BRPI0405567B1 - Methods of Producing a Crude Oil Product and Transport Fuel, Heating Fuel, Lubricants or Chemicals - Google Patents

Methods of Producing a Crude Oil Product and Transport Fuel, Heating Fuel, Lubricants or Chemicals Download PDF

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Publication number
BRPI0405567B1
BRPI0405567B1 BRPI0405567A BRPI0405567B1 BR PI0405567 B1 BRPI0405567 B1 BR PI0405567B1 BR PI0405567 A BRPI0405567 A BR PI0405567A BR PI0405567 B1 BRPI0405567 B1 BR PI0405567B1
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Brazil
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crude oil
catalyst
oil feed
product
content
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Portuguese (pt)
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Scott Lee Wellington
Opinder Kishan Bhan
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Shell Int Research
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Priority to US61889204P priority
Application filed by Shell Int Research filed Critical Shell Int Research
Publication of BRPI0405567A publication Critical patent/BRPI0405567A/en
Publication of BRPI0405567B1 publication Critical patent/BRPI0405567B1/en

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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

Description

DF DF methods; PRODUCING A GROSS OIL PRODUCT

AND TRANSPORT FUEL,

FIELD OF THE INVENTION The present invention generally relates to systems, methods and catalysts for treating crude oil feed and compositions that can be produced using such systems, methods and catalysts. More particularly, certain embodiments described herein relate to systems, methods and catalysts for converting a crude oil feed to a total product, wherein the total product includes a crude oil product which is a 25 ° C liquid mixture. C is 0.101 MPa and has one or more properties that are changed with respect to their respective property of the crude oil feed, RELATED ART DESCRIPTION

Crude oils that have one or more inadequate properties which do not allow crude oils to be economically transported or processed using conventional facilities are commonly referred to as "disadvantageous crude oils".

Disadvantageous crude oils may include acid components that contribute to the total acid value (“TAN”) of the crude oil feed. Disadvantageous crude oils with a relatively high TAN may contribute to corrosion of metallic components during transport and / or processing of the disadvantageous crude oils. Removal of acidic components from disadvantageous crude oils may involve chemically neutralizing the multi-base acidic components.

Alternatively, corrosion-resistant metals may be used in transport equipment and / or processing equipment. The use of corrosion resistant metal consequently entails significant expense and thus, the use of corrosion resistant metal in existing equipment may not be desirable. Another method for inhibiting corrosion may involve the addition of corrosion inhibitors to the disadvantageous crude oils prior to transport and / or processing of the disadvantageous crude oils. The use of corrosion inhibitors may adversely affect the equipment used to process crude oils and / or the quality of products made from crude oils.

Disadvantageous crude oils often contain relatively high levels of residue. Such high levels of waste tend to be difficult and expensive to transport and / or process using conventional facilities.

Disadvantageous crude oils often contain organically bonded heteroatoms (eg sulfur, oxygen and nitrogen). Organically linked heteroatoms, in some situations, may have an adverse effect on catalysts.

Disadvantageous crude oils may include relatively high amounts of metallic contaminants, for example nickel, vanadium and / or iron. During the processing of such crude oils, metal contaminants and / or metal contaminant compounds may deposit on a catalyst surface or on the void volume of the catalyst. Such deposits may cause a decline in catalyst activity.

Coke can form and / or deposit on catalyst surfaces at a rapid rate during the processing of disadvantageous crude oils. It can be costly to regenerate the catalytic activity of a coke contaminated catalyst. The high temperatures used during regeneration may also decrease catalyst activity and / or cause catalyst deterioration.

Disadvantageous crude oils may include metals in the metal salts of organic acids (eg calcium, potassium and / or sodium). Metals in metal salts of organic acids are not typically separated from disadvantageous crude oils by conventional processes, for example desalination and / or acid washing.

Processes often conflict with conventional processes when metals in the metal salts of organic acids are present. Unlike nickel and vanadium, which typically deposit near the outer surface of the catalyst, the metals in the metal salts of organic acids may preferentially deposit in void volumes between the catalyst particles, particularly at the top of the catalyst bed. Contaminant deposits, for example metals in the metal salts of organic acids, at the top of the catalyst bed generally result in an increase in pressure drop across the bed and can effectively clog the catalyst bed. In addition, metals in metal salts of organic acids can cause catalysts to deactivate rapidly.

Disadvantageous crude oils may include organic oxygen compounds. Treatment facilities that process disadvantageous crude oils with an oxygen content of at least 0.002 grams of oxygen per gram of disadvantageous crude may encounter problems during processing. Organic oxygen compounds, when heated during processing, may form superior oxidizing compounds (eg ketones and / or acids formed by oxidation of alcohols and / or acids formed by ether oxidation) which are difficult to remove from crude oil. treated and / or may corrode / contaminate the equipment during processing and cause clogging of the shipping lines.

Disadvantageous crude oils may include hydrogen deficient hydrocarbons. When processing hydrogen-deficient hydrocarbons, consistent amounts of hydrogen generally need to be added, particularly if unsaturated fragments that result from cracking processes are produced. Hydrogenation during processing, which typically involves the use of an active hydrogenation catalyst, may be required to inhibit unsaturated coke-forming fragments. Hydrogen is expensive to produce and / or expensive to transport to treatment facilities.

Disadvantageous crude oils also tend to exhibit instability during processing in conventional installations. Crude oil instability tends to result in phase separation of components during processing and / or formation of undesirable by-products (eg hydrogen sulfide, water and carbon dioxide carbon dioxide).

Conventional processes often lack the ability to change a selected property into a disadvantageous crude without also significantly changing other properties in a disadvantageous crude. For example, conventional processes often lack the ability to significantly reduce TAN in a disadvantageous crude while at the same time only changing the content of certain components (such as sulfur or metal contaminants) in the disadvantageous crude by a desired amount.

Some processes for improving crude oil quality include adding a diluent to disadvantageous crude oils to decrease the weight percentage of components contributing to disadvantageous properties. Adding diluent, however, generally increases costs of treating disadvantageous crude oils due to increased diluent costs and / or costs for handling disadvantageous crude oils. Adding diluent to a disadvantageous crude oil may in some situations diminish the stability of such crude oil.

U.S. Patent Nos. 6,547,957 issued to Sudhakar et al., 6,277,269 issued to Meyers et al., 6,063,266 issued to Grande et al., 5,928,502 issued to Bearden et al., 5,914,030 issued to Bearden et al. , 5,897,769 issued to Trachte et al, 5,871,636 issued to Trachte et al., And 5,851,381 issued to Tanaka et al. Describe various processes, systems and catalysts for processing crude oils. The processes, systems and catalysts described in these patents, however, have limited applicability because of many of the technical problems presented above.

In summary, disadvantageous crude oils generally have undesirable properties (eg, 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 high amounts of undesirable components (eg, residue, organically bonded heteroatoms, metal contaminants, metals in the 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, decreased catalyst life, process clogging and / or increased hydrogen use during treatment. Thus, there is a significant economic and technical need for improved systems, methods and / or catalysts for converting disadvantageous crude oils to more desirable crude oil products. There is also a significant economic and technical need for systems, methods and / or catalysts that can change selected properties in a disadvantageous crude oil while only selectively changing other properties in disadvantageous crude oil.

SUMMARY OF THE INVENTION

The inventions described herein generally relate to systems, methods and catalysts for converting a crude oil feedstock to a total product comprising a crude oil product and, in some embodiments, noncondensable gas. The inventions described herein also generally relate to compositions having novel combinations of components therein. Such compositions may be obtained using the systems and methods described herein. The invention provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a liquid mixture. at 25 ° C and 0.101 MPa, the crude oil feedstock having a TAN of at least 0.3 and at least one of the catalysts having a pore size distribution with an average pore diameter in a range of 90 Å to 180 Å. , with at least 60% of the total number of pores in the pore size distribution having a pore diameter within 45 µm of the average pore diameter, wherein the pore size distribution is as determined by ASTM Method D4282; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.3, at least one of the catalysts having a pore size distribution with an average pore diameter of at least 90  °, as determined. ASTM D4282 and the catalyst having a pore size distribution having, per gram of catalyst, from 0.0001 gram to 0.08 gram of: molybdenum, one or more molybdenum compounds, calculated as molybdenum weight or mixtures thereof ; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feedstock having a TAN of at least 0.3, as determined by ASTM D664, at least one of the catalysts having a pore size distribution with an average pore diameter of at least at least 180 Ã… as determined by ASTM Method D4282 and the catalyst having the pore size distribution comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof ; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feedstock having a TAN of at least 0.3 as determined by Method ASTM D664 and at least one of the catalysts comprises: (a) one or more Periodic Table Column 6 metals , one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof and (b) one or more Periodic Table Column 10 metals, one or more compounds of one or more Periodic Table Column 10 metals or mixtures thereof and wherein a column 10 total metal to column 6 total metal molar ratio is in a range of 1 to 10; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feedstock having a TAN of at least 0.3 and one or more catalysts comprising: (a) a first catalyst, the first catalyst having, per gram of first catalyst, of 0.0001 to 0.06 grams of one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals calculated as weight of metal or mixtures thereof and (b) a second catalyst, the second catalyst having, per gram of second catalyst, at least 0.02 grams of one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals, calculated as weightof metal or mixtures thereof; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a catalyst composition comprising: (a) one or more Periodic Table Column 5 metals, one or more compounds of one or more Periodic Table Column 5 metals or mixtures thereof; (b) a support material having a theta alumina content of at least 0.1 grams of theta alumina per gram of support material as determined by x-ray diffraction; and wherein the catalyst has a pore size distribution with an average pore diameter of at least 230 Å as determined by ASTM Method D4282. The invention also provides a catalyst composition comprising: (a) one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; (b) a support material having a theta alumina content of at least 0.1 grams of theta alumina per gram of support material as determined by x-ray diffraction; and wherein the catalyst has a pore size distribution with an average pore diameter of at least 230 Å as determined by ASTM Method D4282. The invention also provides a catalyst composition comprising: (a) one or more Periodic Table Column 5 metals, one or more compounds of one or more Periodic Table Column 5 metals, one or more Column 6 Table metals Periodic, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof, (b) a support material having a theta alumina content of at least 0.1 grams of theta alumina per gram of support material , as determined by x-ray diffraction; and wherein the catalyst has a pore size distribution with an average pore diameter of at least 230 Å as determined by ASTM Method D4282. The invention also provides a method of producing a catalyst comprising: combining a support with one or more metals to form a support / metal mixture, wherein the support comprises theta alumina and one or more of the metals comprising one or more Column metals. 5 of the Periodic Table, one or more compounds of one or more metals of Column 5 of the Periodic Table or mixtures thereof; heat treating the theta alumina / metal support mixture at a temperature of at least 400 ° C; and forming the catalyst, wherein the catalyst has a pore size distribution with an average pore diameter of at least 230 Å, as determined by ASTM Method D4282. The invention also provides a method of producing a catalyst comprising: combining a support with one or more metals to form a support / metal mixture, wherein the support comprises theta alumina and one or more of the metals comprising one or more Column metals. 6 of the Periodic Table, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; heat treating the theta alumina / metal support mixture at a temperature of at least 400 ° C; and forming the catalyst, wherein the catalyst has a pore size distribution with an average pore diameter of at least 230 Å, as determined by ASTM Method D4282. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.3, at least one of the catalysts having a pore size distribution with an average pore diameter of at least 180 Å as determined. by ASTM Method D4282 and the catalyst having the pore size distribution comprising theta alumina and one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts in the presence of a hydrogen source to produce a total product including the crude oil product, wherein Crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.3, the crude oil feed having an oxygen content of at least 0.0001 grams of oxygen. per gram of crude oil feed and at least one of the catalysts having a pore size distribution with an average pore diameter of at least 90 Å as determined by ASTM Method D4282; and controlling contact conditions to reduce TAN such that the crude oil product has a maximum TAN of 90% of the crude oil feed TAN and to reduce a content of organic oxygen containing compounds such that the crude oil product has an oxygen content of up to 90% of the oxygen content of the crude oil feed, where the TAN is as determined by ASTM Method D664 and the oxygen content is as determined by Method ASTM E385. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feedstock having a TAN of at least 0.1 and at least one of the catalysts having, per gram of catalyst, at least 0.001 gram of one or more metals from Column 6 of Table Periodic, one or more compounds of one or more metals from Column 6 of the Periodic Table, calculated as metal weight or mixtures thereof, and control contact conditions such that a net hourly space velocity in a contact zone is above 10 h ' 1 and the crude oil product has a TAN of at most 90% of the TAN of the crude oil feed where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts in the presence of a hydrogen source to produce a total product including the crude oil product, wherein 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 sulfur content of at least 0.0001 grams of sulfur per gram of crude oil feed and at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof and control the contact conditions as such. that during contact the crude oil feed absorbs molecular hydrogen at a selected rate to inhibit phase separation of the crude oil feed upon contact, the net hourly space velocity in one or more contact zones is above 10 h "1, the crude oil product having a maximum TAN of 90% of the crude oil feed TAN and the crude oil product having a sulfur content of 70 to 130% of the sulfur content of the crude oil feed, wherein the TAN is as determined by ASTM D664 Method and the sulfur content is as determined by ASTM D4294 Method. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts in the presence of a hydrogen gas source to produce a total product including the crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa; and controlling contact conditions such that the crude oil feed during contact absorbs hydrogen at a selected rate to inhibit phase separation of the crude oil feed during contact. The invention also provides a method of producing a product of crude oil, comprising: contacting a hydrogen crude oil feed in the presence of one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa; and controlling contact conditions such that the crude oil feed is contacted with hydrogen in a first hydrogen absorption condition and then in a second hydrogen absorption condition, the first hydrogen absorption condition being different from the second absorption condition. Hydrogen absorption and net hydrogen absorption in the first hydrogen absorption condition are controlled to inhibit the P value of a crude oil feed / total product mixture from decreasing below 1.5 and one or more properties of the crude oil product changes by a maximum of 90% with respect to the respective one or more properties of the low oil feedstock. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts at a first temperature followed by contacting a second temperature to produce a total product including the crude oil product. wherein the crude oil product is a liquid mixture at 25 ° C at 0.101 MPa, the crude oil feed having a TAN of at least 0.3; and control contact conditions such that the first contact temperature is at least 30 ° C lower than the second contact temperature and the very petroleum product has a maximum TAN of 90% relative to the petroleum feed TAN however, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a fine petroleum product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.3, the crude oil feed having a sulfur content of at least 0.0001 grams of sulfur per gram of crude oil feed and at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and controlling contact conditions such that the crude oil product has a TAN of up to 90% of the crude oil feed TAN and the crude oil product has a sulfur content of 70 to 130% of the feed sulfur content crude oil, where the TAN is as determined by ASTM D664 Method and the sulfur content as as determined by ASTM D4294 Method. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a 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 gram residue per gram of crude oil feed and at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and controlling contact conditions such that the crude oil product has a TAN of up to 90% of the crude oil feed TAN, the crude oil product has a residue content of 70 to 130% of the feed residue content crude oil and wherein the TAN is as determined by ASTM D664 Method and the residue content is as determined by ASTM D5307 Method. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.1, the crude oil feed having a VGO content of at least 0.1 gram of VGO per gram of crude oil feed and at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and controlling contact conditions such that the crude oil product has a TAN of up to 90% of the crude oil feed TAN, the crude oil product has a VGO content of 70 to 130% of the feed VGO content crude oil and where the VGO content is as determined by ASTM Method D5307. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.3 and at least one of the catalysts is obtainable by: combining a support with one or more of the Periodic Table Column 6 metals, one or more 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 contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0.101 MPa, the crude oil feed having a viscosity of at least 10 cSt at 37.8 ° C (100 ° F), the crude oil feed having an API gravity of at least 10 and at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and controlling contact conditions such that the crude oil product has a viscosity at 37.8 ° C of at most .90% of the viscosity of the crude oil feed at 37.8 ° C and the crude oil product having a gravity API 70 to 130% of API gravity from crude oil feed, where API gravity is as determined by ASTM D6822 Method and viscosity is as determined by ASTM D2669 Method. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.1 and one or more catalysts comprising: at least one catalyst comprising vanadium, one or more vanadium compounds or mixtures thereof and a catalyst further, wherein the additional catalyst comprises one or more column 6 metals, one or more compounds of one or more column 6 metals or combinations thereof; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa and the crude oil feed has a TAN of at least 0.1; generate hydrogen during contact; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. liquid at 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.1 and at least one of the catalysts comprising vanadium, one or more vanadium compounds or mixtures thereof; and controlling contact conditions such that a contact temperature is at least 200 ° C and the crude oil product has a maximum TAN of 90% of the crude oil feed TAN, where the TAN is as determined by the ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. liquid at 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.1 and at least one of the catalysts comprising vanadium, one or more vanadium compounds or mixtures thereof; providing a gas comprising a hydrogen source during contact, the gas flow being supplied in a direction that is contrary to the flow of the crude oil feed; and controlling contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN, where the TAN is as determined by ASTM Method D664. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed having, per gram of crude oil feed, a total Ni / V / Fe content of at least 0.00002 grams, at least one of the vanadium catalysts, or more vanadium compounds or mixtures thereof and the vanadium catalyst having a pore size distribution with an average pore diameter of at least 180 Å; and control contact conditions such that the crude oil product has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed where the Ni / V / Fe is as determined by ASTM Method D5708. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, at least one of the catalysts comprising vanadium, one or more vanadium compounds or mixtures thereof, the crude oil feed comprising 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 the crude oil feed having, per gram of crude oil feed, a total alkali metal and alkaline earth metal content in the metal salts of the organic acids of at least 0.00001 gram; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the organic acid metal salts of up to 90% of the alkali metal and alkaline earth metal content in the metal salts. organic acids in the crude oil feed, wherein the alkali metal and alkaline earth metal content in the metal salts of the organic acids is determined by Method ASTM D 1318. The invention also provides a method of producing a very petroleum product comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, the crude oil feed comprising a 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 of these, the crude oil feed having, per gram of crude oil feed, a total alkali metal and alkaline earth metal content in the metal salts of organic acids of at least 0.00001 gram and at least one of the catalysts having a distribution pore size with an average pore diameter in a range of 90  to 180 Ã…, with at least 60% of the total number of pores in the pore size distribution having a pore diameter within 45 Ã… of the average pore diameter wherein the pore size distribution is as determined by ASTM Method D4282; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in the metal salts of organic acids of the crude oil feed, wherein the alkali metal and alkaline earth metal content in the metal salts of the organic acids is as determined by Method ASTM D 1318. The invention also provides a method of producing a crude oil product comprising : contacting a crude oil feed with one or more catalysts to produce a total product including crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, the crude oil feed having per gram of crude oil feed a total Ni / V / Fe content of at least 0,00002 grams and at least one of the catalysts having a distribution of pore size with an average pore diameter in a range of 90  ° to 180 µ, with at least 60% of the total number of pores in the pore size distribution having a pore diameter within 45 Ã… of the pore diameter medium, wherein the pore size distribution is as determined by ASTM Method D4282; and control the contact conditions such that the crude oil product has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed where the Ni / V content / Fe is as determined by ASTM Method D5708. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0,101 MPa, the crude oil feed having a total alkali and alkaline earth metal content in the metal salts of organic acids of at least 0,00001 grams per gram of crude oil feed, at least one of the catalysts having a pore size distribution with an average pore diameter of at least 180 Å as determined by ASTM Method D4282 and the catalyst having the pore size distribution comprising one or more Periodic Table Column 6 metals, a or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in the metal salts of organic acids in the crude oil feed, wherein the alkali metal and alkaline earth metal content in the metal salts of organic acids is as determined by ASTM Method D1318. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed comprising 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 crude oil having, per gram of crude oil feed, a total alkaline and alkaline earth metal content in the metal salts of organic acids of at least 0.00001 gram, at least one of the catalysts having a pore size distribution with a average pore diameter of at least 230 Å as determined by ASTM Method D4282 and the catalyst having a pore size distribution comprising giving one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in the metal salts of organic acids in the crude oil feed, wherein the alkali metal and alkaline earth metal content in the metal salts of organic acids is as determined by ASTM Method D1318. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed having a total Ni / V / Fe content of at least 0.00002 grams Ni / V / Fe per gram of crude oil feed, at least one of the catalysts having a pore size distribution with an average pore diameter of at least 230 Å as determined by Method ASTM D4282 and the catalyst having a pore size distribution comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more metals from Column 6 of the Periodic Table or mixtures thereof; and control contact conditions such that the crude oil product has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed where the Ni / V / Fe is as determined by ASTM Method D5708. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0.101 MPa, the crude oil feed comprising 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, the feed of crude oil having a total content per gram of crude oil feed of alkali metal and alkaline earth metal in metal salts of organic acids of at least 0.00001 gram, at least one of the catalysts having a pore size distribution with an average pore diameter of at least 90  ° as determined by ASTM Method D4282 and the catalyst having the pore size distribution has a content of total molybdenum per gram of catalyst from 0,0001 grams to 0,3 grams of molybdenum, one or more molybdenum compounds, calculated as molybdenum weight or mixtures thereof; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in the metal salts of organic acids in the crude oil feed, wherein the alkali metal and alkaline earth metal content in the metal salts of organic acids is as determined by ASTM Method D1318. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed having a TAN of at least 0.3 and the crude oil feed having, per gram of crude oil feed, a total Ni / V / Fe content of at least 0.00002 gram, at least one of the catalysts having a pore size distribution with an average pore diameter of at least 90  °, as determined by ASTM Method D4282 and the catalyst having a total molybdenum content per gram of catalyst, from 0.0001 grams to 0.3 grams of. molybdenum, one or more molybdenum compounds, calculated as molybdenum weight or mixtures thereof; and control contact conditions such that the crude oil product has a TAN of at most 90% of the crude oil feed TAN and the crude oil product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude oil feed where the Ni / V / Fe content is as determined by ASTM Method D5708 and TAN is as determined by ASTM Method D644. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed comprising 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 crude oil having a total content per gram of crude oil feed of alkali metal and alkaline earth metal in metal salts of organic acids of at least 0,00001 gram and at least one of the catalysts comprising: (a) one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and (b) one or more Periodic Table Column 10 metals, one or more compounds of one or more Periodic Table Column 10 metals or mixtures thereof, wherein a molar ratio of Column 10 total metal to Column total metal 6 is in a range from 1 to 10; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in the metal salts of organic acids in the very petroleum feed, wherein the alkali metal and alkaline earth metal content in the metal salts of the organic acids is as determined by Method ASTM D 1318. The invention also provides a method of producing a crude oil product comprising : contacting a crude oil feed with one or more catalysts to produce a total product including 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 total Ni / V / Fe content of at least 0.00002 gram Ni / V / Fe per gram of crude oil feed and at least one of the catalysts comprises: (a ) one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and (b) one or more Periodic Table Column 10 metals, one or more compounds of one or more Periodic Table Column 10 metals or mixtures thereof, wherein a molar ratio of Column 10 total metal to Column total metal 6 is in a range from 1 to 10; and control contact conditions such that the crude oil product has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed where the Ni / V / Fe is as determined by ASTM Method D5708. The invention also provides a method of producing a crude oil product, comprising; contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, the crude oil feed comprising a 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, the crude oil feed having, per gram of crude oil feed, a total content of alkali metal and alkaline earth metal, in the metal salts of organic acids of at least 0.00001 gram and one or more catalysts comprising: (a) a first catalyst, the first catalyst having, per gram of first catalyst, 0.0001 0.06 gram of one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals, calculated as weight of metal or mixtures thereof and (b) a second catalyst, the second catalyst having, per gram of second catalyst, at least 0.02 grams of one or more Periodic Table Column 6 metals, one or more compounds of one or more Column 6 metals of Periodic Table, calculated as weight of metal or mixtures thereof; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in the metal salts of organic acids in the crude oil feed, wherein the alkali metal and alkaline earth metal content in the metal salts of organic acids is as determined by ASTM Method D1318. The invention also provides a method of producing a fine petroleum product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0.101 MPa, the crude oil feed comprising 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, the feed of crude oil having, per gram of petroleum feedstock, a total alkali metal and alkaline earth metal content in the metal salts of organic acids of at least 0,00001 gram and at least one of the catalysts having per gram of catalyst at least least 0.001 gram of one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals, calculated as weight of m etal or mixtures thereof; and controlling the contact conditions such that the net hourly space velocity in a contact zone is above 10 h'1 and the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of the organic acids of 90% or more of the alkali metal and alkaline earth metal content in the metal salts of organic acids in the crude oil feed, where the alkali metal and alkaline earth metal content in the metal salts of organic acids is as determined by the ASTM Method D1318. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. At 25 ° C and 0.101 MPa, the crude oil feed having, per gram of crude oil feed, a total Ni / V / Fe content of at least 0.00002 grams, at least one of the catalysts has, per gram of at least 0.001 gram of one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals, calculated as weight of metal or mixtures thereof and control contact conditions as that the net hourly space velocity in a contact zone is above 10 h'1 and the crude oil product has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the feed. brut oil wherein the Ni / V / Fe content is as determined by ASTM Method D5708. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0,101 MPa, the crude oil feed having, per gram of crude oil 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 at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof and control contact conditions such that the crude oil product have an oxygen content of up to 90% of the oxygen content of the crude oil feed and the crude oil product has a sulfur content of 70 to 130% of the sulfur content of the feed. crude oil, wherein the oxygen content is as determined by ASTM Method E385 and the sulfur content is as determined by Method ASTM D4294. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0,101 MPa, the crude oil feed having, per gram of crude oil feed, a total Ni / V / Fe content of at least 0,00002 grams and a sulfur content of at least 0, 0001 gram of sulfur and at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof and control contact conditions such that the product crude oil has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed and the crude oil product has a sulfur content of 70 to 130% of the feed sulfur Crude oil, where the Ni / V / Fe content is as determined by ASTM D5708 Method and the sulfur content is as determined by ASTM D4294 Method. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0.101 MPa, the crude oil feed comprising 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, the feed of crude oil having, per gram of crude oil feed, a total alkali metal and an alkaline earth metal content in metal salts of organic acids of at least 0,00001 gram and a residue content of at least 0,1 gram residue and at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixture s of these; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in the metal salts of organic acids in the crude oil feed, the crude oil product has a residue content of 70 to 130% of the residue content of the crude oil feed and where the alkali metal and alkaline earth metal content in the acid metal salts Organic matter is as determined by ASTM Method D1318 and residue content is as determined by Method ASTMD5307. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed having, per gram of crude oil feed, a residue content of at least 0.1 gram residue and a total Ni / V / Fe content of at least 0.00002 gram and at least one of the catalysts comprising one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof and control contact conditions such that the product crude oil has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed and the crude oil product has a residue content of 70 to 130% of the feed residue crude oil, where the Ni / V / Fe content is as determined by ASTM Method D5708 and the residue content is as determined by Method ASTM D5307. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. 25 ° C and 0.101 MPa, the crude oil feed comprising 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, the feed of crude oil having, per gram of crude oil feed, a vacuum gas oil (“VGO”) content of at least 0.1 grams and a total alkali metal and alkaline earth metal content in the metal salts of organic acids 0.0001 gram and at least one of the catalysts comprises one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof and control the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and earth alkaline metal content in the metal salts of organic acids in the crude oil feed and the crude oil product has a VGO content of 70 to 130% of the VGO content of the crude oil feed, where the VGO content is as determined by ASTM D5307 Method and the of alkali metal and alkaline earth metal in the metal salts of organic acids is as determined by Method ASTM 01318. The invention also provides a method of producing a crude oil product comprising: contacting a crude oil feed with one or more catalysts for produce a total product including the crude oil product, where the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, Crude oil content having, per gram of crude oil feed, a total Ni / V / Fe content of at least 0.00002 grams and a VGO content of at least 0.1 grams and at least one of the catalysts comprises a or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and control contact conditions such that the crude oil product has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed and the crude oil product has a 70 to 130% of the VGO content of the crude oil feed, where the VGO content is as determined by ASTM D5307 and the Ni / V / Fe content is as determined by ASTM D5708. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. at 25 ° C and 0.101 MPa, the crude oil feed comprising 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 crude oil having, per gram of petroleum feedstock, a total alkali metal and alkaline earth metal content in the metal salts of organic acids of at least 0,00001 gram and at least one of the catalysts is obtainable by: combining a support with one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof to produce a catalyst slider and forming the catalyst by heating a catalyst precursor in the presence of one or more sulfur-containing compounds at a temperature below 400 ° C; and controlling the contact conditions such that the crude oil product has a total alkali metal and alkaline earth metal content in the metal salts of organic acids of up to 90% of the alkali metal and alkaline earth metal content in the metal salts of organic acids in the crude oil feed, where the alkali metal and alkaline earth metal content in the metal salts of organic acids is determined by ASTM Method D1318. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is a mixture. At 25 ° C and 0.101 MPa, the crude oil feed having, per gram of crude oil feed, a total Ni / V / Fe content of at least 0.00002 grams and at least one of the catalysts is obtainable by: combining a support with one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals 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 400 ° C; and control contact conditions such that the crude oil product has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed where the Ni / V content / Fe is as determined by ASTM Method D5708. The invention also provides a crude oil composition having, per gram of crude oil composition: at least 0.001 grams of hydrocarbons having a boiling range distribution between 95 ° C and 260 ° C at 0.101 MPa; at least 0.001 grams of hydrocarbons having a boiling range distribution between 260 ° C and 320 ° C at 0.101 MPa; at least 0.001 grams of hydrocarbons having a boiling range distribution between 320 ° C and 650 ° C at 0.101 MPa; and more than 0 gram, but less than 0.01 gram of one or more catalysts per gram of crude oil product. The invention also provides a crude oil composition having, per gram of composition: at least 0.01 gram of sulfur as determined by ASTM Method D4294; at least 0.2 grams of residue as determined by ASTM Method D5307 and the composition has a weight ratio of MCR content to C5 asphaltenes content of at least 1.5, wherein the 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 of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is condensable to 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 at least one of the catalysts is obtainable by: combining a support with one or more Column 6 metals. 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 contact conditions such that the crude oil product has a MCR content of at most 90% of the MCR content of the crude oil feed, where the MCR content is as determined by ASTM Method D4530. The invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product including the crude oil product, wherein the crude oil product is condensable to 25 ° C and 0.101 MPa, the crude oil feed has an MCR content of at least 0.001 grams per gram of crude oil feed and at least one of the catalysts having a pore size distribution with an average pore diameter in a range. 70 to 180 Å, with at least 60% of the total number of pores in the pore size distribution having a pore diameter within 45 Å of the average pore diameter, wherein the pore size distribution is as determined by ASTM Method D4282; and controlling contact conditions such that the crude oil product has a MCR of up to 90% of the MCR of the crude oil feed where MCR is as determined by ASTM Method D4530. The invention also provides a crude oil composition having, per gram of composition: at most 0.004 grams of oxygen as determined by ASTM Method E385; at most 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 having, per gram of composition: at most 0.004 grams of oxygen as determined by ASTM Method E385; at most 0.003 grams of sulfur as determined by ASTM Method D4294; a maximum of 0.04 grams of basic nitrogen as determined by ASTM Method D2896;

