JP2007514842A - System, method and catalyst for producing crude product - Google Patents

System, method and catalyst for producing crude product Download PDF

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JP2007514842A
JP2007514842A JP2006545473A JP2006545473A JP2007514842A JP 2007514842 A JP2007514842 A JP 2007514842A JP 2006545473 A JP2006545473 A JP 2006545473A JP 2006545473 A JP2006545473 A JP 2006545473A JP 2007514842 A JP2007514842 A JP 2007514842A
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crude
catalyst
crude product
content
total
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JP5107580B2 (en
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オピンダー・キスハン・バーン
スコット・リー・ウェリントン
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シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイShell Internationale Research Maatschappij Besloten Vennootshap
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Priority to PCT/US2004/042430 priority patent/WO2005063939A2/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

Abstract

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

Description

The present invention relates generally to systems, methods and catalysts for treating crude feed and to compositions that can be produced using such systems, methods and catalysts. More particularly, the specific embodiments described herein are one or more properties wherein the crude feed is a liquid mixture at 25 ° C. and 0.101 MPa, each altered with respect to the properties of the crude feed. The present invention relates to systems, methods and catalysts for conversion to total products including crude product.

2. Description of Related Art Crude oils that have one or more inappropriate properties that cannot be transported economically or processed using conventional equipment are usually referred to as “unfavorable crude oils”. Yes.

  Unfavorable crude oil may contain acidic components that contribute to the total acid number (“TAN”) of the crude feed. Unfavorable crude oil with a relatively high TAN can contribute to corrosion of metal components during transportation and / or processing. In order to remove acidic components from disadvantageous crude oil, the acidic components may be chemically neutralized with various bases. Alternatively, a corrosion-resistant metal may be used for transportation equipment and / or processing equipment. The use of corrosion resistant metals is often very expensive and therefore it may not be desirable to use corrosion resistant metals in existing equipment. Other corrosion prevention methods may add a corrosion inhibitor to the crude oil before it is transported and / or processed. However, the use of corrosion inhibitors can adversely affect equipment used to process the crude oil and / or products produced from the crude oil.

  Unfavorable crude oils often contain relatively high levels of residue. Such high levels of residue tend to make it difficult and expensive to transport and / or process using conventional equipment.

Unfavorable crude oils often contain organically bound heteroatoms (eg, sulfur, oxygen and nitrogen). Organically bonded heteroatoms can adversely affect the catalyst in some cases.
Unfavorable crude oils can contain relatively large amounts of metal contaminants, such as nickel, vanadium, and / or iron. During the processing of such crude oil, metal contaminants and / or compounds may be deposited on the surface or voids of the catalyst. Such deposition can reduce the activity of the catalyst.
During the processing of adverse crude oil, coke is produced and / or deposited at a high rate on the catalyst surface. It can be expensive to regenerate the catalytic activity of a catalyst contaminated with coke. High temperatures used during regeneration may reduce the activity of the catalyst and / or degrade the catalyst.

Unfavorable crude oil may contain metals (eg calcium, potassium and / or sodium) in metal salts of organic acids. The metal in the organic acid metal salt is usually not separated from crude oil which is disadvantageous by conventional methods such as desalting and / or washing.
In the conventional method, the metal in the organic acid metal salt often exists. In general, the metal in the organic acid metal salt may preferentially deposit in the voids between the catalyst particles at the top of the catalyst bed, as opposed to nickel and vanadium deposited near the surface of the catalyst. When contaminants, such as metals in organic acid metal salts, are deposited on top of the catalyst bed, the pressure drop in the catalyst bed increases and can effectively block the catalyst bed. In addition, the metal in the organic acid metal salt can quickly deactivate the catalyst.

  Unfavorable crude oil may contain organic oxygen compounds. Processing facilities that process unfavorable crude oil containing 0.002 g or more of oxygen per gram of unfavorable crude oil can have various problems during processing. Upon heating during processing, the organic oxygen compounds may form higher oxidation compounds (eg, ketones and / or acids formed by the oxidation of alcohols and / or acids formed by the oxidation of ethers). These oxidized compounds are difficult to remove from the processed crude oil and / or may contaminate / corrode equipment during processing, resulting in blockages in the transport line.

  Unfavorable crude oil may contain hydrogen deficient hydrocarbons. When treating hydrocarbons deficient in hydrogen, it is generally necessary to add a steady amount of hydrogen, especially when unsaturated fragments are produced by cracking. During processing, hydrogenation with an active hydrogenation catalyst may usually be required to prevent coking of unsaturated pieces. Making hydrogen is expensive and / or transporting it to a processing facility is expensive.

Unfavorable crude oil also tends to show instability during processing with conventional equipment. Crude oil instability is likely to occur during processing due to phase separation of components and / or formation of undesirable by-products (eg, hydrogen sulfide, water and carbon dioxide).
Conventional methods often lack the ability to change selected properties without significantly changing other properties when changing the selected properties of the disadvantaged crude. For example, conventional methods often lack the ability to significantly reduce TAN while simultaneously changing the content of certain components (such as sulfur or metal contaminants) in adverse crude oils to the desired amount.

  Some methods of improving the quality of crude oil include adding diluents to disadvantageous crude oils to reduce the weight percentage of components that give adverse properties. However, the addition of diluents generally increases the cost of processing unfavorable crude oil due to diluent costs and / or increased costs for handling the disadvantaged crude. In some cases, adding diluents to disadvantaged crudes reduces the stability of such crudes.

  USP 6,547,957 of Sudhakar et al., USP 6,277,269 of Meyers et al., USP 6,063,266 of Grande et al., USP 5,928,502 of Bearden et al., USP 5,914,030 of Bearden et al. US Pat. No. 5,897,769 to Trchte et al., USP 5,871,636 to Tachte et al., USP 5,851,381 to Tanaka et al. Describe various methods, systems and catalysts for treating crude oil. However, the methods, systems and catalysts described in these patents have limited applicability due to the many technical problems.

In short, adverse crude oils generally have undesirable properties (eg, relatively high TAN, tendency to destabilize during processing, and / or tendency to consume relatively large amounts of hydrogen during processing). Other undesirable properties include relatively large amounts of undesirable components (eg, residues, organically bonded heteroatoms, metal contaminants, metals in organic acid metal salts, and / or organic oxygen compounds). It is. These characteristics are prone to problems such as increased corrosion, reduced catalyst life, process blockage, and / or increased hydrogen usage during processing in conventional transportation and / or processing equipment.
USP 6,547,957 USP 6,277,269 USP 6,063,266 USP 5,928,502 USP 5,914,030 USP 5,897,769 USP 5,871,636 USP 5,851,381 USP 6,218,333 USP 6,290,841 USP 5,744,025 US Application Publication No. 20030111391 USP 5,468,372 USP 5,688,736

  Accordingly, there is a very economical and technical need for improved systems, methods, and / or catalysts for converting disadvantageous crudes into crude products with more desirable properties. There is also a very economical and technical need for systems, methods, and / or catalysts that can change selected properties of an unfavorable crude oil while selectively changing other properties while selectively changing other properties. .

SUMMARY OF THE INVENTION The invention described herein generally relates to systems, methods and catalysts for converting crude feed into a crude product and, in some embodiments, a total product comprising non-condensable gases. . The invention described herein also relates to novel compositions that generally consist of novel combinations of various components. Such compositions are obtained using the systems and methods described herein.
The present invention relates to a crude oil raw material having a total acid number (TAN) (measured by ASTM method D664) of 0.3 or more, and at least one of the catalysts has a median pore diameter in the range of 90 to 180 mm, At least 25% of the total pore number in the pore size distribution is brought into contact with one or more catalysts exhibiting a pore size distribution (measured by ASTM method D4282) having a pore diameter within 45 mm of the median pore diameter. Manufacturing a total product including a crude product that is a liquid mixture at 0.101 MPa, and controlling the contact conditions so that the TAN of the crude product is 90% or less of the TAN of the crude feed. A method for producing a crude product containing the same is provided.

  Further, the present invention relates to a crude oil raw material having a TAN (measured by ASTM method D664) of 0.3 or more, and at least one catalyst has a pore size distribution having a median pore diameter of 90 mm or more (measured by ASTM method D4282). The catalyst having the pore size distribution is a kind containing 0.0001 to 0.08 g of molybdenum, one or more molybdenum compounds or a mixture thereof, calculated as the weight of molybdenum, per 1 g of the catalyst. A step of producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa by contacting with the above catalyst, and the TAN of the crude product is 90% or less of the TAN of the crude feed. Thus, a method for producing a crude product including a step of controlling contact conditions is also provided.

  Further, the present invention relates to a crude oil raw material having a TAN (measured by ASTM method D664) of 0.3 or more, and at least one catalyst has a pore size distribution having a median pore diameter of 180 mm or more (measured by ASTM method D4282). And the pore size distribution catalyst comprises one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof. A step of producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa by contacting with at least a seed catalyst, and TAN of the crude product is 90% or less relative to TAN of the crude feed Thus, a method for producing a crude product comprising the step of controlling contact conditions is also provided.

  Further, the present invention provides a crude oil raw material having a TAN (measured by ASTM method D664) of 0.3 or more, wherein at least one of the catalysts is (a) one or more metals in the sixth column of the periodic table; One or more compounds of one or more metals in the column, or a mixture thereof, and (b) one or more metals in the tenth column of the periodic table, one or more metals in the tenth column of the periodic table Or a mixture thereof in a liquid mixture at 25 ° C. and 0.101 MPa in contact with one or more catalysts comprising a total column 10 metal to total column 6 metal molar ratio in the range of 1-10. Providing a method for producing a crude product including a step of producing an entire product including a certain crude product, and a step of controlling contact conditions so that the TAN of the crude product is 90% or less of the TAN of the crude product. To do.

  Further, the present invention provides a crude oil raw material having a TAN (measured by ASTM method D664) of 0.3 or more, wherein at least one of the catalysts is (a) one or more metals in the sixth column of the periodic table; A first catalyst having one or more compounds of one or more metals in the column, or mixtures thereof, in the range of 0.0001 to 0.06 g, calculated as the weight of metal per gram of first catalyst, and ( b) Calculate one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof as the weight of metal per gram of the second catalyst. Producing a total product comprising a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa by contacting with one or more catalysts containing a second catalyst having 0.02 g or more, and a crude product Less than 90% of TAN of crude oil raw material So that the method for producing a crude product comprising the step of controlling the contacting conditions are also provided.

  The present invention also provides (a) one or more metals in column 5 of the periodic table, one or more compounds of one or more metals in column 5 of the periodic table, or a mixture thereof, and (b) X-ray diffraction. In addition, the catalyst has a pore size distribution (measured by ASTM method D4282) having a median pore diameter of 230 mm or more. A catalyst composition is also provided.

  The present invention also provides (a) one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof, and (b) X-ray diffraction. In addition, the catalyst has a pore size distribution (measured by ASTM method D4282) having a median pore diameter of 230 mm or more. Also provided is a catalyst composition having.

  The present invention also includes (a) one or more metals in the fifth column of the periodic table, one or more compounds of one or more metals in the fifth column of the periodic table, one or more metals in the sixth column of the periodic table, One or more compounds of one or more metals in the sixth column of the periodic table, or mixtures thereof, and (b) θ-alumina content measured by X-ray diffraction is 0.1 g or more per gram of the support material. In addition to including the support material, the catalyst also provides a catalyst composition having a pore size distribution (measured by ASTM method D4282) having a median pore diameter of 230 mm or greater.

  Furthermore, the present invention is a step of forming a support / metal mixture by combining a support containing θ-alumina and one or more metals, wherein one or more of the metals are included in the periodic table 5th. The process comprising one or more metals in the column, one or more compounds of one or more metals in the fifth column of the periodic table, or mixtures thereof, and the resulting θ-alumina support / metal mixture at 400 ° C. There is also provided a method for producing a catalyst comprising a step of heat-treating at the above temperature and a step of forming a catalyst having a pore size distribution (measured by STM method D4282) having a median pore diameter of 230 mm or more.

  Further, the present invention is a step of forming a support / metal mixture by combining a support containing θ-alumina and one or more metals, wherein one or more of the metals are listed in column 6 of the periodic table. The process comprising one or more metals of the above, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof, and the obtained θ-alumina support / metal mixture at 400 ° C. or higher There is also provided a method for producing a catalyst comprising a step of heat-treating at a temperature of and a step of forming a catalyst having a pore size distribution (measured by ASTM method D4282) having a median pore diameter of 230 mm or more.

  The invention also includes a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa by contacting a crude feed having a TAN (measured by ASTM method D664) of 0.3 or more with one or more catalysts. A process for producing a total product, wherein at least one of the catalysts has a pore size distribution (measured by ASTM method D4282) having a median pore diameter of 180 mm or more, and the catalyst having the pore size distribution Wherein the process comprises θ-alumina and one or more metals from column 6 of the periodic table, one or more compounds of one or more metals from column 6 of the periodic table, or mixtures thereof; and There is also provided a method for producing a crude product comprising a step of controlling contact conditions so that TAN is 90% or less of TAN of crude oil feedstock.

  The present invention also provides a crude material having a TAN (measured by ASTM method D664) of 0.3 or more and an oxygen content (measured by ASTM method E385) of 0.0001 g or more per gram of crude material in the presence of a hydrogen source. Contacting with one or more catalysts to produce a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, wherein at least one of the catalysts has a median pore size The process having a pore size distribution (measured by ASTM method D4282) of 90 mm or more, and the crude product TAN is 90% or less of the crude feedstock TAN, and the crude product oxygen content is There is also provided a method for producing a crude product including a step of controlling contact conditions so that the oxygen content of the crude feed becomes 90% or less.

In addition, the present invention provides a crude feedstock having a TAN (measured by ASTM method D664) of 0.1 or more, at least one of the catalysts is one or more metals in the sixth column of the periodic table, and one of the sixth column in the periodic table. One or more compounds of the above metals, or a mixture thereof, calculated as the weight of the metal per gram of the catalyst, contacted with one or more catalysts containing 0.001 g or more, and at 25 ° C. and 0.101 MPa Manufacturing the entire product including the crude product, which is a liquid mixture, and the hourly space velocity of the liquid in the contact zone exceeds 10 h −1 and the crude product TAN is 90% of the crude feed TAN Also provided is a method for producing a crude product comprising the step of controlling the contact conditions so that:

The present invention also provides a crude material having a TAN (measured by ASTM method D664) of 0.1 or more and a sulfur content (measured by ASTM method D4294) of 0.0001 g or more per gram of crude material in the presence of a hydrogen source. And at least one catalyst comprises one or more metals in the sixth column of the periodic table, one or more compounds of one or more metals in the sixth column of the periodic table, or one or more catalysts containing a mixture thereof. Contacting to produce a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and a proportion of the crude feed selected to prevent phase separation of the crude feed during contact Absorbs molecular hydrogen at one or more of the contact zones and the liquid has a space velocity per hour exceeding 10 h −1 and the crude product has a sulfur content of 70-130% of the crude oil sulfur content. The product TAN is crude oil raw material There is also provided a method for producing a crude product including a step of controlling contact conditions so that the TAN is 90% or less.

  The present invention also includes a step of producing a total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa by contacting the crude feed with one or more catalysts in the presence of a gaseous hydrogen source, Also provided is a method for producing a crude product comprising the step of controlling the contact conditions such that the crude feed absorbs molecular hydrogen at a selected rate to prevent phase separation of the crude feed during contact.

  The present invention also provides a process for producing a crude product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa by contacting the crude feed with hydrogen in the presence of one or more catalysts, and a crude feed Prevents the P-value of the crude feed / total product mixture from falling below 1.5 so that it contacts hydrogen under the first hydrogen absorption condition and then the second hydrogen absorption condition, which is different from the second hydrogen absorption condition Therefore, the contact conditions are such that the total hydrogen absorption at the first hydrogen absorption condition is controlled and that one or more characteristics of the crude product change by 90% or less of the respective characteristics of the crude feed. There is also provided a method for producing a crude product comprising a step of controlling.

  The present invention also provides that a crude feed having a TAN (measured by ASTM method D664) of 0.3 or more is contacted with one or more catalysts at a first temperature and subsequently at a second temperature at 25 ° C. and 0.101 MPa. A step of producing a whole product including a crude product which is a liquid mixture, and the first contact temperature is 30 ° C. or more lower than the second contact temperature, and the TAN of the crude product is 90% or less of the TAN of the crude feed Also provided is a method for producing a crude product comprising a step of controlling contact conditions.

  In addition, the present invention provides a crude material having a TAN (measured by ASTM method D664) of 0.3 or more and a sulfur content (measured by ASTM method D4294) of 0.0001 g or more per 1 g of crude material. In contact with one or more catalysts comprising one or more metals of column 6 of the periodic table, one or more compounds of one or more metals of column 6 of the periodic table, or mixtures thereof, A process for producing a total product including a crude product that is a liquid mixture at 101 MPa, and the crude product TAN is less than 90% of the crude TAN and the crude product sulfur content is the sulfur content of the crude feed Further, a method for producing a crude product including a step of controlling the contact conditions so as to be 70 to 130% is also provided.

  The present invention also provides a crude material having a TAN (measured by ASTM method D664) of 0.1 or more and a residue content (measured by ASTM method D5307) of 0.1 g or more per gram of crude material, at least one kind of catalyst. Is contacted with one or more metals of one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or mixtures thereof, at 25 ° C., A process for producing a total product including a crude product which is a liquid mixture at 0.101 MPa, and the crude product TAN is 90% or less of the crude feedstock TAN and the crude product sulfur content is sulfur of the crude feedstock There is also provided a method for producing a crude product including a step of controlling contact conditions so that the content is 70 to 130%.

  The present invention also provides a crude oil feedstock having a TAN (measured by ASTM method D664) of 0.1 or more and a vacuum gas oil (VGO) content (measured by ASTM method D5307) of 0.1 g or more per gram of crude feedstock. At least one of the compounds in contact with one or more metals in the sixth column of the periodic table, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof. Manufacturing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and the crude product TAN is 90% or less of the crude feedstock TAN and the crude product has a VGO content of There is also provided a method for producing a crude product comprising a step of controlling contact conditions so that the content of crude oil is 70 to 130% of the VGO content.

  Further, the present invention contacts a crude material having a TAN (measured by ASTM method D664) of 0.3 or more and a VGO content (measured by ASTM method D5307) of 0.1 g or more per 1 g of crude material with one or more catalysts. And producing a total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, wherein at least one catalyst comprises a support and one or more of the columns in column 6 of the periodic table. Combined with metal, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof to form a catalyst precursor, which is then less than 500 ° C. in the presence of one or more sulfur-containing compounds And a step of controlling the contact conditions such that the TAN of the crude product is 90% or less of the TAN of the crude feed. Manufacturing method Subjected to.

  The present invention also provides a crude feedstock having a viscosity (measured by ASTM method D2669) of 37.8 ° C. (100 ° F.) and 10 cSt and an API specific gravity (measured by ASTM method D6822) of 10 or more. Is contacted with one or more metals including one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or mixtures thereof, at 25 ° C., Producing a total product including a crude product which is a liquid mixture at 0.101 MPa, and the viscosity of the crude product at 37.8 ° C. is less than 90% of the viscosity of the crude feed at 37.8 ° C. There is also provided a method for producing a crude product including a step of controlling contact conditions such that the API specific gravity of the crude product is 70 to 130% with respect to the API specific gravity of the crude feed.

  The present invention also provides a crude feedstock having a TAN (measured by ASTM method D664) of 0.1 or more, at least one catalyst containing vanadium, one or more compounds of vanadium, or a mixture thereof, and a periodic table. In contact with one or more catalysts containing one or more metals in the column, one or more compounds of one or more metals in the sixth column of the periodic table, or an additional catalyst comprising combinations thereof, 25 A step of producing a whole product including a crude product which is a liquid mixture at 0.1 ° C. at 0.1 ° C., and a step of controlling contact conditions so that the TAN of the crude product is 90% or less of the TAN of the crude feed A method for producing a crude product comprising

  The present invention also includes a crude feedstock having a TAN (measured by ASTM method D664) of 0.1 or more in contact with one or more catalysts, including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa. Production of a crude product including a step of producing a product, a step of generating hydrogen during contact, and a step of controlling contact conditions so that the TAN of the crude product is 90% or less of the TAN of the crude feed. A method is also provided.

