 8 is a graphical representation of WABT plotted against time ("t") for improving the crude feed in the touch zones described in this example. Graph 136 is a representation of the average WABT of the three touch zones plotted against process run hours for contacting a crude feed 5 with the upper, middle and lower catalysts. Over a majority of the process run time, the WABT of the touch zones with only about 20 ° C. On the basis of the relatively stable WABT, it was estimated that the catalytic activity of the catalyst was not affected. Typically, a process run of 3000-3500 hours of a test unit corresponds to 1 year of commercial operation.

This example demonstrates that contact of the crude feed with a catalyst that has a pore size distribution with a median pore diameter of at least 180 A and with additional catalysts that have a pore size distribution with a median pore diameter in a range between 90-180 A, with at least 60% of the total number of pores in the 20 pore size distribution has a pore diameter within 45 A of the median pore diameter, yielded a total product under controlled contact conditions that included the crude product. As measured on the basis of the P value, the stability of the mixture of crude feed and total product was maintained. The crude product had a reduced TAN, a reduced Ni / V / Fe content, a reduced sulfur content and a reduced oxygen content relative to the crude feed, while the residual content and the VGO content of the crude feed product was 90% -110% of those properties of the crude feed.

1027765 - 133 -

Example 6, Touch of a crude feed with two catalysts having a pore size distribution with a median pore diameter in a range between 90-180 Å. The reactor apparatus (apart from the number and content of the contact zones), the catalyst sulfiding method, the cleavage method of the total product and the analysis method of the crude product were the same as described in Example 5. Each catalyst was mixed with an equal volume of silicon carbide .

The flow of the crude feed to the reactor was from the top of the reactor to the reactor bottom. The reactor was filled from bottom to top in the following manner. Silicon carbide was placed on the reactor bottom to serve as the lower support. A lower mixture of catalyst and silicon carbide (80 cm 3) was placed on top of the silicon carbide to form a lower touch zone. The lower catalyst had a pore size distribution with a median pore diameter of 127 Å, with 66.7% of the total number of pores in the pore size distribution having a pore diameter within 32 Å of the median pore diameter. The lower catalyst comprised 0.11 grams of molybdenum and 0.02 grams of nickel per gram of catalyst, with the remainder being supported.

An upper mixture of catalyst and silicon carbide (80 cm 3) was placed on top of the lower touch zone to form the upper touch zone. The top catalyst had a pore size distribution with a median pore diameter of 100 A, with 66.7% of the total number of pores in the pore size distribution having a pore diameter within 20 A of the median pore diameter. The top catalyst comprised 0.03 grams of nickel and 0.12 grams of molybdenum per gram of catalyst, with the remaining alumina being 1027765-134. Silicon carbide was placed on top of the first touch zone to fill empty space and to serve as a preheating zone. The catalyst bed was loaded into a Lindberg stove, which included four heating zones, which corresponded to the preheating zone, the two touch zones, and the lower support.

BS-4 crude-containing raw material (Venezuela) with the in Table 2, Figs. 9 summarized properties, was added to the top of the reactor. The crude feed passed through the preheating zone, the upper touch zone, the. lower, contact zone and the lower carrier of the reactor. The crude feed was contacted with each of the catalysts in the presence of hydrogen gas. The contact conditions were as follows: the ratio of hydrogen gas to the crude feed fed to the reactor was 160 Nm3 / m3 (1000 SCFB), the LHSV was 1 h "1 and the pressure was 6.9 MPa (1014.7 psi) The two touch zones were heated to 260 ° C (500 ° F) and held at 260 ° C (500 ° F) for 287 hours, then the temperature of the two touch zones was raised and maintained in the following order: 270 ° C (525 ° F) for 190 hours, then 288 ° C (550 ° F) for 216 hours, then 315 ° C (600 ° F) for 360 hours and then 343 ° C (650 ° F) for 120 hours, for a total process of 1173 hours.

The total product left the reactor and was split as described in Example 5. The crude oil-containing product had an average TAN of 0.42 and an average API density of 12.5 during processing. The crude product had 0.0023 grams of sulfur, 0.0034 grams of 1027765 - 135 - oxygen, 0.401 grams of VGO and 0.387 grams of residue per gram of crude product.

Additional properties of the crude product are listed in Table 2 in Figs. 9.