at least 0.2 grams of residue as determined by ASTM Method D5307; and the composition has a maximum TAN of 0.5 as determined by ASTM Method D664. The invention also provides a crude oil composition having, per gram of composition: at least 0.001 gram of sulfur as determined by ASTM Method D4294; at least 0.2 grams of residue as determined by ASTM Method D5307; and the composition having a weight ratio of the MCR content to the C5 asphaltenes content of at least 1.5 and the composition having a TAN of at most 0.5, where the TAN is as determined by ASTM D664 Method; MCR weight is as determined by ASTM Method D4530 and C5 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 according to the invention, the feed of crude oil which: (a) has not been treated in a refinery, distilled and / or fractionally distilled ; (b) has components having a carbon number above 4 and the crude oil feed has at least 0.5 grams of such components per gram of crude oil feed; (c) comprises hydrocarbons, a portion of which have: a boiling range distribution below 100 ° C at 0.101 MPa, a boiling range distribution between 100 ° C and 200 ° C at 0.101 MPa, a range distribution boiling 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 a boiling range distribution between 400 ° C and 650 ° C at 0.101 MPa; (d) has per gram of crude oil feed at least: 0.001 gram hydrocarbon having a boiling range distribution below 100 ° C at 0.101 MPa, 0.001 gram hydrocarbon having a boiling range distribution between 100 ° C C and 200 ° C at 0.101 MPa, 0.001 gram of hydrocarbons having a boiling range distribution between 200 ° C and 300 ° C at 0.101 MPa, 0.001 gram of hydrocarbons having a boiling range distribution between 300 ° C and 400 ° C at 0.101 MPa and 0.001 grams of hydrocarbons having a boiling range distribution between 400 ° C and 650 ° 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) comprises nickel, vanadium and iron; (h) has at least 0.00002 grams total Ni / V / Fe per gram of crude oil feed; (i) comprises sulfur; (j) has at least 0.0001 grams or 0.05 grams of sulfur per gram of crude oil feed; (k) has at least 0.001 grams of VGO per gram of crude oil feed; (1) has at least 0.1 gram residue per gram of crude oil 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) comprises 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 according to the invention, crude oil feed which is obtainable by the removal of naphtha and more volatile compounds than naphtha from a petroleum. gross.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, a method of contacting a crude oil feed with one or more catalysts to produce a total product including the product. crude oil feedstock where the crude oil feed and crude oil product both have a C5 asphaltene content and an MCR content, and: (a) a sum of a C5 asphaltene content from the crude oil feed and MCR content of the crude oil feed is S, a sum of an asphaltene content C5 of the crude oil product and a MCR content of the crude oil product is S 'and the contact conditions are controlled such that S' is at most 99 % S; and / or (b) the contact conditions are controlled such that a weight ratio of a crude oil product MCR content to a crude oil product C5 asphaltene content is in the range 1.2 to 2, 0 or 1.3 to 1.9.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, a hydrogen source, wherein the hydrogen source is: (a) gas; (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 according to the invention, a method of contacting a crude oil feed with one or more catalysts to produce a total product including the product. crude oil where the crude oil feed is contacted in a contact zone that is in a facility offshore or linked to it.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, a method comprising contacting a crude oil feed with one or more catalysts in the presence of a gas and / or a hydrogen source and control the contact conditions such that: (a) a ratio of a gaseous hydrogen source to the crude oil feed is in the range of 5 to 800 normal cubic meters of gaseous hydrogen source per cubic meter of crude oil feed contacted with one or more of the catalysts; (b) the selected rate of net hydrogen absorption is controlled by varying a partial pressure of the hydrogen source; (c) the hydrogen absorption rate is such that the very petroleum product has a TAN of less than 0.3, but the hydrogen absorption is less than an amount of hydrogen absorption that will cause substantial phase separation between the crude oil feed and total product during contact; (d) the selected hydrogen absorption rate is in the range of 1 to 30 or 1 to 80 normal cubic meters of the hydrogen source per cubic meter of crude oil feed; (e) the net hourly space velocity of gas and / or the hydrogen source is at least 11 tf1, at least 15 h'1 or at most 20 h'1; (f) a partial pressure of gas and / or hydrogen source is controlled during contact; (g) a contact temperature is in the range of 50 to 500 ° C, a total net hourly space velocity of the gas and / or hydrogen source is in a range of 0.1 to 30 h'1 and the total pressure the gas and / or hydrogen source is in the range 1.0 to 20 MPa; (h) a flow of gas and / or hydrogen source is in a direction that is contrary to a flow of crude oil feed; (i) the crude oil product has an H / C of 70 to 130% of an H / C of the crude oil feedstock; (j) the absorption of hydrogen from the crude oil feedstock is a maximum of 80 and / or in the range of 1 to 80 or 1 to 50 normal cubic meters of hydrogen per cubic meter of crude oil feedstock; (k) the crude oil product has a total Ni / V / Fe content of no more than 90%, a maximum of 50% or a maximum of 10% of the Ni / V / Fe content of the crude oil feedstock; (1) the crude oil product has a sulfur content of 70 to 130% or 80 to 120% of the sulfur content of the crude oil feedstock; (m) the crude oil product has a VGO content of 70 to 130% or 90 to 110% of the VGO content of the crude oil feed; (η) the crude oil product has a residue content of 70 to 130% or 90 to 110% of the residue content of the crude oil feed; (o) the crude oil product has a maximum oxygen content of 90%, a maximum of 70%, a maximum of 50%, a maximum of 40% or a maximum of 10% of the oxygen content of the crude oil feed; (p) the crude oil product has a total alkali metal and alkaline earth metal content, in metal salts of organic acids of not more than 90%, not more than 50% or not more than 10% of alkaline and alkaline earth metal content in the metal salts of organic acids in the crude oil feed; (q) a P value of the crude oil feed during contact is at least 1.5; (r) the crude oil product has a viscosity at 37.8 ° C of a maximum of 90%, a maximum of 50% or a maximum of 10% of the viscosity of the 37.8 ° C crude oil feed; (s) the crude oil product has an API gravity of 70 to 130% of an API gravity of the crude oil feed; and / or (t) the crude oil product has a maximum TAN of 90%, a maximum of 50%, a maximum of 30%, a maximum of 20% or a maximum of 10% of the TAN of the crude oil feedstock and / or in a range from 0.001 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 according to the invention, a method comprising contacting a crude oil feed with one or more catalysts and controlling contact conditions to reduce a content of organic oxygen containing compounds in which: (a) a selected organic oxygen content is reduced such that the crude oil product has a maximum oxygen content of 90% of the oxygen content of the crude oil 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 compounds containing organic oxygen comprises a metal salt of a carboxylic acid, wherein the metal comprises one or more Periodic Table Column 12 metals; (f) the crude oil product has a content of non-carboxylic organic compounds of up to 90% of the content of non-carboxylic organic compounds in the crude oil feed; and / or (g) at least one of the oxygen-containing compounds in the crude oil feed is derived from naphthenic acid or non-carboxylic-containing organic oxygen compounds.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, a method comprising contacting a crude oil feed with one or more catalysts wherein: (a) the feed crude oil is contacted with at least one of the catalysts at a first temperature followed by contact at a second temperature and contact conditions are controlled such that the first contact temperature is at least 30 ° C lower than the second contact temperature. contact; (b) the crude oil feed is contacted with hydrogen in a first hydrogen absorption condition and then in a second hydrogen absorption condition and the temperature of the first absorption condition is at least 30 ° C lower than the temperature of the second absorption condition; (c) the crude oil feed is contacted with at least one of the catalysts at a first temperature followed by contact at a second temperature and contact conditions are controlled such that the first contact temperature is at most 200 ° C lower. than the second contact temperature; (d) hydrogen gas is generated during contact; (e) hydrogen gas is generated during contact and contact conditions are also controlled such that the crude oil feed absorbs at least a portion of the generated hydrogen; (f) the crude oil feed is contacted with a first and second catalyst and the contact of the crude oil feed and the first catalyst forms an initial crude oil product and the initial crude oil product has a maximum TAN of 90% of the TAN of the crude oil feed; and the contact of the initial crude oil product and the second catalyst forms a crude oil product and wherein the crude oil product has a maximum TAN of 90% of the initial crude oil TAN; (g) contact is made in a stacked bed reactor; (h) the contact is made in a boiling bed reactor; (i) the crude oil feed is contacted with an additional catalyst subsequent to contact with one or more catalysts; (j) one or more of the catalysts is a vanadium catalyst and the crude oil feed is contacted with an additional catalyst in the presence of a hydrogen source subsequent to contact with the vanadium catalyst; (k) hydrogen is generated at a rate in the range of 1 to 20 normal cubic meters per cubic meter of crude oil feed; (1) hydrogen is generated during contact, crude oil feed is contacted with an additional catalyst in the presence of a gas and at least a portion of the hydrogen generated and contact conditions are also controlled such that a gas flow is present. in a direction that is contrary to the flow of crude oil feed and a flow of generated hydrogen; (m) the crude oil feed is contacted with a vanadium catalyst at a first temperature and subsequently with an additional catalyst at a second temperature and contact conditions are controlled such that the first temperature is at least 30 ° C lower than that the second temperature; (η) hydrogen gas is generated during contact, the crude oil feed is contacted with an additional catalyst and contact conditions are controlled such that the additional catalyst absorbs at least a portion of the generated hydrogen; and / or (o) the crude oil feed is subsequently contacted with an additional catalyst at a second temperature and 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 according to the invention, a method comprising contacting a crude oil feed with one or more catalysts wherein: (a) the catalyst is a sustained catalyst and the support comprises alumina, silica, silica alumina, titanium oxide, zirconium oxide, magnesium oxide or mixtures thereof, (b) the catalyst is a sustained catalyst and the support is porous; (c) the method further comprises an additional catalyst which has been heat treated at a temperature above 400 ° C prior to sulfurization; (d) a life of at least one of the catalysts is at least 0.5 year; and / or (e) at least one of the catalysts is in a fixed or crushed bed in the crude oil feedstock.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, a method comprising contacting a crude oil feed with one or more catalysts, at least one of the catalysts is a sustained catalyst or a bulky metal catalyst and the sustained catalyst or bulky metal catalyst: (a) comprises one or more metals from Columns 5 to 10 of the Periodic Table, one or more compounds of one or more metals from Columns of 5 to 10 of the Periodic Table or mixtures thereof, (b) has per gram of catalyst at least 0.0001 gram, from 0.0001 to 0.6 gram or from 0.001 to 0.3 gram of one or more Column metals from 5 to 10 of the Periodic Table, one or more compounds of one or more metals from Columns 5 to 10 of the Periodic Table or mixtures thereof; (c) comprises one or more metals from Columns 6 to 10 of the Periodic Table, one or more compounds of one or more metals from Columns 6 to 10 of the Periodic Table or mixtures thereof; (d) comprises one or more metals from Columns 7 to 10 of the Periodic Table, one or more compounds of one or more metals from Columns 7 to 10 of the Periodic Table or mixtures thereof; (e) has, per gram of catalyst, from 0.0001 to 0.6 gram or from 0.001 to 0.3 gram of one or more metals from Columns 7 to 10 of the Periodic Table, one or more compounds of one or more metals from Columns 7 to 10 of the Periodic Table or mixtures thereof; (f) comprises one or more metals from Columns 5 to 6 of the Periodic Table; one or more compounds of one or more metals from Columns 5 to 6 of the Periodic Table or mixtures thereof; (g) comprises one or more Periodic Table Column 5 metals, one or more compounds of one or more Periodic Table Column 5 metals or mixtures thereof, (h) has per gram of catalyst at least 0.0001 gram 0.0001 to 0.6 gram, 0.001 to 0.3 gram, 0.005 to 0.1 gram, or 0.01 to 0.08 gram of one or more metals from Column 5 of the Periodic Table, one or more more compounds of one or more metals from Column 5 of the Periodic Table or mixtures thereof; (i) comprises one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof, (j) has per gram of catalyst from 0.0001 to 0 , 6 grams, 0.001 to 0.3 grams, 0.005 to 0.1 grams, 0.01 to 0.08 grams 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; (k) comprises one or more Periodic Table Column 10 metals, one or more compounds of one or more Periodic Table Column 10 metals or mixtures thereof, (1) has, per gram of catalyst, from 0.0001 to 0 , 6 grams or from 0.001 to 0.3 grams of one or more Periodic Table Column 10 metals, one or more compounds of one or more Periodic Table Column 10 metals 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) comprises molybdenum, one or more molybdenum compounds or mixtures thereof; (q) has, per gram of catalyst, from 0.001 to 0.3 gram or from 0.005 to 0.1 gram of molybdenum, one or more molybdenum compounds or mixtures thereof, (r) comprises tungsten, one or more tungsten compounds or mixtures thereof; (s) has, per gram of catalyst, from 0.001 to 0.3 gram of tungsten, one or more tungsten compounds or mixtures thereof, (t) comprises one or more Periodic Table Column 6 metals and one or more Tungsten metals Column 10 of the Periodic Table, wherein the molar ratio of the metal of column 10 to the metal of column 6 is 1 to 5; (u) comprises one or more Periodic Table Column 15 elements, one or more compounds of one or more Periodic Table Column 15 elements or mixtures thereof; (v) has, per gram of catalyst, from 0.00001 to 0.06 gram of one or more Periodic Table Column 15 elements, one or more compounds of one or more Periodic Table Column 15 elements 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 grams 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 according to the invention, a method of forming a catalyst comprising combining a support with one or more metals to form a support / metal mixture. wherein the support comprises theta alumina and heat treating the theta alumina / metal support mixture at a temperature of at least 400 ° C and further comprising: (a) combining the support / metal mixture with water to form a paste and extrude the folder; (b) obtaining theta alumina by heat treating the 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 according to the invention, a method comprising contacting a crude oil feed with one or more catalysts, wherein the size distribution of The pore of at least one of the catalysts has: (a) an average pore diameter of at least 60 Å, at least 90 Å, at least 180 Å, at least 200 Å, at least 230 Å, at least 300 Å 230 Â, at most 500 Â or in a range of 90 to 180 Â, 100 to 140 Â, 120 to 130 Â, 230 to 250 Â, 180 to 500 Â, 230 to 500 Â; or from 60 to 300 Å; (b) at least 60% of the total number of pores has a pore diameter within 45 Å, 35 Å or 25 Å, of the average pore diameter; (c) a surface 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 of at least 220 m2 / g; and / or (d) a total pore volume of at least 0.3 cm3 / g, at least 0.4 cm3 / g, at least 0.5 cm3 / g or at least 0.7 cm3 / g .