  The present invention also provides a crude feedstock having a TAN (measured by ASTM method D664) of 0.1 or more, at least one of the catalysts containing one or more compounds including vanadium, one or more compounds of vanadium, or a mixture thereof. Contacting the catalyst to produce a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and the contact temperature is 200 ° C. or higher and the TAN of the crude product is relative to the TAN of the crude feed There is also provided a method for producing a crude product including a step of controlling the contact conditions so that it is 90% or less.

  The present invention also provides a crude feedstock having a TAN (measured by ASTM method D664) of 0.1 or more, at least one catalyst comprising vanadium, one or more compounds of vanadium, or a mixture thereof. A step of producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa in contact with a catalyst, and supplying a hydrogen source-containing gas in a gas flow in a direction opposite to that of the crude feed during the contact. And a method for producing a crude product including a step of controlling contact conditions such that the TAN of the crude product is 90% or less of the TAN of the crude feed.

  The present invention also provides a crude feedstock having a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude feedstock, wherein at least one of the catalysts is vanadium and one or more compounds of vanadium. Or a mixture thereof, wherein the vanadium catalyst is contacted with one or more catalysts having a pore size distribution with a median pore diameter of 180 mm or more, and a crude oil production that is a liquid mixture at 25 ° C. and 0.101 MPa Control the contact conditions so that the total Ni / V / Fe content of the crude product is 90% or less of the total Ni / V / Fe content of the crude raw material. There is also provided a method for producing a crude product comprising the steps of:

  The present invention also includes 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 a mixture thereof, A crude material having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude material, at least one of the catalysts being one or more compounds of vanadium and vanadium Or a total product comprising a crude product, which is a liquid mixture at 25 ° C. and 0.101 MPa, in contact with one or more catalysts comprising a mixture thereof, or an organic acid metal salt of a crude product So that the total content of alkali metal and alkaline earth metal is 90% or less with respect to the total content of alkali metal and alkaline earth metal in the organic acid metal salt of the crude oil raw material, Method for producing a crude product comprising the step of controlling the tactile conditions are also provided.

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt A crude material having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude material, at least one of the catalysts has a median pore diameter of 90 In contact with one or more catalysts exhibiting a pore size distribution (measured by ASTM method D4282) having a pore size in the range of ~ 180% and having a pore diameter of not less than 45% of the median pore diameter, with more than 60% of the total number of pores Producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and a total content of alkali metals and alkaline earth metals in the organic acid metal salt of the crude product So it becomes 90% or less with respect to the total content of alkali metals and alkaline earth metals in metal salts of organic acids of the crude feed, the production method of the crude product comprising the step of controlling the contacting conditions are also provided.

  The present invention also relates to a crude material having a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude material, and at least one of the catalysts has a median pore diameter of 90 to 180%. And one or more kinds of pore size distributions (measured by ASTM method D4282) in which 60% or more of the total number of pores in the pore size distribution has a pore diameter within 45 mm of the median pore diameter Contacting the catalyst to produce a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and the total Ni / V / Fe content of the crude product is the total Ni / There is also provided a method for producing a crude product including a step of controlling contact conditions so that the V / Fe content is 90% or less.

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt A crude material having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude material, at least one of the catalysts has a median pore diameter of 180 径The pore size distribution (measured by ASTM method D4282) is as described above, and the catalyst of the pore size distribution is composed of one or more metals in the sixth column of the periodic table and one or more metals in the sixth column of the periodic table. Producing a total product comprising a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa by contacting with one or more catalysts comprising one or more compounds, or mixtures thereof, and crude product Organic acids Control the contact conditions so that the total content of alkali metal and alkaline earth metal in the metal salt is 90% or less of the total content of alkali metal and alkaline earth metal in the organic acid metal salt of crude oil There is also provided a method for producing a crude product comprising the steps of:

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt A crude material having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude material, at least one of the catalysts has a median pore diameter of 230Å The pore size distribution (measured by ASTM method D4282) is as described above, and the catalyst of the pore size distribution is composed of one or more metals in the sixth column of the periodic table and one or more metals in the sixth column of the periodic table. Producing a total product comprising a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa by contacting with one or more catalysts comprising one or more compounds, or mixtures thereof, and crude product Organic acids Control the contact conditions so that the total content of alkali metal and alkaline earth metal in the metal salt is 90% or less of the total content of alkali metal and alkaline earth metal in the organic acid metal salt of crude oil There is also provided a method for producing a crude product comprising the steps of:

  The present invention also provides a crude feedstock having a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude feedstock, and at least one of the catalysts has a median pore diameter of 230 mm or more. It has a certain pore size distribution (measured by ASTM method D4282), and the catalyst of the pore size distribution is one or more metals in the sixth column of the periodic table and one or more metals in the sixth column of the periodic table A step of producing a total product comprising a crude product, which is a liquid mixture at 25 ° C. and 0.101 MPa, in contact with one or more catalysts comprising the above compounds, or mixtures thereof, and the sum of the crude products There is also provided a method for producing a crude product including a step of controlling contact conditions such that the Ni / V / Fe content is 90% or less with respect to the total Ni / V / Fe content of the crude raw material.

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt A crude material having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude material, at least one of the catalysts has a median pore diameter of 90% The pore size distribution (measured by ASTM method D4282) is as described above, and the catalyst of the pore size distribution is calculated by calculating molybdenum, one or more molybdenum compounds or a mixture thereof as the weight of molybdenum per gram of catalyst. To produce a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa in contact with one or more catalysts containing 0.0001 to 0.3 g And the total content of alkali metal and alkaline earth metal in the organic acid metal salt of the crude product is 90% of the total content of alkali metal and alkaline earth metal in the organic acid metal salt of the crude raw material. Also provided is a method for producing a crude product comprising the step of controlling the contact conditions so that:

  The present invention also provides a crude material having a TAN (measured by ASTM method D664) of 0.3 or more and a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude material. At least one of the catalysts has a pore size distribution (measured by ASTM method D4282) having a median pore diameter of 90 mm or more, and the catalyst of the pore size distribution is one or more kinds of molybdenum per gram of the catalyst. A crude product that is a liquid mixture at 25 ° C. and 0.101 MPa in contact with one or more catalysts containing a total of 0.0001-0.3 g of molybdenum compounds or mixtures thereof, calculated as the weight of molybdenum The crude product TAN is 90% or less of the crude feed TAN, and the crude product has a total Ni / V / Fe content of Such that 90% or less relative to the total Ni / V / Fe content of the raw materials, the manufacturing method of the crude product comprising the step of controlling the contacting conditions are also provided.

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt Crude oil feedstock having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude feedstock, at least one of the catalysts is (a) periodic table One or more metals in column 6, one or more compounds of one or more metals in column 6 of the periodic table, or mixtures thereof; and (b) one or more metals in column 10 of the periodic table, periodic table One or more compounds of one or more metals in column 10 or mixtures thereof are contacted with one or more catalysts comprising a total column 10 metal to total column 6 metal molar ratio in the range of 1-10. At 25 ° C. and 0.101 MPa with a liquid mixture The total production of the product including the crude oil product, and the total content of alkali metal and alkaline earth metal in the organic acid metal salt of the crude product is alkali metal and alkali in the organic acid metal salt of the crude material There is also provided a method for producing a crude product including a step of controlling contact conditions such that the total content of earth metals is 90% or less.

  The present invention also provides a crude feedstock having a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude feedstock, wherein at least one of the catalysts is (a) column 6 of the periodic table One or more metals, one or more compounds of one or more metals in column 6 of the periodic table, or mixtures thereof; and (b) one or more metals in column 10 of the periodic table, column 10 of the periodic table. Contacting one or more compounds of one or more metals, or a mixture thereof with one or more catalysts comprising a total column 10 metal to total column 6 metal molar ratio in the range of 1-10, Producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and the total Ni / V / Fe content of the crude product is equal to the total Ni / V / Fe content of the crude feed The contact condition is controlled so that it is 90% or less. Also it provides method for producing a crude product comprising extent.

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt A crude oil raw material having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude oil raw material is (a) one or more kinds in the sixth column of the periodic table. A metal, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof, calculated as the weight of the metal per 1 g of the first catalyst, is contained in 0.0001 to 0.06 g. One catalyst and (b) one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof per gram of the second catalyst Calculated as 1 type containing 0.02g or more Contacting the above catalyst to produce a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and alkali metals and alkaline earth metals in the organic acid metal salt of the crude product There is also a method for producing a crude product including a step of controlling the contact conditions so that the total content of is 90% or less with respect to the total content of alkali metals and alkaline earth metals in the organic acid metal salt of the crude oil raw material. provide.

The present invention also includes 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 a mixture thereof, and an organic acid metal salt A crude material having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude material, at least one catalyst is One or more metals, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof, calculated as the weight of metal per gram of catalyst, and containing one or more metals containing 0.001 g Producing a total product comprising a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa in contact with the catalyst, and the hourly space velocity of the liquid in the contact zone exceeds 10 h −1 ; Living The total content of alkali metal and alkaline earth metal in the organic acid metal salt of the product is 90% or less with respect to the total content of alkali metal and alkaline earth metal in the organic acid metal salt of the crude oil raw material. Also provided is a method for producing a crude product comprising a step of controlling contact conditions.

The present invention also provides a crude feedstock having a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude feedstock, and at least one catalyst is one of the sixth column of the periodic table. One or more catalysts containing 0.001 g or more of the above metals, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof, calculated as the weight of the metal per 1 g of the catalyst. Producing a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and a space velocity of liquid in the contact zone per hour exceeding 10 h −1 and producing crude oil There is also provided a method for producing a crude product including a step of controlling contact conditions such that the total Ni / V / Fe content of the product is 90% or less with respect to the total Ni / V / Fe content of the crude raw material.

  The present invention also provides a crude material having an oxygen content (measured by ASTM method E385) of 0.0001 g or more per gram of crude material and a sulfur content (measured by ASTM method D4294) of 0.0001 g or more of gram of crude material, At least one of the catalysts is one or more catalysts containing one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or mixtures thereof. Producing a total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and producing a crude product with an oxygen content of the crude product of 90% or less relative to the oxygen content of the crude product. There is also provided a method for producing a crude product including a step of controlling contact conditions such that the sulfur content of the product is 70 to 130% with respect to the sulfur content of the crude oil raw material.

  In addition, the present invention provides a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude oil feedstock and a sulfur content (measured by ASTM method D4294) of 0.0001 g or more per gram of crude oil feedstock. One crude feedstock, at least one of the catalysts contains one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof 1 Producing a total product, including a crude product, which is a liquid mixture at 25 ° C. and 0.101 MPa, in contact with more than one catalyst, and the total Ni / V / Fe content of the crude product is A crude product comprising a step of controlling contact conditions such that the sulfur content of the crude product is 70 to 130% with respect to the sulfur content of the crude feed at 90% or less of the total Ni / V / Fe content. Made of The method is also provided.

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt The total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) is 0.00001 g or more per gram of crude oil feedstock, and the residual content (measured by ASTM method D5307) is 0.000 per gram of crude oil feedstock. 1 g or more of crude raw material, at least one of the catalysts is one or more metals in the sixth column of the periodic table, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof. Producing a total product comprising a crude product, which is a liquid mixture at 25 ° C. and 0.101 MPa, in contact with one or more containing catalysts, and alkali metals in the organic acid metal salt of the crude product and A The total content of potash earth metal is 90% or less with respect to the total content of alkali metals and alkaline earth metals in the organic acid metal salt of crude oil raw material, and the crude product residue content contains crude oil raw material residue There is also provided a method for producing a crude product including a step of controlling the contact conditions so that the amount is 70 to 130%.

  In addition, the present invention has a residue content (measured by ASTM method D5307) of 0.1 g or more per gram of crude feed and a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude feed. In the crude oil raw material, at least one of the catalysts contains one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof. Producing a total product comprising a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa in contact with one or more catalysts, and the total Ni / V / Fe content of the crude product is a crude feed The step of controlling the contact conditions so that the crude product residue content is 70 to 130% of the crude material residue content at 90% or less of the total Ni / V / Fe content of Production of crude product The method is also provided.

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt The total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) is 0.0001 g or more per gram of crude material, and the content of vacuum gas oil (VGO) (measured by ASTM method D5307) is crude material. 1 g or more of a raw material of crude oil that is 0.1 g or more per gram, one or more compounds of one or more metals in column 6 of the periodic table, one or more metals in column 6 of the periodic table, or In contact with one or more catalysts containing the mixture to produce a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and in an organic acid metal salt of the crude product Arca The total content of metal and alkaline earth metal is 90% or less of the total content of alkali metal and alkaline earth metal in the organic acid metal salt of the crude oil raw material, and the VGO content of the crude product contains the VGO of the crude oil raw material. There is also provided a method for producing a crude product including a step of controlling the contact conditions so that the amount is 70 to 130%.

  In addition, the present invention has a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude material and a VGO content (measured by ASTM method D5307) of 0.1 g or more per gram of crude material. One crude feedstock, at least one of the catalysts contains one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof 1 Producing a total product, including a crude product, which is a liquid mixture at 25 ° C. and 0.101 MPa, in contact with at least a seed catalyst, and the crude product has a total Ni / V / Fe content of the crude feed A crude product comprising a step of controlling contact conditions such that the VGO content of the crude product is 70 to 130% of the VGO content of the crude feed at 90% or less of the total Ni / V / Fe content. Made of The method is also provided.

  The present invention also includes 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 a mixture thereof, and an organic acid metal salt A crude material having a total content of alkali metal salt and alkaline earth metal salt (measured by ASTM method D1318) of 0.00001 g or more per gram of crude material is brought into contact with one or more catalysts, A process for producing a total product comprising a crude product which is a liquid mixture at 101 MPa, wherein at least one of the catalysts is a support, one or more metals in column 6 of the periodic table, column 6 of the periodic table A catalyst precursor in combination with one or more compounds of one or more metals, or mixtures thereof, which is then heated at a temperature below 400 ° C. in the presence of one or more sulfur-containing compounds. To form And the total content of alkali metals and alkaline earth metals in the organic acid metal salt of the crude product is the total content of alkali metals and alkaline earth metal in the organic acid metal salt of the crude raw material. On the other hand, a method for producing a crude product including a step of controlling contact conditions so as to be 90% or less is also provided.

  In addition, the present invention provides a crude raw material having a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude raw material with one or more types of catalyst, 25 ° C., 0.101 MPa In which a crude product which is a liquid mixture is produced, wherein at least one of the catalysts is a support, one or more metals in column 6 of the periodic table, 1 of column 6 of the periodic table. Combining with one or more compounds of one or more metals, or mixtures thereof, to form a catalyst precursor, which is then heated at a temperature below 400 ° C. in the presence of one or more sulfur-containing compounds to form a catalyst. And the step of controlling the contact conditions so that the total Ni / V / Fe content of the crude product is 90% or less with respect to the total Ni / V / Fe content of the crude raw material. Including crude oil products The method is also provided.

  Further, the present invention relates to a hydrocarbon having a boiling range of 95 to 260 ° C. at 0.101 MPa per crude oil composition at 0.001 g or more, and a hydrocarbon having a boiling range of 260 to 320 ° C. at 0.101 MPa to a crude oil composition. 0.001 g or more per gram, hydrocarbon having a boiling range of 320 to 650 ° C. at 0.101 MPa, 0.001 g or more per gram of crude oil composition, and one or more catalysts exceeding 0 g per gram of crude oil composition. A crude oil composition containing less than 01 g is also provided.

In addition, the present invention contains 0.01 g or more of sulfur (measured by ASTM method D4294) and 0.2 g or more of residue (measured by ASTM method D5307) per 1 g of the composition, and MCR content (weight, ASTM). Law D4530 measured at) to C 5 asphaltenes content (weight, the weight ratio of the measurement) by ASTM method D2007 also provides oil compositions it is 1.5 or more.

  The present invention also provides a crude oil which has a MCR content (measured by ASTM method D4530) of 0.001 g or more per 1 g of crude feed and is brought into contact with one or more catalysts and can be condensed at 25 ° C. and 0.101 MPa. A step of producing a total product including products, wherein at least one of the catalysts comprises a support, one or more metals in column 6 of the periodic table, one of one or more metals in column 6 of the periodic table. The catalyst precursor obtained by combining with one or more compounds, or a mixture thereof, to form a catalyst precursor, which is then heated at a temperature of less than 500 ° C. in the presence of one or more sulfur-containing compounds. There is also provided a method for producing a crude product comprising a step and a step of controlling contact conditions such that the MCR content of the crude product is 90% or less of the MCR content of the crude feed.

  Further, the present invention provides a crude material having an MCR content (measured by ASTM method D4530) of 0.001 g or more per gram of crude material, and at least one of the catalysts has a median pore diameter in the range of 70 to 180 mm, And at least 60% of the total number of pores in the pore size distribution is contacted with one or more catalysts showing a pore size distribution (measured by ASTM method D4282) having a pore diameter within 45 mm of the median pore diameter, A process for producing a total product including a crude product condensable at 25 ° C. and 0.101 MPa, and contact conditions such that the MCR content of the crude product is 90% or less of the MCR content of the crude feed. There is also provided a method for producing a crude product comprising a step of controlling.

  In addition, the present invention has an oxygen content of 0.004 g or less (measured by ASTM method E385), sulfur of 0.003 g or less (measured by ASTM method D4294), and a residue of 0.3 g or more (ASTM). A crude oil composition is also provided, as measured by Method D5307.

  Further, according to the present invention, oxygen is 0.004 g or less (measured by ASTM method E385), sulfur is 0.003 g or less (measured by ASTM method D4294), and basic nitrogen is 0.04 g or less per 1 g of crude oil composition (ASTM And a crude oil composition containing 0.2 g or more of residue (measured by ASTM method D5307) and having a TAN of 0.5 or less (measured by ASTM method D664).

Further, the present invention contains not less than 0.001 g of sulfur (measured by ASTM method D4294) and 0.2 g or more of residue (measured by ASTM method D5307), and also has an MCR content (measured by ASTM method D4530) versus C 5. A crude oil composition having a weight ratio of asphaltene content (measured by ASTM method D2007) of 1.5 or more and TAN of 0.5 or less (measured by ASTM method D664) is also provided.

  In some embodiments, the present invention also provides the following crude feed in combination with one or more of the methods or compositions of the present invention. This crude oil feedstock contains (a) 0.5 g or more of a component having 5 or more carbon atoms per gram of crude feedstock, which is not treated, distilled and / or fractionally distilled at a refinery, and (c) Some hydrocarbons have a boiling range distribution of less than 100 ° C. at 0.101 MPa, a boiling range distribution of 100 to 200 ° C. at 0.101 MPa, a boiling range distribution of 200 to 300 ° C. at 0.101 MPa, and 300 at 0.101 MPa. A hydrocarbon having a boiling range distribution of ˜400 ° C. and a hydrocarbon having a boiling range distribution of 400 to 650 ° C. at 0.101 MPa, and (d) a hydrocarbon having a boiling range distribution of 0.101 MPa and less than 100 ° C. 0.001 g or more, boiling point range distribution of 0.101 MPa and 100 to 200 ° C. hydrocarbon 0.001 g or more, boiling point range distribution of 0.101 MPa and 200 to 300 ° C. 0.001 g or more of hydrogen fluoride, 0.001 g or more of hydrocarbon at 300 to 400 ° C. with a boiling range distribution of 0.101 MPa, and 0.001 g or more of hydrocarbon at 400 to 650 ° C. with a boiling range distribution of 0.101 MPa (E) TAN is 0.1 or more, 0.3 or more, or 0.3 to 20, 0.4 to 10, or 0.5 to 5, and (f) the initial boiling point is 0.101 MPa. 200 g or higher, (g) containing nickel, vanadium, and iron, (h) the total Ni / V / Fe content is 0.00002 g or more per gram of crude material, (i) containing sulfur, (j ) Sulfur content is at least 0.0001 g / g crude oil feedstock, (k) VGO content is 0.001 g or more per g crude feedstock, and (l) Residue content per g crude feedstock. 0 1 m or more, (m) containing 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 a mixture thereof, (o) containing at least one zinc salt of an organic acid, and / or (p) containing at least one arsenic salt of an organic acid.