This example demonstrates that contacting the crude feed with the catalysts having a pore size distribution with a median pore diameter in a range between 90-180 Å yielded a crude product containing a lowered TAN, a lowered Ni / V / Fe had content and a reduced oxygen content relative to the properties of the crude feed, while the residual content and the VGO content of the crude product was 99% and 100% of the respective properties of the crude food.

Example 7, Touch of a crude oil feed with two catalysts. The reactor apparatus (apart from the number and content of the contact zones), the catalysts, the cleavage method of the total product, the analysis of the crude product and the catalyst sulfiding method were the same as described in Example 6.

A crude-oiled feedstock (BC-10 crude-oiled raw material) with the in Table 3, Figs. 10 summarized properties were added to the top of the reactor. The crude feed passed through the pre-heating zone, the upper touch zone, the lower touch zone, and the lower support of the reactor. The contact conditions were as follows: the ratio of hydrogen gas to crude feed fed to the reactor was 80 Nm3 / m3 (500 SCFB), the LHSV was 2 hl and the pressure was 6.9 MPa (1014.7 psi). ). The. two touch zones were gradually heated to 343 ° C (650 ° F). A total process run time was 1007 hours.

1027765 - 136 -

The crude product had an average TAN of 0.16 and an average API density of 16.2 during processing. The crude product had 1.9 wtppm of calcium, 6 wtppm of sodium, 0.6 wtppm of zinc and 3 wtppm of potassium. The crude-containing product had 0.0033 grams of sulfur, 0.002 grams of oxygen, 0.376 grams of VGO, and 0.401 grams of residue per gram of crude oil-containing product.

Additional properties of the crude product are listed in Table 3 in FIG. 10.

This example demonstrates that contacting the crude feed with the selected catalysts with pore size distributions in a range of 90-180 A yielded a crude product containing a reduced TAN and a reduced total calcium, sodium, zinc and had potassium content while sulfur content, VGO content and residue content of the crude product were 76%, 94% and 103% of the respective properties of the crude feed. Examples 8-11, Touch of a crude feed with four catalyst systems and under different contact conditions. Each reactor device (apart from the number and content of the contact zones), each catalyst sulfiding method, each total product cleavage method and each crude product analysis was the same as described in Example 5. All catalysts were mixed with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part of catalyst, unless stated otherwise. The flow of crude feed through each reactor was from the top of the reactor to the reactor bottom. Silicon carbide was placed at the bottom of each reactor to serve as the lower support. Each reactor had a lower touch zone and an upper touch zone.

1027765 - 137 -

After the catalyst and silicon carbide mixtures were placed in the contact zones of each reactor, silicon carbide was placed on top of the upper contact zone to fill void space and serve as a preheating zone in each reactor. Each reactor was charged to a Lindberg stove, which included four heating zones corresponding to the preheating zone, the two touch zones, and the lower support.

In Example 8, a non-annealed mixture of molybdenum / nickel catalyst and silicon carbide (48 cm 3) was placed in the lower touch zone. The catalyst comprised 0.166 grammes of molybdenum, 0.047 grammes of nickel and 0.021 grammes of phosphorus, with the remaining alumina carrier per gram of catalyst.

A mixture of molybdenum catalyst and silicon carbide (12 cm 3), the catalyst having a pore size distribution with a median pore diameter of 180 Å, was placed in the upper touch zone. The molybdenum catalyst had a total content of 0.04 grams of molybdenum per gram of catalyst, with the remainder of the support including at least 0.50 grams of gamma-alumina per gram of support.

In Example 9, a non-annealed mixture of molybdenum / cobalt catalyst and silicon carbide (48 cm 3) was placed in both contact zones. The non-calcined molybdenum / cobalt catalyst comprised 0.133 grams of molybdenum, 0.043 grams of cobalt and 0.021 grams of phosphorus and, for the rest, alumina support.

A mixture of molybdenum catalyst and silicon carbide (12 cm 3) was placed in the upper contact zone. The molybdenum catalyst was the same as that in the upper touch zone of Example 8.

1027765 - 138 -

In Example 10, the molybdenum catalyst as described for the upper touch zone of Example 8 was mixed with silicon carbide and placed in both touch zones (60 cm 3).