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, a method comprising contacting a crude oil feed with one or more sustained 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 per gram support at least 0.5 gram gamma alumina; (d) has per gram support at least 0.3 gram or at least 0.5 gram theta alumina; (e) comprises alpha alumina, gamma alumina, delta alumina, theta alumina or a mixture thereof; (f) has a maximum of 0.1 gram of alpha alumina per gram of support.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, a vanadium catalyst which: (a) has a pore size distribution with an average pore diameter of at least 60 Â; (b) comprises a support, the support comprising theta alumina and the vanadium catalyst has a pore size distribution with an average pore diameter of at least 60 Å; (c) comprises one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; and / or (d) has, per gram of catalyst, at least 0.001 gram of one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, a crude oil product having: (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) not more than 0,000009 grams of alkali metal and alkaline earth metal in metal salts of organic acids per gram of crude oil product; (c) a maximum of 0.00002 grams of Ni / V / Fe per gram of crude oil product; and / or (d) more than 0 gram, but less than 0.01 gram, of at least one of the catalysts per gram of crude oil product.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to 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 according to the invention, a method comprising contacting a crude oil feed with one or more catalysts to produce a total product comprising a crude oil product, the method further comprising: (a) combining the crude oil product with a crude oil that is the same or different from the crude oil feed to form a suitable mixture for transportation; (b) combining the crude oil product with a crude oil that is the same or different from the crude oil feedstock to form a suitable mixture for the treatment facilities; (c) fractionate the crude oil product; and / or (d) fractionate the crude oil product into one or more distillate fractions and produce 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 according to the invention, a sustained catalyst composition which: (a) is at least 0.3 grams or at least 0, 5 gram of alumina theta per gram of support; (b) comprises delta alumina in the support; (c) has at most 0.1 gram of alpha alumina per gram of support; (d) has a pore size distribution with an average pore diameter of at least 230 Å; (e) has a pore volume of the pore size distribution of at least 0.3 cm / g or at least 0.7 cm / g; (f) has a surface area Τ Λ of at least 60 m / g or at least 90 m / g; (g) comprises one or more metals from Columns 7 to 10 of the Periodic Table, one or more compounds of one or more metals from Columns 7 to 10 of the Periodic Table or mixtures thereof; (h) comprises one or more Periodic Table Column 5 metals, one or more compounds of one or more Periodic Table Column 5 metals or mixtures thereof; (i) has per gram of catalyst from 0.0001 to 0.6 gram or 0.001 to 0.3 gram of one or more Column 5 metals, one or more Column 5 metal compounds or mixtures thereof; (j) comprises one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; (k) has per gram of catalyst from 0.0001 to 0.6 gram or 0.001 to 0.3 gram of one or more Column 6 metals, one or more Column 6 metal compounds or mixtures thereof, ( 1) comprises vanadium, one or more vanadium compounds or mixtures thereof; (m) comprises 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 according to the invention, a crude oil composition which: (a) has a TAN of at most 1, at most 0.5 , at most 0.3 or at most 0.1; (b) has per gram of composition at least 0.001 grams of hydrocarbons having a boiling range distribution 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 hydrocarbons having a boiling range distribution between 260 ° C and 320 ° C at 0.101 MPa; and at least 0.001 grams of hydrocarbons having a boiling range distribution 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) has, per gram of composition, at least 0.001 gram or at least 0.01 gram total nitrogen; and / or (e) has a maximum of 0.00005 grams of total 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 according to the invention, a very petroleum composition comprising one or more catalysts and at least one of the catalysts: (a) has a pore size distribution having an average pore diameter of at least 180 Å, a maximum of 500 Å and / or in a range of 90 to 180 Å, 100 to 140 Å, 120 to 130 Å; (b) has an average pore diameter of at least 90 Å, with more than 60% of the total number of pores in the pore size distribution having a pore diameter within 45 Å, 35 Å or 25 Å of the pore size. middle pore; (c) has a surface area of at least 100 m / g, at least 120 m / g or at least 220 m2 / g; (d) comprises a support; and the support comprises alumina, silica, silica alumina, titanium oxide, zirconium oxide, magnesium oxide, zeolite and / or mixtures thereof; (e) comprises one or more metals from Columns 5 to 10 of the Periodic Table, one or more compounds of one or more metals from Columns 5 to 10 of the Periodic Table or mixtures thereof; (f) comprises one or more Periodic Table Column 5 metals, one or more compounds of one or more Periodic Table Column 5 metals or mixtures thereof; (g) has per gram of catalyst at least 0.0001 gram of one or more column 5 metals, one or more column 5 metal compounds or mixtures thereof; (h) comprises one or more Periodic Table Column 6 metals, one or more compounds of one or more Periodic Table Column 6 metals or mixtures thereof; (i) has per gram of catalyst at least 0.0001 gram of one or more column 6 metals, one or more column 6 metal compounds or mixtures thereof; 0 comprises one or more Periodic Table Column 10 metals, one or more compounds of one or more Periodic Table Column 10 metals, or mixtures thereof and / or (k) comprises one or more Periodic Table Column 15 elements, one or more compounds of one or more elements of Periodic Table Column 15 or mixtures thereof.

In other embodiments, features of specific embodiments of the invention may be combined with features of other embodiments of the invention. For example, the features of one embodiment of the invention may be combined with features of any of the other embodiments.

In other embodiments, crude petroleum products are obtainable by any of the methods and systems described herein.

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

BRIEF DESCRIPTION OF DRAWINGS

The advantages of the present invention will be apparent to those skilled in the art with the benefit of the following detailed description and with reference to the accompanying drawings in which: FIG. 1 is a schematic of one embodiment of a contact system.

FIGS. 2A and 2B are schematic embodiments of contact systems that include two contact zones.

FIGS. 3A and 3B are schematic embodiments of contact systems that include three contact zones. FIG. 4 is a schematic of an embodiment of a separation zone in combination with a contact system. FIG. 5 is a schematic of an embodiment of a mixing zone in combination with a contact system. FIG. 6 is a schematic of an embodiment of a combination of a separation zone, a contact system and a mixing zone. FIG. 7 is a tabulation of representative properties of crude oil feed and fine oil product for one embodiment of contacting the crude oil feed with three catalysts. FIG. 8 is a graphical representation of the temperature versus weighted average bed length of an embodiment of contacting the crude oil feed with one or more catalysts. FIG. 9 is a tabulation of representative properties of crude oil feed and crude oil product for one embodiment of contacting the crude oil feed with two catalysts. FIG. 10 is another tabulation of representative properties of the well oil feed and the well oil product for one embodiment of contacting the well oil feed with two catalysts. FIG. 11 is a tabular feedstock and feedstock products for embodiments of contacting feedstock feeds with four different catalyst systems. FIG. 12 is a graphical representation of the P-value of short oil products versus driving time for embodiments of contacting short oil feeds with four different catalyst systems. FIG. 13 is a graphical representation of net hydrogen uptake by btto oil feeds versus driving time for embodiments of contacting btto oil feeds with four different catalyst systems. FIG. 14 is a graphical representation of the residue content, expressed as weight percent, of crude oil products versus driving time for embodiments of contacting crude oil feeds with four different catalyst systems. FIG. 15 is a graphical representation of the change in API gravity of crude oil products versus driving time for embodiments of contacting the crude oil feed 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 versus driving time for embodiments of contacting crude oil feeds with four different catalyst systems. FIG. 17 is a tabulation of representative properties of well oil feed and well oil products for embodiments of contacting well oil feed with catalyst systems that include various amounts of a molybdenum catalyst and a vanadium catalyst, with a catalyst system including a vanadium catalyst and a molybdenum / vanadium catalyst with glass beads. FIG. 18 is a tabulation of the feedstock properties and feedstock products for embodiments of contacting feedstock feeds with one or more catalysts at various net hourly spatial speeds. FIG. 19 is a tabulation of the properties of mixed oil feeds and mixed oil products for embodiments of contacting mixed oil feeds at various contact temperatures.

Although the invention is susceptible to various modifications and alternative embodiments, its specific embodiments are shown by way of example in the drawings. Drawings may not be to scale.

It is to be understood that the drawings and detailed description thereof are not intended to limit the invention to the particular form disclosed, but rather is intended to encompass 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 are described in more detail herein. The terms used herein are defined as follows. “ASTM” refers to the American Standard Testing and Materials.

“Gravity” refers to API gravity at 15.5 ° C (60 ° F). API severity is as determined by the ASTM D6822 Method. The atomic hydrogen percentage and the atomic carbon percentage of the crude oil feedstock and crude oil product are as determined by ASTM Method D5291.

Boiling range distributions for the crude oil feed, total product and / or crude oil product are as determined by ASTM Method D5307 unless otherwise noted. "C5 Asphaltenes" refers to asphaltenes that are insoluble in pentane. The C5 asphaltenes content is as determined by ASTM Method D2007. "Column X Metal (s)" refers to one or more Periodic Table Column X metals and / or one or more compounds of one or more Periodic Table Column X metals, where X is a number of column (for example, 1 to 12) of the Periodic Table. For example, "Column 6 metal (s)" refers to one or more Periodic Table Column 6 metals and / or one or more compounds of one or more Periodic Table Column 6 metals. “Column X Element (s)” refers to one or more Periodic Table Column X elements and / or one or more composed of one or more Periodic Table Column X elements, where X is a number of column (for example, 13 to 18) of the Periodic Table. For example, "Column 15 Element (s)" refers to one or more elements of Periodic Table Column 15 and / or one or more composed of one or more Periodic Table Column 15 elements.

Within the scope of this application, the weight of a Periodic Table metal, the weight of a compound of a Periodic Table metal, the weight of a Periodic Table element, or the weight of a compound of a Periodic Table element is calculated as metal weight or the weight of the element.

For example, if 0.1 gram Mo03 is used per gram catalyst, the calculated weight of molybdenum metal in the catalyst is 0.067 gram per gram catalyst. “Content” refers to the weight of a component in a substrate (for example, a crude oil feed, a total product or a crude oil product) expressed as a weight fraction or weight percentage based on the total substrate weight. . “Wtppm” refers to parts per million by weight. “Crude Oil / Total Product Feed Mixture” refers to the mixture that comes into contact with the catalyst during the process. "Distillate" refers to hydrocarbons having a boiling range distribution between 204 ° C (400 ° F) and 343 ° C (650 ° F) at 0.101 MPa. The distillate content is as determined by ASTM Method D5307. "Heteroatoms" refers to oxygen, nitrogen and / or sulfur contained in the molecular structure of a hydrocarbon. The heteroatom content is as determined by ASTM Method 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 when in the presence of a crude oil feed and catalyst react to provide hydrogen to the compound (s) in the crude oil feed. A source of hydrogen may include, but is not limited to hydrocarbons (e.g., C1 to C4 hydrocarbons such as methane, ethane, propane, butane), water or mixtures thereof. A mass balance can be conducted to assess the net amount of hydrogen supplied to the compound (s) in the crude oil feed. “Flat plate crush strength” refers to the compressive force required to crush a catalyst. Flat plate crush strength is as determined by ASTM Method D4179. “LHSV” refers to a volumetric net feed rate per total catalyst volume and is expressed in hours (h'1). The total catalyst volume is calculated by the sum of all 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, hereinafter referred to as "STP") or a composition that includes a combination of a or more compounds that are liquid in STP with one or more compounds that are solid in STP. "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 the metal salts of organic acids is as determined by ASTM Method D133.

“Micro Carbon Residue” (“MCR”) content refers to an amount of carbon residue that remains after evaporation and pyrolysis of a substrate. The MCR content is as determined by Method ASTMD4530. "Naphtha" refers to hydrocarbon components with a boiling range distribution 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. Ni / V / Fe content is as determined by ASTM Method D5708. “NmVm3” refers to the normal cubic meters of gas per cubic meter of crude oil feed. "Non-carboxylic organic oxygen compounds" refers to organic oxygen compounds that do not have a carboxylic group (-C02-). Non-carboxylic organic oxygen compounds include, but are not limited to ethers, cyclic ethers, alcohols, aromatic alcohols, ketones, aldehydes, or combinations thereof, which do not have a carboxylic group. “Noncondensable gas” refers to components and / or component mixtures that are gases in STP. “P value (peptization)” or “P value” refers to a numerical value, which represents the tendency for asphaltenes to flocculate in very low oil feed. The determination of the P value is described by J. J.

Heithaus in Measurement and Significance of Asphaltene Peptization, Journal of the Institute of Petroleum, Vol. 48, Number 458, February 1962, ρρ. 45 to 53. “Pore Diameter”, “Average Pore Diameter” and “Pore Volume” refer to Pore Diameter, Average Pore Diameter and Pore Volume as determined by ASTM Method D4284 (Mercury Porosimetry in contact angle equal to 140 °). A micromeritics® A9220 instrument (Micromeritics Inc., Norcross, Georgia, U.S.A.) can be used to determine these values. "Residue" refers to components that have a boiling range distribution above 538 ° C (1000 ° F) as determined by ASTM Method D5307. “NMCB” refers to the normal cubic meter of gas per barrel of crude oil feed. “Surface area” of a catalyst is as determined by ASTM Method D3663. “TAN” refers to a total acid value expressed as milligrams (“mg”) of KOH per gram (“g”) of sample. TAN is as determined by the ASTM D664 Method. "VGO" refers to hydrocarbons having a boiling range distribution between 343 ° C (650 ° F) and 538 ° C (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). Viscosity is as determined using ASTM Method D445.

In the context of this application, it should be understood that if the value obtained for a property of the tested substrate is outside the limits of the test method, the test method can be matured and / or recalibrated. to test for such a property.

Crude oils may be produced and / or retortified from hydrocarbon-containing formations and then stabilized. Crude oils may include crude oil. Crude oils are generally solid, semi-solid and / or liquid. Stabilization may include, but is not limited to, the removal of non-condensable gases, water, salts or combinations thereof from crude oil to form a stabilized crude oil. Such stabilization can often occur at or near retort production and / or purification sites.

Stabilized crude oils have typically not been distilled and / or fractionally distilled in a treatment plant to produce multiple components with specific boiling range distributions (eg, naphtha, distillates, VGO and / or lubricating oils). Distillation includes, but is not limited to, atmospheric distillation methods and / or vacuum distillation methods, undistilled and / or non-fractionated stabilized crude oils may include components having a carbon number above 4 in quantities of at least minus 0.5 gram of components per gram of crude oil. Examples of stabilized crude oils include whole crude oils, refined crude oils, desalinated crude oils, desalinated refined crude oils or combinations thereof. "Refined" refers to a crude oil that has been treated such that at least some of the components having a boiling point below 35 ° C at 0.101 MPa (95 ° F at 1 atm) have been removed. Typically, refined crude oils will have a content of at most 0.1 grams, at most 0.05 grams or at most 0.02 grams of such components per gram of refined crude.

Some stabilized crude oils have properties that allow stabilized crude oils to be transported to conventional treatment facilities by transport shippers (eg pipelines, trucks or ships). Other crude oils have one or more inappropriate properties that make them disadvantageous. Disadvantageous crude oils may be unacceptable to a transport shipper and / or a treatment facility, thus communicating a low economic value to the disadvantageous crude oil. The economic value may be such that a reservoir that includes disadvantageous crude oil that is deemed too expensive to produce, transport and / or treat.

The properties of disadvantageous crude oils may include, but are not limited to: (a) TANs of at least 0.1, at least 0.3; b) viscosity of at least 10 cSt; c) API severity of maximum 19; (d) a total Ni / V / Fe content of at least 0,00002 grams or at least 0,0001 grams Ni / V / Fe per gram of crude oil; e) a total heteroatom content of at least 0.005 grams of heteroatoms per gram of crude oil; (f) a residue content of at least 0,01 grams of residue per gram of crude oil; (g) a C5 asphaltene content of at least 0,04 grams of C5 asphaltenes per gram of crude oil; h) an MCR content of at least 0.002 grams of MCR per gram of crude oil; (i) a metal content in the metal salts of organic acids of at least 0,00001 grams of metals per gram of crude oil; or j) combinations thereof. In some embodiments, the disadvantageous crude oil may include, per gram of disadvantageous crude, at least 0.2 gram residue, at least 0.3 gram residue, at least 0.5 gram residue or at least 0 gram. .9 grams of residue. In some embodiments, disadvantageous crude oil may have a TAN in the range of 0.1 or 0.3 to 20.0.3 or 0.5 to 10 or 0.4 or 0.5 to 5. disadvantageous crude oils per gram of disadvantageous crude may have a sulfur content of at least 0.005 grams, at least 0.01 grams or at least 0.02 grams.

In some embodiments, disadvantageous crude oils have properties including, but not limited to: a) TAN of at least 0.5; (b) an oxygen content of at least 0,005 grams of oxygen per gram of crude oil feed; (c) a C5 asphaltene content of at least 0,04 grams of C5 asphaltenes per gram of crude oil feed; d) a higher than desired viscosity (eg> 10 cSt for an API gravity feed of at least 10; e) a metal content in the metal salts of organic acids of at least 0.00001 grams of metals per gram of crude oil; or f) combinations thereof.

Disadvantageous crude oils may include, per gram of disadvantageous crude: at least 0.001 grams, at least 0.005 grams or at least 0.01 grams of hydrocarbons having a boiling range distribution 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 hydrocarbons having a boiling range distribution 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 having a boiling range distribution 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 hydrocarbons having a boiling range distribution between 400 ° C and 650 ° C at 0.101 MPa.