  In some embodiments, the present invention also provides a crude feed obtained by removing naphtha and more volatile compounds than naphtha from crude in combination with one or more of the methods or compositions of the present invention. To do.

In some embodiments, the present invention also provides the following methods in combination with one or more of the methods or compositions of the present invention. This method is a crude feed containing C 5 asphaltenes and MCR is contacted with one or more catalysts, a method to produce a total product that includes a crude product containing C 5 asphaltenes and MCR, (a) so that the total S of the C 5 asphaltenes content and MCR content of the crude product 'is 99% or less relative to the total S of the C 5 asphaltenes content and MCR content of the crude feed, controls the contacting conditions and / or (b) so that the weight ratio of C 5 asphaltenes content of MCR content to the crude product of the crude product is in the range of 1.2 to 2.0 or 1.3 to 1.9, The contact condition is controlled.

  In some embodiments, the present invention is combined with one or more of the methods or compositions of the present invention to: (a) gaseous, (b) hydrogen gas, (c) methane, (d) light hydrocarbons, Also provided is a hydrogen source that is (e) an inert gas and / or (f) a mixture thereof.

  In some embodiments, the present invention, in combination with one or more of the methods or compositions of the present invention, provides the crude feed with one or more in a contact zone that is on or connected to an offshore facility. Also provided is a method for producing a total product, including a crude product, in contact with a catalyst.

In some embodiments, the present invention combines crude oil feed with one or more catalysts in the presence of a gas and / or hydrogen source in combination with one or more of the methods or compositions of the present invention. The steps for producing the total product, including the product, and the contact conditions are as follows: (a) a gaseous hydrogen source 5 to 1 m 3 of crude raw material in which the ratio of gaseous hydrogen source to crude feed is in contact with one or more catalysts. 800 standard m 3 range, (b) selected total hydrogen absorption rate is controlled by partial pressure of hydrogen source, (c) crude product TAN is less than 0.3, but hydrogen absorption is in contact The hydrogen absorption rate is controlled to be less than the amount of hydrogen absorption that substantially causes phase separation between the crude feed and the total product, and (d) the selected hydrogen uptake is hydrogen per 1 m 3 of crude feed. Source 1-30 or 1-80 standard m 3 in range, (e) gas and Beauty / or space velocity of the liquid hourly hydrogen source 11h -1 or more, 15h -1 or more, or 20h -1 or less, in contact (f), the partial pressure of the gas and / or hydrogen source is controlled, (G) the contact temperature is in the range of 50 to 500 ° C., the total liquid space velocity per hour of the gas and / or hydrogen source is in the range of 0.1 to 30 h −1 , and the gas and / or hydrogen source The pressure is in the range of 1.0-20 MPa, (h) the gas and / or hydrogen source stream is in the opposite direction to the crude feed stream, and (i) the crude product H / C is the crude feed H / C 70 to 130% of C, (j) the hydrogen absorption of the crude feed is in the range of 80 standard m 3 or less hydrogen per 1 m 3 of crude feed and / or 1 to 80 or 1 to 50 standard m 3 , (K) Total Ni / V / Fe content of crude product (ASTM method D5708) ) Is 90% or less, 50% or less, or 10% or less with respect to the Ni / V / Fe content of the crude material, and (l) the sulfur content of the crude product is 70% with respect to the sulfur content of the crude material. (M) the crude product has a VGO content of 70-130% or 90-110% of the crude product's VGO content, and (n) a crude product residue. The product content is 70 to 130% or 90 to 110% with respect to the residual content of the crude material, and (o) the oxygen content of the crude product is 90% or less, 70% with respect to the oxygen content of the crude material. 50% or less, 40% or less, or 10% or less, and (p) the total content of alkali metal and alkaline earth metal in the organic acid metal salt in the crude product is Of alkali metals and alkaline earth metals 90% or less, 50% or less, or 10% or less of the amount, (q) the P value of the crude oil raw material in contact is 1.5 or more, and (r) the viscosity of the crude product at 37.8 ° C. Is 90% or less, 50% or less, or 10% or less with respect to the viscosity at 37.8 ° C. of the crude material, and (s) the API specific gravity of the crude product is 70 to 130% with respect to the API specific gravity of the crude material. And / or (t) the TAN of the crude product is 90% or less, 50% or less, 30% or less, 20% or less, 10% or less, and / or 0.001 to 0.5 relative to the TAN of the crude material. There is also provided a method including a step of controlling to be in the range of 0.01 to 0.2, or 0.05 to 0.1.

  In some embodiments, the present invention combines a crude feed with one or more catalysts in combination with one or more of the methods or compositions of the present invention to produce a total product including a crude product. The process and the contact conditions are controlled to reduce the organic oxygen-containing compound, and (a) the oxygen content of the crude product is selected so as to be 90% or less of the oxygen content of the crude raw material. The content of the organic oxygen compound is reduced, (b) at least one compound of the organic oxygen-containing compound contains a metal salt of a carboxylic acid, and (c) at least one compound of the organic oxygen-containing compound is a carboxylic acid. An alkali metal salt of an acid; (d) at least one compound of an organic oxygen-containing compound contains an alkaline earth metal salt of a carboxylic acid; and (e) at least one compound of an organic oxygen-containing compound is Carboxylic acid gold Salt (provided that the metal contains one or more metals in column 12 of the periodic table), and (f) the content of the non-carboxylated organic compound in the crude product is the non-carboxyl content in the crude feed There is also a method including the control step of 90% or less with respect to the content of the organic compound and / or (g) at least one of the oxygen-containing compounds in the crude oil raw material is generated from a naphthenic acid or carboxyl-free organic oxygen compound. provide.

In some embodiments, the invention comprises a method comprising contacting a crude feed with one or more catalysts in combination with one or more of the inventive process or composition comprising: (a) a crude feed Is brought into contact with at least one kind of catalyst at the first temperature and then at the second temperature, and the contact condition is controlled so that the first contact temperature is 30 ° C. or more lower than the second contact temperature. b) The crude raw material is brought into contact with hydrogen under the first hydrogen absorption condition and then under the second hydrogen absorption condition, and the temperature of the first hydrogen absorption condition is lower by 30 ° C. than the temperature of the second hydrogen absorption condition; c) The crude feedstock is brought into contact with at least one of the catalysts at the first temperature and then at the second temperature, and the contact condition is such that the first contact temperature is 200 ° C. or lower than the second contact temperature. (D) hydrogen gas is generated during the contact, and (e During the contact, hydrogen gas is generated and the contact conditions are controlled so that the crude feed absorbs at least part of the generated hydrogen. (F) The crude feed is brought into contact with the first catalyst and the second catalyst, The contact with the first catalyst produces a first crude product having a TAN that is 90% or less of the TAN of the crude feed, and the first crude product is produced by the contact between the first crude product and the second catalyst. Producing a crude product having a TAN that is 90% or less relative to the TAN of the product, (g) contacting in a stacked bed reactor, (h) contacting in a boiling bed reactor, (i) crude feedstock (1) one or more of the catalysts is a vanadium catalyst and the crude feed is contacted with the vanadium catalyst and then the presence of a hydrogen source. Under contact with additional catalyst, (k) The iodine is generated in the range of crude feed 1 m 3 per 20 standard m 3, (l) in contact, to generate hydrogen, additional crude feed in the presence of at least a portion of the gas and / or hydrogen generated catalyst And the contact conditions are controlled so that the gas flow is in the opposite direction of the crude feed and generated hydrogen, and (m) the crude feed is brought into contact with the vanadium catalyst at the first temperature, followed by the second The contact condition is controlled so that the first temperature is 30 ° C. or more lower than the second temperature, and (n) hydrogen gas is generated during the contact, and the crude feed is added Contacting the catalyst and controlling the contact conditions such that the additional catalyst absorbs at least a portion of the generated hydrogen gas and / or (o) subsequently contacting the crude feed with the additional catalyst at a second temperature; Second temperature is 18 ℃ so that the above also provides the method of controlling the contacting conditions.

  In some embodiments, the present invention is a method comprising contacting a crude feed with one or more catalysts in combination with one or more of the methods or compositions of the present invention, wherein (a) the catalyst comprises A catalyst supported on a support comprising alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or a mixture thereof; and (b) the catalyst is a catalyst supported on a porous support. (C) the process further comprises an additional catalyst heat-treated at a temperature above 400 ° C. prior to sulfiding, (d) at least one life of the catalyst is 0.5 years or more and / or ( e) The method also provides that the at least one catalyst is in a fixed bed or slurried in a crude feed.

  In some embodiments, the present invention also provides a method comprising contacting a crude feed with one or more catalysts in combination with one or more of the methods or compositions of the present invention. Here, at least one of the catalysts is a supported catalyst or a bulk metal catalyst, and the supported catalyst or the bulk metal catalyst is (a) one or more metals in columns 5 to 10 of the periodic table, periodic table 5th. 1 to 1 or more compounds of 1 or more types of metals of 10th column, or mixtures thereof, (b) 1 or more types of metals of 5th to 10th column of periodic table per 1g of catalyst, 5th to 10th of periodic table Containing 0.0001 g or more, or 0.0001 to 0.6 g or 0.001 to 0.3 g of one or more compounds of one or more metals in the column, (c) Periodic Table 6 Including one or more metals in columns 10 to 10, one or more compounds of one or more metals in columns 6 to 10 of the periodic table, or a mixture thereof, (d) one of columns 7 to 10 in the periodic table The above metals, one or more compounds of one or more metals in columns 7 to 10 of the periodic table, or mixtures thereof (E) 1 g of one or more metals in columns 7 to 10 of the periodic table, one or more compounds of one or more metals in columns 7 to 10 of the periodic table, or a mixture thereof per 1 g of catalyst. 0001-0.6g or 0.001-0.3g inclusive, (f) one or more metals in columns 5-6 of the periodic table, one or more metals in columns 5-6 of the periodic table (G) one or more metals of the fifth column of the periodic table, one or more compounds of one or more metals of the fifth column of the periodic table, or a mixture thereof, (H) 0.0001 g or more of one or more metals in the fifth column of the periodic table, one or more compounds of one or more metals in the fifth column of the periodic table, or a mixture thereof per 1 g of the catalyst. 0001-0.6g, 0.001-0.3g, 0.005-0.1g or 0.01-0.08g, Including one or more metals in the sixth column of the periodic table, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof; (j) per 1 g of catalyst in the sixth column of the periodic table One or more metals, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof is 0.0001 to 0.6 g, 0.001 to 0.3 g, 0.005 to 0 0.1 g or 0.01 to 0.08 g, (k) one or more metals in column 10 of the periodic table, one or more compounds of one or more metals in column 10 of the periodic table, or mixtures thereof (1) one or more metals in column 10 of the periodic table, one or more compounds of one or more metals in column 10 of the periodic table, or a mixture thereof per gram of catalyst 0.0001-0 1.6 g or 0.001 to 0.3 g, (m) one or more compounds of vanadium, vanadium, or Including (n) nickel, one or more compounds of nickel, or mixtures thereof; (o) including cobalt, one or more compounds of cobalt, or mixtures thereof; and (p) molybdenum One or more compounds of molybdenum, or a mixture thereof, and (q) 0.001 to 0.3 g or 0.005 of one or more compounds of molybdenum, molybdenum, or a mixture thereof per gram of catalyst. Containing 0.1 g of (r) tungsten, one or more compounds of tungsten, or mixtures thereof; (s) 0.1 g of molybdenum, one or more compounds of molybdenum, or mixtures thereof per gram of catalyst; 001-0.3g, and (t) one or more metals in column 6 of the periodic table and one or more metals in column 10 of the periodic table in a ratio of column 10 metal to column 6 metal 1 to Containing (u) one or more elements of column 15 of the periodic table, one or more compounds of one or more elements of column 15 of the periodic table, or a mixture thereof, (v) per gram of catalyst, Containing 0.00001 to 0.06 g of one or more elements in the 15th column of the periodic table, one or more compounds of 1 or more elements in the 15th column of the periodic table, or a mixture thereof, (w) phosphorus, One or more compounds of phosphorus or a mixture thereof, (x) containing 0.1 g or less of α-alumina per gram of catalyst, and / or (y) 0.5 g or more of θ-alumina per gram of catalyst contains.

  In some embodiments, the present invention also provides a method of forming a catalyst in combination with one or more of the methods or compositions of the present invention. This method comprises the steps of combining a support containing θ-alumina with one or more metals to form a support / metal mixture and heat treating the θ-alumina support / metal mixture at a temperature of 400 ° C. or higher. And (a) the step of extruding the paste by forming the paste by mixing the support / metal mixture with water, and (b) heat-treating the alumina at a temperature of 800 ° C. or higher, and θ-alumina And / or (c) sulfiding the catalyst.

In some embodiments, the present invention also provides a method comprising contacting a crude feed with one or more catalysts in combination with one or more of the methods or compositions of the present invention. In this way, the at least one pore size distribution of the catalyst has the following: (a) median pore size of 60 to 90, 90 to 180, 200 to 230, 300 to 300, 230 to 500, -180cm, 100-140mm, 120-130mm, 230-250mm, 180-500mm, 230-500mm or 60-300mm, (b) 60% or more of the total number of pores is within 45mm of the median pore diameter (C) a surface area of 60 m 2 / g or more, 90 m 2 / g or more, 100 m 2 / g or more, 120 m 2 / g or more, 150 m 2 / g or more, 200 m 2 / g or more, or 220m and 2 / g or more, and / or (d) the total volume of all the pores is 0.3 cm 3 / g or more, 0.4 cm 3 / g or more, .5cm 3 / g or more, or 0.7 cm 3 / g or more.

  In some embodiments, the present invention also provides a method comprising contacting a crude feed with one or more catalysts supported on a support in combination with one or more of the methods or compositions of the present invention. . Here, the support includes (a) alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or a mixture thereof, and / or zeolite, and (b) γ-alumina and / or δ- (C) containing 0.5 g or more of γ-alumina per gram of support, (d) containing 0.3 g or more or 0.5 g or more of θ-alumina per gram of support, (e) It contains α-alumina, γ-alumina, δ-alumina, θ-alumina, or a mixture thereof, and (f) contains 0.1 g or less of α-alumina per 1 g of support.

  In some embodiments, the present invention also provides a vanadium catalyst in combination with one or more of the methods or compositions of the present invention. The vanadium catalyst has (a) a pore size distribution having a median pore diameter of 60 mm or more, (b) a pore size having a θ-alumina-containing support and a median pore diameter of 60 mm or more. (C) one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof; (d) 1 g of catalyst In general, it contains 0.001 g or more of one or more metals in the sixth column of the periodic table, one or more compounds of one or more metals in the sixth column of the periodic table, or a mixture thereof.

In some embodiments, the present invention also provides a crude product in combination with one or more of the methods or compositions of the present invention. This crude product has (a) TAN of 0.1 or less, or 0.001 to 0.5, 0.01 to 0.2, or 0.05 to 0.1, and (b) an organic acid metal Contains 0.000009 g or less of alkali metal and alkaline earth metal per gram of crude product in salt, (c) contains 0.00002 g or less of Ni / V / Fe per gram of crude product, and / or (d ) More than 0 g and less than 0.01 g of at least one catalyst per 1 g of crude product.
In some embodiments, the present invention is used in combination with one or more of the methods or compositions of the present invention, one or more alkali metal salts of one or more organic acids, one of one or more organic acids. Also provided are the above alkaline earth metal salts, or mixtures thereof. Here, (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 present invention combines a crude feed with one or more catalysts in combination with one or more of the methods or compositions of the present invention to produce a total product comprising a crude product. A method is also provided. The method further comprises (a) blending a crude feed with a crude that is the same as or different from the crude feed to form a blend suitable for transport; (b) whether the crude feed is the same as the crude feed. Or in combination with different crude oils to form a blend suitable for processing equipment, (c) fractionating the crude product, and / or (d) one or more distillations of the crude product. Rectifying the product fraction to produce a transportation fuel from at least one of the distillate fractions.

In some embodiments, the present invention also provides a catalyst composition supported on a support in combination with one or more of the methods or compositions of the present invention. This catalyst composition contains (a) 0.3 g or more or 0.5 g or more of θ-alumina per 1 g of support, (b) contains δ-alumina in the support, and (c) 1 g of support. The composition contains 0.1 g or less of α-alumina, (d) has a pore size distribution with a median pore diameter of 230 mm or more, and (e) the pore volume of the pores in the pore size distribution is 0. .3cm is a 3 / g or more, or 0.7 cm 3 / g or more, (f) and a surface area of 60 m 2 / g or more or 90m 2 / g or more, (g) the period 7-10 column one or more tables Metal, one or more compounds of one or more metals in columns 7-10, or a mixture thereof, (h) one or more metals in column 5 of the periodic table, one or more of column 5 One or more compounds of the above metals, or mixtures thereof, (i) one or more metals in column 5 of the periodic table, One or more compounds of one or more metals, or mixtures thereof, containing 0.0001 to 0.6 g or 0.001 to 0.3 g per gram of catalyst, (j) one or more of column 6 of the periodic table A metal, one or more compounds of one or more metals in column 6, or a mixture thereof, (k) one or more metals in column 6 of the periodic table, one or more metals in column 6 1 or more compounds, or a mixture thereof, 0.0001 to 0.6 g or 0.001 to 0.3 g per gram of catalyst, (l) one or more compounds of vanadium, vanadium, or their Including (m) molybdenum, one or more compounds of molybdenum, or mixtures thereof; (n) including tungsten, one or more compounds of tungsten, or mixtures thereof; (o) cobalt, cobalt One or more compounds of Includes a mixture thereof and / or (p) nickel, one or more compounds of nickel, or a mixture thereof.

  In some embodiments, the present invention also provides a crude oil composition in combination with one or more of the methods or compositions of the present invention. In this crude oil composition, (a) TAN is 1 or less, 0.5 or less, 0.3 or less, or 0.1 or less, and (b) the boiling range distribution is 0.101 MPa per gram of the composition and is 95 to 260. ° C hydrocarbons at 0.001 g or more, boiling point range distribution of 0.101 MPa and 260-320 ° C hydrocarbons at 0.001 g or more, 0.005 g or more, or 0.01 g or more, and boiling point range distribution of 0.101 MPa 0.001 g or more of hydrocarbon at 320 to 650 ° C., (c) 0.0005 g or more of basic nitrogen per gram of composition, and (d) 0.001 g or more of total nitrogen per gram of composition or 0 0.01 g or more, and / or (e) 0.00005 g or less of total nickel and vanadium per gram of the composition.

In some embodiments, the present invention also provides a crude oil composition comprising one or more catalysts in combination with one or more of the methods or compositions of the present invention. Here, at least one of the catalysts has (a) a pore size distribution having a median pore diameter of 180 to 500 mm and / or a range of 90 to 180 mm, 100 to 140 mm, 120 to 130 mm, (B) A pore having a median pore diameter of 90 mm or more and exceeding 60% of the total number of pores in the pore size distribution has a median pore diameter within 45 mm, 35 mm, or 25 mm. And (c) a surface area of 100 m 2 / g or more, 120 m 2 / g or more or 220 m 2 / g or more, and / or (d) alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide And (e) one or more metals in columns 5-10 of the periodic table, one or more metals in columns 5-10 of the periodic table. Compound, also (F) one or more metals in the fifth column of the periodic table, one or more compounds of one or more metals in the fifth column, or a mixture thereof, and (g) a periodic table Containing at least 0.0001 g of one or more metals in column 5, one or more compounds of one or more metals in column 5, or a mixture thereof per gram of catalyst, (h) column 6 of periodic table Including one or more metals, one or more compounds of one or more metals in column 6, or mixtures thereof, (i) one or more metals in column 6 of the periodic table, one of columns 6 One or more compounds of the above metals, or a mixture thereof, containing 0.0001 g or more per gram of catalyst, (j) one or more metals in column 10 of the periodic table, one or more metals in column 10 And / or a mixture thereof and / or (k) one or more elements of column 15 of the periodic table One or more compounds of one or more elements of the column 15, or mixtures thereof.