In Example 11, a non-annealed mixture of molybdenum / nickel catalyst and silicon carbide (48 cm 3) was placed in the lower touch zone. The non-calcined molybdenum / nickel catalyst comprised 0.09 grams of molybdenum, 0.025 grams of nickel and 0.01 grams of phosphorus, with the remainder of aluminum support per gram of catalyst.

A mixture of molybdenum catalyst and silicon carbide (12 cm 3) was placed in the upper touch zone. The molybdenum catalyst was the same as that in the upper touch zone of Example 8.

The crude oil-containing raw material from the Mars platform (Gulf of Mexico) was filtered, then heated in an oven for 12-24 hours at a temperature of 93 ° C (200 ° F) to provide the crude-containing feed with the 4, FIG. 11 summarized properties for Examples 8-20 11. In these examples, the crude feed was fed to the top of the reactor. The crude feed passed through the pre-heating zone, the upper touch zone, the lower touch zone, and the lower support of the 25 reactor. The crude feed was contacted with each of the catalysts in the presence of hydrogen gas. The contact conditions for each example were as follows: the ratio of hydrogen gas to crude feed during contact was 160 Nm3 / m3 (1000 SCFB) and the total pressure of each system was 6.9 MPa (1014.7 psi). The LHSV was 2.0 h "1 during the first 200 touch hours and was then lowered to 1.0 h" 1 during the remaining touch periods. The 1027765 - 139 temperature in all touch zones was 343 ° C (650 ° F) for 500 After 500 hours, the temperatures in all touch zones were controlled as follows: the temperature in the touch zones was raised to 354 ° C (670 ° F), kept at 354 ° C for 200 hours, and increased to 366 ° C (690 ° C) F), held at 366 ° C for 200 hours, raised to 371 ° C (700 ° F), held at 371 ° C for 1000 hours, raised to 385 ° C (725 ° C), at 3.85 ° C for 200 hours then raised to a final temperature of 399 ° C (750 ° C) and kept at 399 ° C for 200 hours, for a total contact time of 2300 hours.

The crude oil products were analyzed periodically to determine TAN, hydrogen uptake by the crude oil feed, P value, VGO content, residue content and oxygen content. The average property values of the crude oil products produced in Examples 8-11 are listed in Table 5 in Figs. 11.

FIG. 12 is a graphical representation of the P value of the crude product ("P"), plotted against the process run time ("t"), for each of the catalyst systems of Examples 8-11. The crude feed had a P value of at least 1.5. Charts 140, 142, 144 and 146 show the P value of the crude product obtained by contacting the crude feed with the four catalyst systems of Examples 8-11 respectively. In the catalyst systems of Examples 8-10, the P value of the crude product remained at least 1.5 for 2300 hours. In Example 11, the P value was greater than 1.5 during the majority of the process run time. At the end of the procedure (2300 hours) from 1027765 - 140 -

Example 11 the P value was 1.4. From the P value of the crude product for each test, it can be deduced that the crude feed remained relatively stable in each test during contact (the crude feed showed, for example, no phase separation). As shown in FIG. 12, the P value of the crude product remained relatively constant during significant portions of each test, except in Example 10, where the P value increased.

FIG. 13 is a graphical representation of net hydrogen uptake by crude feed ("H2"), plotted against process run time ("t"), for four catalyst systems in the presence of hydrogen gas. Charts 148, 150, 152, 154 show the net hydrogen uptake obtained by contacting the crude feed with each of the catalyst systems of Examples 8-11 respectively. The net hydrogen uptake by a crude feed during a process run period of 2300 hours was in a range between 7-48 Nm3 / m3 (43.8-300 SCFB). As shown in FIG. 13, the net hydrogen uptake of the crude feed during each test was relatively constant.

FIG. 14 is a graphical representation of the residue content, expressed as a percentage by weight, of crude product ("R"), plotted against the process run time ("t"), for each of the catalyst systems of Examples 8-11. In each of the four tests, the crude product had a residual content of 88-90% of the residual content of the crude feed.

Charts 156, 158, 160, 162 represent the residual content of the crude product obtained by contacting the crude feed with 1027765.

The catalyst systems of Examples 8-11, respectively. As shown in FIG. 14, the residual content of the crude product remained relatively constant during significant parts of each test.