Disadvantageous crude oils may include, per gram of disadvantageous crude: at least 0.001 grams, at least 0.005 grams or at least 0.01 grams of hydrocarbons having a boiling range distribution 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 hydrocarbons having a boiling range distribution 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 having a boiling range distribution 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 having a boiling range distribution 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 hydrocarbons having a boiling range distribution between 400 ° C and 650 ° C at 0.101 MPa.

Some disadvantageous crude oils may include, per gram of disadvantageous crude, at least 0.001 grams, at least 0.005 grams or at least 0.01 grams of hydrocarbons having a boiling range distribution of at most 100 ° C at 0.101 MPa, in addition to boiling components. Typically, disadvantageous crude oil has, per gram of disadvantageous crude oil, a content of such hydrocarbons of at most 0.2 grams or at most 0.1 grams.

Some disadvantageous crude oils may include, per gram of disadvantageous crude, at least 0.001 grams, at least 0.005 grams or at least 0.01 grams of hydrocarbons having a boiling range distribution of at least 200 ° C at 0.101 MPa.

Some disadvantageous crude oils may include, per gram of disadvantageous crude, at least 0.001 grams, at least 0.005 grams or at least 0.01 grams of hydrocarbons having a boiling range distribution of at least 650 ° C.

Examples of disadvantageous crude oils that could be treated using the processes described herein include, but are not limited to, crude oils from the following regions of the world: the Gulf Coast of the United States and Southern California, Canada's tar sands, Santos and Campos Brazilian Basins, Egyptian Gulf of Suez, Chad, North Sea of the United Kingdom, Coast of Angola, Chinese Bohai Bay, Venezuelan Zulia, Malaysia and Indonesian Sumatra. Treatment of disadvantageous crude oils may enhance the properties of disadvantageous crude oils such that the crude oils are acceptable for transport and / or treatment.

A disadvantageous crude oil and / or crude that should be treated here is referred to as "crude oil feed". THE

crude oil feed can be refined as described herein. The crude oil product resulting from the treatment of the crude oil feed, as described herein, is generally suitable for transportation and / or treatment. The properties of the crude oil product produced as described herein are closer to the corresponding properties of West Texas Intermediate oil than the crude oil feed or closer to the corresponding Brent crude oil properties than the crude oil feed, highlighting thus the economic value of the crude oil feed. Such crude oil product may be refined with less or no pretreatment, thereby enhancing refining efficiencies. Pretreatment may include desulphurisation, demetallization and / or atmospheric distillation to remove impurities. Treatment of a crude oil feed according to the inventions described herein may include contacting the crude oil feed with the catalyst (s) in a contact zone and / or combinations of two or more contact zones. In a contact zone, at least one property of a crude oil feed may be changed by contacting the crude oil feed with one or more catalysts with respect to the same property as the crude oil feed. In some embodiments, contact is made in the presence of a hydrogen source. In some embodiments, the hydrogen source is one or more hydrocarbons which under certain contact conditions react to provide relatively small amounts of hydrogen to the compound (s) in the mixed oil feed. FIG. I is a schematic of contact system 100 including contact zone 102A, the crude oil feed enters contact zone 102 via conduit 104. A contact zone may be a reactor, a portion of a reactor, portions of a reactor or combinations thereof. Examples of a contact zone include a stacked bed reactor, a fixed bed reactor, a boiling bed reactor, a continuously stirred tank reactor (“CSTR”), a fluidized bed reactor, a spray reactor and a liquid / liquid contactor. In certain embodiments, the contact system is in or away from an offshore facility. The contact of the crude oil feed with the catalyst (s) in the contact system 100 may 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 oil feed with a first catalyst of the two catalysts may reduce the crude oil feed TAN. Subsequent contact of the reduced TAN crude oil feed with the second catalyst decreases heteroatom content and increases API gravity. In other embodiments, the TAN, viscosity, Ni / V / Fe content, heteroatom content, residue content, API gravity or combinations of these crude oil product properties change by at least 10%. with respect to the same properties of the crude oil feed after contact of the crude oil feed with one or more catalysts.

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

Contact conditions in the contact zone may include, but are not limited to, temperature, pressure, hydrogen source flow, crude oil feed flow, or combinations thereof. Contact conditions in some embodiments are controlled to produce a crude oil product with specific properties. The temperature in the contact zone may range from 50 to 500 ° C, 60 to 440 ° C, 70 to 430 ° C or 80 to 420 ° C. The pressure in a contact zone can range from 0.1 to 20 MPa, 1 to 12 MPa, 4 to 10 MPa, or 6 to 8 MPa. The LHSV of the crude oil feed will generally range from 0.1 to 30, 1.0.5 to 25 h, 1.1 to 20 h, 1.5 to 15 h, or 2 to 10 h. 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 (eg hydrogen gas), a ratio of hydrogen gas source to crude oil feed typically ranges from 0.1 to 100,000 Nm3 / m3, 0, 5 to 10,000 Nm3 / m3,1 to 8,000 Nm3 / m3, 2 to 5,000 Nm3 / m3, 5 to 3,000 Nm3 / m3, or 10 to 800 Nm3 / m3 contacted with the catalyst (s). The hydrogen source, in some embodiments, is combined with carrier gas (s) and recirculated through the contact zone. The carrier gas may be, for example, nitrogen, helium and / or argon. The carrier gas may facilitate the flow of crude oil feed and / or the flow of hydrogen source in the contact zone (s). The carrier gas may also enhance the mixture in the contact zone (s). In some embodiments, a hydrogen source (e.g. hydrogen, methane or ethane) may be used as a carrier gas and recirculated through the contact zone. The hydrogen source may enter contact zone 102 concurrently with the crude oil feed in conduit 104 or separately via conduit 106. In contact zone 102, contact of the crude oil feed with a catalyst produces a total product that includes a crude oil product, and, in some embodiments, gas. In some embodiments, a carrier gas is combined with the crude oil feed and / or the hydrogen source in conduit 106. The total product may exit contact zone 102 and enter separation zone 108 via conduit 110. .

In the separation zone 108, the crude oil and gas product may be separated from the total product using generally known separation techniques, for example gas-liquid separation. The crude oil product may leave the separation zone 108 via conduit 112 and then be transported to conveyors, pipelines, storage containers, refineries, other processing zones or a combination thereof. The gas may include gas formed during processing (eg hydrogen sulfide, carbon dioxide and / or carbon monoxide), excess hydrogen gas source and / or carrier gas. Excess gas may be recycled to the purified contact system 100, transported to other processing zones, storage vessels or combinations thereof.

In some embodiments, contacting the crude oil feed with the catalyst (s) to produce a total product is accomplished in two or more contact zones. The total product may be separated to form crude oil and gas product (s).

FIGS. 2 to 3 are schematic embodiments of the contact system 100 that includes two or three contact zones. In FIGS. 2A and 2B, contact system 100 includes contact zones 102 and 114. FIGS. 3A and 3B include contact zones 102,114, 116. In FIGS. 2A and 3A, contact zones 102, 114, 116 are represented as separate contact zones in a reactor. The crude oil feed enters contact zone 102 via conduit 104.

In some embodiments, the carrier gas is combined with the hydrogen source in the conduit 106 and is introduced into the contact zones as a mixture. In certain embodiments as shown in FIGS. 1,3A and 3B, the hydrogen source and / or carrier gas may enter one or more crude oil feed contact zones separately via conduit 106 and / or in a direction contrary to the oil feed flow. through, for example, conduit 106 '. Addition of the hydrogen source and / or carrier gas contrary to the flow of the crude oil feed may enhance the mixing and / or contact of the crude oil feed with the catalyst. Contact of the crude oil feed with catalyst (s) in the contact zone 102 forms a feed stream. The supply current flows from the contact zone 102 to the contact zone 114. In FIGS. 3A and 3B, the supply current flows from contact zone 114 to contact zone 116.

Contact zones 102, 114, 116 may include one or more catalysts. As shown in FIG. 2B, the supply current exits contact zone 102 through conduit 118 and enters contact zone 114.

As shown in FIG. 3B, the supply current exits contact zone 114 via conduit 118 and enters contact zone 116. The supply current may be contacted with additional catalyst (s) in contact zone 114 and / or zone 116 to form the total product. Total product exits contact zone 114 and / or contact zone 116 and enters separation zone 108 via conduit 110. Blended petroleum product and / or gas is separated from total product. The fine petroleum product exits the separation zone 108 via conduit 112. FIG. 4 is a schematic of an embodiment of a separation zone upstream of contact system 100. Disadvantageous crude oil (refined or unrefined) enters separation zone 120 via conduit 122. In separation zone 120, At least a portion of the disadvantageous crude oil is separated using techniques known in the art (e.g. spraying, membrane separation, pressure reduction) to produce the crude oil feed. For example, water may be at least partially separated from disadvantageous crude oil.

In another example, components having a boiling range distribution below 95 ° C or below 100 ° C may be at least partially separated from disadvantageous crude oil to produce the crude oil feed. In some embodiments, at least a portion of naphtha and more volatile compounds than naphtha are separated from disadvantageous crude oil. In some embodiments, at least a portion of the separate components exits the separation zone 120 via conduit 124. The crude oil feed obtained from the separation zone 120, in some embodiments, includes a mixture of components with a boiling range distribution of at least 100 ° C or, in some embodiments, a boiling range distribution of at least 120 ° C. Typically, the separate crude oil feed includes a mixture of components with a boiling range distribution from 100 to 1000 ° C, 120 to 900 ° C or 200 to B00 ° C. At least a portion of the crude oil feedstock exits the separation zone 120 and enters the contact system 100 (see, for example, the contact zones in FIGS. 1 to 3) via conduit 126 to be further processed for contact. form a crude oil product. In some embodiments, the separation zone 120 may be positioned upstream or downstream of a desalination unit. After processing, the crude oil product exits contact system 100 via conduit 112.

In some embodiments, the crude oil product is combined with a crude oil that is the same as the crude oil feed or different. For example, the crude oil product may be combined with a crude oil having a different viscosity thereby resulting in a mixed product having a viscosity that is between the viscosity of the crude oil product and the viscosity of crude oil. In another example, the crude oil product may be combined with crude oil having a different TAN, thereby producing a product that has a TAN that is between the crude oil product and the crude oil TAN. The combined product may be suitable for transportation and / or treatment.

As shown in FIG. 5, in certain embodiments, the crude oil feed enters the contact system 100 via conduit 104 and at least a portion of the crude oil product exits the contact system 100 via conduit 128 and is introduced into the zone. In mixing zone 130, at least a portion of the crude oil product is combined with one or more process streams (for example, a hydrocarbon stream such as naphtha produced from the separation of one or more feeds). crude oil, a crude oil, a crude oil feed or mixtures thereof to produce a blended product. Process streams, crude oil feed, crude oil or mixtures thereof are fed directly into or upstream of the mixing zone 130 via conduit 132. A mixing system may be located in mixing zone 130 or next to her. The combined product may meet product specifications designated by refineries and / or shipping carriers. Product specifications include, but are not limited to, an API range, severity limit, TAN, viscosity, or combinations thereof. The combined product leaves the mixing zone 130 via conduit 134 to be transported or processed.

In FIG. 6, disadvantageous crude oil enters the separation zone 120 through conduit 122 and disadvantageous crude oil is separated as previously described to form the crude oil feed. The crude oil feed then enters the contact system 100 via conduit 126. At least some disadvantageous crude oil components exit separation zone 120 via conduit 124.

At least a portion of the crude oil product exits contact system 100 and enters blending zone 130 through conduit 128. Other process streams and / or crude oils enter blending zone 130 directly or via conduit 132 and They are combined with the crude oil product to form a blended product. The combined product leaves the mixing zone 130 via conduit 134.

In some embodiments, the crude oil product and / or the mixed product is transported to a refinery and / or treatment facility. The crude oil product and / or the mixed product may be processed to produce commercial products such as transport fuel, heating fuel, lubricants or chemicals. Processing may include distilling and / or fractionally distilling the crude oil product and / or combined product to produce one or more distillate fractions. In some embodiments, the crude oil product, the mixed product and / or one or more distillate fractions may be hydrotreated.

In some embodiments, the crude oil product has a TAN of at most 90%, at most 50%, at most 30% or at most 10% of the TAN of the crude oil feed. In some embodiments, the crude oil product has a TAN in the range of 1 to 80%, 20 to 70%, 30 to 60%, or 40 to 50% of the TAN of the crude oil feed. In certain embodiments, the crude oil product has a TAN of a maximum of 1, a maximum of 0.5, a maximum of 0.3, a maximum of 0.2, a maximum of 0.1, or a maximum of 0.05. The TAN of the crude oil product will often be at least 0.0001 and more often at least 0.001. In some embodiments, the TAN of the crude oil 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 embodiments, the crude oil product has a total Ni / V / Fe content of up to 90%, up to 50%, up to 10%, up to 5%, or up to 3% of Ni content. / V / Fe of the crude oil feed. The crude oil product, in some embodiments, has a total Ni / V / Fe content in a range of 1 to 80%, 10 to 70%, 20 to 60%, or 30 to 50% Ni / V content. V / Fe of crude oil feed. In certain embodiments, the crude product has per gram of crude product a total Ni / V / Fe content in a range of 1 x 10 7 gram to 5 x 10 5 gram, 3 x 10 '7 gram to 2 x 10'5 gram or 1 x 10'6 gram to 1 x 10'5 gram. In certain embodiments, crude oil has a maximum of 2 x 10.5 gram of Ni / V / Fe. In some embodiments, the total Ni / V / Fe content of the mixed oil product is 70 to 130%, 80 to 120% or 90 to 110% of the Ni / V / Fe content of the mixed oil feed.

In some embodiments, the very petroleum product has a total metal content in the metal salts of organic acids of not more than 90%, a maximum of 50%, a maximum of 10% or a maximum of 5% of the total metal content of the salts. Metals of Organic Acids in Bto Oil Feed. In certain embodiments, the very petroleum product has a total metal content in the metal salts of organic acids in a range of 1 to 80%, 10 to 70%, 20 to 60%, or 30 to 50% of the total content. metals in the metal salts of organic acids in the petroleum feed. Organic acids which 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, phenanthrenic acids and benzoic acid. The metal portion of the metal salts may include alkali metals (eg lithium, sodium and potassium), alkaline earth metals (eg magnesium, calcium and barium), Column 12 metals (eg zinc and cadmium), metals from Column 15 (e.g. arsenic), metals from Column 6 (e.g. chrome) or mixtures thereof.

In certain embodiments, the crude oil product has a total metal content in the metal salts of organic acids per gram of crude oil product, in a range of 0.0000001 gram to 0.00005 gram, of 0.0000003 gram to 0,00002 gram or 0,000001 gram to 0,00001 gram of metals in the metal salts of organic acids per gram of crude oil product. In some embodiments, a total metal content in the organic acid metal salts of the crude oil product is 70 to 130%, 80 to 120% or 90 to 110% of the total metal content in the organic acid metal salts in the feed of crude oil.

In certain embodiments, the API gravity of the crude oil product produced from the contact of the short oil feed with the catalyst under contact conditions is 70 to 130%, 80 to 120%, 90 to 110%, or 100 to 100%. 130% gravity API of bmto oil feed. In certain embodiments, the API gravity of the crude oil product is 14 to 40.15 to 30 or 16 to 25.

In certain embodiments, the fine petroleum product has a viscosity of at most 90%, at most 80% or at most 70% of the viscosity of the fine oil feed. In some embodiments, the low oil product has a viscosity in the range of 10 to 60%, 20 to 50% or 30 to 40% of the viscosity of the low oil feed. In some embodiments, the viscosity of the very crude oil product is at most 90% of the viscosity of the very crude oil feed while the API gravity of the crude oil product is 70 to 130%, 80 to 120% or 90 to 90%. 110% API gravity of crude oil feed.

In some embodiments, the crude oil product has a total heteroatom content of up to 90%, up to 50%, up to 10%, or up to 5% of the total heteroatom content of the crude oil feed. In certain embodiments, the crude oil product has a total heteroatom content of at least 1%, at least 30%, at least 80% or at least 99% of the total heteroatom content of the crude oil feed.

In some embodiments, the sulfur content of the crude oil product may be a maximum of 90%, a maximum of 50%, a maximum of 10% or a maximum of 5% of the sulfur content of the crude oil product. In certain embodiments, the crude oil 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 oil feed. In some embodiments, the sulfur content of the crude oil product is 70 to 130%, 80 to 120% or 90 to 110% of the sulfur content of the crude oil feed.

In some embodiments, the total nitrogen content of the crude oil product may be a maximum of 90%, a maximum of 80%, a maximum of 10%, or a maximum of 5% of a total nitrogen content of the crude oil feed. In certain embodiments, the crude oil 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 oil feed.

In some embodiments, the basic nitrogen content of the crude oil product may be a maximum of 95%, a maximum of 90%, a maximum of 50%, a maximum of 10%, or a maximum of 5% of the basic nitrogen content of the feed. crude oil. In certain embodiments, the crude oil 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 oil feed.

In some embodiments, the oxygen content of the crude oil product may be a maximum of 90%, a maximum of 50%, a maximum of 30%, a maximum of 10%, or a maximum of 5% of the oxygen content of the crude oil feed. . In certain embodiments, the crude oil 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 oil feed. In some embodiments, the oxygen content of the crude oil product is in the range of 1 to 80%, 10 to 70%, 20 to 60%, or 30 to 50% of the oxygen content of the crude oil feed. In some embodiments, the total content of carboxylic acid compounds of the crude oil product may be a maximum of 90%, a maximum of 50%, a maximum of 10%, a maximum of 5% of the content of carboxylic acid compounds in the feed. crude oil. In certain embodiments, the crude oil 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 feed. of crude oil.

In some embodiments, selected organic oxygen compounds may be reduced in the crude oil feed.

In some embodiments, carboxylic acids and / or metal salts of carboxylic acids may be chemically reduced prior to non-carboxylic-containing organic oxygen compounds. Carboxylic acids and non-carboxylic-containing organic oxygen compounds in a crude oil product may be differentiated by analyzing the crude oil product using generally known spectroscopic methods (eg infrared analysis, mass spectrometry and / or gas chromatography). The crude oil product in certain embodiments 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 oil feed and the TAN of crude oil product is a maximum of 90%, a maximum of 70%, a maximum of 50% or a maximum of 40% of the TAN of the crude oil feedstock. In certain embodiments, the crude oil 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 oil feed and the petroleum product. Crude oil has a TAN of at least 1%, at least 30%, at least 80% or at least 99% of the TAN of the crude oil feed.

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

In some embodiments, the crude oil product includes in its molecular structures from 0.05 to 0.15 grams or from 0.09 to 0.13 grams of hydrogen per gram of crude oil. The crude oil product may include, in its molecular structure, from 0.8 to 0.9 grams or from 0.82 to 0.88 grams of carbon per gram of crude oil product.

A ratio of atomic hydrogen to atomic carbon (H / C) of the crude oil product may be within 70 to 130%, 80 to 120% or 90 to 110% of the atomic H / C ratio of the crude oil feed. A crude oil product atomic H / C ratio within 10 to 30% of the crude oil feed atomic H / C ratio indicates that the absorption and / or consumption of hydrogen in the process is relatively small and / or that hydrogen is produced in situ. The crude oil product includes components with a boiling range. In some embodiments, the crude oil product includes per gram of crude oil: at least 0.001 gram or 0.001 to 0.5 gram hydrocarbons having a boiling range distribution of at most 100 ° C to 0.101 MPa; at least 0.001 gram or 0.001 to 0.5 gram hydrocarbons having a boiling range distribution between 100 ° C and 200 ° C at 0.101 MPa; at least 0.001 gram or 0.001 to 0.5 gram hydrocarbons having a boiling range distribution between 200 ° C and 300 ° C at 0.101 MPa; at least 0.001 gram or 0.001 to 0.5 gram hydrocarbons having a boiling range distribution between 300 ° C and 400 ° C at 0.101 MPa; and at least 0.001 gram or 0.001 to 0.5 gram hydrocarbons having a boiling range distribution between 400 ° C and 538 ° C at 0.101 MPa.

In some embodiments the crude oil product includes per gram of crude oil product at least 0.001 gram hydrocarbons having a boiling range distribution of at most 100 ° C at 0.101 MPa and / or at least 0.001 gram of hydrocarbon. hydrocarbons having a boiling range distribution between 100 ° C and 200 ° C at 0.101 MPa.

In some embodiments, the crude oil product may have at least 0.001 grams or at least 0.01 grams of naphtha per gram of fine oil product. In other embodiments, the crude oil product may have a naphtha content of at most 0.6 grams or at most 0.8 grams of naphtha per gram of crude oil product.

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

In certain embodiments, the crude oil product has a VGO content of 70 to 130%, 80 to 120% or 90 to 110% of the VGO content of the crude oil feed. In some embodiments, the crude oil product has, per gram of crude oil, a VGO content in the range 0.00001 to 0.8 gram, 0.001 to 0.5 gram, 0.002 to 0, 4 grams or from 0.001 to 0.3 grams.