In further embodiments, features of certain embodiments of the invention may be combined with features of other embodiments of the invention. For example, one embodiment of the invention may be combined with any of the other embodiments.
In further embodiments, the crude product is obtained in any of the methods and systems described herein.
In further embodiments, other features may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages of the present invention will become apparent to those skilled in the art from the following detailed description, taken in conjunction with the accompanying drawings.
FIG. 1 is a schematic diagram of one embodiment of a contact system.
2A and 2B are schematic views of one embodiment of a contact system having two contact zones.
3A and 3B are schematic views of one embodiment of a contact system having three contact zones.
FIG. 4 is a schematic diagram of one embodiment of a blending band in combination with a contact system.
FIG. 5 is a schematic diagram of one embodiment of a blending band in combination with a contact system.
FIG. 6 is a schematic diagram of one embodiment combining a separation zone, a contact system, and a blending zone.

FIG. 7 is a representative characterization table for crude feed and crude product in one embodiment where the crude feed is contacted with three catalysts.
FIG. 8 is a graph of loaded average bed temperature versus operating length for one embodiment of contacting a crude feed with one or more catalysts.
FIG. 9 is a representative characterization table for a crude feed and crude product in one embodiment where the crude feed is contacted with two catalysts.
FIG. 10 is another exemplary characteristic table for a crude feed and crude product in one embodiment where the crude feed is contacted with two catalysts.
FIG. 11 is a table of crude feed and crude product in an embodiment in which a crude feed is contacted with four different catalyst systems.
FIG. 12 is a graph of crude product P-value versus operating time for an embodiment in which a crude feed is contacted with four different catalyst systems.
FIG. 13 is a graph of total hydrogen absorption versus operating time for a crude feed in an embodiment where the crude feed is contacted with four different catalyst systems.
FIG. 14 is a graph of crude product residue content (% by weight) versus operating time for an embodiment in which a crude feed is contacted with four different catalyst systems.

FIG. 15 is a graph of the change in API specific gravity versus operating time of a crude product in an embodiment in which a crude feed is contacted with four different catalyst systems.
FIG. 16 is a graph of crude product oxygen content (% by weight) versus operating time for an embodiment in which a crude feed is contacted with four different catalyst systems.
FIG. 17 illustrates a crude feed and crude product in an embodiment in which the crude feed is contacted with a catalyst system comprising various amounts of molybdenum and vanadium catalysts; a catalyst system comprising a vanadium catalyst and a molybdenum / vanadium catalyst; and glass beads. It is a typical characteristic table.
FIG. 18 is a crude feed and crude product characterization table for embodiments in which a crude feed is contacted with one or more catalysts at various liquid hourly space velocities.

FIG. 19 is a table of characteristics of crude feed and crude product in embodiments where the crude feed is contacted at various contact temperatures.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are illustrated in the drawings. These drawings cannot have a constant reduction ratio. The drawings and detailed description thereof are not intended to limit the invention to the particular forms disclosed, but on the contrary, the invention is intended to be within the spirit and scope of the invention as defined by the appended claims. It should be understood that all variations, equivalents and alternatives are included.

DETAILED DESCRIPTION Particular embodiments of the present invention will now be described in further detail. The terms used are defined as follows.
“ASTM” refers to American Standard Testing and Materials.
“API specific gravity” refers to API specific gravity at 15.5 ° C. (60 ° F.). API specific gravity is measured by ASTM method D6822.
The proportion (%) of hydrogen atoms and the proportion (%) of carbon atoms in crude feed and crude product are measured by ASTM method D5291. Unless otherwise indicated, the boiling range distribution of crude feed, total product and / or crude product is measured by ASTM method D5307.
Say the asphaltenes insoluble in pentane and "C 5 asphaltenes". C 5 asphaltenes content is as determined by ASTM Method D2007.

"Column X metal" refers to one or more compounds of one or more metals in column X of the periodic table and / or one or more metals in column X of the periodic table. However, X is equivalent to the column number (for example, 1-12) of a periodic table. For example, “sixth column metal” refers to one or more compounds of one or more metals in column 6 of the periodic table and / or one or more metals in column 6 of the periodic table.
“Column X element” refers to one or more elements in column X of the periodic table and / or one or more compounds of one or more elements in column X of the periodic table. However, X is equivalent to the column number (for example, 13-18) of a periodic table. For example, “15th column element” refers to one or more compounds in the 15th column of the periodic table and / or one or more compounds of 1 or more elements in the 15th column of the periodic table.

In the scope of this application, the weight of the periodic table metal, the weight of the compound of the periodic table metal, the weight of the periodic table element, or the weight of the compound of the periodic table element is calculated as the weight of the metal or the weight of the element. For example, if 0.1 g of MoO 3 is used per gram of catalyst, the calculated weight of molybdenum metal in the catalyst is 0.067 g per gram of catalyst.
“Content” refers to the weight of a component in a substrate expressed as a weight fraction or percentage by weight relative to the total weight of the substrate (eg, crude feed, total product or crude product). “Weight ppm” refers to parts by weight per million parts by weight.
"Crude feed / total product mixture" refers to the mixture that is contacted with the catalyst during processing.

“Distillate” refers to a hydrocarbon having a boiling range distribution of 204 ° C. (400 ° F.) to 343 ° C. (650-F) at 0.101 MPa. The distillate content is measured by ASTM method D5307.
“Heteroatom” refers to oxygen, nitrogen and / or sulfur contained in the molecular structure of a hydrocarbon. The heteroatom content is measured by ASTM method E385 for oxygen, D5762 for total nitrogen, and D4294 for sulfur. “Total basic nitrogen” refers to nitrogen compounds having a pKa of less than 40. Basic nitrogen ("bn") is measured by ASTM method D2896.

“Hydrogen source” refers to a compound when hydrogen and / or a reaction in the presence of a crude material and a catalyst to give hydrogen to a compound in the crude material. As the hydrogen source, hydrocarbons (e.g. methane, ethane, propane, C 1 -C 4 hydrocarbons such as butane), water, or mixtures thereof. A material balance may be performed to evaluate the total amount of hydrogen imparted to the compound in the crude oil feedstock.

“Plate crushing strength” refers to the compressive force required to destroy the catalyst. The flat plate crushing strength is measured by ASTM method D4179.
“LHSV” refers to the volume ratio (rate) of the liquid crude feed per total volume of the catalyst and is expressed in time (h −1 ). The total volume of the catalyst is calculated by adding up the volumes of all the catalysts in the contact zone described here.

“Liquid mixture” refers to a composition comprising one or more compounds that are liquid at standard temperature and pressure (25 ° C., 0.101 MPa; hereinafter referred to as “STP”), or one or more liquids in STP. And a composition comprising one or more compounds that are solid in STP.
The “periodic table” refers to a periodic table defined in November 2003 by the International Union of Pure and Applied Chemistry (IUPAC).

  “Metal in an organic acid metal salt” refers to an alkali metal, alkaline earth metal, zinc, arsenic, chromium, or a combination thereof. The metal content in the organic acid metal salt is measured by ASTM method D1318. “Microcarbon residue” (“MCR”) refers to the amount of carbon residue remaining after evaporation and pyrolysis of the substrate. The MCR content is measured by ASTM method D4530.

“Naphtha” refers to a hydrocarbon having a boiling range distribution of 38 ° C. (100 ° F.) to 200 ° C. (392 ° F.) at 0.101 MPa. Naphtha content is measured by ASTM method D5307.
“Ni / V / Fe” refers to nickel, vanadium, iron, or a combination thereof.
“Ni / V / Fe content” refers to the content of nickel, vanadium, iron, or a combination thereof. The Ni / V / Fe content is measured by ASTM method D5708.

“Nm 3 / m 3 ” refers to the standard m 3 of gas per m 3 of crude feed.
The “carboxyl-free organic oxygen compound” refers to an organic oxygen compound that does not contain a carboxyl (—CO 2 —) group. Non-carboxylable organic oxygen compounds include, but are not limited to, ethers, cyclic ethers, alcohols, aromatic alcohols, ketones, aldehydes, or combinations thereof that do not contain any carboxyl groups.

“Non-condensable gas” refers to components and / or mixtures of components that are gases in STP.
“P (decoagulation) value” refers to a numerical value indicating the solidification tendency of asphaltenes in crude oil raw materials. The method for measuring the P value is described in J. Org. J. et al. Heithaus “Measurement and Significance of Asphaltene Peptization”, Journal of Petroleum, Vol. 48, No. 458, February 1962, p. 45-53.

“Pore diameter”, “median pore diameter” and “pore volume” are the pore diameter, median pore diameter and pore volume measured by ASTM method D4284 (measurement of mercury porosity at a contact angle of 140 °). To tell. For measurement of these values, micromeritics (registered trademark) A9220 (Micromeritics Inc., Norcross, Georgia, USA) can be used.
“Residue” refers to a component having a boiling point range distribution above 538 ° C. (1000 ° F.) as measured by ASTM method D5307.

“SCFB” refers to standard cubic feet of gas per barrel of crude feed.
The “surface area” of the catalyst is measured by ASTM method D3663.
“TAN” refers to the total acid number expressed as mg KOH / g sample. TAN is measured by ASTM method D664.
“VGO” refers to a hydrocarbon having a boiling range distribution of 343 ° C. (650 ° F.) to 538 ° C. (1000 ° F.) at 0.101 MPa. The VGO content is measured by ASTM method D5307.

“Viscosity” refers to kinematic viscosity at 37.8 ° C. (100 ° F.). Viscosity is measured by ASTM method D445.
In the context of this application, if the values obtained when testing for substrate properties are outside the limits of the test method, the test method may be modified and / or recalibrated to test such properties. Should be understood.

  Crude oil may be produced and / or retorted from a hydrocarbon-containing blend and then stabilized. The crude oil may contain crude oil. Crude oil is generally solid, semi-solid, and / or liquid. Stabilization methods include, but are not limited to, methods that remove non-condensable gases, water, salts, or combinations thereof from crude oil to form stabilized crude oil. Such stabilization may often be performed at or near the manufacturing and / or carbonization site.

  Stabilized crude oil is typically not distilled or rectified in a processing facility to produce multiple components (eg, naphtha, distillate, VGO, and / or lubricating oil) having a specific boiling range distribution. Examples of the distillation method include, but are not limited to, an atmospheric distillation method and / or a vacuum distillation method. Undistilled and / or non-rectified crude oil may contain a component having 5 or more carbon atoms in an amount of 0.5 g or more per gram of crude oil. Examples of stabilized crudes include whole crude, topped crude, desalted crude, topped desalted crude, or combinations thereof. “Topped” refers to a crude oil that has been treated such that at least some of the components having a boiling point of less than 35 ° C. (less than 95 ° F. at 1 atmosphere) at 0.101 MPa are removed. Usually, topped crude oil contains 0.1 g or less, 0.05 g or less, or 0.02 g or less of these components per 1 g of topped crude oil.

  Some stabilized crude oils have the property of being transportable to conventional processing equipment by transport carriers (eg, pipelines, trucks or ships). Other crude oils have one or more inappropriate properties that are disadvantageous. Unfavorable crude oil may be unacceptable to transportation carriers and / or processing facilities, and therefore has a low economic value for disadvantaged crude oil. This economic value may be such that a reservoir containing adverse crude oil is considered too expensive to manufacture, transport and / or process.

Disadvantageous characteristics of crude oil include, but are not limited to: (a) TAN is 0.1 or more, 0.3 or more, b) Viscosity is 10 cSt or more, c) API specific gravity is 19 or less, d) Total Ni / V / Fe content of 0.00002 g or more per gram of crude oil or 0.0001 g or more, e) Total heteroatom content of 0.005 g or more per gram of crude oil, (f) Residue content of 0.01 g per gram of crude oil above, g) C 5 asphaltenes content of crude oil 1g per 0.04g least, h) MCR content of more than 0.002g per crude 1g, i) 0 per crude 1g content of metals in metal salts of organic acids. 00001 g or more, or j) a combination thereof. In some embodiments, the disadvantaged crude may contain 0.2 g or more, 0.3 g or more, 0.5 g or more, or 0.9 g or more of residue per gram of the crude oil. In some embodiments, the disadvantaged crude may have a TAN in the range of 0.1 or 0.3 to 20, 0.3 or 0.5 to 10, 0.4 or 0.5 to 5. In certain embodiments, the disadvantaged crude oil may contain 0.005 g or more, 0.01 g or more, or 0.02 g or more of sulfur per gram of the crude oil.

Disadvantaged crudes, but are not limited to, the following characteristics: (a) TAN of 0.5 or more, b) the oxygen content of the crude feed 1g per 0.005g above, c) C 5 asphaltenes content 0.04 g or more per gram of crude feed, d) For crude feed having an API specific gravity of 10 or more, the viscosity is higher than the desired viscosity (eg> 10 cSt), e) the metal content in the organic acid metal salt per gram of crude oil 0.00001 g or more, or f) a combination thereof.

  Unfavorable crude oil is 0.001 g or more, 0.005 g or more, or 0.01 g or more of hydrocarbon at 95 to 200 ° C. per 1 g of the crude oil at a boiling range distribution of 0.101 MPa; ˜300 ° C. hydrocarbon at 0.01 g or more, 0.005 g or more, or 0.001 g or more; at a boiling point range distribution of 0.101 MPa, 300 to 400 ° C. hydrocarbon at 0.001 g or more, 0.005 g or more, or 0.001 g or more. 01 g or more; and a boiling point range distribution of 0.101 MPa, the hydrocarbon at 400 to 650 ° C. may be contained 0.001 g or more, 0.005 g or more, or 0.01 g or more.

  Unfavorable crude oil is 0.001 g or more, 0.005 g or more or 0.01 g or more of hydrocarbons having a boiling point range distribution of 0.101 MPa per gram of crude oil; 0.001 g or more, 0.005 g or more or 0.01 g or more of hydrocarbon at 200 ° C .; 0.001 g or more, 0.005 g or more or 0.01 g of hydrocarbon at 200 to 300 ° C. at a boiling point range distribution of 0.101 MPa Or more; 0.001 g or more, 0.005 g or more, or 0.01 g or more of hydrocarbon at 300 to 400 ° C. at a boiling range distribution of 0.101 MPa; and 400 to 650 ° C. of hydrocarbon at a boiling range distribution of 0.101 MPa You may contain 0.001g or more, 0.005g or more, or 0.01g or more.

  Some disadvantageous crude oils, in addition to components with boiling points above 100 ° C., hydrocarbons with a boiling range distribution of 0.101 MPa at 100 ° C. or less, 0.001 g or more, 0.005 g or more or 0 .01g or more may be contained. Generally, disadvantaged crude oils may contain no more than 0.2 g or 0.1 g of such hydrocarbons per gram of crude oil.

Some disadvantageous crude oils may contain 0.001 g or more, 0.005 g or more, or 0.01 g or more of hydrocarbons with a boiling range distribution of 0.101 MPa at 200 ° C. or more per gram of the crude oil.
Some disadvantageous crude oils may contain 0.001 g or more, 0.005 g or more, or 0.01 g or more of hydrocarbons having a boiling range distribution of 0.101 MPa and 650 ° C. or more per gram of the crude oil.

  Examples of unfavorable crudes that may be processed in the manner described herein include, but are not limited to, the following regions of the world: US Gulf Coast and Southern California, Canada's Tar Sands, Brazil Santos and Campos Basin in Egypt, Suez Canal in Egypt, Chad, North Sea in England, Offshore Angola, Bohai Bay in China, Zulia in Venezuela, Malaysia, and Sumatra in Indonesia.

  Crude oil to be processed and / or disadvantaged crude is referred to herein as “crude raw material”. The crude feed may be topped as described herein. Crude oil products obtained from the processing of crude feed are generally suitable for transport and / or processing. The properties of the crude product produced as described herein are closer to the corresponding properties of West Texas Intermediate crude than the crude feed, or closer to the corresponding properties of Brent crude, thus increasing the economic value of the crude feed . Such crude oil products can be refined with little or no pretreatment, thus increasing the refining efficiency. Pretreatment may include desulfurization, demetallization and / or atmospheric distillation to remove impurities.

  The treatment of the crude feed according to the present invention as described herein may include treatment with a catalyst in one contact zone and / or two or more contact zones. In the contact zone, at least one characteristic of the crude feed can be changed compared to that of the crude feed by contacting the crude feed with one or more catalysts. In some embodiments, the contacting is performed in the presence of a hydrogen source. In some embodiments, the hydrogen source is one or more hydrocarbons that react under specified contact conditions to provide a relatively small amount of hydrogen to the compounds in the crude feed.

  FIG. 1 is a schematic representation of a contact system 100 having a contact zone 102. Crude oil feed enters contact zone 102 via conduit 104. The contact zone may be a reactor, a part of the reactor, a plurality of parts of the reactor, or a combination thereof. Examples of contact zones include stacked bed reactors, fixed bed reactors, ebullated bed reactors, continuous stirred tank reactors (“CSTR”), fluidized bed reactors, spray reactors, and liquid / liquid contactors. It is done. In some embodiments, the contact system is on or coupled to an offshore facility. Contact between the crude oil feedstock and the catalyst in the contact system 100 may be continuous or batch.

  The contact zone may contain one or more (for example, two) catalysts. In some embodiments, contacting the crude feed with the first of the two catalysts can reduce the TAN of the crude. Subsequently, the contact of the crude oil having a reduced TAN with the second catalyst decreases the heteroatom content and increases the API specific gravity. In other embodiments, after contacting the crude feed with one or more catalysts, the crude product TAN, viscosity, Ni / V / Fe content, heteroatom content, residue content, API gravity, or these The combination of properties varies by more than 10% compared to the same properties of the crude feed.

  In some embodiments, the volume of catalyst in the contact zone ranges from 10-60%, 20-50%, or 30-40% by volume relative to the total volume of crude feed in the contact zone. In some embodiments, the catalyst and crude feed slurry contains 0.001 to 10 g, 0.005 to 5 g, or 0.01 to 3 g of catalyst per 100 g of crude feed in the contact zone.

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

When the hydrogen source is supplied as a gas (for example, hydrogen gas), the ratio of the gaseous hydrogen source to the crude oil raw material is usually 0.1 to 100,000 Nm 3 / m 3 , 0.5 to 10,000 Nm 3 / m 3. 1 to 8,000 Nm 3 / m 3 , 2 to 5,000 Nm 3 / m 3 , 5 to 3,000 Nm 3 / m 3 , or 10 to 800 Nm 3 / m 3 . In some embodiments, the hydrogen source is recycled to the contact zone in combination with a carrier gas. The carrier gas can be, for example, nitrogen, helium and / or argon. The carrier gas facilitates the flow of crude feed and / or the flow of hydrogen source in the contact zone. The carrier gas can also enhance mixing in the contact zone. In some embodiments, a hydrogen source (eg, hydrogen, methane or ethane) may be used as a carrier gas and recycled to the contact zone.

  The hydrogen source may enter the contact zone 102 either in parallel with the crude feed in conduit 104 or separately via conduit 106. In contact zone 102, the contact between the crude feed and the catalyst produces a total product, including a crude product, and in some embodiments, a gas. In some embodiments, the carrier gas is combined with a crude feed and / or a hydrogen source in conduit 106. All products may exit contact zone 102 and enter separation zone 108 via conduit 110.

  In the separation zone 108, the crude product and gas can be separated from the total product using known separation techniques such as gas-liquid separation. The crude product exits separation zone 108 via conduit 112 and can then be transported to transport carriers, pipelines, storage vessels, refineries, other processing zones, or combinations thereof. Gases include gases produced during processing (eg, hydrogen sulfide, carbon dioxide, and / or carbon monoxide), excess gaseous hydrogen source, and / or carrier gas. Excess gas may be recycled to the contact system 100, purified, and transported to other processing zones, storage vessels, or combinations thereof.

In some embodiments, the contact between the crude feed and the catalyst to produce the entire product occurs in more than one contact zone. All products can be separated to produce crude product and gas.
2 and 3 are schematic views of an embodiment of a contact system 100 having two or three contact zones. 2A and 2B, the contact system 100 has contact zones 102,114. 3A and 3B, the contact zones 102, 114, and 116 are provided. 2A and 3A, the contact zones 102, 114, 116 are shown as separate contact zones in one reactor. Crude oil feed enters contact zone 102 via conduit 104.