FIG. 15 is a graphical representation of the change in API density of the crude product ("Δ API"), plotted against the process run time ("t"), for each of the catalyst systems of Examples 8-11. Charts 164, 166, 168, 170 represent the API density of the crude product obtained by contacting the crude feed with the catalyst systems of Examples 8-11, respectively. In each of the four tests, each crude oil-containing product had a viscosity in the range of 58.3.3-72.7 cSt. The API density of each crude product increased by 1.5 to 4.1 degrees. The increased API density corresponds to an API density of the crude oil products in a range of 21.7-22.95. The API density in this area is 110-117% of the API 20 density of the crude feed.

FIG. 16 is a graphical representation of the oxygen content, expressed as a percentage by weight, of the crude product ("O *"), plotted against the process run time ("t"), for each of the catalyst systems of Examples 8-11. Charts 172, 174, 176, 178 show the oxygen content of the crude product obtained by contacting the crude feed with the catalyst systems of Examples 8-11 respectively. Each crude oil-containing product had an oxygen content of at most 16% of the crude oil feed. During each test, each crude product had an oxygen content in a range of 0.0014-0.0015 grams per 1027765 - 142 grams of crude product. As shown in FIG. 16, the oxygen content of the crude product remained relatively constant after a period of 200 hours of contact. The relatively constant oxygen content of the crude product shows that selected organic oxygen compounds are reduced during the contact. Since the TAN was also lowered in these examples, it can be deduced that. at least a portion of the carboxyl-containing organic oxygen compounds is selectively lowered relative to the non-carboxyl-containing organic oxygen compounds.

In Example 11, at reaction conditions of 371 ° C (700 ° F), a pressure of 6.9 MPa (1014.7 psi) and a ratio of hydrogen to crude feed of 160 Nm 3 / m3 (1000 SCFB), was the reduction in the MCR content of the crude feed 17.5% by weight, based on the weight of the crude feed. At a temperature of 399 ° C (750 ° F), at the same pressure and ratio of hydrogen to crude feed, the reduction in the MCR content of the crude feed was 25.4% by weight based on the weight of the crude feed.

In Example 9, at reaction conditions of 371 ° C (700 ° F), a pressure of 6.9 MPa (1014.7 psi) and a ratio of hydrogen to crude feed of 160 Nm3 / m3 (1000 SCFB), the reduction in the MCR content of the crude feed was 17.5% by weight based on the weight of the crude feed.

At a temperature of 399 ° C (750 ° F), at the same pressure and ratio of hydrogen to crude oil feed, the reduction in the MCR content of the crude oil feed was 19% by weight, at based on the weight of the crude feed.

This greater reduction in the MCR content of the crude feed shows that the non-annealed catalyst of metals from Columns 6 and reduction in the MCR content at higher temperatures makes it easier than the non-annealed catalyst of metals from Columns 6 and 9.

These examples demonstrate that contact of a crude oil-containing feed with a relatively high TAN (TAN

of 0.8) with one or more catalysts to yield the crude product while maintaining the stability of the mixture of crude feed and total product and with a relatively low net hydrogen uptake. Selected properties of the crude oil product were at most 70% of the same properties of the crude oil feed, while selected properties of the crude oil product were within 20-30% of the same properties of the crude oil feed.

. Specifically, as shown in Table 4, each of the crude-containing products was produced with a net hydrogen uptake by the crude-containing feeds of at most 44 Nm 3 / m3 (275 SCFB). Such products had an average TAN of at most 4% of the crude feed and an average total Ni / V content of at most 61% of the total Ni / V content of the crude feed, while maintaining a P value for the crude feed of more than 3. The average residue level of each crude product was 88-90% of the residue of the crude feed. The average VGO content of each crude product was 115-117% of the VGO content 1027765 - 144 - of the crude feed. The average API density of each crude product was 110-117% of the API density of the crude feed, while the viscosity of each crude product was at most 45% of the viscosity of the crude food was.