In some embodiments, the crude oil product has a residue content of 70 to 130%, 80 to 120% or 90 to 110% of the waste oil feedstock content. The crude oil product may have, per gram of crude oil product, a residue content in the range of 0.00001 to 0.8 gram, 0.0001 to 0.5 gram, 0.0005 to 0.4 gram. from 0.001 to 0.3 grams, from 0.005 to 0.2 grams or from 0.01 to 0.1 grams.

In certain embodiments, the fine petroleum product has a MCR content of 70 to 130%, 80 to 120% or 90 to 110% of the MCR content of the crude oil feed, while the fine petroleum product has a MCR content. C5 asphaltenes not more than 90%, not more than 80% or not more than 50% of the C5 asphaltenes content of the low oil feed. In certain embodiments, the C5 asphaltenes content of the well oil feed is at least 10%, at least 60% or at least 70% of the C5 asphaltenes content of the well oil feed as the MCR content of the petroleum product This is within 10 to 30% of the MCR content of the crude oil feed. In some embodiments, decreasing the asphaltenes C5 content of the well oil feed while maintaining a relatively stable MCR content may increase the stability of the well oil feed / total product mixture.

In some embodiments, the C5 asphaltenes content and the MCR content may be combined to produce a mathematical relationship between the high viscosity components in the fine petroleum product relative to the high viscosity components in the fine petroleum feedstock. For example, a sum of a crude oil feed C5 asphaltene content and a crude oil feed MCR content may be represented by S. A sum of a crude oil product asphaltene Cs content and a MCR content of the crude oil product may be represented by S '. The sums can be compared (S 'to S) to assess the net reduction in the high viscosity components in the low oil feedstock. The S 'of the crude oil product may be in the range of 1 to 99%, 10 to 90% or 20 to 80% S. In some embodiments, a ratio of MCR content of the crude oil product to the Cs asphaltenes content is in a range of 1.0 to 3.0.1.2 to 2.0 or 1.3 to 1.9.

In certain embodiments, the crude oil product has a MCR content that is at most 90%, at most 80%, at most 50%, or at most 10% of the MCR content of the crude oil feed.

In some embodiments, the crude oil product has an MCR content in the range of 1 to 80%, 10 to 70%, 20 to 60%, or 30 to 50% of the MCR content of the crude oil feed. The fine petroleum product has, in some embodiments, from 0.0001 to 0.1 gram, 0.005 to 0.08 gram, or 0.01 to 0.05 gram MCR per gram of crude oil product.

In some embodiments, the fine petroleum product includes more than 0 grams, but less than 0.01 grams, 0.000001 to 0.001 grams, or 0.00001 to 0.0001 grams of total catalyst per gram of fine oil product. The catalyst may assist in stabilization of the very petroleum product during transport and / or treatment. The catalyst may inhibit corrosion, inhibit friction and / or increase water separation capabilities of the very petroleum product. The methods described herein may be configured to add one or more catalysts described herein to the crude oil product during treatment. The fine petroleum product produced from contact system 100 has different 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 content or combinations thereof; e) reduced residue content; f) reduced C5 asphaltene content; g) reduced MCR content; h) increased API severity; (i) a low content of metals in the metal salts of organic acids; or j) combinations thereof. In some embodiments, one or more properties of the crude oil product in relation to the crude oil feed may be selectively changed while other properties are not much changed or not substantially changed. For example, it may be desirable to selectively reduce only the TAN in a crude oil feed without also significantly changing the amount of other components (eg sulfur, residue, Ni / V / Fe or VGO). In this way, the absorption of hydrogen during contact can be "concentrated" in reducing TAN rather than reducing other components. Thus, the crude oil feed TAN can be reduced while using less hydrogen, as less of such hydrogen is also being used to reduce other components in the crude oil feed. If, for example, a disadvantageous crude oil has a high TAN, but a sulfur content that is acceptable to meet treatment and / or transport specifications, then such crude oil feed can be more efficiently treated to reduce TAN without also reduce sulfur.

Catalysts used in one or more embodiments of the inventions may include one or more bulky metals and / or one or more metals in a support. The metals may be in elemental form or in the form of a metal compound. The catalysts described herein may be introduced into the contact zone as a precursor and then become active as a catalyst in the contact zone (for example, when sulfur and / or a sulfur-containing crude oil feed are contacted with the precursor). . The catalyst or combination of catalysts used as described herein may or may not be commercial catalysts. Examples of commercial catalysts that are considered to be used 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; DN800; DN2118; DN2318; DN3100; DN3110; DN3300; DN3310; RC400; RC410; RN412; RN400; RN420; RN440; RN450; RN650; RN5210; RN5610; RN5650; RM430; RM5030; Z603; Z623;

Z673: Z703; Z713; Z723; Z753; and Z763, which are available from CRI

International, Inc. (Houston, Texas, U.S.A.).

In some embodiments, catalysts used to change the properties of the crude oil feed include one or more Column 5 to 10 metals in a support. Columns 5 to 10 metal (s) 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 may have, per gram of catalyst, a total column metal content (s) of 5 to 10 of at least 0.0001 gram, at least 0.001 gram, at least 0.01 gram or in a range of 0, 0001 to 0.6 grams, 0.005 to 0.3 grams, 0.001 to 0.1 grams, or 0.01 to 0.08 grams. In some embodiments, the catalyst includes Column 15 element (s) in addition to Column 5 to 10 metal (s). Examples of Column 15 elements include phosphorus. The catalyst may have a total Column 15 element content per gram of catalyst in the range 0.000001 to 0.1 gram, 0.00001 to 0.06 gram, 0.00005 to 0.03 gram or 0, 0001 to 0.001 grams.

In certain embodiments, a catalyst includes Column 6 metal (s). The catalyst may have, per gram of catalyst, a total Column 6 metal (s) content of at least 0.0001 grams, at least 0.000 grams. 01 gram, at least 0.02 gram and / or in a range of 0.0001 to 0.6 gram, 0.001 to 0.3 gram, 0.005 to 0.1 gram or 0.01 to 0.08 gram. In some embodiments, the catalyst includes from 0.0001 to 0.06 grams of Column 6 metal (s) per gram of catalyst. In some embodiments, the catalyst includes Column 15 element (s) in addition to Column 6 metal (s).

In some embodiments, the catalyst includes a combination of Column 6 metal (s) with one or more Column 5 metals and / or Column 7 through 10. A molar ratio of Column 6 metal to Column 5 metal may be in a range from 0.1 to 20.1 to 10 or 2 to 5. A molar ratio of Column 6 metal to Column 7 to 10 metal molar may be in the range 0.1 to 20, 1 to 10 or 2 to 5. In some embodiments, the catalyst includes Column 15 element (s) in addition to combining Column 6 metal (s) with one or more Column 5 and / or 7-10 metal. In this embodiment, the catalyst includes Column 6 metal (s) and Column 10 metal (s). A molar ratio of total Column 10 metal to total Column 6 metal in the catalyst may be in the range of 1 to 10 or 2 to 5. In certain embodiments, the catalyst includes Column 5 metal (s) and Column 10 metal (s). A molar ratio of the total metal of Column 10 to the total metal of Column 5 in the catalyst may be in a range of 1 to 10 or 2 to 5.

In some embodiments, the metal (s) from Columns 5 to 10 are incorporated or deposited on a support to form the catalyst. In certain embodiments, the column (s) metal (s) 5 to 10 in combination with the column (s) member (s) 15 are incorporated or deposited on the support to form the catalyst. In embodiments in which the metal (s) and / or element (s) are supported, the weight of the catalyst includes the entire support, all metal (s) and all (s). the elements). The support may be porous and may include refractory oxides, porous carbon-based materials, zeolites or combinations thereof. The refractory oxides may include, but are not limited to, alumina, silica, silica alumina, titanium oxide, zirconium oxide, magnesium oxide or mixtures thereof. The supports may be obtained from a commercial manufacturer such as Criterion Catalysts and Technologies LP (Houston, Texas, U.S.A.). Porous carbon based materials 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.). The support in some embodiments is prepared such that the support has an average pore diameter of at least 150 Å, at least 170 Å or at least 180 Å. In certain embodiments, a support is prepared by forming an aqueous paste of the support material.

In some embodiments, an acid is added to the pulp to aid in pulp extrusion. Water and dilute acid are added in such amounts and by methods as required 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. The paste can be extruded and cut using catalyst extrusion methods and generally known catalyst cutting methods to form extrudates. Extrudates may be heat treated at a temperature in the range of 5 to 260 ° C or 85 to 235 ° C for a period of time (for example, for 0.5 to 8 hours) and / or until the content humidity of the extruder has reached a desired level. The heat treated extrudate may further be heat treated at a temperature in the range of 800 to 1200 ° C or 900 to 1100 ° C to form the support having an average pore diameter of at least 150 °.

In certain embodiments, the support includes gamma alumina, theta alumina, delta alumina, alpha alumina or combinations thereof. The amount of gamma alumina, delta alumina, alpha alumina or combinations thereof per gram of catalyst support may be in the range of 0.0001 to 0.99 gram, 0.001 to 0.5 gram, 0.01 to 0, 1 gram or at most 0.1 gram as determined by x-ray diffraction. In some embodiments, the support has, alone or in combination with other alumina forms, a theta alumina content per gram of support in a range of 0.1 to 0.99 grams, 0.5 to 0, 9 grams or 0.6 to 0.8 grams as determined by x-ray diffraction. In some embodiments, the support may be at least 0.1 gram, at least 0.3 gram, at least 0.5 gram or at least 0.8 gram of theta alumina as determined by x-ray diffraction.

Sustained catalysts may be prepared using generally known catalyst preparation techniques. Examples of catalyst preparations are described in U.S. Patent Nos. 6,218,333 issued to Gabrielov et al., 6,290,841 issued to Gabrielov et al., And 5,744,025 issued to Boon et al. and U.S. Patent Application Publication 20030111391 issued to Bhan.

In some embodiments, the support may be impregnated with metal to form a catalyst. In certain embodiments, the support is heat treated at temperatures in the range of 400 to 1200 ° C, 450 to 1000 ° C, or 600 to 900 ° C prior to impregnation with a metal. In some embodiments, impregnation aids may be used during catalyst preparation. Examples of impregnation aids include a component of citric acid, ethylenediaminetetraacetic acid (EDTA), ammonia or mixtures thereof.

In certain embodiments, a catalyst may be formed by adding or incorporating the metal (s) from Columns 5 to 10 to the heat treated ("overlap") formed mixtures. Overlapping a metal on top of the heat treated formed support having a substantially or relatively uniform concentration of metal often provides beneficial catalytic properties of the catalyst. Heat treating a support formed after each metal overlap tends to improve the catalytic activity of the catalyst. Methods for preparing a catalyst using overlapping methods are described in U.S. Patent Application Publication 20030111391 to Bhan. Columns 5 to 10 metal (s) and support may be mixed with suitable mixing equipment to form a Column 5 to 10 / support metal (s) mixture. The metal mixture (s) from Columns 5 to 10 / support may be mixed using suitable mixing equipment. Examples of suitable mixing equipment include weighing machines, stationary or masseur casings, Muller mixers (e.g., batch type or continuous type), impact mixers, and any other generally known mixer or known general device, which will adequately provide the metal mixture (s) from Columns 5 to 10 / support. In certain embodiments, the materials are mixed until the metal (s) of Columns 5 through 10 are substantially and homogeneously dispersed in the support.

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

In some embodiments, the catalyst may be heat treated in the presence of hot air and / or oxygen rich air at a temperature in the range of 400 ° C to 1000 ° C to remove volatile matter such that at least a portion of the Columns 5 through 10 are converted to the corresponding metal oxide.

In other embodiments, however, the catalyst may be heat treated in the presence of air at temperatures in the range of 35 to 500 ° C (e.g. below 300 ° C, below 400 ° C or below 500 ° C). C) for a period of time in a range of 1 to 3 hours to remove most volatile components without converting the metals from Columns 5 to 10 to the metal oxide. Catalysts prepared by such a method are generally alluded to as "uncalcined" catalysts. When catalysts are prepared in this manner in combination with a sulfide method, the active metals may be substantially dispersed in the support. Preparations of such catalysts are described in U.S. Patent 6,218,333 issued to Gabrielov et al. and 6,290,841 issued to Gabrielov et al.

In certain embodiments, a theta alumina support may be combined with column 5 to 10 metal metals to form a column 5 to 10 theta alumina / metal support mixture. Columns 5 to 10 can be heat treated at a temperature of at least 400 ° C to form the catalyst having a pore size distribution with an average pore diameter of at least 230 °. Typically, such heat treatment is conducted at temperatures of up to 1200 ° C.

In some embodiments, the support (a commercial support or a support prepared as described herein) may be combined with a sustained catalyst and / or a bulky metal catalyst. In some embodiments, the sustained catalyst may include Column 15 metal (s). For example, the sustained catalyst and / or the bulky metal catalyst may be ground to a powder with an average particle size of 1 to 50 microns, 2 to 45 microns, or 5 to 40 microns. The powder may be combined with support 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 having a pore size distribution with an average pore diameter in a range of 80 to 200 Å or 90 to 180 Å. or 120 to 130 Å.

Combining the catalyst with the support allows, in some embodiments, at least a portion of the metal to reside beneath the surface of the embedded metal catalyst (e.g., embedded in the support), leading to less metal on the surface than otherwise. would occur in the non-embedded metal catalyst. In some embodiments, having less metal on the catalyst surface extends catalyst life and / or catalytic activity by allowing at least a portion of the metal to move to the catalyst surface during use. Metals can move to the catalyst surface by erosion of the catalyst surface during catalyst contact with a crude oil feed. Interleaving and / or mixing the catalyst components changes, in some embodiments, the structured order of the column 6 metal in the crystal structure of the column 6 oxide to a substantially random order of the column 6 metal in the crystal structure of the embedded catalyst . The metal order of Column 6 can be determined using x-ray powder diffraction methods. The order of elemental metal in the catalyst relative to the order of elemental metal in the metal oxide can be determined by comparing the peak order of the column 6 metal over a column 6 oxide x-ray diffraction spectrum with the peak order of Column 6 metal on a catalyst x-ray diffraction spectrum. From the magnification and / or absence of patterns associated with column 6 metal in an x-ray diffraction spectrum, it can be estimated that column 6 metal (s) is / are substantially randomly ordered in the structure. crystal clear.

For example, molybdenum trioxide and alumina support having an average pore diameter of at least 180 Â ° may be combined to form an alumina / molybdenum trioxide mixture. Molybdenum trioxide has a definite standard (e.g., defined peaks D0oi, D002 and / or D003). The Column 6 alumina / trioxide mixture can be heat treated at a temperature of at least 538 ° C (1000 ° F) to produce a catalyst that does not exhibit a molybdenum dioxide standard over a one-ray diffusion spectrum. x (for example, an absence of the Dooi peak).

In some embodiments, catalysts may be characterized by pore structure. Various parameters of pore structure include, but are not limited to pore diameter, pore volume, surface areas, or combinations thereof. The catalyst may have a distribution of the total amount of pore sizes versus pore diameters. The average pore diameter of the pore size distribution may be in the range 30 to 1000 Å, 50 to 500 Å or 60 to 300 Å. In some embodiments, catalysts including at least 0.5 gram gamma alumina per gram catalyst have a pore size distribution with an average pore diameter in a range of 60 to 200 Å; 90 to 180, 100 to 140, or 120 to 130. In other embodiments, catalysts including at least 0.1 gram theta alumina per gram catalyst have a pore size distribution with an average pore diameter in a range of 180 to 500 Å, 200 to 300 Å or 230 to 250 Â. In some embodiments, the average pore diameter of the pore size distribution is at least 120 Ã… at least 150 Â, at least 180 Â, at least 200 Â, at least 220 Â, at least 230  or minus 300 Â. Such average pore diameters are typically at most 1000 µm. The catalyst may have a pore size distribution with an average pore diameter of at least 60 Å or at least 90 Å.

In some embodiments, the catalyst has a pore size distribution with an average pore diameter in a range of 90 to 180 Å, 100 to 140 Å or 120 to 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 Å or 25 Å of the average pore diameter. In certain embodiments, the catalyst has a pore size distribution with an average pore diameter in a range of 70 to 180 Â °, with at least 60% of a total number of pores in the pore size distribution having a diameter. pore size within 45 Å, 35 Λ or 25 Å of the average pore diameter.

In embodiments where the average pore diameter of the pore size distribution is at least 180 Å, at least 200 Å, or at least 230 Å, greater than 60% of a total number of pores in the pore size distribution. pore has a pore diameter within 50 Å, 70 Å or 90 Å of the average pore diameter. In some embodiments, the catalyst has a pore size distribution with an average pore diameter in a range of 180 to 500 Â, 200 to 400 Â, or 230 to 300 Á, with at least 60% of a total number of pores in the pore size distribution having a pore diameter within 50 Â °, 70 Â or 90 Â ° of the average pore diameter.

In some embodiments, the pore pore volume ■ η ·} may be at least 0.3 cm / g, at least 0.7 cm / g or at least 0.9 Λ cm / g. In certain embodiments, pore pore volume may range from 0.3 to 0.99 cm 3 / g, 0.4 to 0.8 cm3 / g or 0.5 to 0.7 cm3 / g. The catalyst having a pore size distribution with an average pore diameter in a range of 90 to 180 Å may have, in some embodiments, a surface area of at least 100 m2 / g, at least 120 m2 / g. at least 170 m2 / g, at least 220 m2 or at least 270 m2 / g. Such a surface area may be in a range of 100 to 300 m2 / g, 120 to 270 m2 / g, 130 to 250 m2 / g, or 170 to 220 m2 / g.

In certain embodiments, the catalyst having a pore size distribution with an average pore diameter in a range of 180 to 300 Å may have a surface area of at least 60 m 2 / g, at least 90 m / g, at least 100 m / g, at least 120 m / g or at least 270 m2 / g. Such a surface area may be in a range of 60 to 300 m2 / g, 90 to 280 m2 / g, 100 to 270 m2 / g, or 120 to 250 m2 / g.

In certain embodiments, the catalyst exists in formed forms, for example pellets, cylinders and / or extruded. The catalyst typically has a flat plate crush strength in the range of 50 to 500 N / cm, 60 to 400 N / cm, 100 to 350 N / cm, 200 to 300 N / cm, or 220 to 280 N / cm.

In some embodiments, the catalyst and / or catalyst precursor is sulfide to form metal sulfides (prior to use) using techniques known in the art (e.g., the ACTICAT® process, CRI International, Inc.). In some embodiments, the catalyst may be dried then sulfide. Alternatively, the catalyst may be sulfide in situ by contacting the catalyst with a crude oil feed that includes sulfur containing compounds. In situ sulfurization may utilize hydrogen sulfide gas in the presence of hydrogen or liquid phase sulfurizing agents such as organo sulfur compounds (including alkyl sulfides, polysulfides, thiols and sulfoxides). Ex situ sulfurization processes are described in U.S. Patent 5,468,372 issued to Seamans et al. And 5,688,736 issued to Seamans et al.

In certain embodiments, a first type of catalyst ("first catalyst") includes Column 5 to 10 metal (s) in combination with a support and has a pore size distribution with an average pore diameter. in a range of 150 to 250 Â. The first catalyst may have a surface area of at least 100 m / g. THE

pore volume of the first catalyst may be at least 0.5 cm3 / g. The first catalyst may have a gamma alumina content of at least 0.5 grams of gamma alumina and typically a maximum of 0.9999 grams of gamma alumina per gram of first catalyst. The first catalyst has, in some embodiments, a total metal (s) content of Column 6 per gram of catalyst in a range of 0.0001 to 0.1 gram. The first catalyst is capable of removing a portion of Ni / V / Fe from a crude oil feed by removing a portion of the TAN-contributing components from a crude oil feed by removing at least a portion of C5 asphaltenes from a feed. crude oil by removing at least a portion of the metals in the metal salts of the organic acids in the crude oil feed or combinations thereof. Other properties (eg sulfur content, VGO content, API gravity, residue content or combinations thereof) may exhibit relatively small changes when the crude oil feed is contacted with the first catalyst. Being able to selectively change the properties of a crude oil feed while only changing other properties in relatively small quantities can allow the crude oil feed to be more efficiently treated. In some embodiments, one or more first catalysts may be used in any order.

In certain embodiments, the second type of catalyst ("second catalyst") includes Column 5 to 10 metal (s) in combination with a support and has a pore size distribution with an average pore diameter in a range from 90  to 180 Â. At least 60% of the total number of pores in the pore size distribution of the second catalyst has a pore diameter within 45 µm of the average pore diameter. Contact of the crude oil feed with the second catalyst under suitable contact conditions may produce a crude oil product that has selected properties (eg TAN) significantly changed from the same properties as the crude oil feed while other properties are only changed in a small amount. A hydrogen source, in some embodiments, may be present during contact. The second catalyst can reduce at least a portion of the TAN contributing components of the crude oil feed, at least a portion of the relatively high viscosity contributing components, and reduce at least a portion of the Ni / V / Fe content of the product. of crude oil. Additionally, contacting crude oil feeds with the second catalyst may produce a crude oil product with a relatively small change in sulfur content relative to the sulfur content of the crude oil feed.