  In some embodiments, the carrier gas is combined with the hydrogen source in conduit 106 and introduced as a mixture into the contact zone. In certain embodiments, as shown in FIGS. 1, 3A, 3B, the hydrogen source and / or carrier gas is separately via conduit 106 and / or in the opposite direction to the crude feed stream, eg, via conduit 106 ′, One or more contact zones may be entered along with the crude feed. Adding a hydrogen source and / or carrier gas as opposed to a crude feed stream can enhance mixing and / or contact between the crude feed and the catalyst.

A feed stream is generated by contact of the crude feed with the catalyst in the contact zone 102. The raw material stream flows from the contact zone 102 to the contact zone 114. In FIGS. 3A and 3B, the raw material stream flows from the contact zone 114 to the contact zone 116.
Contact zones 102, 114, 116 may contain one or more catalysts. As shown in FIG. 2B, the feed stream exits contact zone 102 via conduit 118 and enters contact zone 114. As shown in FIG. 3B, the feed stream exits contact zone 114 via conduit 118 and enters contact zone 116.

  The feed stream can be contacted with additional catalyst in contact zone 114 and / or contact zone 116 to produce a total product. All products exit contact zone 114 and / or contact zone 116 and enter separation zone 108 via conduit 110. Crude product and / or gas is separated from the total product. The crude product exits separation zone 108 via conduit 112.

  FIG. 4 is a schematic diagram of one embodiment of a separation zone upstream of the contact system 100. Unfavorable crude oil (which may or may not be topped) enters separation zone 120 via conduit 122. The separation zone 120 separates at least a portion of the unfavorable crude oil using a separation technique known in the art (eg, sparging, membrane separation, reduced pressure) to produce a crude feedstock. For example, water can be at least partially separated from unfavorable crude oil. In another example, a crude feedstock can be produced by separating at least a portion of the components having a boiling range distribution below 95 ° C or below 100 ° C from adverse crude oil. In some embodiments, naphtha and at least some of the more volatile compounds than naphtha are separated from adverse crude oil. In some embodiments, at least some of these separated components exit separation zone 120 via conduit 124.

  In some embodiments, the crude feed obtained in the separation zone 120 is a mixture of multiple components with a boiling range distribution of 100 ° C. or higher in some embodiments, or in some embodiments a mixture of multiple components with a boiling range distribution of 120 ° C. or higher. contains. Usually, the separated crude oil raw material contains a mixture of a plurality of components having a boiling range distribution of 100 to 1000 ° C, 120 to 900 ° C, or 200 to 800 ° C. At least a portion of the crude feed exits the separation zone 120 and enters the contact zone 100 via conduit 126 (see, for example, the contact zone of FIGS. 1-3) and is further processed to produce a crude product. In some embodiments, the separation zone 120 can be located upstream or downstream of the desalination unit. After processing, the crude product exits contact system 100 via conduit 112.

  In some embodiments, the crude product is blended with a crude that is the same as or different from the crude feed. For example, the crude product can be combined with crude oils having different viscosities to obtain a blended product having a viscosity between that of the crude product and that of the crude product. In another example, it may be blended with crude oils of different TANs to obtain a product having a TAN between the crude product TAN and the crude TAN. Such blended products may be suitable for transport and / or processing.

  As shown in FIG. 5, in certain embodiments, crude oil enters contact system 100 via conduit 104, and after at least a portion of the resulting crude product exits contact system 100 via conduit 128, Introduced into the blending zone 130. In blending zone 130, at least a portion of the crude product is one or more process streams (eg, naphtha-like hydrocarbon streams resulting from the separation of one or more crude feeds), crude oil, crude feed or mixtures thereof. Combined to produce a blended product. Process streams, crude oil, crude feed or mixtures thereof are introduced directly into the blending zone 130 or upstream of such blending zone via conduit 132. A mixing system may be provided in or near the blending zone. The blended product may meet product specifications specified by refineries and / or transportation carriers. Product specifications include, but are not limited to, API specific gravity, TAN, viscosity, or limits or ranges of combinations thereof. The blended product exits blend zone 130 via conduit 134 for transport or processing.

  In FIG. 6, unfavorable crude oil enters separation zone 120 from conduit 122 and is separated as described above to form a crude feed. The crude feed then enters the contact system 100 through conduit 126. At least some of the components separated from the unfavorable crude leaves the separation zone 120 via conduit 124. At least a portion of the crude product exits contact system 100 and enters conduit 130 through conduit 128. Other process streams and / or crude oil enter the blending zone 130 directly or via conduit 132 and combine with the crude product to form a blended product. The blended product exits blend zone 130 via conduit 134.

  The crude product and / or blended product is transported to refineries and / or processing facilities. The crude product and / or blended product may be processed to produce industrial products such as transportation fuels, heating fuels, lubricants or chemicals. Processing includes distillation and / or fractional distillation of the crude product and / or blend product to produce one or more distillate fractions. In some embodiments, the crude product, blend product and / or one or more distillate fractions may be hydrogenated.

  In some embodiments, the crude product TAN is 90% or less, 50% or less, 30% or less, or 10% or less relative to the TAN of the crude feed. In some embodiments, the crude product TAN ranges from 1-80%, 20-70%, 30-60%, or 40-50% of the crude feed TAN. In some embodiments, the crude product has a TAN of 1 or less, 0.5 or less, 0.3 or less, 0.2 or less, 0.1 or less, or 0.05 or less. The TAN of the crude product is often greater than or equal to 0.0001 and more often greater than or equal to 0.001. In some embodiments, the TAN of the crude product may range from 0.001 to 0.5, 0.01 to 0.2, or 0.05 to 0.1.

In some embodiments, the crude product has a total Ni / V / Fe content of 90% or less, 50% or less, 10% or less, 5% or less, or the total Ni / V / Fe content of the crude feed. 3% or less. In some embodiments, the crude product has a total Ni / V / Fe content of 1-80%, 10-70%, 20-60%, or 30 relative to the total Ni / V / Fe content of the crude feed. It is in the range of ˜50%. In certain embodiments, the total Ni / V / Fe content in the crude product is 1 × 10 −7 to 5 × 10 −5 g, 3 × 10 −7 to 2 × 10 −5 g, or 1 × 10. It is in the range of −6 to 1 × 10 −5 g. In a particular embodiment, the crude product has a Ni / V / Fe content of 2 × 10 −5 g or less. In some embodiments, the crude product has a total Ni / V / Fe content in the range of 70-130%, 80-120%, or 90-110% relative to the total Ni / V / Fe content of the crude feed. It is.

  In some embodiments, the total content of metals in the organic acid metal salt in the crude product is 90% or less, 50% or less, 10% or less with respect to the total content of the metal in the organic acid metal salt in the crude feed. Or 5% or less. In a particular embodiment, the total content of metals in the organic acid metal salt in the crude product is 1-80%, 10-70%, 20 relative to the total content of metal in the organic acid metal salt in the crude feed. It is in the range of -60% or 30-50%. Organic acids that 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 acid, phenanthreic acid, and benzoic acid. The metal portion of the metal salt includes alkali metals (eg, lithium, sodium, potassium), alkaline earth metals (eg, magnesium, calcium, barium), column 12 metals (eg, zinc, cadmium), column 15 metals (eg, arsenic) ), Column 6 metals (e.g. chromium) or mixtures thereof.

  In certain embodiments, the total metal content of the organic acid metal salt in the crude product is from 0.0000001 to 0.00005 g, 0.0000003 to 0.00002 g, or 0.000001 to 0.001 g per gram of crude product. The range is 00001 g. In some embodiments, the total metal content of the organic acid metal salt in the crude product is 70-130%, 80-120%, or 90-110 based on the total metal content of the organic acid metal salt in the crude feed. % Range.

In certain embodiments, the API specific gravity of the crude product produced by contacting the crude feed and catalyst under contact conditions is 70-130%, 80-120%, 90-110% relative to the crude feed API specific gravity. Or it is the range of 100 to 130%. In certain embodiments, the crude product has an API specific gravity of 14-40, 15-30, or 16-25.
In certain embodiments, the viscosity of the crude product is 90% or less, 80% or less, or 70% or less relative to the viscosity of the crude feed. In some embodiments, the viscosity of the crude product ranges from 10-60%, 20-50%, or 30-40% relative to the viscosity of the crude feed. In some embodiments, the viscosity of the crude product is 90% or less relative to the viscosity of the crude feed, but the API specific gravity of the crude product is 70-130%, 80-120%, or 90% relative to the crude feed API. It is in the range of ~ 110%.

In some embodiments, the total heteroatom content of the crude product is 90% or less, 50% or less, 10% or less, or 5% or less relative to the total heteroatom content of the crude feed. In some embodiments, the total heteroatom content of the crude product is 1% or greater, 30% or greater, 80% or greater, or 99% or greater relative to the total heteroatom content of the crude feed.
In some embodiments, the crude product has a sulfur content of 90% or less, 50% or less, 10% or less, or 5% or less relative to the sulfur content of the crude feed. In certain embodiments, the sulfur content of the crude product is 1% or greater, 30% or greater, 80% or greater, or 99% or greater relative to the sulfur content of the crude feed. In some embodiments, the sulfur content of the crude product ranges from 70-130%, 80-120%, or 90-110% relative to the sulfur content of the crude feed.

In some embodiments, the total nitrogen content of the crude product may be 90% or less, 80% or less, 10% or less, or 5% or less relative to the total nitrogen content of the crude feed. In certain embodiments, the total nitrogen content of the crude product is 1% or greater, 30% or greater, 80% or greater, or 99% or greater relative to the total nitrogen content of the crude feed.
In some embodiments, the crude product has a basic nitrogen content of 95% or less, 90% or less, 50% or less, 10% or less, or 5% or less relative to the basic nitrogen content of the crude feed. In certain embodiments, the crude product has a basic nitrogen content of 1% or greater, 30% or greater, 80% or greater, or 99% or greater relative to the basic nitrogen content of the crude feed.

  In some embodiments, the oxygen content of the crude product may be 90% or less, 50% or less, 30% or less, 10% or less, or 5% or less relative to the oxygen content of the crude feed. In certain embodiments, the oxygen content of the crude product is 1% or greater, 30% or greater, 80% or greater, or 99% or greater relative to the oxygen content of the crude feed. In some embodiments, the oxygen content of the crude product ranges from 1-80%, 10-70%, 20-60%, or 30-50% relative to the oxygen content of the crude feed. In some embodiments, the total content of carboxylic acid compounds in the crude product is 90% or less, 50% or less, 10% or less, or 5% or less relative to the total content of carboxylic compounds in the crude feed. It may be. In certain embodiments, the total content of carboxylic acid compounds in the crude product is 1% or more, 30% or more, 80% or more, or 99% or more with respect to the total content of carboxylic acid compounds in the crude feed. is there.

  In some embodiments, selected organic oxygen compounds may be reduced in the crude feed. In some embodiments, the carboxylic acid and / or carboxylic acid metal salt may be chemically reduced before the carboxyl-free organic oxygen compound. Carboxylic acid and non-carboxylated organic oxygen compounds in the crude product can generally be distinguished by analysis of the crude product using known spectroscopic methods (eg, infrared analysis, mass spectrometry, and / or gas chromatography).

  In certain embodiments, the oxygen content of the crude product is 90% or less, 80% or less, 70% or less, or 50% or less relative to the oxygen content of the crude feed, and the crude product TAN is It is 90% or less, 70% or less, 50% or less, or 40% or less with respect to TAN of a raw material. In certain embodiments, the oxygen content of the crude product is 1% or more, 30% or more, 80% or more, or 99% or more with respect to the oxygen content of the crude feed, and the crude product TAN is: It is 1% or more, 30% or more, 80% or more, or 99% or more with respect to TAN of crude oil raw material.

  Furthermore, the content of the carboxylic acid and / or carboxylic acid metal salt in the crude product is 90% or less, 70% or less, 50% or less with respect to the content of the carboxylic acid and / or carboxylic acid metal salt in the crude material. Or 40% or less, and the content of the non-carboxylated organic oxygen compound in the crude product is 70 to 130%, 80 to 120%, or the content of the noncarboxylated organic oxygen compound in the crude feed It may be in the range of 90-110%.

  In some embodiments, the crude product contains 0.05 to 0.15 g or 0.09 to 0.13 g hydrogen per gram of crude product in the molecular structure. The crude product may contain 0.8 to 0.9 g or 0.82 to 0.88 g of carbon per gram of crude product in the molecular structure. The ratio of hydrogen to carbon atoms (H / C) of the crude product may be in the range of 70-130%, 80-120%, or 90-110% relative to the H / C atomic ratio of the crude feed. . If the H / C atomic ratio of the crude product is within 10-30% relative to the H / C atomic ratio of the crude feed, less hydrogen is absorbed and / or consumed in this process and / or Indicates to generate.

  Crude oil products contain components in a certain boiling range. In some embodiments, the crude product has a boiling range distribution of 0.001 g or more, or 0.001 to 0.5 g of hydrocarbons with a boiling range distribution of 0.101 MPa and 100 ° C. or less per gram of crude product; 0.001 g or more of hydrocarbon at 100 to 200 ° C. at 0.101 Mpa, or 0.001 to 0.5 g; 0.001 g or more of hydrocarbon at 200 to 300 ° C. at a boiling point range distribution of 0.101 Mpa, or 0.001 g. 0.001 g or more of hydrocarbons having a boiling point range distribution of 0.101 MPa and 300 to 400 ° C., or 0.001 to 0.5 g; and a boiling range distribution of 400 to 538 ° C. with 0.101 MPa. Contains 0.001 g or more, or 0.001 to 0.5 g of hydrocarbon.

In some embodiments, the crude product has a boiling range distribution of 0.101 MPa and 100 ° C. or less hydrocarbons at 0.001 g or more and / or a boiling range distribution of 0.101 Mpa per gram of crude product. Contains 0.001 g or more of hydrocarbon at 200 ° C.
In some embodiments, the crude product may contain 0.001 g or more or 0.01 g or more of naphtha per gram of crude product. In other embodiments, the crude product may contain naphtha at a content of 0.6 g or less or 0.8 g or less per gram of crude product.

In some embodiments, the distillate content of the crude product ranges from 70-130%, 80-120%, or 90-110% relative to the distillate content of the crude feed. The distillate content of the crude product may range from 0.00001 to 0.5 g, 0.001 to 0.3 g, or 0.002 to 0.2 g per gram of crude product.
In certain embodiments, the crude product has a VGO content in the range of 70-130%, 80-120%, or 90-110% relative to the VGO content of the crude feed. In some embodiments, the crude product has a VGO content of 0.00001 to 0.8 g, 0.001 to 0.5 g, 0.002 to 0.4 g, or 0.001 to 0.000 per gram of crude product. The range is 3 g.

  In some embodiments, the crude product residue content ranges from 70-130%, 80-120%, or 90-110% relative to the crude feed residue content. The residue content of the crude product is 0.00001-0.8 g, 0.0001-0.5 g, 0.0005-0.4 g, 0.001-0.3 g, 0.005 per gram of crude product. It is the range of -0.2g or 0.01-0.1g.

MCR content of the crude product in certain embodiments, from 70 to 130% relative to MCR content of the crude feed, 80% to 120%, or 90-110% of the is in the range, C 5 asphaltenes of the crude product content is 90% or less relative to C 5 asphaltenes content of the crude feed, 80% or less, or 50% or less. C 5 asphaltenes content of the crude product in certain embodiments, more than 10% relative to C 5 asphaltenes content of the crude feed, at least 60%, or 70% or more, MCR content of the crude product In the range of 10 to 30% of the MCR content of the crude oil raw material. In some embodiments, while maintaining the MCR content of relatively stable, reducing the C 5 asphaltenes content of the crude product, may stability of the crude feed and / or total product mixture improves Absent.

In some embodiments, to obtain a mathematical relationship between the high viscosity components in the crude product relative to the high viscosity components in the crude feed may be combined with C 5 asphaltenes content and MCR content. For example, if the sum of the MCR content of the crude oil raw material and the C 5 asphaltene content of the crude oil raw material is S, and the sum of the MC content of the crude product and the C 5 asphaltene content of the crude product is S ′ These sums can be compared (S 'vs. S) to evaluate the total weight loss of high viscosity components in the crude feed. The crude feedstock S ′ may range from 1 to 99%, 10 to 90%, or 20 to 80% of S. MCR content The ratio of C 5 asphaltenes content of the crude product in some embodiments, 1.0~3.0,1.2~2.0, or in the range of 1.3 to 1.9 is there.

  In certain embodiments, the MCR content of the crude product is 90% or less, 80% or less, 50% or less, or 10% or less relative to the crude feed. In some embodiments, the MCR content of the crude product ranges from 1-80%, 10-70%, 20-60%, or 30-50% relative to the MCR content of the crude feed. In some embodiments, the crude product contains 0.0001-0.1 g, 0.005-0.08 g, or 0.01-0.05 g of MCR per gram of crude product.

  In some embodiments, the crude product contains more than 0 g and less than 0.01 g, 0.000001 to 0.001 g, or 0.00001 to 0.0001 g of catalyst per gram of crude product. This catalyst helps stabilize the crude product during transportation and / or processing. The catalyst can also prevent corrosion and friction and / or improve the water separation capacity of the crude product. The methods described herein may be configured to add one or more catalysts described herein to the crude product during processing.

The crude product produced with the contact system 100 has different properties than the crude feed. Such properties include, but are not limited to: a) reduced TAN, b) reduced viscosity, c) reduced total Ni / V / fe content, d) sulfur, oxygen, nitrogen or their reduction of combinatorial content, e) reduction of the residue content, f) C 5 reduced asphaltenes content, g) reduction of MCR content, h) increased API gravity, i) metals in metal salts of organic acids Reducing the content, j) or a combination thereof. In some embodiments, one or more characteristics of the crude product relative to the crude feed may be selectively changed without significantly or substantially changing other characteristics. For example, it may be desirable to selectively reduce only the TAN of the crude feedstock without significantly changing the amount of other components (eg, sulfur, residue, Ni / V / fe, or VGO) other than TAN. In this way, the hydrogen absorption during contact is not enriched with other components, but can be “rich” with a decrease in TAN. Accordingly, while reducing the amount of hydrogen used, such a small amount of hydrogen is also used to reduce other components in the crude oil feed, so that the TAN of the crude feed can be reduced. For example, unfavorable crude oil has a high TAN, but if the sulfur content is acceptable to meet processing and / or transportation standards, such crude feed will be more efficient without reducing sulfur. TAN can be reduced by processing.

  The catalyst used in one or more embodiments of the present invention may contain one or more bulk metals and / or metals supported on a support. These metals may be elemental or in the form of metal compounds. The catalyst described herein may be introduced as a precursor into the contact zone (eg, contacting sulfur and / or a sulfur-containing crude feed with the precursor) and then active as a catalyst in the contact zone. The catalyst or combination of catalysts used may or may not be a commercial product. Examples of commercial catalysts used 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; Z703; Z703 Z713; Z723; Z753; and Z763 (obtained from CRI International, Inc., Houston, Texas, USA).

  In some embodiments, the catalyst used to change the properties of the crude feedstock comprises columns 5-10 metal on the support. Columns 5-10 include, but are not limited to, vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum, or A mixture thereof may be mentioned. Columns 5 to 10 metal content of the catalyst is 0.0001 g or more, 0.001 g or more, 0.01 g or more, or 0.0001 to 0.6 g, 0.005 to 0.3 g, 0.001 per 1 g of the catalyst. It may be in the range of ~ 0.1g or 0.01-0.08g. In some embodiments, the catalyst contains column 15 elements in addition to column 5-10 metals. An example of an element in the fifteenth column is phosphorus. The total content of the 15th column element of the catalyst was in the range of 0.000001 to 0.1 g, 0.00001 to 0.06 g, 0.00005 to 0.03 g or 0.0001 to 0.001 g per gram of catalyst. It's okay.