Examples 12-14: Touching a crude feed with catalysts having a pore size distribution with a median pore diameter of at least 180 A, with minimal hydrogen consumption. In Examples 12-14, each reactor device (apart from the number and content of the contact zones), each catalyst sulfiding method, each total product cleavage method and each crude product analysis was the same as described in Example 5. All catalysts were mixed with a equal volume of silicon carbide. The flow of the crude feed to each reactor was from the top of the reactor to the reactor bottom. Silicon carbide was placed at the bottom of each reactor to serve as the lower support. Each reactor contained a touch zone. After the catalyst and silicon carbide mixtures were placed in the contact zone of each reactor, silicon carbide was placed on top of the upper contact zone 25 to fill void space and to serve as a preheating zone in each reactor. Each reactor was loaded into a Lindberg stove which included three heating zones corresponding to the preheating zone, the touch zone and the lower support. The crude feed was contacted with each of the catalysts in the presence of hydrogen gas. 1027765 - 145 -

A mixture of catalyst and silicon carbide (40 cm 3) was placed on top of the silicon carbide to form the contact zone. In Example 12, the catalyst was the vanadium catalyst as prepared in Example 2. In Example 13, the catalyst was the molybdenum catalyst as prepared in Example 3. In Example 14, the catalyst was the molybdenum / vanadium catalyst as prepared in Example 4.

The contact conditions for Examples 12-14 were as follows: the ratio of hydrogen to the crude feed fed to the reactor was 160 Nm3 / m3 (1000 SCFB), the LHSV was 1 hr-1 and the pressure was 6.9 MPa (1014.7 psi). The touch zones were heated stepwise over a period to 343 ° C (650 ° F) and kept at 343 ° C for 120 hours, with a total process run time of 360 hours.

The total products left the touch zones and were split as described in Example 5. For each catalyst system the net hydrogen uptake during the contact was determined. In Example 12, the net hydrogen uptake was -10.7 Nm3 / m3 (-65 SCFB) and the crude product had a TAN of 6.75. In Example 13, the net hydrogen uptake was in a range of 2.2-3.0 Nm3 / m3 (13.9-18.7 SCFB) and the crude-containing product had a TAN in a range of 0.3 -0.5. In

Example 14, during the contact of the crude feed with the molybdenum / vanadium catalyst, the net hydrogen uptake was in the range of -0.05 Nm3 / m3 to 0.6 Nm3 / m3 (-0.36 SCFB to 4 SCFB) and the crude product had a TAN in the range of 0.2-0.5.

Based on the values for net hydrogen uptake during contact, it was estimated that during the contact of the crude feed with the vanadium catalyst, hydrogen was generated at a rate of 10.7 Nm 3 / m3 (65 SCFB). Generation of hydrogen during contacting allows less hydrogen to be used in the process relative to an amount of hydrogen used in conventional processes to improve disadvantaged crude properties. The need for less hydrogen during contact tends to reduce the processing costs of a crude-containing raw material.

In addition, contacting the crude feed with the molybdenum / vanadium catalyst produced a crude product with a TAN lower than the TAN of the crude product produced with the individual molybdenum catalyst. Examples 15-18. Touch of a crude feed with a vanadium catalyst and an additional catalyst. Each reactor device (apart from the number and content of the contact zones), each catalyst sulfiding method, each total product cleavage method and each crude product analysis were the same as described in Example 5. All catalysts were mixed with silicon carbide in a volume ratio of 2 parts of silicon carbide to 1 part of catalyst, unless stated otherwise. The flow of crude feed to each reactor was from the top of the reactor to the reactor bottom. Silicon carbide was placed at the bottom of each reactor to serve as the lower support. Each reactor had a lower touch zone and an upper touch zone. After the mixtures of catalyst and silicon carbide were placed in the contact zones of each reactor, silicon carbide was placed on top of the upper contact zone to fill void space and to serve as a preheating zone in each reactor. Each reactor was charged into a Lindberg stove which included four heating zones that corresponded to the preheating zone, the two touch zones and the lower support.

In each example, the vanadium catalyst prepared as described in Example 2 and used with the additional catalyst.

In Example 15, an additional mixture of catalyst and silicon carbide (45 cm 3) was placed in the lower touch zone, the additional catalyst being the molybdenum catalyst prepared by the method described in Example 3. The mixture of vanadium catalyst and silicon carbide (15 cm 3) was placed in the upper touch zone.

In Example 16, an additional mixture of catalyst and silicon carbide (30 cm 3) was placed in the lower touch zone, the additional catalyst being the molybdenum catalyst prepared by the method described in Example 3. The mixture of vanadium catalyst and silicon carbide (30 cm 3) was placed in the upper touch zone.