For example, the crude oil product may have a sulfur content of 70% to 130% of the sulfur content of the crude oil feed. The crude oil product may also exhibit relatively minor changes in distillate content, VGO content and residue content in relation to the crude oil feed.

In some embodiments, the crude oil feed may have a relatively low Ni / V / Fe content (eg maximum 50 wtppm), but a TAN, asphaltene content or metal content in the metallic salts of organic acids. relatively high. A relatively high TAN (for example, a TAN of at least 0.3) can make the oil feed very unacceptable for transportation and / or refining. A very disadvantageous petroleum with a relatively high C5 asphaltene content may exhibit less processing stability compared to other relatively low C5 asphaltene crude oils. Contact of the low oil feed with secondary catalysts can remove acidic and / or asphaltene components C5 contributing 0 TAN of the low oil feed. In some embodiments, reduction of C5 asphaltenes and / or TAN contributing components may reduce the viscosity of the crude oil / total product feed mixture relative to the viscosity of the low oil feed. In certain embodiments, one or more combinations of secondary catalysts may enhance the stability of the mixture of the total product / crude oil product, increase the catalyst life, allow minimal liquid hydrogen uptake by the crude oil feed or combinations thereof, when used to treat crude oil feed as described herein.

In some embodiments, a third type of catalyst ("third catalyst") may be obtainable by combining a column 6 metal support (s) to produce a catalyst precursor. The catalyst precursor may be heated in the presence of one or more sulfur-containing compounds at a temperature below 500 ° C (e.g., below 482 ° C) for a relatively short period of time to form the third non-calcined catalyst. Typically, the catalyst precursor is heated to at least 100 ° C for 2 hours. In certain embodiments, the third catalyst may have, per gram of catalyst, an element content of Column 15 in a range of 0.001 to 0.03 gram, 0.005 to 0.02 gram or 0.008 to 0.01 gram. The third catalyst may exhibit significant activity and stability when used to treat the crude oil feed as described herein. In some embodiments, the catalyst precursor is heated to temperatures below 500 ° C in the presence of one or more sulfur compounds. The third catalyst can reduce at least a portion of the TAN-contributing components of the crude oil feed, reduce at least a portion of the metals in the metal salts of organic acids, reduce a Ni / V / Fe content of the crude oil product. and reduce the viscosity of the crude oil product. Additionally, contacting crude oil feeds with the third catalyst may produce a crude oil product with a relatively small change in sulfur content relative to the sulfur content of the crude oil feed and with relatively minimal absorption of liquid hydrogen from the feed. of crude oil. For example, a crude oil product may have a sulfur content of 70% to 130% of the sulfur content of the crude oil feed. The crude oil product produced using the third catalyst may also exhibit relatively minor changes in API gravity, distillate content, VGO content and residue content relative to the crude oil feed. The ability to reduce TAN, metals in organic salt metal salts, Ni / V / Fe content and crude oil product viscosity while also only changing the API gravity, distillate content, VGO content and the residue content in relation to the crude oil feed may allow the crude oil product to be used by a variety of treatment facilities. The third catalyst, in some embodiments, may reduce at least a portion of the MCR content of the crude oil feed while maintaining stability of the crude oil / total product feed. In certain embodiments, the third catalyst may have a column 6 metal (s) content in the range of 0.0001 to 0.1 gram, 0.005 to 0.05 gram or 0.001 to 0.01 gram and a of metal (s) Column 10 in a range from 0.0001 to 0.05 gram, 0.005 to 0.03 gram or 0.001 to 0.01 gram per gram of catalyst. A metal catalyst (s) from Columns 6 and 10 may facilitate the reduction of at least a portion of the MCR contributing components in the crude oil feed at temperatures in the range of 300 to 500 ° C or 350 to 450 ° C. and pressures in the range 0.1 to 10 MPa, 1 to 8 MPa or 2 to 5 MPa.

In certain embodiments, a fourth type of catalyst ("fourth catalyst") includes Column 5 metal (s) in combination with a theta alumina support. The fourth catalyst has a pore size distribution with an average pore diameter of at least 180 Â °. In some embodiments, the average pore diameter of the fourth catalyst may be at least 220 Å, at least 230 Å, at least 250 Å, or at least 300 Å. The support may include at least 0.1 gram, at least 0.5 gram, at least 0.8 gram or at least 0.9 gram of theta alumina per gram of support. The fourth catalyst may include, in some embodiments, at most 0.1 gram of Column 5 metal (s) per gram of catalyst and at least 0.0001 gram of Column 5 mepha (s) per gram of catalyst. In certain embodiments, the column 5 metal is vanadium.

In some embodiments, the crude oil feed may be contacted with an additional catalyst subsequent to contact with the fourth 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, commercial catalysts described herein or combinations thereof.

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

In certain embodiments, a fifth type of catalyst ("fifth catalyst") includes Column 6 metal (s) in combination with a theta alumina support. The fifth catalyst has a pore size distribution with an average pore diameter of at least 180 Å, at least 220 Å, at least 230 Å, at least 250 Å, at least 300 Å or at most 500 Å. 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 support. In some embodiments, the support has an alpha alumina content below 0.1 gram alpha alumina per gram catalyst. The catalyst includes, in some embodiments, at most 0.1 gram of Column 6 metal (s) per gram of catalyst and at least 0.0001 gram of Column 6 metal (s) per gram of catalyst. In some embodiments, Column 6 metal (s) are molybdenum and / or tungsten.

In certain embodiments, the net absorption of hydrogen from the crude oil feed may be relatively low (for example, from 0.01 to 100 Nm3 / m3, 180 Nm3 / m3, 5 to 50 Nm3 / m3 or 10 to 30 Nm3 / m3) when the crude oil feed is contacted with the fifth catalyst at a temperature in the range of 310 to 400 ° C, 320 to 370 ° C or 330 to 360 ° C. The net absorption of hydrogen from the crude oil feed, in some embodiments, may be in the range of 1 to 20 Nm3 / m3.2 to 15 Nm3 / m3 or 3 to 10 Nm3 / m3. The crude oil product produced from the contact of the crude oil feed with the fifth catalyst may have a maximum of 90%, a maximum of 80%, a maximum of 50% or a maximum of 10% of a TAN of the crude oil feed. . The crude oil product TAN can be in the range of 0.01 to 0.1, 0.03 to 0.05, or 0.02 to 0.03.

In certain embodiments, a sixth type of catalyst ("sixth catalyst") includes Column 5 metal (s) and Column 6 metal (s) in combination with the theta alumina support. The sixth catalyst has a pore size distribution with an average pore diameter of at least 180 µm. In some embodiments, the average pore size distribution pore diameter may be at least 220 Å, at least 230 Å, at least 250 Å, at least 300 Å or at most 500 Å. The support may include at least 0.1 gram, at least 0.5 gram, at least 0.8 gram, at least 0.9 gram or at most 0.99 gram of theta alumina per gram of support. The catalyst may include, in some embodiments, a total of Column 5 metal (s) and Column 6 metal (s) of at most 0.1 grams per gram of catalyst and at least 0.0001 grams of metal ( Column 5 (s) and Column 6 metal (s) per gram of catalyst. In some embodiments, the total column 6 metal to total column 5 molar ratio may be in the range 0.1 to 20.1 to 10 or 2 to 5.

In certain embodiments, the column 5 metal is vanadium and the column 6 metal (s) are molybdenum and / or tungsten.

When the crude oil feed is contacted with the sixth catalyst at a temperature in the range of 310 to 400 ° C, 320 to 370 ° C or 330 to 360 ° C, the net hydrogen absorption by the feed Λ Λ -S Λ of crude oil can be in a range of -10 Nm / m to 20 Nm / m, -7 λλ 2¾ 33 33 Nm / malO Nm / m or -5 Nm / m to 5 Nm / m. The negative net absorption of hydrogen is an indication that hydrogen is being generated in situ. The crude oil product produced from the contact of the crude oil feed with the sixth catalyst may have a maximum of 90%, a maximum of 80%, a maximum of 50%, a maximum of 10% or at least 1% of a TAN. of the crude oil feed. The crude oil product TAN can be in the range of 0.01 to 0.1.0.02 to 0.05 or 0.03 to 0.04. Low net hydrogen absorption during contact of the crude oil feed with the fourth, fifth or sixth catalysts reduces the overall hydrogen demand during processing while producing a crude oil product that is acceptable for transportation and / or treatment. Since hydrogen production and / or transportation is expensive, minimizing the use of hydrogen in a process lowers overall processing costs.

In certain embodiments, a seventh type of catalyst ("seventh catalyst") has a total Column 6 metal content (s) in a range of 0.0001 to 0.06 grams of Column 6 metal (s) per gram of catalyst. Column 6 metal is molybdenum and / or tungsten. The seventh catalyst is beneficial in producing a crude oil product that has a maximum TAN of 90% of the crude oil feed TAN.

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

Selecting the catalyst (s) from this order and controlling operating conditions may allow a crude oil product to be produced that has TAN and / or selected properties changed relative to the crude oil feed while other oil feed properties. raw are not significantly changed. The resulting crude oil product may have enhanced feedstock properties and thus be more acceptable for transportation and / or refining. Arrangement of two or more catalysts in a selected sequence can control the sequence of property improvements for crude oil feed. For example, TAN, API gravity, at least a portion of asphaltenes Q, at least a portion of iron, at least a portion of nickel and / or at least a portion of vanadium in the crude oil feed may be reduced before at least a portion of heteroatoms in the crude oil feed is reduced. Catalyst arrangement and / or selection may, in some embodiments, improve catalyst lives and / or stability of the crude oil / total product feed mixture. Improving catalyst life and / or stability of the crude oil / total product feed mixture during processing may allow a contact system to operate for at least 3 months, at least 6 months, or at least 1 year without replacement. of the catalyst in the contact zone.

The selected catalyst combinations may allow at least a portion of the Ni / V / Fe, at least a portion of the C5 asphaltenes, at least a portion of the metals in the metal salts of the organic acids, at least a portion of the contributing components to be reduced. for TAN, at least a portion of the residue or combinations thereof from the crude oil feedstock before other properties of the crude oil feedstock are changed while maintaining stability of the crude oil feedstock / total product mix during processing (eg keep a crude oil feed P value above 1.5).

Alternatively, asphaltenes C5, TAN and / or API gravity may be incrementally reduced by contacting the crude oil feed with selected catalysts, the ability to incrementally and / or selectively change the properties of the crude oil feed may allow the stability of the feed mix. crude oil / total product feed is maintained during processing.

In some embodiments, the first catalyst (described above) may be positioned upstream of a series of catalysts. Such positioning of the first catalyst may allow the removal of high molecular weight contaminants, metal and / or metal contaminants in the metal salts of organic acids, while maintaining the stability of the crude oil / total product feed mixture. The first catalyst allows, in some embodiments, the removal of at least a portion of Ni / V / Fe, removal of acidic components, removal of components that contribute to a decrease in the life of other catalysts in the system or combinations thereof. from the crude oil feed. For example, reducing at least a portion of C5 asphaltenes in the crude oil / total product feed to crude oil mixture inhibits clogging of other downstream catalysts, and thus increases the length of time the system can be operated without catalyst replenishment. Removal of at least a portion of Ni / V / Fe from the crude oil feed may, in some embodiments, increase the life of one or more catalysts positioned after the first catalyst. The second catalyst (s) and / or third catalyst (s) may be positioned downstream of the first catalyst.

Further contact of the crude oil / total product feed mixture with the second catalyst (s) and / or third catalyst (s) may further reduce TAN, reduce the Ni / V / Fe, reduce sulfur content, reduce oxygen content and / or reduce metal content in metal salts of organic acids.

In some embodiments, contacting the crude oil feed with the second catalyst (s) and / or the third catalyst (s) may produce a crude oil feed mixture. / total product having a low TAN, a reduced sulfur content, a low oxygen content, a low metal content in the metal salts of organic acids, a reduced asphaltene content, a reduced viscosity or combinations thereof with respect to their properties of the crude oil feed while maintaining the stability of the crude oil / total product feed mixture during processing. The second catalyst may be positioned in series, with the second catalyst being upstream of the third catalyst or vice versa. The ability to release hydrogen to specified contact zones tends to minimize hydrogen use during contact. Combinations of catalysts that facilitate hydrogen generation on contact and catalysts that absorb a relatively low amount of hydrogen during contact can be used to change selected properties of a crude oil product relative to the same properties as the low oil feedstock. . For example, the fourth catalyst may 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 only changing other properties of the crude oil feed by the selected quantities and / or while maintaining the stability of the crude oil / total product feed. The order and / or number of catalysts may be selected to minimize net hydrogen absorption while maintaining stability of the crude oil / total product feed. The minimum net hydrogen absorption allows the residue content, VGO content, distillate content, API gravity or combinations of these from the crude oil feed to be maintained within 20% of their respective crude oil feed properties, while TAN and / or viscosity of crude oil product is at most 90% of TAN and / or viscosity of crude oil feed. Reducing the net hydrogen uptake by the very low oil feed can produce a crude oil product that has a boiling range distribution similar to the boiling point distribution of the crude oil feed and a reduced TAN relative to the feed oil TAN. crude oil. The atomic H / C of the crude oil product may also change only in relatively small quantities compared to the atomic H / C of the crude oil feed. Hydrogen generation in specific contact zones may allow selective addition of hydrogen to other contact zones and / or allow selective reduction of crude oil feed properties.

In some embodiments, the fourth catalyst (s) may be positioned upstream, downstream or between additional catalyst (s) described herein. Hydrogen may be generated during contact of the very low oil feed with the fourth catalyst (s) and hydrogen may be released to the contact zones that include the additional catalyst (s). ). The release of hydrogen may be contrary to the flow of crude oil feed. In some embodiments, hydrogen release may be concurrent with the flow of crude oil feed.

For example, in a stacked configuration (see, for example, FIG. 2B), hydrogen may be generated during contact in a contact zone (for example, contact zone 102 in FIG. 2B) and hydrogen may be generated. released to an additional contact zone (for example, contact zone 114 in FIG. 2B) in a direction that is contrary to the flow of the crude oil feed. In some embodiments, hydrogen flow may be concurrent with crude oil feed flow. Alternatively, in a stacked configuration (see, for example, FIG. 313), hydrogen may be generated during contact in a contact zone (for example, contact zone 102 in FIG. 3B). A hydrogen source may be released to a first additional contact zone in a direction that is contrary to the flow of the crude oil feed (for example, add hydrogen through conduit 106 'to contact zone 114 in FIG. 3 B) and to a second additional contact zone in a direction that is concurrent with the flow of the crude oil feed (e.g., adding hydrogen through conduit 106 'to the contact zone 116 in FIG. 3B).

In some embodiments, the fourth catalyst and the sixth catalyst are used in series, with the fourth catalyst being upstream of the sixth catalyst or vice versa. Combining the fourth catalyst with an additional catalyst (s) may reduce TAN, reduce the Ni / V / Fe content and / or reduce a metal content in the organic acid metal salts with low net hydrogen uptake. crude oil feed. Low net hydrogen absorption may allow other properties of the crude oil product to be changed only in small quantities relative to the same properties as the crude oil feed.

In some embodiments, two of the seventh different catalysts may be used in combination. The seventh catalyst used upstream of the seventh downstream catalyst may have a total column 6 metal content (s) per gram of catalyst in a range of 0.0001 to 0.06 gram. The seventh downstream catalyst may have a total column 6 metal content (s) per gram of the seventh downstream catalyst which is equal to or greater than the total column 6 metal content in the seventh upstream catalyst or at least 0.02 gram of Column 6 metal (s) per gram of catalyst. In some embodiments, the position of the seventh upstream catalyst and the seventh downstream catalyst may be reversed. The ability to use a relatively small amount of catalytically active metal in the seventh downstream catalyst may allow other properties of the crude oil product to be changed only in small amounts relative to the same properties of the crude oil feed (for example, a relatively small change). small in heteroatom content, API gravity, residue content, VGO content or combinations thereof). Contacting the crude oil feed with the seventh upstream and downstream catalysts can produce a crude oil product that has a maximum of 90%, a maximum of 80%, a maximum of 50%, a maximum of 10% or at least 1% of the TAN of the crude oil feed. In some embodiments, the crude oil feed TAN may be incrementally reduced by contact with the seventh upstream and downstream catalysts (for example, contact of the crude oil feed with a catalyst to form an initial crude oil product with properties changed relative to the crude oil feed and then contact of the initial crude oil product with an additional catalyst to produce the crude oil product with changed properties relative to the initial crude oil product). The ability to incrementally reduce TAN can help maintain the stability of the crude oil / total product feed mixture during processing.

In some embodiments, catalyst selection and / or catalyst ordering in combination with controlled contact conditions (eg, crude oil feed temperature and / or feed rate) may assist in reducing hydrogen uptake by feed. maintaining the stability of the crude oil feed / total product mixture during processing and changing one or more properties of the crude oil product relative to the respective properties of the crude oil feedstock. The stability of the crude oil / total product feed mixture may be effected by the various stages separating from the crude oil / total product feed mixture. Phase separation may be caused, for example, by the insolubility of the crude oil feed and / or crude oil product in the crude oil feed / total product mixture, asphaltenes flocculation of the crude oil feed / total product mixture, precipitation of components of the crude oil / total product feed mixture or combinations thereof.

At certain times during the contact period, the crude oil and / or total product feed concentration in the crude oil / total product feed mixture may change. As the concentration of total product in the crude oil feed / total product mixture changes due to the formation of crude oil product, the solubility of the crude oil feed components and / or components of the total product in the crude oil feed mixture / Total product tends to change. For example, the crude oil feed may contain components that are soluble in the crude oil feed at the beginning of processing. As the properties of the very petroleum feed changes (eg, TAN, MCR, C5 asphaltenes, the value valor or combinations thereof), the components may tend to become less soluble in the crude oil / total product feed mixture. In some examples, the crude oil feed and the total product may form two phases and / or become insoluble with each other. Changes in solubility may also result in the formation of two or more phases in the crude oil / total product feed mixture. The formation of two phases through asphaltene flocculation, change in feed and crude product feed concentration and / or component precipitation tends to shorten the life of one or more of the catalysts.

Additionally, process efficiency can be reduced. For example, repeated treatment of the crude oil / total product feed mixture may be necessary to produce a crude oil product with desired properties.

During processing, the P value of the crude oil feed / total product mixture can be monitored and the process stability, crude oil feed and / or crude oil / total product feed mixture can be evaluated. Typically, a P value of at most 1.5 indicates that asphaltenes flocculation from the crude oil feed generally occurs. If the P value is initially at least 1.5 and such P value increases or is relatively stable during contact, then this indicates that the crude oil feed is relatively stable during contact. The stability of the crude oil / total product feed mixture, as assessed by the P value, can be controlled by controlling the contact conditions, the selection of catalysts, the selective order of catalysts or combinations thereof. Such control of contact conditions may include controlling LHSV, temperature, pressure, hydrogen absorption, crude oil feed flow or combinations thereof.

In some embodiments, contact temperatures are controlled such that C5 asphaltenes and / or other asphaltenes are removed while maintaining the MCR content of the crude oil feed. Reduction of MCR content through hydrogen absorption and / or higher contact temperatures may result in the formation of two phases that may reduce the stability of the crude oil / total product feed mixture and / or life of one or more of the two. catalysts. Control of contact temperature and hydrogen absorption in combination with the catalysts described herein allows C5 asphaltenes to be reduced while the MCR content of the crude oil feed changes only in a relatively small amount.

In some embodiments, contact conditions are controlled such that temperatures in one or more contact zones may be different. Operating at different temperatures allows for selective change in crude oil feed properties while maintaining the stability of the crude oil / total product feed mix. The crude oil feed enters a first contact zone at the beginning of a process. A first contact temperature is the temperature in the first contact zone. Other contact temperatures (for example, the second temperature, third temperature, fourth temperature, et cetera) are the temperatures in the contact zones that are positioned after the first contact zone. A first contact temperature may be in a range of 100 to 420 ° C and a second contact temperature may be in a range that is 20 to 100 ° C, 30 to 90 ° C, or 40 to 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 reduce 0 TAN and / or 0 C5 asphaltenes content in a crude oil product relative to the TAN and / or C5 asphaltenes content of the crude oil feed to a greater degree than the amount TAN and / or asphaltene C5 reduction, if any, when the first and second contact temperatures are the same as or within 10 ° C of each other.

For example, a first contact zone may include a first catalyst (s) and / or a fourth catalyst (s) and a second contact zone may include other catalyst (s) described herein. The first contact temperature may be 350 ° C and the second contact temperature may be 300 ° C. Contacting the crude oil feed in the first contact zone with the first catalyst and / or fourth catalyst at the highest temperature prior to contact with the other catalyst (s) in the second contact zone may result in more than the reduction of TAN and / or C5 asphaltenes in the crude oil feed compared to the reduction of TAN and / or C5 asphaltenes in the same crude oil feed when the first and second contact temperatures are within 10 ° C.