  In certain embodiments, the catalyst comprises a column 6 metal. The total column 6 metal content of the catalyst is 0.0001 g or more, 0.01 g or more, 0.02 g or more, and / or 0.0001 to 0.6 g, 0.001 to 0.3 g, 0. It may be in the range of 005 to 0.1 g or 0.01 to 0.08 g. In some embodiments, the catalyst contains 0.0001-0.06 g of die 6 column metal per gram of catalyst. In some embodiments, the catalyst contains a column 15 element in addition to the column 6 metal.

  In some embodiments, the catalyst contains a combination of column 6 metal and column 5 metal and / or column 7-10 metal. The molar ratio of column 6 metal to column 5 metal may range from 0.1-20, 1-10, or 2-5. The molar ratio of column 6 metal to columns 7-10 may be in the range of 0.1-20, 1-10, or 2-5. In some embodiments, the catalyst contains a column 15 element in addition to the combination of column 6 metal with column 5 metal and / or column 7-10. In another embodiment, the catalyst contains column 6 metal and column 10 metal. The molar ratio of total column 10 metal to total column 6 metal in the catalyst ranges from 1-10 or 2-5. In a particular embodiment, the catalyst contains column 5 metal and column 10 metal. The molar ratio of total column 10 metal to total column 5 metal in the catalyst ranges from 1-10 or 2-5.

  In some embodiments, Columns 5-10 metal is introduced or supported on the support to form a catalyst. In certain embodiments, column 5-10 metals are combined with column 15 elements to be introduced or supported on the support to form a catalyst. In embodiments carrying metals and / or elements, the weight of the catalyst includes all supports, all metals and all elements. The support may be porous and includes refractory oxides, porous carbon-based materials, zeolites, or combinations thereof. Refractory oxides include, but are not limited to, alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or combinations thereof. Supports are available from market manufacturers such as Criterion Catalysts and Technologies LP (Houston, Texas, USA). Examples of the porous carbon-based material include, but are not limited to, activated carbon and / or porous graphite. Examples of zeolites include Y-zeolite, β-zeolite, mordenite zeolite, ZSM-5 zeolite, and ferrierite zeolite. Zeolites can be obtained from commercial manufacturers such as Zeolist (Valley Forge, PA, USA).

  In some embodiments, the support is made from a support having an average pore size of 150 mm or more, 170 mm or more, or 180 mm or more. In certain embodiments, the support is made by molding an aqueous paste of the support material. In some embodiments, an acid is added to the paste to aid in the extrusion of the paste. Water and dilute acid are added in the amount and / or manner required to impart the desired consistency to the extrudable paste. Examples of acids include, but are not limited to nitric acid, acetic acid, sulfuric acid, and hydrochloric acid.

  The paste may be extruded and cut using generally known catalyst extrusion methods and catalyst cutting methods to form extrudates. The extrudate may be heat treated at a temperature range of 5 to 260 ° C. or 85 to 235 ° C. for a predetermined time (eg, 0.5 to 8 hours) and / or dried until the moisture content of the extrudate reaches a desired level. The heat-treated extrudate may be heat-treated at a temperature in the range of 800 to 1200 ° C or 900 to 1100 ° C in order to form a support having an average pore diameter of 150 mm or more.

  In certain embodiments, the support comprises γ-alumina, θ-alumina, δ-alumina, α-alumina, or combinations thereof. The amount of γ-alumina, δ-alumina, α-alumina, or a combination thereof is 0.0001-0.99 g, 0.001-0.5 g per gram of catalyst support, as measured by X-ray diffraction. It may be in the range of 0.01 to 0.1 g, or 0.1 g or less. In some embodiments, the θ-alumina content of the support, as measured by X-ray diffraction, is 0.1-0.99 g / g support, alone or in combination with other forms of alumina, .5 to 0.9 g or 0.6 to 0.8 g. In some embodiments, the support contains 0.1 g or more, 0.3 g or more, 0.5 g or more, or 0.8 g or more of θ-alumina as measured by X-ray diffraction.

The catalyst is generally produced using a known catalyst production method. Examples of catalyst preparation methods include USP 6,218,333 by Gabrilov et al., USP 6,290,841 by Gabrilov et al, USP 5,744,025 by Boon et al, and US Application Publication No. 20030111391.
In some embodiments, the support may be impregnated with a metal to form a catalyst. In certain embodiments, the support may be heat treated at a temperature in the range of 400-1200 ° C, 450-1000 ° C, or 600-900 ° C before impregnating the metal. In some embodiments, an impregnation aid may be used during catalyst manufacture. Examples of the impregnation aid include a citric acid component, ethylenediaminetetraacetic acid (EDTA), ammonia, or a mixture thereof.

  In certain embodiments, the catalyst may be formed by adding or introducing a column 5-10 metal ("overlaying") to the heat-treated shaped mixture of the support. Advantageous catalytic properties are often obtained when a metal is overlaid on a heat treated shaped support having a substantially uniform or relatively uniform metal concentration. When the shaped support is heat-treated after each metal is overlaid, the catalytic activity of the catalyst tends to be improved. A method for producing a catalyst using the overlay method is described in Bhan et al. 20030111391.

  To form the column 5-10 metal / support mixture, the column 5-10 metal may be mixed in a suitable mixing device. The Group 5-10 metal / support mixture may be mixed using a suitable mixing device. Examples of suitable mixing devices are generally known, such as tumblers, fixed shells or troughs, muller mixers (eg batch type or continuous type), impact mixers, etc. Or a generally known apparatus. In certain embodiments, these materials are mixed until the Columns 5-10 metal is substantially uniformly dispersed in the support.

In some embodiments, after compounding the support and metal, the catalyst is heated to a temperature of 150-750 ° C, 200-740 ° C, or 400-730 ° C.
In some embodiments, the catalyst is present in the presence of hot air and / or oxygen-rich air to remove volatiles so that at least a portion of the Group 5-10 metal is converted to the corresponding metal oxide. Below, you may heat-process at the temperature of 400-1000 degreeC.

  However, in other embodiments, to remove most volatile components without converting column 5-10 metal to metal oxide, 35 to 500 ° C (eg, less than 300 ° C, less than 400 ° C, or less than 500 ° C). The catalyst may be heat treated in the presence of air at a temperature in the range of 1-3) for a time in the range of 1-3 hours. Catalysts made in this way are generally referred to as “green” catalysts. When the catalyst is made in this way in combination with the sulfiding method, the active metal can be substantially dispersed in the support. The preparation of such catalysts is described in US Pat. No. 6,218,333 and USP 6,290,841 by Gabriel et al.

  In certain embodiments, the θ-alumina support may be combined with a Group 5-10 metal to form a θ-alumina support / Columns 5-10 metal mixture. The θ-alumina support / columns 5-10 metal mixture may be heat treated at a temperature of 400 ° C. or higher to form a catalyst having a pore size distribution with a median pore diameter of 230 mm or more. Usually, such heat treatment is performed at a temperature of 1200 ° C. or lower.

  In some embodiments, a support (either a commercially available support or a support made as described herein) may be combined with a supported catalyst and / or a bulk metal catalyst. In some embodiments, the supported catalyst may contain a column 15 metal. For example, the supported catalyst and / or the bulk metal catalyst may be crushed into a powder having an average particle size of 1 to 50 μ, 2 to 45 μ, or 5 to 40 μ. This powder may be combined with a support to form an embedded metal catalyst. In some embodiments, the powder is combined with a support to form a catalyst having a pore size distribution with a median pore size in the range of 80-200cm, 90-180cm, or 120-130cm; Extrusion may be done by standard methods.

  In some embodiments, when the catalyst and support are combined, at least a portion of the metal is present below the surface of the embedded metal catalyst (eg, embedded in the support), thereby preventing the metal catalyst from being embedded. Less metal than on the surface. In some embodiments, less metal on the catalyst surface increases catalyst life and / or activity by moving at least a portion of the metal to the catalyst surface during contact. These metals may migrate to the catalyst surface due to erosion of the catalyst surface during contact between the catalyst and the crude feed.

  In some embodiments, due to internal addition and / or mixing of the catalyst components, the structuring order of the column 6 metal in the column 6 oxide crystal structure is approximately that of the column 6 metal in the crystal structure of the embedded catalyst. Change to a random order. Column 6 The order of metals can be measured by powder X-ray diffraction. The order of the elemental metal in the catalyst relative to the order of the elemental metal in the metal oxide is the order of the peak of the column 6 metal in the X-ray diffraction of the column 6 oxide and the order of the peak in the X-ray diffraction spectrum of the catalyst. It can be measured by comparing with the order of the peak of column 6 metal. From the broadening and / or absence of patterns associated with column 6 metal in the X-ray diffraction spectrum, it can be estimated that the column 6 metal is almost randomly aligned in the crystal structure.

For example, an alumina / molybdenum trioxide mixture can be formed by combining molybdenum trioxide and an alumina support having a median pore diameter of 180 mm or more. Molybdenum trioxide has a well-defined pattern (eg, well-defined D 001 , D 002 , and / or D 003 peaks). The alumina / column 6 trioxide mixture can be heat treated at a temperature of 538 ° C. (1000 ° F.) or higher to produce a catalyst that does not show a molybdenum dioxide pattern in the X-ray diffraction spectrum (eg, no D001 peak). .

  In some embodiments, the catalyst is characterized by a pore structure. Various pore structure parameters include, but are not limited to, pore diameter, pore volume, surface area, or combinations thereof. The catalyst may have a total amount of pore size versus pore size distribution. The median pore diameter of this pore size distribution may be in the range of 30-1000cm, 50-500cm, or 60-300cm. In some embodiments, the catalyst containing 0.5 g or more of γ-alumina per gram of catalyst has a pore size in the range of median pore diameter in the range of 60-200 mm, 90-180 mm, 100-140 mm, or 120-130 mm. Have a distribution. In other embodiments, a catalyst containing 0.1 g or more of θ-alumina per gram of catalyst has a pore size distribution with a median pore diameter in the range of 180-500 mm, 200-300 mm, or 230-250 mm. In some embodiments, the median pore diameter of the pore size distribution is 120Å or more, 150Å or more, 180Å or more, 200Å or more, 220Å or more, 230Å or more, or 300Å or more. Such median pore diameter is usually 1000 mm or less.

  The catalyst may have a pore size distribution with a median pore size of 60 mm or more or 90 mm or more. In some embodiments, the catalyst has a pore size distribution with a median pore size in the range of 90-180, 100-140, or 120-130 and 60% of the total number of pores in the pore size distribution. The above has a pore diameter within 45 mm, 35 mm, or 25 mm of the median pore diameter. In a particular embodiment, the catalyst has a pore size distribution with a median pore diameter in the range of 70-180 cm, and more than 60% of the total pore number in the pore size distribution is within 45 mm of the median pore diameter, It has a pore diameter of 35 mm or less, or 25 mm or less.

  In embodiments where the median pore diameter of the pore size distribution is 180 mm or more, 200 mm or more, or 230 mm or more, pores that exceed 60% of the total number of pores in the pore size distribution are 50 mm of the median pore diameter. Within, 70 mm, or 90 mm. In some embodiments, the catalyst has a median pore diameter in the range of 180-500 mm, 200-400 mm, or 230-300 mm, and more than 60% of the total number of pores in the pore size distribution is the median pore diameter. The pore diameter is within 50 mm, within 70 mm, or within 90 mm.

Pore volume of pores in some embodiments, 0.3 cm 3 / g or more, may be at 0.7 cm 3 / g or more, or 0.9 cm 3 / g or more. In certain embodiments, the pore volume of the pores, a range of 0.3~0.99cm 3 /g,0.4~0.8cm 3 / g or 0.5~0.7cm 3 / g You can.
In some embodiments, the catalyst having a pore size distribution with a median pore diameter in the range of 90-180 mm has a surface area of 100 m 2 / g or more, 120 m 2 / g or more, 170 m 2 / g or more, 220 m 2. / G or more, or 270 m 2 / g or more. Such a surface area may be in the range of 100-300 m 2 / g, 120-270 m 2 / g, 130-250 m 2 / g, or 170-220 m 2 / g.

In a particular embodiment, the catalyst having a pore size distribution with a median pore diameter in the range of 180-300 mm has a surface area of 60 m 2 / g or more, 90 m 2 / g or more, 100 m 2 / g or more, 120 m. It is 2 / g or more, or 270 m 2 / g or more. Such surface area may range from 60 to 300 m 2 / g, 90 to 280 m 2 / g, 100 to 270 m 2 / g, or 120 to 250 m 2 / g.
In certain embodiments, the catalyst is present in shaped form, such as pellets, cylinders and / or extrudates. The catalyst usually has a flat plate crushing 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 may form metal sulfides (prior to use) using techniques known in the art (eg, ACTICAT® method, CRI International, Inc.). To sulfidize. Alternatively, the catalyst may be sulfurized in situ by contact of the catalyst with a crude feed containing sulfur-containing compounds. In situ sulfidation may utilize gaseous hydrogen sulfide in the presence of hydrogen or liquid phase sulfiding agents such as organic sulfur compounds (such as alkyl sulfides, polysulfides, thiols, and sulfoxides). Ex-situ sulfidation methods are described in Seamans et al. USP 5,468,372 and Seamans et al. USP 5,688,736.

In a particular embodiment, the first type of catalyst ("first catalyst") comprises a column 5-10 metal in combination with a support and has a pore size distribution in the range of median pore size ranging from 150 to 250 mm. Have. The surface area of the first catalyst may be 100 m 2 / g or more. The pore volume of the first catalyst may be 0.5 cm 3 / g or more. The γ-alumina content of the first catalyst is 0.5 g or more, and the first catalyst usually contains γ-alumina of 0.9999 g or less per 1 g of the first catalyst. In some embodiments, the total column 6 metal content of the first catalyst ranges from 0.0001 to 0.1 g / g catalyst. First catalyst is to remove a portion from the crude feed of Ni / V / Fe, removal of a portion of the components that contribute to TAN of the crude feed, removing at least a portion of the C 5 asphaltenes from the crude feed , At least a portion of the metal of the organic acid metal salt in the crude feed can be removed, or combinations thereof. Changes in other properties (eg, sulfur content, VGO content, API specific gravity, residue content, or combinations thereof) may be relatively small when the crude feed is contacted with the catalyst. While selectively changing the properties of the crude material, other properties need only be relatively small, so that the crude material can be processed more efficiently. In some embodiments, the one or more first catalysts may be used in any order.

  In a particular embodiment, the second type of catalyst ("second catalyst") comprises a column 5-10 metal in combination with a support and has a pore size distribution in the range of median pore size in the range of 90-180 mm. Have. In the pore size distribution of the second catalyst, 60% or more of the total number of pores has a pore diameter within 45 mm of the median pore diameter. By contacting the crude feed with the second catalyst under suitable contact conditions, the selected properties (eg, TAN) vary greatly compared to the same properties of the crude feed, while other properties change only slightly. Can manufacture things. In some embodiments, a hydrogen source may be present during the contacting.

  The second catalyst reduces at least some of the components that contribute to the TAN of the crude feed and at least some of the components that contribute to the relatively high viscosity, as well as the Ni / V / Fe of the crude product. At least some can be reduced. Furthermore, a crude product with a relatively small change in the sulfur content relative to the sulfur content of the crude feed can be produced by contacting the crude feed with the second catalyst. For example, the sulfur content of the crude product is 70-130% with respect to the sulfur content of the crude feed. Moreover, the change of the distillate content, VGO content, and residue content of the crude product with respect to the crude material is relatively small.

In some embodiments, the crude feedstock has a relatively low Ni / V / Fe content (eg, 50 ppm by weight or less), but the TAN, asphaltene content, or metal content of the organic acid metal salt is relatively high (or high). ). If the TAN is relatively high (e.g. 0.3 or higher), the crude feed cannot be accepted for transport and / or refining. C 5 asphaltenes content is relatively large disadvantaged crude is likely poor stability during processing than relatively small other crudes C 5 asphaltenes content. By contacting the crude material with the second catalyst, acidic components and / or C 5 asphaltenes that contribute to TAN can be removed from the crude material. In some embodiments, the reduction in components and / or C 5 asphaltenes contributing to TAN, compared to the viscosity of the crude feed, can reduce the viscosity of the crude feed and / or total product mixture. In certain embodiments, the combination of one or more of the second catalysts can enhance the stability of the crude feed and / or the total product mixture, increase catalyst life, and provide the crude feed when using the crude feed described herein. To minimize the total hydrogen absorption or to combine them.

  In some embodiments, a third type of catalyst ("third catalyst") is obtained by combining a support with a column 6 metal to produce a catalyst precursor. The catalyst precursor can be heated in the presence of one or more sulfur-containing compounds at a temperature of less than 500 ° C. (eg, less than 482 ° C.) for a relatively short time to form an unfired third catalyst. Usually, the catalyst precursor is heated at 100 ° C. or higher for 2 hours. In certain embodiments, the third catalyst contains column 15 elements in a content ranging from 0.001 to 0.03 g, 0.005 to 0.02 g, or 0.008 to 0.01 g per gram of catalyst. It's okay. The third catalyst can exhibit significant activity and stability when used in the processing of the crude feed described herein. In some embodiments, the catalyst precursor is heated to a temperature below 500 ° C. in the presence of one or more sulfur compounds.

  The third catalyst reduces at least part of the components contributing to TAN of the crude oil feed, reduces at least part of the metal of the organic acid metal salt, and at least part of Ni / V / Fe of the crude product. And the viscosity of the crude oil feedstock can be reduced. Further, the contact between the crude feed and the third catalyst can produce a crude product in which the change in sulfur content relative to the sulfur content of the crude feed is relatively small and the total hydrogen absorption by the crude feed is minimal. For example, the sulfur content of the crude product is 70-130% with respect to the sulfur content of the crude feed. Also, the crude product produced using the third catalyst may have relatively little change in API specific gravity, distillate content, VGO content, and residue content relative to the crude feedstock. TAN, organic acid metal salt metal, Ni / V / Fe content, and crude product viscosity with only minor changes in API specific gravity, distillate content, VGO content, and residue content on crude feed The ability to reduce or reduce the oil allows the crude product to be used in various processing facilities.

  In some embodiments, the third catalyst can reduce at least a portion of the MCR content of the crude feed while maintaining the crude feed / total product stability. In certain embodiments, the third catalyst comprises column 6 metal in a content ranging from 0.0001 to 0.1 g, 0.005 to 0.05 g, or 0.001 to 0.01 g per gram of catalyst. The column metal may be contained at a content in the range of 0.0001 to 0.05 g, 0.005 to 0.03 g, or 0.001 to 0.01 g per 1 g of the catalyst. The sixth and tenth column metal catalysts are those of MCR in the crude feed at temperatures in the range of 300-500 ° C or 350-450 ° C and pressures in the range of 0.1-10 MPa, 1-8 MPa, or 2-5 MPa. Helps reduce at least some of the causative components.

  In a particular embodiment, the fourth type of catalyst (“fourth catalyst”) contains column 5 metal in combination with a θ-alumina support. The fourth catalyst has a pore size distribution with a median pore diameter of 180 mm or more. In some embodiments, the median pore size of the fourth catalyst may be 220 mm or more, 230 mm or more, 250 mm or more, or 300 mm or more. The support contains 0.1 g or more, 0.5 g or more, 0.8 g or more, or 0.9 g or more of θ-alumina per 1 g of the support. The fourth catalyst contains 0.15 g or less of the fifth column metal per 1 g of catalyst and 0.0001 g or more. In a particular embodiment, the column 5 metal is vanadium.

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

In some embodiments, hydrogen may be generated while the crude feed is contacted with the fourth catalyst at a temperature in the range of 300-400 ° C, 320-380 ° C, or 330-370 ° C. The TAN of the crude product produced by such contact may be 90% or less, 80% or less, 50% or less, or 10% or less with respect to TAN of the crude raw material. The amount of hydrogen generation may be in the range of 1-50 Nm 3 / m 3 , 10-40 Nm 3 / m 3 , or 15-25 Nm 3 / m 3 . The crude product Ni / V / Fe content is 90% or less, 80% or less, 70% or less, 50% or less, 10% or less, or 1% of the total Ni / V / Fe content of crude oil That's all.