In Example 17, a mixture of additional catalyst and silicon carbide (30 cm 3) was placed in the lower touch zone, the additional catalyst being the molybdenum / vanadium catalyst as prepared in Example 4. The mixture of vanadium catalyst and silicon carbide (30 cm 3) was placed in the upper touch zone.

1 0? 7 7 65 - 148 -

In Example 18, Pyrex® (Glass Works Corporation, New York, U.S.A.) beads (30 cm 3) were placed in each touch zone.

For Examples 15-18, crude-containing raw material (Santos basin, Brazil) was used that

FIG. 17 summarized properties were added to the top of the reactor. The crude feed passed through the preheating zone, the upper touch zone, the lower touch zone, and the lower support of the reactor. The crude feed was contacted with each of the catalysts in the presence of hydrogen gas. The contact conditions for each example were as follows: the ratio of hydrogen gas to the crude feed fed to the reactor was 160 Nm 3 / m3 (1000 SCFB)

during the first 86 hours and 80 Nm3 / m3 (500 SCFB) during the remaining period, the LHSV was 1 h -1 and the pressure was 6.9 MPa (1014.7 psi). The touch zones were heated stepwise over a period to 343 ° C (650 ° F) and for a total process run time of 1400 hours at 343 ° C

taken into account.

These examples demonstrate that contact in the presence of a source of hydrogen from a crude feed with a catalyst from Column 5 metal, which had a pore size distribution with a median pore diameter of 350,, in combination with an additional catalyst that had a pore size distribution with had a median pore diameter in a range of 250-300 Å, yielding a crude-containing product with properties that have changed compared to the same properties of the crude-containing feed, while other properties of the crude-containing product to a limited extent compared to the same properties of the crude oil-containing diet. Moreover, a relatively low hydrogen uptake by the crude feed was observed during processing.

Specifically, as shown in Table 5, FIG. 17, the crude product has a TAN of up to 15% of the TAN of the crude feed for Examples 15-17. The crude oil products produced in Examples 15-17 each had a total Ni / V / Fe content of at most 44%, an oxygen content of at most 50% and a viscosity of at most 75% relative to the same properties of the crude-oiled food. In addition, the crude oil-containing products produced in Examples 15-17 each had an API density of 100-103% of the API density of the crude feed.

In contrast, the crude-oil-produced product (Example 18) produced under non-catalytic conditions yielded a product with increased viscosity and reduced API density relative to the viscosity and API-density of the crude feed. It may perhaps be inferred from the increased viscosity and the reduced API density that coking and / or polymerization of the crude feed was initiated.

Examples 19. Touch of a crude-oiled diet with different LHSV. The contact systems and the catalysts were the same as described in Example 6. The properties of the crude feeds are listed in Table 6 in FIG. 18. The contact conditions were as follows: the ratio of hydrogen gas to the crude feed fed to the reactor was 160 Nm3 / m3 (1000 SCFB), the pressure 1027765 - 150 - was 6.9 MPa (1014.7 psi) and the the temperature of the contact zones was 371 ° C (700 ° F) during the total process run time. In Example 19, during contact, the LHSV was increased over a period from 1 h -1 to 12 h "1.5 for 48 hours at 12 h * 1, and then the LHSV was increased to 20.7 h -1 and for 96 held at 20.7 h -1 for 1 hour.

In Example 19, the crude product was analyzed to determine TAN, viscosity, density, VGO content, residue content, heteroatoms content and metal content in metal salts of organic acids during the periods in which the LHSV 12 h "1 and 20.7 h "was 1.

Average values for the properties of the crude oil products are given in Table 6, Figs. 18.

As shown in Table 6, FIG. 18, the crude product of Example 19 had a reduced TAN and a reduced viscosity relative to the TAN and the viscosity of the crude feed, while the API density of the crude product was 104-110% of was the API density of the crude feed. A weight ratio MCR content to C5 asphaltenes content was. . least 1.5. The sum of the MCR content and Cs asphaltenes content was reduced compared to the sum of the MCR content and C5 asphaltenes content of the crude feed. From the weight ratio MCR content to Cs asphaltenes content and the reduced sum of the MCR content and C5 asphaltenes it can be deduced that asphaltenes are lowered rather than components that have a tendency to coke.