EXAMPLES

Non-limiting examples of carrier preparation, catalyst preparations and systems with selected catalyst arrangement and controlled contact conditions are given below.

Example 1. Preparation of a Catalyst Support. A support was prepared by grinding 576 grams of alumina (Criterion Catalysts and Technologies LP, Michigan City, Michigan, U.S.A.) with 585 grams of water and 8 grams of glacial nitric acid for 35 minutes. The resulting milled mixture was extruded through a 1.3 Trilobe® matrix plate, dried between 90 and 125 ° C and then calcined at 918 ° C, which resulted in 650 grams of a calcined support with a mean pore diameter of 182 Â. The calcined support was placed in a Lindberg oven. The temperature of the oven was raised between 1000 and 1100 ° C in 1.5 hours and then kept in this range for 2 hours to produce the support. The support included per gram of support 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. The support had a surface area of 110 m2 / g and a total pore volume of 0.821 cm 3 / g. The support had a pore size distribution with an average pore diameter of 232 µm, with 66.7% of the total number of pores in the pore size distribution having a pore diameter within 85 µm of the average pore diameter.

This example demonstrates how to prepare a support that has a pore size distribution of at least 180 µm and includes at least 0.1 gram of theta alumina.

Example 2, Preparation of a Vanadium Catalyst Having a Pore Size Distribution With an Average Pore Diameter of At Least 230 Ã…. Vanadium catalyst was prepared as follows. The alumina support prepared by the method described in Example 1 was impregnated with a vanadium impregnating solution prepared by combining 7.69 grams of VOSO4 with 82 grams of deionized water.

A pH of the solution was 2.27. The alumina support (100 g) was impregnated with the vanadium impregnating solution, aged for 2 hours with occasional stirring, dried at 125 ° C for several hours and then calcined at 480 ° C for 2 hours. The resulting catalyst contained 0.04 grams of vanadium per gram of catalyst, with the remainder being the support. The vanadium catalyst had a pore size distribution with an average pore diameter of 350 Å, a pore volume of 0.69 cm 3 / g and a surface area of 110 m2 / g.

Additionally, 66.7% of the total number of pores in the pore size distribution of the vanadium catalyst had a pore diameter within 70 µm of the average pore diameter.

This example demonstrates the preparation of a Column 5 catalyst having a pore size distribution with an average pore diameter of at least 230 Å.

Example 3. Preparation of a Molybdenum Catalyst Having a Pore Size Distribution With an Average Pore Diameter of At Least 230 µm. The molybdenum catalyst was prepared as follows. 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 (ΝΗ4) 2Μθ2θ7, 6.38 grams of Mo03,1.12 grams of 30% H202, 0.27 grams of monoethanolamine (MEA) and 6, 51 grams of deionized water to form a mud. The slurry was heated to 65 ° C until the solids 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 support (100 grams) was impregnated with the molybdenum impregnation solution, aged for 2 hours with occasional stirring, dried at 125 ° C for several hours and then calcined at 480 ° C for 2 hours. The resulting catalyst contained 0.04 grams of molybdenum per gram of catalyst, with the rest being the support. The molybdenum catalyst had a pore size distribution with an average pore diameter of 250 Å, a pore volume of 0.77 cm 3 / g and a surface area of 116 m2 / g. Additionally, 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 average pore diameter.

This example demonstrates the preparation of a Column 6 metal catalyst having a pore size distribution with an average pore diameter of at least 230 Å.

Example 4. Preparation of a Molybdenum / Vanadium Catalyst having a Pore Size Distribution With an Average Pore Diameter of at least 230 µm. The molybdenum / vanadium catalyst was prepared as follows. The alumina support prepared by the method described in Example 1 was impregnated with a molybdenum / vanadium impregnating solution prepared as follows. A first solution was made by combining 2.14 grams of (NH4) 2Mo207, 3.21 grams of M0O3, 0.56 grams of 30% hydrogen peroxide (H2O), 0.14 grams of monoethanolamine (MEA) and 3.28 grams of deionized water to form a mud. The slurry was heated to 65 ° C until the solids 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 solution and the second solution were combined and sufficient deionized water was added to bring the combined solution volume to 82 ml to produce the molybdenum / vanadium impregnation solution. The alumina was impregnated with the molybdenum / vanadium impregnating solution, aged for 2 hours with occasional stirring, dried at 125 ° C for several hours and then calcined at 480 ° C for 2 hours. The resulting catalyst contained per gram of catalyst 0.02 grams of vanadium and 0.02 grams of molybdenum, with the remainder being the support. The molybdenum / vanadium catalyst had a pore size distribution with an average pore diameter of 300 µm.

This example demonstrates the preparation of a Column 6 metal catalyst and a Column 5 metal having a pore size distribution with an average pore diameter of at least 230 Å.

Example 5. Contacting a Crude Oil Feed With Three Catalysts. A tubular reactor with a centrally positioned thermal well was equipped with thermocouples to measure temperatures throughout a catalyst bed. The catalyst bed was formed by filling the space between the thermal well and a reactor inner wall with catalysts and silicon carbide (grade 20, Stanford Materials;

Aliso Viejo, CA). Such silicon carbide is believed to have low catalytic properties, if any, under the process conditions described herein.

All catalysts were combined with an equal volumetric amount of silicon carbide before placing the mixture within the reactor contact zone portions. The crude oil feed flow to the reactor went from the top of the reactor to the reactor output. The silicon carbide was positioned at the bottom of the reactor to serve as a bottom support. A catalyst / bottom silicon carbide mixture (42 cm) was positioned on top of the silicon carbide to form a bottom contact zone. The bottom catalyst had a pore size distribution with an average pore diameter of 77 Å, with 66.7% of the total number of pores in the pore size distribution having a pore diameter within 20 Å of the pore diameter. medium. The bottom catalyst contained 0.095 gram molybdenum and 0.025 gram nickel per gram catalyst, with the rest being an alumina support.

A catalyst / intermediate silicon carbide mixture (56 cm) was positioned on top of the bottom contact zone to form an intermediate contact zone. The intermediate catalyst had a pore size distribution with an average 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 average pore diameter. . The intermediate catalyst contained 0.02 grams of nickel and 0.08 grams of molybdenum per gram of catalyst, with the rest being an alumina support.

A top catalyst / silicon carbide mixture (42 cm3) was positioned on top of the intermediate contact zone to form a top contact zone. The top catalyst had a pore size distribution with an average pore diameter of 192 Å and contained 0.04 gram molybdenum per gram catalyst, with the remainder being primarily a gamma alumina support.

Silicon carbide was positioned at the top of the top contact zone to fill the dead space and to serve as a preheat zone. The catalyst bed was loaded into a Lindberg furnace that included five heating zones that correspond to the preheating zone, the top, middle and bottom contact zones, and the bottom support.

The catalysts were sulphide by introducing a 5% by volume hydrogen sulfide gas mixture and 95% by volume hydrogen gas within the contact zones at a rate of 1.5 liters of gas mixture per volume (ml) of catalyst total (silicon carbide was not counted as part of the catalyst volume). Contact zone temperatures were raised to 204 ° C (400 ° F) within 1 hour and maintained at 204 ° C for 2 hours. After maintaining at 204 ° C, the contact zones were incrementally increased to 316 ° C (600 ° F) at a rate of 10 ° C (50 ° F) per hour. Contact zones were maintained at 316 ° C for one hour, then incrementally raised to 370 ° C (700 ° F) in 1 hour and maintained at 370 ° C for two hours. Contact zones were allowed to cool to room temperature.

Crude oil from the Mars platform in the Gulf of Mexico was filtered, then heated in a greenhouse at 93 ° C (200 ° F) for 12 to 24 hours to form the crude oil feed having the properties summarized in Table 1, FIG. . 7. The crude oil feed was fed to the top of the reactor. The crude oil feed flowed through the preheat zone, top contact zone, intermediate contact zone, bottom contact zone and reactor bottom support. The crude oil feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions were as follows: hydrogen gas to crude oil feed to reactor ratio was 328 Nm3 / m3 (2000 SCFB), LHSV was 1 h '' and pressure was 6.9 MPa (1014 , 7 psi). The three contact zones were heated to 370 ° C (700 ° F) and held at 370 ° C for 500 hours. The temperatures of the three contact zones were then increased and maintained in the following sequence: 379 ° C (715 ° F) for 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. Total product (ie crude oil and gas product) left the catalyst bed. The total product was introduced into a gas-liquid phase separator. In the gas-liquid phase separator, the total product was separated into crude oil and gas product. The amount of gas entering the system was measured by a mass flow controller. The amount of gas exiting the system was measured by a wet test meter. The crude oil product was periodically analyzed to determine a percentage by weight of crude oil product components. The results listed are averages of the determined weight percentages of the components. The properties of the crude oil product are summarized in Table 1 of FIG. 7

As shown in Table 1, the crude oil product had, per gram of crude oil, a sulfur content of 0.0075 grams, a residue content of 0.255 grams, an oxygen content of 0.0007 grams. The crude oil product had a ratio of MCR content to C5 asphaltenes content of 1.9 and a TAN of 0.09. Total nickel and vanadium was 22.4 wtppm.

Catalyst lifes were determined by measuring a weighted average bed temperature ("WABT") versus the travel length of the crude oil feed. Catalyst lives can be correlated with catalyst bed temperature.

It is believed that as catalyst life decreases, a WABT increases. FIG. 8 is a graphical representation of WABT versus time ("t") for improving crude oil feed in contact zones described in this example. Plot 136 represents the average WABT of the three contact zones versus driving time hours for contacting a crude oil feed with the top, middle and bottom catalysts. For most of the driving time, the WABT's contact zones only changed by approximately 20 ° C. From a relatively stable WABT it was possible to estimate that the catalytic activity of the catalyst was not affected. Typically, a pilot unit driving time from 3000 to 3500 hours correlates with 1 year of commercial operation.

This example demonstrates that contacting the crude oil feed with a catalyst having a pore size distribution with an average pore diameter of at least 180 Å and additional catalysts having a pore size distribution with an average pore diameter in a range. 90 to 180 Λ, with at least 60% of the total number of pores in the pore size distribution having a pore diameter within 45 µm of the average pore diameter, with controlled contact conditions, produced a total product that included crude oil product. As measured by the P value, the stability of the crude oil feed / total product mixture was maintained. The crude oil product had reduced TAN, reduced Ni / V / Fe content, reduced sulfur content and reduced oxygen content relative to the crude oil feed, while the residue content and VGO content of the crude oil product. was 90% to 110% of these properties of the crude oil feed.

Example 6. Contacting a Crude Oil Feed with Two Catalysts That Have a Pore Size Distribution with an Average Pore Diameter in a Range Between 90 to 180 Å. The reactor apparatus (except for the number and content of the contact zones), the catalyst sulfide method, the total product separation method and the crude oil product analysis method were the same as described in Example 5. Each catalyst was mixed with an equal volume of silicon carbide. The crude oil feed flow to the reactor went from the top of the reactor to the bottom of the reactor. The reactor was filled from the bottom to the top as follows. The silicon carbide was positioned at the bottom of the reactor to serve as a bottom support. A bottom catalyst / silicon carbide mixture (80 cm3) was positioned on top of the silicon carbide to form a bottom contact zone. The bottom catalyst had a pore size distribution with an average 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 pore diameter. medium. The bottom catalyst included 0.11 gram molybdenum and 0.02 gram nickel per gram catalyst, with the rest being support.

A top catalyst / silicon carbide mixture (80 cm3) was positioned on top of the bottom contact zone to form the top contact zone. The top catalyst had a pore size distribution with an average pore diameter of 100 µm, with 66.7% of the total number of pores in the pore size distribution having a pore diameter within 20  of the pore diameter. medium. The top catalyst included 0.03 grams of nickel and 0.12 grams of molybdenum per gram of catalyst, with the rest being alumina. Silicon carbide was positioned on top of the first contact zone to fill the dead space and to serve as a preheat zone. The catalyst bed was loaded into a Lindberg furnace which included four heating zones corresponding to the preheating zone, the two contact zones and the bottom support.

BS-4 crude oil (Venezuela) having the properties summarized in Table 2, FIG. 9, was fed to the top of the reactor. Low oil feed flowed through the preheat zone, the top contact zone, the bottom contact zone, and the reactor bottom support. The crude oil feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions were as follows: the ratio of hydrogen gas to crude oil feed supplied 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 contact zones were heated to 260 ° C (500 ° F) and held at 260 ° C (500 ° F) for 287 hours. The temperatures of the two contact zones were then increased and maintained in the following sequence: 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 driving time of 1173 hours. The total product left the reactor and was separated as described in Example 5. The crude oil product had an average TAN of 0.42 and an average API gravity of 12.5 during processing. The crude oil product had, per gram of crude oil, 0.0023 grams of sulfur, 0.0034 grams of oxygen, 0.441 grams of VGO and 0.378 grams of residue.

Additional properties of the crude oil product are listed in TABLE 2 in FIG. 9

This example demonstrates that contacting the crude oil feed with the catalysts having pore size distributions with an average pore diameter in a range of 90 to 180 Å produced a very low petroleum product that had a reduced TAN, a Ni content. / V / Fe and a reduced oxygen content in relation to the properties of the low oil feed, while the residue content and VGO content of the low oil product were 99% and 100% of the respective feed properties of fine oil.

Example 7. Contacting a Low Oil Feed With Two Catalysts. The reactor apparatus (except for number and content of contact zones), catalysts, total product separation method, crude oil product analysis and catalyst sulfide method were the same as described in Example 6.

A crude oil feed (BC-10 crude oil) having the properties summarized in Table 3, FIG. 10, was fed into the top of the reactor. The crude oil feed flowed through the preheat zone, top contact zone, bottom contact zone, and bottom support of the reactor. The contact conditions were as follows: ratio of hydrogen gas to crude oil feed supplied to the reactor was 80 Nm3 / m3 (500 SCFB), LHSV was 2 h'1 and pressure was 6.9 MPa (1014.7 psi). The two contact zones were incrementally heated to 343 ° C (650 ° F). A total driving time was 1007 hours. The crude oil product had an average TAN of 0.16 and an average API gravity of 16.2 during processing. The crude oil product had 1.9 wtppm calcium, 6 wtppm sodium, 0.6 wtppm zinc and 3 wtppm potassium. The crude oil product had, per gram of crude oil, 0.0033 grams of sulfur, 0.002 grams of oxygen, 0.376 grams of VGO and 0.401 grams of residue. Additional properties of the crude oil product are listed in Table 3 in FIG. 10

This example demonstrates that the contact of the crude oil feed with the selected catalysts with pore size distributions in a range of 90 to 180 Å produced a crude oil product that had a reduced TAN, a calcium, sodium, zinc content. and reduced total potassium while the sulfur content, VGO content and residue content of the crude oil product were 76%, 94% and 103% of their respective crude oil feed properties.

Examples 8 to 11. Contacting a Crude Oil Feed With Four Catalyst Systems and Under Various Contact Conditions. Each reactor apparatus (except for number and content of contact zones), each catalyst sulfide method, each total product separation method, and each crude oil product analysis were 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 catalyst unless otherwise indicated. The crude oil feed flow through each reactor went from the top of the reactor to the bottom of the reactor. The silicon carbide was positioned at the bottom of each reactor to serve as a bottom support. Each reactor had a bottom contact zone and a top contact zone. After the catalyst / silicon carbide mixtures were placed in the contact zones of each reactor, the silicon carbide was positioned on top of the top contact zone to fill the dead space and to serve as a preheat zone in each reactor. reactor. Each reactor was loaded into a Lindberg furnace that included four heating zones that correspond to the preheating zone, the two contact zones, and the bottom support.

In Example 8, a non-calcined molybdenum / nickel / silicon carbide catalyst mixture (48 cm) was positioned in the bottom contact zone. The catalyst included per gram of catalyst 0.146 grams of molybdenum, 0.047 grams of nickel and 0.021 grams of phosphorus, with the remainder being alumina support.

A mixture of molybdenum catalyst / silicon carbide (12 cm3) with the catalyst having a pore size distribution with an average pore diameter of 180 Â was positioned in the top contact zone. The molybdenum catalyst had a total content of 0.04 gram molybdenum per gram catalyst, with the rest being support that included at least 0.50 gram gamma alumina per gram support.

In Example 9, an uncalcined molybdenum / cobalt / silicon carbide catalyst mixture (48 cm) was positioned in both contact zones. The uncalcified molybdenum / cobalt catalyst included 0.143 grams of molybdenum, 0.043 grams of cobalt and 0.021 grams of phosphorus with the rest being alumina support.

A molybdenum / silicon carbide catalyst mixture (12 cm3) was placed in the top contact zone. The molybdenum catalyst was the same as in the top contact zone of Example 8.

In Example 10, the molybdenum catalyst as described in the top contact zone of Example 8 was mixed with silicon carbide and positioned in both contact zones (60 cm3).

In Example 11, a non-calcined molybdenum / nickel / silicon carbide catalyst mixture (48 cm3) was positioned in the bottom contact zone. The uncalcified molybdenum / nickel catalyst included, per gram of catalyst, 0.09 gram of molybdenum, 0.025 gram of nickel and 0.01 gram of phosphorus, with the rest being alumina support.

A molybdenum / silicon carbide catalyst mixture (12 cm3) was placed in the top contact zone. The molybdenum catalyst was the same as in the top contact zone of Example 8. The Mars (Gulf of Mexico) crude oil product was filtered, then heated in a greenhouse to a temperature of 93 ° C (200 ° F ) for 12 to 24 hours to form the crude oil feed for Examples 8 to 11 having the properties summarized in Table 4, FIG. 11. The crude oil feed was fed at the top of the reactor in these examples. The crude oil feed flowed through the preheat zone, top contact zone, bottom contact zone, and bottom support of the reactor. The crude oil feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions for each example were as follows: the ratio of hydrogen gas to crude oil 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 hours of contact and then decreased to 1.0 h'1 during the remaining contact times. Temperatures in all contact zones were 343 ° C (650 ° F) for 500 contact hours. After 500 hours, temperatures in all contact zones were controlled as follows: temperature in contact zones was raised to 354 ° C (670 ° F), maintained at 354 ° C for 200 hours; raised to 366 ° C (690 ° F), maintained at 366 ° C for 200 hours; raised to 371 ° C (700 ° F) maintained at 371 ° C for 1000 hours; raised to 385 ° C (725 ° F) maintained at 385 ° C for 200 hours; then raised to a final temperature of 399 ° C (750 ° C) and held at 399 ° C for 200 hours for a total contact time of 2300 hours.

Low oil products were periodically analyzed to determine TAN, hydrogen uptake by crude oil feed, P value, VGO content, residue content and oxygen content. Average values for the properties of crude oil products produced in Examples 8 through 11 are listed in Table 5 in FIG. 11. FIG. 12 is a graphical representation of the crude oil product P value ("P") versus the driving time ("t") for each of the catalyst systems of Examples 8 through 11. The crude oil feed had a value of P of at least 1.5. Plots 140,142, 144 and 146 represent the P value of the crude oil product obtained by contacting the crude oil feed with the four catalyst systems of Examples 8 through 11 respectively. For 2300 hours, the P value of the crude product remained at least 1.5 for the catalyst systems of Examples 8 through 10. In Example 11, the P value was above 1.5 for most of the time. driving At the end of driving (2300 hours) for Example 11, the P value was 1.4. From the P value of the crude oil product for each test, it can be deduced that the crude oil feed in each test remained relatively stable during contact (for example, the crude oil feed did not phase out).

As shown in FIG. 12, the P value of the crude oil product remained relatively constant during significant portions of each test, except for Example 10, where the P value increased. FIG. 13 is a graphical representation of the net hydrogen absorption by the crude oil feed (“H2”) versus the driving time (“t”) for the four catalyst systems in the presence of hydrogen gas. Plots 148,150 152,154 represent the net hydrogen absorption obtained by contacting the crude oil feed with each of the catalyst systems of Examples 8 through 11, respectively. The net absorption of hydrogen by a crude oil feed over a driving time of 2300 hours was in the range of 7 to 48 Nm3 / m3 (43.8 to 300 SCFB). As shown in FIG. 13, the net hydrogen absorption of the crude oil feed was relatively constant during each test. FIG. 14 is a graphical representation of the residue content, expressed as a percentage by weight, of crude oil product ("R") versus conduction time ("t") for each of the catalyst systems of Examples 8 to 11. In each of the four tests, the crude oil product had a residue content of 88 to 90% of the residue content of the crude oil feed. Plots 156, 158, 160, 162 represent the residue content of the crude oil product obtained by contacting the crude oil feed with the catalyst systems of Examples 8 through 11, respectively. As shown in FIG. 14, the residue content of the crude oil product remained relatively constant over significant portions of each test. FIG. 15 is a graphical representation of the change in API gravity of crude oil product (“Δ API”) versus driving time (“t”) for each of the catalyst systems of Examples 8 through 11. Plots 164, 166,168,170 represent the API gravity of the crude oil product obtained by contacting the crude oil feed with the catalyst systems of Examples 8 through 11, respectively. In each of the four tests, each crude oil product had a viscosity in the range of 58.3 to 72.7 cSt. The API gravity of each crude oil product increased by 1.5 to 4.1 degrees. The increased API gravity corresponds to an API gravity of crude oil products in a range of 21.7 to 22.95. The API gravity in this range is 110 to 117% of the API gravity of the crude oil feed. FIG. 16 is a graphical representation of the oxygen content, expressed in weight percent, of the crude oil product ('Of') versus the driving time ('t') for each of the catalyst systems of Examples 8 through 11. Plots 172,174,176,178 represent the oxygen content of the crude oil product obtained by contacting the crude oil feed with the catalyst systems of Examples 8 through 11, respectively. Each crude oil product had a maximum oxygen content of 16% of the crude oil feed. Each crude oil product had an oxygen content in the range of 0.0014 to 0.0015 gram per gram of crude oil during each test. As shown in FIG. 16, The oxygen content of the crude product remained relatively constant after 200 hours of contact time. The relatively constant oxygen content of the crude oil product demonstrates that the selected organic oxygen compounds are reduced during 0 contact. Since TAN was also reduced in these examples, it can be deduced that at least a portion of the carboxylic-containing organic oxygen compounds are selectively reduced in the non-carboxylic-containing organic oxygen compounds.