  In a particular embodiment, the fifth type of catalyst (“fifth catalyst”) contains column 6 metal in combination with a θ-alumina support. The fifth catalyst has a pore size distribution with a median pore diameter of 180 mm or more, 220 mm or more, 230 mm or more, 250 mm or more, 300 mm or more, or 500 mm or less. The support contains θ-alumina at a content of 0.5 g or more, 0.5 g or more, or 0.999 g or less per 1 g of the support. In some embodiments, the support contains alpha-alumina at a content of less than 0.1 g / g support. In some embodiments, the catalyst contains no more than 0.1 g and no more than 0.0001 g of column 6 metal per gram of catalyst. In some embodiments, the column 6 metal is molybdenum and / or tungsten.

In certain embodiments, when the crude feed is contacted with the fifth catalyst at a temperature in the range of 310-400 ° C, 320-370 ° C, or 330-360 ° C, the total hydrogen absorption by the crude feed may be relatively low. (e.g. 0.01~100Nm 3 / m 3, 1~80Nm 3 / m 3, 5~50Nm 3 / m 3, or 10~30Nm 3 / m 3). In some embodiments, the total hydrogen absorption by the crude feed may be 1-20 Nm 3 / m 3 , 2-15 Nm 3 / m 3 , or 3-10 Nm 3 / m 3 . The TAN of the crude product produced by contacting the crude feed with the fifth catalyst may be 90% or less, 80% or less, 50% or less, 10% or less with respect to TAN of the crude feed. The TAN of the crude product may range from 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”) contains column 5 metal and column 6 metal in combination with a θ-alumina support. The sixth catalyst has a pore size distribution with a median pore diameter of 180 mm or more. In some embodiments, the median pore size of the pore size distribution is 220 cm or more, 230 cm or more, 250 cm or more, 300 cm or more, or 500 mm or less. The support may contain θ-alumina in a content of 0.1 g or more, 0.5 g or more, 0.8 g or more, 0.9 g or more, or 0.99 g or less per gram of support. In some embodiments, the support contains Column 5 metal and Column 6 metal in a total content of 0.1 g or less per gram of catalyst and 0.0001 g or more. In some embodiments, the molar ratio of column 6 metal to column 5 metal may range from 0.1-20, 1-10, or 2-5. In a particular embodiment, the column 5 metal is vanadium and the column 6 metal is molybdenum and / or tungsten.

When the crude material is brought into contact 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 total hydrogen absorption amount by the crude material is −10 to 20 Nm 3 / m 3 , −7 ~10Nm 3 / m 3, or may range from -5~5Nm 3 / m 3. Negative total hydrogen absorption is an indicator that hydrogen is generated in the field. The TAN of the crude product produced by contacting the crude feed with the sixth catalyst may be 90% or less, 80% or less, 50% or less, 10% or less, or 1% or more with respect to the TAN of the crude feed . The TAN of the crude product may range from 0.01 to 0.1, 0.02 to 0.05, or 0.03 to 0.04.

Transportation and / or processing acceptance of crude raw materials while reducing the total required amount of hydrogen during processing if the total hydrogen absorption is small during contact between the crude raw material and the fourth, fifth or sixth catalyst Can produce a crude product capable of Since the production and / or transportation of hydrogen is expensive, if the amount of hydrogen used is small during processing, the overall processing cost is reduced.
In a particular embodiment, the seventh type of catalyst (“seventh catalyst”) contains column 6 metal in a total content ranging from 0.0001 to 0.06 g / g catalyst. Column 6 The metal is molybdenum and / or tungsten. The seventh catalyst is useful for producing a crude product with a TAN of 90% or less relative to the crude feed.

Other embodiments of the first, second, third, fourth, fifth, sixth and seventh catalysts may be made and / or used as described herein.
By selecting the catalyst of the present application and controlling the operating conditions, it is possible to produce a crude product in which the TAN and selected properties for the crude feed vary, while other properties of the crude feed do not change significantly. The resulting crude product has improved properties compared to the crude feed and is therefore acceptable for transportation and / or refining.

Arranging two or more kinds of catalysts in a selected order makes it possible to control the order of improving the characteristics of the crude oil feedstock. For example TAN in the crude feed, API gravity, at least a portion of the C 5 asphaltenes, at least a portion of the iron, at least a portion of the nickel, and / or at least a portion of the vanadium, at least a portion of the heteroatoms in the crude feed Can be reduced or reduced before it decreases.
In some embodiments, the arrangement and / or selection of multiple catalysts can improve catalyst life and / or stability of the crude feed / total product mixture. By improving the catalyst life during processing and / or the stability of the crude feed / total product mixture, the contact system can be operated for more than 3 months, more than 6 months, or more than 1 year without replacing the catalyst in the contact system.

By combining selected catalysts, other properties of the crude feed can be achieved while maintaining the stability of the crude feed / total product mixture during processing (eg, maintaining the P value of the crude feed greater than 1.5). from crude feed before changing, at least a portion of the Ni / V / Fe, at least a portion of the C 5 asphaltenes, at least a portion of the metal of the organic acid metal salt, at least a portion of the components that contribute to TAN, residual At least some of the objects, or combinations thereof, can be reduced or reduced. Or by contact with a selected catalyst and crude feed, C 5 asphaltenes can incrementally decrease the TAN and / or API gravity. The ability to incrementally and / or selectively change the properties of the crude feed allows the stability of the crude feed / total product mixture to be maintained during processing.

In some embodiments, the first catalyst (described above) may be located upstream of the series of catalysts. Such an arrangement of the first catalyst allows removal of high molecular weight contaminants, metal contaminants, and / or metals of the organic acid metal salt while maintaining the stability of the crude feed / total product mixture.
In some embodiments, the first catalyst removes at least a portion of Ni / V / Fe from the crude feed, removal of acidic components, and removal of components that contribute to reducing the life of the catalyst in the contact system. Or a combination thereof. For example, at least a portion of the C 5 asphaltenes from the crude feed / total product mixture is reduced as compared with the crude feed, is prevented clogging of other catalysts positioned downstream, thus, not replace catalytic, contacting system The time that can be operated is extended. In some embodiments, removing at least a portion of the Ni / V / Fe from the crude feed increases the life of the one or more catalysts disposed after the first catalyst.

  The second catalyst and / or the third catalyst may be disposed downstream of the first catalyst. By further contacting the crude feed / total product mixture with the second and / or third catalyst, the TAN is further reduced, the Ni / V / Fe content is reduced, the sulfur content is reduced, and the oxygen is reduced. The content can be reduced and / or the metal content of the organic acid metal salt can be reduced.

  In some embodiments, contact between the crude feed and the second and / or third catalyst ensures that the stability of the crude feed / total product mixture is maintained during processing, as compared to the respective properties of the crude feed. TAN is reduced, sulfur content is reduced, oxygen content is reduced, metal content of organic acid metal salt is reduced, asphaltene content is reduced, or a combination of them, crude feed / total production Product mixtures can be produced. The second catalyst may be placed in series with the third catalyst upstream of the third catalyst or vice versa.

  The ability to deliver hydrogen to a specific contact zone tends to reduce the amount of hydrogen used during the contact. Using a combination of a catalyst that easily generates hydrogen during contact and a catalyst that absorbs a relatively small amount of hydrogen during contact, the selected properties of the crude product are changed relative to the same properties of the crude feed. Can be made. For example, changing selected properties of a crude feed while changing only other properties other than the selected properties of the crude feed in selected amounts and / or maintaining the stability of the crude feed / total product mixture Therefore, the fourth catalyst may be used in combination with the first catalyst, the second catalyst, the third catalyst, the fifth catalyst, the sixth catalyst and / or the seventh catalyst. The order and / or number of multiple catalysts may be selected to minimize the total hydrogen uptake while maintaining the stability of the crude feed / total product mixture. With the minimum total hydrogen absorption, the TAN and / or viscosity of the crude product is less than 90% of the TAN and / or viscosity of the crude feed, while the VGO content, distillate content, API specific gravity of the crude feed, Or their combination can be maintained within 20% of the respective properties of the crude feed.

By reducing the total amount of hydrogen absorbed by the crude oil raw material, it is possible to produce a crude oil product having a boiling range distribution similar to that of the crude oil raw material and having a lower TAN than the crude oil TAN. The H / C atomic ratio of the crude product may also change only relatively small compared to the H / C atomic ratio of the crude feed.
The generation of hydrogen in a specific contact zone makes it possible to selectively add hydrogen to other contact zones and / or to selectively reduce or reduce the properties of crude oil feedstock. In some embodiments, the fourth catalyst may be located upstream, downstream, or between the additional catalysts described herein. Hydrogen may be generated during contact between the crude feed and the fourth catalyst or may be delivered to a contact zone having additional catalyst. The delivery of hydrogen may be countercurrent to the crude feed stream. In some embodiments, the hydrogen delivery may be co-current with the crude feed stream.

  For example, in a stacked configuration (eg, see FIG. 2B), hydrogen may be generated during contact in one contact zone (eg, contact zone 102 in FIG. 2B), and crude oil in another contact zone (eg, contact zone 114 in FIG. 2B). It may be delivered in the opposite direction of the raw material flow. In some embodiments, the hydrogen stream may be co-current with the crude feed stream. Alternatively, in a stacked structure (eg, see FIG. 3B), hydrogen may be generated during contact in one contact zone (eg, contact zone 102 in FIG. 3B). The hydrogen source may be delivered to the first additional contact zone in the opposite direction of the crude feed flow (eg, in FIG. 3B, hydrogen is added to the contact zone 114 from conduit 106 ') and to the second additional contact zone. May be delivered in a direction parallel to the crude feed stream (eg, in FIG. 3B, hydrogen is added to contact zone 116 from conduit 106 ').

  In some embodiments, a large catalyst and a sixth catalyst may be used in series such that the fourth catalyst is upstream of the sixth catalyst or vice versa. By combining the fourth catalyst with another catalyst, the TAN is decreased, the Ni / V / Fe content is decreased, and / or the metal content of the organic acid metal salt is decreased. Absorption may decrease. If the total hydrogen uptake is low, other properties of the crude product may change slightly compared to the same properties of the crude feed.

In some embodiments, two different seventh catalysts may be used in combination. The seventh catalyst used upstream of the downstream seventh catalyst may contain column 6 metal in a total content ranging from 0.0001 to 0.06 g per gram of catalyst. The downstream seventh catalyst contains the sixth column metal in a total content equal to or higher than that of the upstream seventh catalyst per 1 g of the downstream seventh catalyst or 0.02 g or more of the sixth column metal per 1 g of the catalyst. It's okay. In some embodiments, the positions of the upstream seventh catalyst and the downstream seventh catalyst may be reversed. The ability to use relatively small amounts of catalytically active metals in the downstream seventh catalyst may only slightly alter other properties of the crude product the same properties of the crude feed (eg, heteroatom content, API specific gravity, There is relatively little change in residue content, VGO content, or combinations thereof).
TAN produces less than 90%, less than 80%, less than 50%, less than 10%, or more than 1% crude product by contacting crude oil with the seventh catalyst upstream and downstream it can. In some embodiments, the TAN of the crude feed may be progressively reduced by contact with the upstream and downstream seventh catalyst (eg, the contact between the crude feed and the catalyst has changed relative to the crude feed. An initial crude product with properties is produced, and then contact of the initial crude product with an additional catalyst produces a crude product with altered properties compared to the initial crude product). The ability to incrementally reduce TAN may help maintain the stability of the crude feed / total product mixture during processing.

  In some embodiments, catalyst selection and / or multi-catalyst order combined with contact condition control reduces hydrogen uptake by the crude feed and stabilizes the crude feed / total product mixture during processing. And may help to change one or more properties of the crude product as compared to the respective properties of the crude feed. The stability of the crude feed / total product mixture can be affected by various phases that separate from the crude feed / total product mixture. Phase separation can be achieved, for example, when the crude feed and / or total product mixture does not dissolve in the crude feed / total product mixture, asphaltenes aggregate from the crude feed / total product mixture, in the crude feed / total product mixture. It may be due to the components precipitating or a combination thereof.

During contact, the concentration of the crude feed and / or the total product mixture may change at a particular time. When the concentration of all products in the crude feed / total product mixture changes due to the formation of all products, the solubility of the crude feed components and / or the total product components in the crude feed / total product mixture changes. Tend to. For example, the crude product may contain components that are soluble in the crude feed at the beginning of processing. Properties of the crude material (e.g. TAN, MCR, C 5 asphaltenes, P value, or combinations thereof) the changes, these components may solubility in crude feed / total product mixture tends to decrease Absent. In some examples, the crude feed and the entire product may form two phases and / or become insoluble in each other. Due to changes in solubility, the crude feed / total product mixture may form more than one phase. One or more lifespan of the catalyst tends to decrease due to two-phase formation due to asphaltene agglomeration, crude feedstock and total product concentration changes, and / or component precipitation. In addition, processing efficiency may be reduced. For example, it may be necessary to repeatedly process the crude feed / total product mixture to produce a crude product having the desired properties.

  During processing, the P value of the crude feed / total product mixture may be monitored and the stability of the process, crude feed, and / or crude feed / total product mixture may be evaluated. A P value of 1.5 or less generally indicates that asphaltenes have aggregated from the crude product. The P value is 1.5 or more at the initial stage, and if this P value increases or is relatively stable during the contact, it indicates that the crude raw material is relatively stable during the contact. The stability of the crude feed / total product mixture evaluated by the P value may be controlled by controlling contact conditions, catalyst selection, multiple catalyst selection order, or a combination thereof. Control of such contact conditions includes LHSV, temperature, pressure, hydrogen absorption, crude feed stream, or combinations thereof.

Contact temperature is in some embodiments, while maintaining the MCR content of the crude feed, C 5 asphaltenes and / or other asphaltenes are controlled at a temperature as removed. Decreasing the MCR content due to hydrogen absorption and / or high contact temperatures may form two phases that may reduce the stability of the crude feed / total product mixture and / or the lifetime of one or more of the catalysts. Absent. In combination with the catalyst described herein, by controlling the contacting temperature and hydrogen uptake, while simply changing relatively small MCR content of the crude feed, it can be reduced C 5 asphaltenes.

In some embodiments, the contact conditions are controlled so that the temperature of one or more contact zones is different. Operating at different temperatures can selectively change the properties of the crude feed while maintaining the stability of the crude feed / total product mixture. At the start of processing, the crude feed enters the first contact zone. The first contact temperature is the temperature of the first contact zone. Other contact temperatures (for example, the second temperature, the third temperature, the fourth temperature, etc.) are the temperatures of the contact zone disposed after the first contact zone. The first contact temperature may be in the range of 100-420 ° C, and the second contact temperature is in the range of 20-100 ° C, 30-90 ° C, or 40-60 ° C different from the first contact temperature. It's okay. In some embodiments, the second contact temperature is higher than the second contact temperature. When the different contact temperatures, compared to the TAN and / or C 5 asphaltenes content of the crude feed, TAN and / or C 5 asphaltenes content of the crude product, or the first and second contact temperature is the same, 10 to each other It may decrease to a greater extent than a decrease or decrease in TAN and / or C 5 asphaltenes content (if any) when it is within ° C.

For example, the first contact zone may contain a first catalyst and / or a fourth catalyst, and the second contact zone may contain other catalysts described herein. The first contact temperature may be 350 ° C and the second contact temperature may be 300 ° C. If the crude oil raw material and the first catalyst and / or the fourth catalyst are brought into contact with each other in the first contact zone at a high temperature before contacting with another catalyst in the second contact zone, the first contact temperature and the second contact temperature are 10 ℃ compared to decrease or reduction in TAN and / or C 5 asphaltenes content of the crude feed in the case within it, TAN and / or C 5 asphaltenes content of the same crude feed may be reduced or substantially reduced .

  Non-limiting examples of support production, catalyst production, and systems with selective catalyst arrangement, and controlled contact conditions are described below.

Example 1 Preparation of Catalyst Support A support was prepared by grinding 576 g of Alumina (Criterion Catalysts and Technologies LP, Michigan, Michigan, USA) with 585 g of water and 8 g of glacial nitric acid for 35 minutes. Was extruded at 1.3 Trilobe ™ die plate, dried at 90-125 ° C. and then calcined at 918 ° C. to obtain 650 g of a calcined support with a median pore size of 182 mm. The temperature of the furnace was raised to 1000-1100 ° C. over 1.5 hours and then held for 2 hours to produce a support, which was measured by X-ray diffraction and measured γ− per gram of support. 0.0003 g of alumina, 0.0008 g of α-alumina, 0.0208 g of δ-alumina, and 0.008 of θ-alumina. The support had a surface area of 110 m 2 / g and a total pore volume of 0.821 cm 3 / g. The support had a median pore diameter of 232 mm and a total pore size distribution of A pore size distribution was shown in which 66.7% of the number of pores had a pore diameter within 85 mm of the median pore diameter.
This example shows a method for producing a support having a pore size distribution of 180 mm or more and 0.1 g or more of θ-alumina.

Example 2: Production of vanadium catalyst having a pore size distribution with a median pore diameter of 230 mm or more A vanadium catalyst was produced by the following method. The alumina support produced by the method described in Example 1 was impregnated with a vanadium impregnation solution made by blending 7.69 g of VOSO 4 with 82 g of deionized water. The pH of the solution is 2.27.
An alumina support (100 g) was impregnated in a vanadium 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 obtained catalyst contains 0.04 g of vanadium per 1 g of the catalyst, and the balance is the support. This vanadium catalyst had a pore size distribution with a median pore diameter of 350 mm, a pore volume of 0.69 cm 3 / g, and a surface area of 110 m 2 / g. Furthermore, 66.7% of the total number of pores in the pore size distribution of the vanadium catalyst had a pore diameter within 70 mm of the median pore diameter.
This example shows a method for producing a fifth column metal catalyst having a pore size distribution with a median pore diameter of 230 mm or more.

Example 3: Production of a molybdenum catalyst having a pore size distribution with a median pore diameter of 230 mm or more A molybdenum catalyst was produced by the following method. The alumina support produced by the method described in Example 1 was impregnated with a molybdenum impregnation solution. This molybdenum impregnation solution consists of (NH 4 ) 2 Mo 2 O 7 4.26 g, MoO 3 6.38 g, 30% H 2 O 2 1.12 g, monoethanolamine (MEA) 0.27 g and deionized water 6. It was made by blending 51 g to form a slurry. The slurry was heated at 65 ° C. until the solid dissolved. The heated solution was cooled to room temperature. The pH of the solution is 5.36. The solution volume was adjusted to 82 mL with deionized water.

An alumina support (100 g) was impregnated in a 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 contains 0.04 g of molybdenum per gram of catalyst, with the balance being the support. This molybdenum catalyst had a pore size distribution with a median pore diameter of 250 mm, a pore volume of 0.77 cm 3 / g, and a surface area of 116 m 2 / g. Furthermore, 67.7% of the total number of pores in the pore size distribution of the vanadium catalyst had a pore diameter within 86 mm of the median pore diameter.
This example shows a method for producing a sixth column metal catalyst having a pore size distribution with a median pore diameter of 230 mm or more.

Example 4: Production of a molybdenum / vanadium catalyst having a pore size distribution with a median pore diameter of 230 mm or more A molybdenum / vanadium catalyst was produced by the following method. The alumina support produced by the method described in Example 1 was impregnated with a molybdenum / vanadium impregnation solution made as follows. (NH 4 ) 2 Mo 2 O 7 2.14 g, MoO 3 3.21 g, 30% hydrogen peroxide (H 2 O 2 ) 0.56 g, monoethanolamine (MEA) 0.14 g and deionized water 3.28 g To form a slurry to form a first solution. The slurry was heated at 65 ° C. until the solid dissolved. The heated solution was cooled to room temperature.

A second solution was made by blending 3.57 g of VOSO 4 with 40 g of deionized water. The first solution and the second solution were blended, and sufficient deionized water was added until a 82 ml volume blended solution was made to make a molybdenum / vanadium impregnation solution. The alumina support was impregnated with a molybdenum / vanadium 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 contains 0.02 g vanadium and 0.02 molybdenum per gram of catalyst, with the balance being the support. This molybdenum / vanadium catalyst had a pore size distribution with a median pore size of 300mm.
This example shows a method for producing a column 6 metal and a column 5 metal-containing catalyst having a pore size distribution with a median pore diameter of 230 mm or more.