The crude product also had a total potassium, sodium, zinc and calcium content of at most 60% of the total content of the same metals in the crude feed. The sulfur content of the crude product was 80-90% of the sulfur content of the crude feed.

Examples 6 and 19 show that the touch conditions can be controlled such that an LHSV through the touch zone is greater than 10 h "1, compared to a method that has an LHSV of 1 h-1 to produce crude oil products with similar The ability to selectively change a property of a crude feed at specific liquid transfer rates per hour of more than 10 hours makes it possible to carry out the touch process in barrels of reduced size compared to commercial ones. available barrels A smaller barrel size can make it possible to carry out treatment of disadvantaged crudes at production locations with size limitations (for example offshore facilities).

Example 20, Touch of a crude feed 20 at various contact temperatures. The contact systems and the catalysts were the same as described in Example 6. The crude feed containing the in Table 7. FIG. The above-mentioned properties were fed to the top of the reactor and contacted with the two catalysts in the two contact zones in the presence of hydrogen to form a crude product. The two touch zones were operated at different temperatures.

The contact conditions in the upper touch zone were as follows: the LHSV was 1 h -1; the temperature in the upper touch zone was 260 ° C (500 ° F); the ratio of hydrogen to crude oil feed was 160 Nm3 / m3 (1000 SCFB); and the pressure was 6.9 MPa (1014.7 psi).

The touch conditions in the lower touch zone were as follows: the LHSV was 1 h -1; the temperature in the lower touch zone was 315 ° C

(600 ° F); the ratio of hydrogen to crude feed was 160 Nm3 / m3 (1000 SCFB); and the pressure was 6.9 MPa (1014.7 psi).

The total product left the lower touch zone 10 and was fed into the gas-liquid phase separator. In the gas-liquid phase separator, the total product was split into the crude product and gas. The crude product was analyzed periodically to determine the TAN and Cs asphaltenes content.

Average values for the properties of crude oil-containing product obtained during the production run are given in Table 7, FIG. 19. The crude feed had a TAN of 9.3 and a Cs asphaltenes content of 0.055 grams of Cs asphaltenes per gram of crude feed. The crude product had an average TAN of 0.7 and an average C5 asphaltenes content of 0.039 grams of Cs asphaltenes per gram of crude product. The C5 asphaltenes content of the crude product was at most 71% of the C5-25 asphaltenes content of the crude product.

The total content of potassium and sodium in the crude oil product was at most 53% of the total content of the same metals in the crude oil feed. The TAN of the crude product was at most 10% of the TAN of the crude feed. A P value of 1.5 or higher was maintained during contact.

1027765 - 153 -

As demonstrated in Examples 6 and 20, having a first (in this case, upper) contact temperature that is 50 ° C lower than the contact temperature of the second (in this case, 5 lower) zone tends to decrease the decrease in to increase the C5 asphaltenes content in the crude oil product compared to the Cs asphaltenes content of the crude feed.

In addition, the reduction in metal content in metal salts of organic acids was enhanced with the help of controlled temperature differences. For example, the reduction in the total potassium and sodium content of the crude oil-containing product from Example 20 was enhanced compared to the reduction in the total potassium and sodium content of the crude-oil-containing product from Example 6 at a relatively constant stability of the mixture of crude feed and total product for each example, as measured by the P value.

Use of a lower temperature in a first touch zone allows removal of the high molecular weight compounds (e.g. C5 asphaltenes and / or metal salts of organic acids) that have a tendency to polymer formation and / or compounds with physical properties such as softness and / or tackiness (e.g. gums and / or tar types). Removal of these compounds at a lower temperature makes it possible to remove such compounds before clogging and covering the catalysts 30, thereby extending the service life of the catalysts disposed after the first contact zone and operated at higher temperatures.

1027765 - 154 -

Example 21, Touch of a crude feed and a catalyst as a slurry. In some embodiments, a bulk metal catalyst and / or a catalyst according to the application (0.0001-5 grams or 0.02-4.5 grams of catalyst per 100 grams of crude feed) can be slurried with the crude feed and the following conditions are reacted: temperature in a range of 85-425 ° C (185-797 ° F), pressure in a range of 0.5-10 MPa and a ratio of hydrogen source to crude feed of 16-1600 Nm3 / m3 during a certain period. After sufficient reaction time to produce the crude product, the crude product is separated from the catalyst and / or residual crude feed using a separation device such as a filter and / or centrifuge. The crude product may have an altered TAN, iron, nickel and / or vanadium content and a reduced Cs asphaltenes content relative to the crude feed.