In Example 11, under the reaction conditions of 37PC (700 ° F), a pressure of 6.9 MPa (1014.7 psi) and a hydrogen to feed ratio of 160 Nm3 / m3 (1000 SCFB), the Reduction of the MCR content of the crude oil feed was 17.5% by weight, based on the weight of the crude oil feed. At a temperature of 399 ° C (750 ° F), at the same pressure and hydrogen ratio for crude oil feed, the reduction in MCR content of the crude oil feed was 25.4 wt.% Based on wt. of the crude oil feed.

In Example 9, under the reaction conditions of 371 ° C (700 ° F), a pressure of 6.9 MPa (1014.7 psi) and a hydrogen to feed ratio of 160 Nm3 / m3 (1000 SCFB) , the reduction in the MCR content of the crude oil feed was 17.5% by weight based on the weight of the crude oil feed. At a temperature of 399 ° C (750 ° F), at the same pressure and hydrogen ratio for crude oil feed, the reduction in the MCR content of the crude oil feed was 19 wt.% Based on feed weight. of crude oil. The increased reduction in the MCR content of the crude oil feed demonstrates that the uncalcined Columns 6 and 10 metal catalyst facilitates the reduction of the MCR content at higher temperatures than the uncalcined Columns 6 and 9 metal catalyst.

These examples demonstrate that contacting a relatively high TAN with a relatively high TAN (0.8 TAN) with one or more catalysts produces the crude oil product while maintaining the stability of the crude oil / total product feed mixture. and with relatively small net hydrogen absorption. The selected crude oil product properties were at most 70% of the same properties as the crude oil feed, while the selected crude oil product properties were within 20-30% of the same crude oil feed properties.

Specifically, as shown in Table 4, each of the crude oil products was produced with a net absorption of ■! hydrogen by crude oil feeds of up to 44 Nm / m (275 SCFB). Such products had an average TAN of at most 4% of the crude oil feed and an average total Ni / V content of at most 61% of the total Ni / V content of the crude oil feed, while maintaining a P value for crude oil feed above 3. The average residue content of each crude oil product was 88 to 90% of the residue content of the crude oil feed. The average VGO content of each crude oil product was 115 to 117% of the VGO content of the crude oil feed. The average API gravity of each crude oil product was 110 to 117% of the API gravity of the oil feed. while the viscosity of each crude oil product was at most 45% of the viscosity of the crude oil feed.

Examples 12 through 14: Contacting a Crude Oil Feed With Catalysts Having a Pore Size Distribution With an Average Pore Diameter of At Least 180 Â ° C With Minimum Hydrogen Consumption. In Examples 12 through 14, each reactor apparatus (except for number and content of contact zones), each catalyst sulfide method, each total product separation method, and each crude oil product analysis were the same as described. in Example 5. All catalysts were mixed with an equal volume of silicon carbide. The crude oil feed flow for each reactor was from the top of the reactor to the bottom of the reactor. The silicon carbide was positioned at the bottom of each reactor to serve as a bottom support.

Each reactor contained a contact zone. After the catalyst / silicon carbide mixtures were placed in the contact zone of each reactor, the silicon carbide was positioned on top of the top contact zone to fill the dead space and to serve as a preheat zone in each reactor. reactor. Each reactor was loaded into a Lindberg furnace that included three heating zones corresponding to the preheating zone, the contact zone and the bottom support. The crude oil feed was contacted with each catalyst in the presence of hydrogen gas.

A catalyst / silicon carbide mixture (40 cm3) was positioned on top of the silicon carbide to form the contact zone. For Example 12, the catalyst was vanadium catalyst as prepared in Example 2. For Example 13, catalyst was molybdenum catalyst as prepared in Example 3. For Example 14, catalyst was molybdenum / vanadium catalyst as prepared in Example 4.

The contact conditions for Examples 12 through 14 were as follows: hydrogen to feed ratio of crude oil supplied to the reactor was 160 Nm3 / m3 (1000 SCFB), LHSV was 1 h'1 and pressure was 6.9 MPa (1014.7 psi). Contact zones have been incrementally heated to 343 ° C (650 ° F) over a period of time and maintained at 343 ° C for 120 hours for a total driving time of 360 hours.

Total products exited the contact zones and were separated as described in Example 5. The net hydrogen absorption during contact was determined for each catalyst system. In Example 12, the net hydrogen uptake was -10.7 Nm3 / m3 (-65 SCFB) and the crude oil product had a TAN of 6.75. In Example 13, the 1st net hydrogen absorption was in a range of 2.2 to 3.0 Nm / m (13.9 to 18.7 SCFB) and the crude oil product had a TAN in a range of 0 , 3 to 0.5. In Example 14, during the contact of the crude oil feed with the molybdenum / vanadium catalyst, the net hydrogen absorption was in a range of -0.05 Nm3 / m3 to 0.6 Nm3 / m3 (-0.36 SCFB 4.0 SCFB) and the crude oil product had a TAN in a range of 0.2 to 0.5. From the net hydrogen absorption values during contact, it was estimated that hydrogen was generated at a rate of 10.7 Nm / m (65 SCFB) during crude oil feed contact and vanadium catalyst. . Hydrogen generation during contact allows less hydrogen to be used in the process compared to the amount of hydrogen used in conventional processes to improve the properties of disadvantageous crude oils. The requirement for less hydrogen during contact tends to lower the processing costs of a crude oil.

Additionally, the contact of the crude oil feed with the molybdenum / vanadium catalyst produced a crude oil product with a TAN that was lower than the TAN of the crude oil product produced from the individual molybdenum catalyst.

Examples 15 to 18. Contacting a Crude Oil Feed With a Vanadium Catalyst and an Additional Catalyst.

Each reactor apparatus (except for number and content of contact zones), each catalyst sulfide method, each total product separation method, and each crude oil product analysis were 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 catalyst unless otherwise indicated. The crude oil feed flow to each reactor went from the top of the reactor to the bottom of the reactor. The silicon carbide was positioned at the bottom of each reactor to serve as a bottom support. Each reactor had a bottom contact zone and a top contact zone. After the catalyst / silicon carbide mixtures were placed in the contact zones of each reactor, silicon carbide was positioned on top of the top contact zone to fill the dead space and to serve as a preheat zone in each reactor. . Each reactor was loaded into a Lindberg furnace that included four heating zones corresponding to the preheating zone, the two contact zones, and the bottom support.

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

In Example 15, an additional catalyst / silicon carbide mixture (45 cm3) was positioned in the bottom contact zone, with the additional catalyst being the molybdenum catalyst prepared by the method described in Example 3. The vanadium / catalyst mixture Silicon carbide (15 cm3) was positioned in the top contact zone.

In Example 16, an additional catalyst / silicon carbide mixture (30 cm3) was positioned in the bottom contact zone, with the additional catalyst being the molybdenum catalyst prepared by the method described in Example 3. The vanadium / catalyst mixture Silicon carbide (30 cm) was positioned in the top contact zone.

In Example 17, an additional catalyst / silicon mixture (30 cm 3) was positioned in the bottom contact zone, with the additional catalyst being the molybdenum / vanadium catalyst as prepared in Example 4. The vanadium / catalyst mixture Silicon carbide (30 cm) was positioned in the top contact zone.

In Example 18, Pyrexo beads (Glass Works Corporation, New York, U.S.A.) (30 cm) were positioned in each contact zone. Crude oil (Santos Basin, Brazil) for examples 15 to 18 having the properties summarized in Table 5, FIG. 17 was fed into the top of the reactor. The crude oil feed flowed through the preheat zone, top contact zone, bottom contact zone, and bottom support of the reactor. The crude oil feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions for each example were as follows: the ratio of hydrogen gas to crude oil feed supplied to the reactor was 160 Nm / m (1000 SCFB) for the first 86 hours and 80 Nm3 / m3 (500 SCFB) for the remaining time, the LHSV was 1 h'1 and the pressure was 6.9 MPa (1014.7 psi). Contact zones have been incrementally heated to 343 ° C (650 ° F) over a period of time and maintained at 343 ° C for a total driving time of 1400 hours.

These examples demonstrate that contacting a crude oil feedstock with a Column 5 metal catalyst having a pore size distribution with an average pore diameter of 350 Å in combination with an additional catalyst having a pore size distribution with an average pore diameter in a range of 250 to 300 Â °, in the presence of a hydrogen source, produces a crude oil product with properties that change relative to the same crude oil feed properties, while only changing in small quantities. other properties of the crude oil product in relation to the same properties as the crude oil feed. Additionally, during processing, relatively small hydrogen uptake by the crude oil feed was observed.

Specifically, as shown in Table 5, FIG. 17, the crude oil product has a TAN of at most 15% of the crude oil feed TAN for Examples 15 to 17. The crude oil products produced in Examples 15 to 17 each had a total Ni content / V / Fe of maximum 44%, an oxygen content of maximum 50% and viscosity of maximum 15% with respect to the same properties as the crude oil feed. Additionally, the crude oil products produced in Examples 15 to 17 each had an API gravity of 100 to 103% of the API gravity of the crude oil feed.

In contrast, crude oil product produced under non-catalytic conditions (Example 18) produced a product with increased viscosity and decreased API gravity relative to the viscosity and API gravity of the increased viscosity and decreased API gravity crude feed, it may be possible deduce that cooking and / or polymerization of the crude oil feed has been initiated.

Examples 19. Contacting a Crude Oil Feed at Multiple LHSV, The contact systems and catalysts were the same as described in Example 6. The properties of the crude oil feeds are listed in Table 6 in FIG. 18. The contact conditions were as follows: a hydrogen gas to crude oil feed to reactor ratio was 160 Nm3 / m3 (1000 SCFB), pressure was 6.9 MPa (1014.7 psi) and contact zone temperature was 371 ° C (700 ° F) during total driving time. In Example 19, LHSV during contact was increased over a time period of 1 h'1 to 12 h'1, maintained at 12 h'1 for 48 hours and then LHSV was increased to 20.7 h'1 and maintained at 20.7 h -1 for 96 hours.

In Example 19, the crude oil product was analyzed to determine TAN, viscosity, density, VGO content, residue content, heteroatom content and metal content in the organic acid metal salts during the time periods when the LHSV was at 12 h'1 and 20.7 h "1. Average values for the properties of crude oil products are shown in Table 6, FIG. 18.

As shown in Table 6, FIG. 18, the crude oil product for Example 19 had a low TAN and a low viscosity relative to the TAN and viscosity of the low oil feed, while the API gravity of the crude oil was 104 to 110% of the API gravity. of the crude oil feed. A weight ratio of MCR content to C5 asphaltenes content was at least 1.5. The sum of the MCR content and C5 asphaltenes content was reduced relative to the sum of the MCR content and C5 asphaltenes content of the crude oil feed. From the weight ratio of the MCR content to the C5 asphaltenes content and the reduced sum of the MCR and C5 asphaltenes content, it can be deduced that asphaltenes rather than components that have a tendency to form coke are being reduced. The crude oil product also had a total potassium, sodium, zinc and calcium content of up to 60% of the total content of the same metals as the crude oil feed. The sulfur content of the crude oil product was 80 to 90% of the sulfur content of the crude oil feed.

Examples 6 and 19 demonstrate that contact conditions can be controlled such that an LHSV across the contact zone is greater than 10 h'1, as compared to a process having an LHSV of 1 h'1, to produce products. of crude oil with similar properties. The ability to selectively change a property of a crude oil feed at net hourly space speeds greater than 10 h'1 allows the contact process to be performed in containers smaller than commercially available containers.

A smaller container size may allow the treatment of disadvantageous crude oils to be carried out at production sites of restricted size (eg offshore installations).

Example 20. Contacting a Very Fine Oil Feed at Various Contact Temperatures. The contact systems and catalysts were the same as described in Example 6. The crude oil feed having the properties listed in Table 7 in FIG. 19 was added to the top of the reactor and contacted with the two catalysts in the two contact zones in the presence of hydrogen to produce a crude oil product. The two contact zones were operated at different temperatures.

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

The contact conditions in the bottom contact zone were as follows: LHSV was 1 h'1, the temperature in the bottom contact zone was 315 ° C (600 ° F); a hydrogen to crude oil feed ratio was 160 Nm3 / m3 (1000 SCFB); and the pressure was 6.9 MPa (1014.7 psi). The total product left the bottom contact zone and was introduced into the gas-liquid phase separator. In the gas-liquid phase separator, the total product was separated into the crude oil and gas product. The crude oil product was periodically analyzed to determine TAN and C5 asphaltene content.

Average values for the crude oil product properties obtained while driving are listed in Table 7, FIG. 19. The crude oil feed had a TAN of 9.3 and a C5 asphaltene content of 0.055 grams of C5 asphaltenes per gram of crude oil feed. The crude oil product had an average TAN of 0.7 and an average C5 asphaltene content of 0.039 grams of C5 asphaltenes per gram of crude oil. The C5 asphaltenes content of the crude oil product was at most 71% of the C5 asphaltenes content of the crude oil product. The total potassium and sodium content in the crude oil product was at most 53% of the total content of the same metals in the crude oil feed. The crude oil product TAN was a maximum of 10% of the crude oil feed TAN. A P value of 1.5 or higher was maintained during 0 contact.

As shown in Examples 6 and 20, having a first (in this case, top) contact temperature that is 50 ° C lower than the contact temperature of the second (in this case, bottom) zone tends to highlight the reduction in C5 asphaltenes content in the crude oil product in relation to the C5 asphaltenes content of the crude oil feed.

Additionally, the reduction of the metal content in the metal salts of organic acids was enhanced using controlled temperature differentials. For example, the reduction in the total potassium and sodium content of the crude oil product of Example 20 was enhanced relative to the reduction in the total potassium and sodium content of the crude oil product of Example 6 with a stability of the petroleum feed mixture. relatively constant gross product / total product for each example as measured by the P value.

Using a lower temperature than a first contact zone allows the removal of high molecular weight compounds (eg C5 asphaltenes and / or metal salts of organic acids) that have a tendency to form polymers and / or compounds having physical properties. softness and / or stickiness (eg gums and / or tars). Removing these compounds at a lower temperature allows such compounds to be removed before they clog and coat the catalysts, thereby extending the life of catalysts operating at higher temperatures that are positioned after the first contact zone.

Example 21. Contacting a Crude Oil Feed and a Catalyst as a Mud. A bulky metal catalyst and / or an on-demand catalyst (0.0001 to 5 grams or 0.02 to 4 grams of catalyst per 100 grams of crude oil feed) may be, in some embodiments, formed in sludge with crude oil feed and reacted under the following conditions: temperature in a range of 85 to 425 ° C (185 to 797 ° F), pressure in a range of 0.5 to 10 MPa, and hydrogen source to feed ratio. crude oil from 16 to 1600 Nm3 / m3 over a period of time. After sufficient reaction time to produce the crude oil product, the crude oil product is separated from the catalyst and / or residual crude oil feed using a separating apparatus such as a filter and / or centrifuge. The crude oil product may have a changed TAN, iron, nickel and / or vanadium content and a reduced C5 asphaltene content relative to the crude oil feed.

Other modifications and alternative embodiments of various aspects of the invention will be apparent to those skilled in the art in view of this disclosure. Accordingly, this description is to be construed as illustrative only and is for the purpose of disclosing to those skilled in the art the general manner of carrying out the invention. It is to be understood that the embodiments of the invention shown and described herein should be taken as examples of embodiments. Elements and materials may be substituted 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 would be apparent to a person skilled in the art after having the benefit of this 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.

Claims (16)

1. Method of producing a crude oil product from a crude oil feed, the crude oil product of which is a liquid mixture at 25 ° C and 0,101 MPa, and whose crude oil product has a total acid value ( 90% of the crude oil feedstock TAN, the TAN being determined by the ASTM D664 method, which comprises the steps of: contacting the crude oil feedstock with one or more catalysts comprising one or more metals from column 5 of the periodic table and / or one or more compounds of one or more metals from column 5, at a first temperature followed by contact at a second temperature to produce a total product including the crude oil product, wherein the crude oil feed has a TAN dc of at least 0.3; and. control contact conditions at a temperature in the range of 50 ° C to 500 ° C, a pressure in the range 0.1 MPa to 20 MPa, and a volumetric liquid feed rate per total catalyst volume (LHSV) of the oil feed in the range O.lh 1 to 30b'1 such that the first contact temperature is at least 30 ° C and at most 2 (X) ° C lower than the second contact temperature.
2. Method of producing a crude oil product from a crude oil feedstock, whose crude oil product is a liquid mixture at 25 ° C to 0.101 MPa, and whose crude oil product has a total acid value (TAN). ) not more than 90% of the crude oil feed TAN, the TAN being determined by the ASTM D664 method, characterized in that it comprises the steps of: contacting the crude oil feed with one or more catalysts to produce a product total including crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa and the crude oil feed has a TAN of at least 0.1, with at least one of the catalysts being a catalyst sustained or a bulky metal catalyst comprising vanadium, one or more vanadium compounds or mixtures thereof; and, control the contact conditions at a pressure in the range 0.1 MPa to 20 MPa, a volumetric net feed rate per total catalyst volume (LHSV) of the very low oil feed in the range 0.1h_1 to 30111 and such that the contact temperature is at least 200 ° C.
Method according to either of claims 1 or 2, characterized in that the TAN of the crude oil product is at most 50% or at most 10% of the TAN of the crude oil feed.
Method according to either of claims 1 or 2, characterized in that the TAN of the crude oil product is in the range of 1 to 80%, 20 to 70%, 30 to 60% or 40 to 50%. of the TAN of the very low oil feed.
Method according to any one of claims 1 to 4, characterized in that the TAN of the crude oil product is in the range of 0.001 to 0.5, 0.01 to 0.2 or 0.05. at 0.1.
Method according to any one of claims 1 to 5, characterized in that the TAN of the very low oil feed is in the range 0.3 to 20, 0.4 to 10 or 0.5 to 5. .
A method according to any one of claims 1 to 6, characterized in that at least one catalyst comprises one or more metals from columns 6 to 10 of the periodic table and / or one or more compounds from one or more metals from columns from 6 to 10.
Method according to any one of claims 1 to 7, characterized in that at least one catalyst comprises one or more column 15 elements of the periodic table and / or one or more compounds of one or more column elements 15.
A method according to any one of claims 1 to 8, characterized in that at least one catalyst has a pore size distribution with an average pore diameter of at least 60 Å, at least 90 Å, at least 180 Å. Â or at least 230 Â as determined by the ASTM D4282 method.
A method according to any one of claims 1 to 9, characterized in that at least one catalyst has a pore size distribution such that at least 60% of the total number of pores in the pore size distribution has a diameter. pore size within 70 Â, 45 Â, 35 Â or 25 Â of the average pore diameter.
A method according to any one of claims 1 to 10, characterized in that the very short oil feed is contacted in a contact zone that is in an offshore facility or connected thereto.
A method according to any one of claims 1 to 11, characterized in that the contacting step comprises contacting the very petroleum feed in the presence of a gas comprising a hydrogen source, an inert gas or mixtures thereof.
A method according to any one of claims 1 to 12, further comprising the step of combining the crude oil product with a crude oil that is the same as the crude oil feed or different to form a mixture. .
A method of producing transport fuel, heating fuel, lubricants or chemicals, which comprises processing a crude oil product or a mixture obtained by the method defined in any one of claims 1 to 13.
A method according to claim 14, characterized in that the processing comprises distilling the crude oil product or the mixture into one or more distillate fractions.
Method according to either of claims 14 or 15, characterized in that the processing comprises hydrotreatment.
BRPI0405567 2003-12-19 2004-12-15 Methods of Producing a Crude Oil Product and Transport Fuel, Heating Fuel, Lubricants or Chemicals BRPI0405567B1 (en)

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