In view of this description, further modifications and alternative embodiments of various aspects of the invention will be apparent to those skilled in the art. This description is, therefore, to be construed as merely illustrative and serves to demonstrate to those skilled in the art the general mode of implementation of the invention. It is to be understood that the forms of the invention shown and described herein are to be construed as examples of embodiments. Elements and materials may be used in place of those illustrated and described herein, parts and processes may be reversed, and certain features of the invention may be used independently, all as is apparent to those skilled in the art after benefiting from these. description of the invention. Changes may be made to the elements described herein without departing from the spirit and scope of the invention as described in the following claims.

j 1027765

Claims (15)

  1. A method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to form a total product comprising inter alia the crude product, the crude oil-containing product at 25 ° C and 0.101 MPa is a liquid mixture, the crude-containing feed being one or more. alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids or mixtures thereof, wherein the crude oil feed per gram of crude oil feed comprises a total content of alkali metal and alkaline earth metal in metal salts of organic acids of at least 0.00001 grams and wherein the one or more catalysts comprise: (a) a first catalyst, said first catalyst having 0.0001 grams to 0.06 grams per gram of first catalyst of: one or more metals from Column 6 of the Periodic
  2. The method of claim 1, wherein the crude feed is contacted with the second catalyst after contact with the first catalyst.
    2. System, one or more compounds of one or more metals from Column 6 of the Periodic System, calculated as a weight of metal, or mixtures thereof; and (b) a second catalyst, which second catalyst has at least 0.02 grams per gram of second catalyst of: one or more metals from Column 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic System, calculated as a weight of metal, or mixtures thereof; and 1027765 - 157 - controlling the contact conditions such that the crude product has a total alkali metal and alkaline earth metal content in metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the crude feed, wherein the content of alkali metal and alkaline earth metal in metal salts of organic acids is as determined by ASTM method D1318.
  3. 3. Method according to claims 1 or 2, wherein a total content of metal / (metals) from Column 6 per gram of second catalyst is equal to or higher than the total content of metal / (metals) from Column 6 in the first catalyst.
  4. 4. A method according to any one of claims 1-3, wherein the total content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude product is at most 50%, at most 10% or at most 5% of the content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude feed.
  5. 5. A method according to any one of claims 1-3, wherein the total content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude product is in a range of 1-80%, 10-70%, 20-60% or 30-50% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the crude feed. / 1027765 - 158 -
  6. The method of any one of claims 1-5, wherein the crude product contains 0.0000001 grams to 0.00005 grams, 0.0000003 grams to 0.00002 grams or 0.000001 grams to 0.00001 grams of alkali metal and alkaline earth metal in 5 has metal salts of organic acids per gram of crude product.
  7. A method according to any one of claims 1-6, wherein the first and / or the second catalyst has a pore size distribution with a median pore diameter of at least 10 60 A, at least 90 A, at least 180 A or at least 230, as determined by ASTM method D4282.
  8. 8. Method according to any of claims 1-7, wherein the first and / or the second catalyst has a pore size distribution such that at least 60% of the total number of pores in the pore size distribution has a pore diameter within 70 A, 45 A, 35 A or 25 A of the median pore diameter.
  9. 9. A method according to any one of claims 1-8, wherein contacting comprises contacting in the presence of a hydrogen source.
  10. The method of any one of claims 1-9, wherein the TAN of the crude feed is in a range of 0.3 to 20, 0.4 to 10 or 0.5 to 5.
  11. 11. A method according to any one of claims 1-10, wherein the method further comprises combining the crude-containing product with a crude-containing raw material which may or may not be the same as the crude-containing feed, forming a mixture .
  12. 12. Crude oil product or mixture that can be obtained with a method according to any one of claims 1-11.
  13. A method for producing transport fuel, fuel, lubricants or chemical products, comprising processing a crude-containing product or a mixture according to claim 12.
  14. 14. Method according to claim 13, wherein the processing comprises distilling the crude product or the mixture into one or more distillate fractions.
  15. The method of claims 13 or 14, wherein the processing comprises hydrogenating treatment. 1027765
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