Example 5: Contact between crude oil feed and three catalysts A tubular reactor with a thermowell in the center was equipped with a thermocouple to measure the temperature in the catalyst bed. The catalyst bed was formed by filling the space between the reactor thermowell and the inner wall with catalyst and silicon carbide (20-grid, Stanford Materials, Aliso Viejo, Canada). Such silicon carbide is considered low even if it has catalytic properties under the processing conditions described here. After all the catalyst had been blended with an equal volume of silicon carbide, this mixture was placed in the contact zone of the reactor.

The crude feed stream to the reactor is from the top to the bottom of the reactor. Silicon carbide was placed at the bottom of the tower to serve as a tower bottom support. A tower bottom catalyst / silicon carbide mixture (42 cm 3 ) was placed on the silicon carbide to form a tower bottom contact zone. The bottom catalyst has a pore size distribution with a median pore diameter of 77 mm, and 66.7% of the total pore number in the pore size distribution has a pore diameter within 20 mm of the median pore diameter. It was. The bottom catalyst contains 0.095 g of molybdenum and 0.025 g of nickel per gram of catalyst, with the balance being the alumina support.

An intermediate catalyst / silicon carbide mixture (56 cm 3 ) was placed on the bottom contact zone to form an intermediate contact zone. The intermediate catalyst has a pore size distribution with a median pore diameter of 98 mm, and 66.7% of the total number of pores in the pore size distribution has a pore diameter within 24 mm of the median pore diameter. It was. The intermediate catalyst contains 0.02 g of nickel and 0.08 g of molybdenum per gram of catalyst, with the balance being the alumina support.

A top catalyst / silicon carbide mixture (42 cm 3 ) was placed on the middle contact zone to form a top contact zone. The tower top catalyst has a pore size distribution with a median pore diameter of 192 mm, contains 0.04 g of molybdenum per gram of catalyst, and the balance is a γ-alumina support.
Silicon carbide was placed on the top contact zone to fill the dead space and serve as a preheating zone. This catalyst bed was loaded into a Lindberg furnace. This furnace has five heating zones corresponding to a preheating zone, a tower top contact zone, an intermediate zone contact zone, a tower bottom contact zone, and a tower bottom support.

  In these contact zones, a gaseous mixture of 5% by volume of hydrogen sulfide and 95% by volume of hydrogen gas is mixed with 1.5% of the gaseous mixture per 1 ml volume of total catalyst (silicon carbide is not calculated as part of the catalyst volume). Introduced at a rate of liters, the catalyst was sulfided. The temperature in the contact zone was raised to 204 ° C. (400 ° F.) over 1 hour and held at this temperature for 2 hours. After holding at 204 ° C, the temperature in the contact zone was gradually increased to 316 ° C (600 ° F) at a rate of 10 ° C (50 ° F) per hour. The contact zone was maintained at 316 ° C. for 1 hour, then gradually increased to 370 ° C. (700 ° F.) over 1 hour and held at this temperature for 2 hours. The contact zone was cooled to ambient temperature.

Crude oil from the Mars platform in the Gulf of Mexico was filtered and then heated in an oven at 93 ° C. (200 ° F.) for 12-24 hours to form a crude feedstock having the properties shown in Table 1 of FIG. This crude raw material was supplied to the top of the reactor and flowed to the preheating zone, the top contact zone, the middle contact zone, the bottom contact zone and the bottom support. The crude feed contacted each catalyst in the presence of hydrogen gas. The contact conditions are as follows. The ratio of hydrogen gas to crude oil feed fed to the reactor is 328 Nm 3 / m 3 (2000 SCFB), LHSV is 1 h −1 , and the pressure is 6.9 MPa (1014.7 psi). The three contact zones were heated to 370 ° C. (700 ° F.) and maintained at this temperature for 500 hours. The temperature of the three contact zones was then changed in the following order: 379 ° C. (715 ° F.) for 500 hours, then 388 ° C. (730 ° F.) for 500 hours, then 390 ° C. (734 ° F.) for 1800 hours, then 394 ° C. Heated and maintained at (742 ° F.) for 2400 hours.

All products (ie crude product and gas) exited the catalyst bed and were then introduced into the gas-liquid phase separator. In the gas-liquid separator, the entire product was separated into crude product and gas. The gas input of this system was measured with a mass flow controller. The gas exiting the system was measured with a wet test meter. The crude product was analyzed periodically to determine the weight percentage of its components. The indicated result is the average of the weight ratio (%) of the measured component. The properties of the crude product are summarized in Table 1 of FIG.
As shown in Table 1, the crude product contained 0.0075 g sulfur, 0.255 g residue, and 0.0007 g oxygen per gram of crude product. The ratio of MCR content vs. C 5 asphaltenes content of the crude product is 1.9, TAN was 0.09. The total amount of nickel and vanadium was 22.4 ppm by weight.

  The life of the catalyst was determined by measuring the load average bed temperature ("WABT") versus the run length of the crude feed. The life of the catalyst may be correlated with the temperature of the catalyst bed. It is believed that WABT increases with decreasing catalyst life. FIG. 8 is a graph of WABT vs. time (“t”) for the improvement of crude feed in the contact zone described in this example. Point 136 represents the average WABT of the three contact zones versus the operating time (hr) of contact between the crude feed and the top catalyst, middle catalyst and bottom catalyst. Over most of the run time, the WABT in the contact zone has only changed by about 20 ° C. Thus, from the relatively stable WABT, it can be evaluated that the catalytic activity of the catalyst was not affected. Typically, the pilot unit's operating time of 3000-3500 hours correlates with one year of industrial operation.

  In this example, under controlled contact conditions, the crude raw material has one catalyst having a pore size distribution with a median pore diameter of 180 mm or more and a pore size distribution with a median pore diameter of 90 to 180 mm or more, 60% of the total number of pores in the pore size distribution represents an example of producing a total product including a crude product by contacting with another catalyst having a pore size within 45 mm of the median pore size. As can be seen from the measured P values, the stability of the crude feed / total product mixture was maintained. The TAN, Ni / V / Fe content, sulfur content and oxygen content of the crude product are reduced or reduced respectively compared to the crude feed, while the residual content and VGO content of the crude product are 90-110% of these properties of the crude feed.

Example 6: Contact between crude oil feedstock and two types of catalysts having a pore size distribution with a median pore diameter of 90 to 180 mm or more Reactor (excluding the number of contact zones and contents), catalyst sulfidation method, total production The product separation method and the crude product analysis method are the same as in Example 5. Each catalyst was mixed with an equal volume of silicon carbide.

The crude feed stream to the reactor is from the top to the bottom of the reactor. The reactor was charged from the bottom to the top as follows. Silicon carbide was placed at the bottom of the tower to serve as a tower bottom support. A tower bottom catalyst / silicon carbide mixture (80 cm 3 ) was placed on the silicon carbide to form a tower bottom contact zone. The bottom catalyst has a pore size distribution with a median pore diameter of 127 mm, and 66.7% of the total number of pores in the pore size distribution has a pore diameter within 32 mm of the median pore diameter. It was. The bottom catalyst contains 0.11 g of molybdenum and 0.02 g of nickel per 1 g of catalyst, and the balance is the support.

A top catalyst / silicon carbide mixture (80 cm 3 ) was placed on the bottom contact zone to form a top contact zone. The tower top catalyst has a pore size distribution with a median pore diameter of 100 mm, and 66.7% of the total number of pores in the pore size distribution has a pore diameter within 20 mm of the median pore diameter. It was. The tower top catalyst contains 0.03 g of nickel and 0.12 g of molybdenum per 1 g of the catalyst, and the balance is alumina. Silicon carbide was placed on the top contact zone to fill the dead space and serve as a preheating zone. This catalyst bed was loaded into a Lindberg furnace. This furnace has a preheating zone, two contact zones, and four heating zones corresponding to the bottom support.

BS-4 crude oil (Venezuela) having the characteristics shown in Table 2 of FIG. 9 was fed to the top of the reactor. This crude raw material was passed through the preheating zone, the tower top contact zone, the tower bottom contact zone and the tower bottom support of the reactor. The crude feed contacted each catalyst in the presence of hydrogen gas. The contact conditions are as follows. The ratio of hydrogen gas to crude oil feed fed to the reactor is 160 Nm 3 / m 3 (1000 SCFB), LHSV is 1 h −1 , and the pressure is 6.9 MPa (1014.7 psi). These two contact zones were heated to 260 ° C. (500 ° F.) and maintained at this temperature for 287 hours. The temperature of the two contact zones is then changed in the following order: 270 ° C. (525 ° F.) 190 hours, then 288 ° C. (550 ° F.) 216 hours, then 315 ° C. (600 ° F.) 360 hours, then 343 ° C. Heated and maintained at (650 ° F.) for 120 hours, ie, a total operating time of 1173 hours.

All products exiting the reactor were separated as in Example 5. During processing, the crude product had an average TAN of 0.42 and an average API specific gravity of 12.5. The crude product contained 0.0023 g of sulfur, 0.0034 g of oxygen, 0.441 g of VGO and 0.378 g of residue per gram of crude product.
In this example, a crude product was produced by contacting a crude feed with a catalyst having a pore size distribution with a median pore size of 90 to 180 mm. / Fe content and oxygen content are reduced or reduced, respectively, compared to crude oil feed, while crude product residue content and VGO content are 99% and 100% of the respective properties of the crude feed Met.

Example 7: Contact of crude raw material with two types of catalyst The reactor (excluding the number and contents of contact zones), catalyst, separation method of all products, analysis of crude product and sulfidation method of catalyst are described in Example 6. Is the same.
Crude oil feedstock (BC-10 crude oil) having the characteristics shown in Table 3 of FIG. 10 was fed to the top of the reactor. Crude oil feed was passed through the reactor preheat zone, tower top contact zone, tower bottom contact zone and tower bottom support. The contact conditions are as follows. The ratio of hydrogen gas to crude oil feed fed to the reactor is 80 Nm 3 / m 3 (500 SCFB), LHSV is 2 h −1 , and the pressure is 6.9 MPa (1014.7 psi). These two contact zones were incrementally heated to 343 ° C. (650 ° F.). Total operating time is 1007 hours.

During processing, the crude product had an average TAN of 0.16 and an average API specific gravity of 16.2. The crude product contained 1.9 ppm by weight of calcium, 6 ppm by weight of sodium, 0.6 ppm by weight of zinc, and 3 ppm by weight of potassium. The crude product contained 0.0033 g of sulfur, 0.002 g of oxygen, 0.376 g of VGO and 0.401 g of residue per gram of crude product. Other properties of the crude product are shown in Table 3 of FIG.
In this example, a crude product was contacted with a selected catalyst having a pore size distribution with a median pore size of 90-180 mm to produce a crude product, but the crude product TAN; calcium The total content of sodium, zinc, and potassium is reduced or reduced, respectively, compared to the crude oil feed, while the sulfur content, VGO content and residue content of the crude product are They were 76%, 94%, and 103%.

Examples 8 to 11: Contact between crude oil feedstock and four types of catalyst systems under various contact conditions Reactors (excluding the number and contents of contact zones), catalyst sulfidation methods, separation methods for all products, and The analysis method for each crude product is the same as in Example 5. Unless otherwise indicated, all catalysts were mixed with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part catalyst. The crude feed stream in each reactor is from the top to the bottom. Silicon carbide was placed at the bottom of each reactor in order to serve as a bottom support. Each reactor has a bottom contact zone and a top contact zone. After the catalyst / silicon carbide mixture was placed in the contact zone of each reactor, silicon carbide was placed on the top contact zone in each reactor to fill the dead space and serve as a preheating zone. Each reactor was loaded into a Lindberg furnace having a preheating zone, two contact zones, and four heating zones corresponding to the bottom support.

In Example 8, the unfired molybdenum / nickel catalyst / silicon carbide mixture (48 cm 3 ) was placed in the bottom contact zone. This catalyst contains 0.146 g of molybdenum, 0.047 g of nickel, and 0.021 g of phosphorus per gram of catalyst, with the balance being the alumina support.
A molybdenum catalyst / silicon carbide mixture (12 cm 3 ) having a pore size distribution with a median pore size of the catalyst of 180 mm was placed in the top contact zone. The molybdenum catalyst contains a total of 0.04 g of molybdenum per 1 g of the catalyst, and the balance is a support containing 0.50 g or more of γ-alumina per 1 g of the support.

In Example 9, an unfired molybdenum / cobalt catalyst / silicon carbide mixture (48 cm 3 ) was placed in both contact zones. The uncalcined molybdenum / cobalt catalyst contains 0.143 g of molybdenum, 0.043 g of cobalt and 0.021 g of phosphorus, with the balance being the alumina support.
A molybdenum catalyst / silicon carbide mixture (12 cm 3 ) was placed in the top contact zone. This molybdenum catalyst is the same as in the top contact zone of Example 8.
In Example 10, the molybdenum catalyst described in the top contact zone of Example 8 was mixed with silicon carbide and placed in both contact zones (60 cm 3 ).

In Example 11, an unfired molybdenum / nickel catalyst / silicon carbide mixture (48 cm 3 ) was placed in both contact zones. The unfired molybdenum / nickel catalyst contains 0.09 g of molybdenum, 0.025 g of nickel and 0.01 g of phosphorus per gram of catalyst, with the balance being the alumina support.
A molybdenum catalyst / silicon carbide mixture (12 cm 3 ) was placed in the top contact zone. This molybdenum catalyst is the same as in the top contact zone of Example 8.

Crude oil from the Mars platform (gulf of Mexico) and then heated in an oven at 93 ° C. (200 ° F.) for 12-24 hours to produce the crude oil of Examples 8-11 having the characteristics shown in Table 4 of FIG. Raw material was formed. This crude feed was fed to the top of each reactor in these examples and flowed to the preheating zone, the top contact zone, the bottom contact zone and the bottom support. The crude feed contacted each catalyst in the presence of hydrogen gas. The contact conditions for each example are as follows. The hydrogen gas to crude oil feed ratio fed to the reactor is 160 Nm 3 / m 3 (1000 SCFB), the total pressure of each system is 6.9 MPa (1014.7 psi), and the LHSV is the first 200 hours of contact. 2.0 h -1, then the rest of the contact time was reduced to 1.0 h -1. The temperature of the entire contact zone was 343 ° C. (650 ° F.) after 500 hours of contact, and the temperature of the entire contact zone after 500 hours was controlled as follows. The temperature of the contact zone is raised to 354 ° C. (670 ° F.) and held at this temperature for 200 hours, then raised to 366 ° C. (690 ° F.), held at this temperature for 200 hours, and then 371 ° C. (700 ° F.). F) and held at this temperature for 1000 hours, then raised to 385 ° C. (725 ° F.), held at this temperature for 200 hours, then raised to a final temperature of 399 ° C. (750 ° F.) For 200 hours. Total contact time is 2300 hours.

  The crude product was analyzed periodically to measure the TAN of the crude product, the amount of hydrogen absorbed by the crude feed, the P value, the VGO content, the residue content and the oxygen content. The average characteristic values of the crude products produced in Examples 8 to 11 are summarized in Table 5 in FIG.

  FIG. 12 is a graph of crude product P-value (“P”) versus operating time for each catalyst system of Examples 8-11. The P value of the crude oil raw material was 1.5 or more. Points 140, 142, 144, and 146 represent the P values of the crude product obtained by contacting the crude feed with the catalyst systems of Examples 8-11, respectively. In the catalyst systems of Examples 8-10, the P value remained above 1.5 for 2300 hours. In Example 11, the P value exceeded 1.5 during most of the operating time. At the end of the operation of Example 11 (2300 hours), the P value was 1.4. From the P value of the crude product in each test, it can be estimated that the crude feed in each test remained relatively stable during contact (eg, the crude feed did not phase separate). As shown in FIG. 12, the P value of the crude product remained relatively constant for most of each test, except when the P value increased as in Example 10.

FIG. 13 is a graph of total hydrogen uptake (“H 2 ”) by crude feed versus operating time (“t”) for four catalyst systems in the presence of hydrogen gas. Points 148, 150, 152, 154 represent the total hydrogen absorption obtained by contacting the crude feed with each catalyst system of Examples 8-11, respectively. The total amount of hydrogen absorbed by the crude feed over 2300 hours of operation was 7 to 48 Nm 3 / m 3 (43.8 to 300 SCFB). As shown in FIG. 13, the total amount of hydrogen absorbed by the crude oil raw material was relatively stable during each test.

  FIG. 14 is a graph of crude product residue content (“R”) (expressed as weight percent) versus operating time (“t”) for each of the catalyst systems of Examples 8-11. In each of the four tests, the crude product residue content was 88-90% of the crude feedstock residue content. Points 156, 158, 160, 162 represent the residual content of the crude product obtained by contacting the crude feed with each catalyst system of Examples 8-11, respectively. As shown in FIG. 14, the crude product residue content remained relatively stable during most of each test.

  FIG. 15 is a graph of crude product API specific gravity change (“ΔAPI”) versus operating time (“t”) for each of the catalyst systems of Examples 8-11. Points 164, 166, 168, 170 represent the API specific gravity of the crude product obtained by contacting the crude feed with each catalyst system of Examples 8-11, respectively. In each of the four tests, the viscosity of each crude product ranged from 58.3 to 72.7 cSt. The API specific gravity of each crude product increased by 1.5-4.1 degrees. This increased API gravity corresponds to the API gravity of the crude product in the range of 21.7-22.95. The API specific gravity in this range is 110 to 117% with respect to the API specific gravity of the crude raw material.

FIG. 16 is a graph of crude product oxygen content (“O 2 ”) (expressed as weight percent) versus operating time (“t”) for each of the catalyst systems of Examples 8-11. Points 172, 174, 176, 178 represent the oxygen content of the crude product obtained by contacting the crude feed with each catalyst system of Examples 8-11, respectively. During each test, the oxygen content of each crude product ranged from 0.0014 to 0.0015 g / g crude product. As shown in FIG. 16, the crude product oxygen content remained relatively stable after a contact time of 200 hours. Thus, the relatively constant oxygen content of the crude product indicates that the selected organic oxygen compound has decreased during contact. In these examples, since TAN also decreased, it can be presumed that at least a part of the carboxyl-containing organic oxygen compound was selectively reduced compared to the non-carboxyl-containing non-containing organic oxygen compound.

In Example 11, under the reaction conditions of 371 ° C. (700 ° F.), pressure 6.9 MPa (1014.7 psi), hydrogen to crude feed ratio 160 Nm 3 / m 3 (1000 SCFB), the crude feed MCR content is 17.5% by weight based on the weight of At the same pressure and hydrogen to crude feed ratio except that the temperature was 399 ° C. (750 ° F.), the MCR content of the crude feed decreased by 25.4% by weight based on the weight of the crude feed.
In Example 9, under the reaction conditions of 371 ° C. (700 ° F.), pressure 6.9 MPa (1014.7 psi), hydrogen to crude feed ratio 160 Nm 3 / m 3 (1000 SCFB), the crude feed MCR content is 17.5% by weight based on the weight of At the same pressure and hydrogen to crude feed ratio, except that the temperature was 399 ° C. (750 ° F.), the MCR content of the crude feed decreased by 19% by weight based on the weight of the crude feed.

The increase in the decrease in the MCR content of the crude oil raw material in this way is that the unfired column 6 and column 10 metal catalyst tends to decrease the MCR content at higher temperatures than the unfired column 6 and column 9 metal catalyst. Indicates to do.
These examples show relatively low total hydrogen uptake while maintaining the stability of the crude feed / total product mixture by contacting the crude feed with a relatively high TAN (TAN 0.8) with one or more catalysts. Indicates that a crude product will be produced. The selected properties of the crude product were less than 70% of the same properties of the crude feed, while the selected properties of the crude product were within 20-30% of the same properties of the crude feed.

Specifically, as shown in Table 4, crude products having a total hydrogen absorption amount of 44 Nm 3 / m 3 (275 SCFB) or less were produced. These products maintain a P value of greater than 3 relative to the crude feed, while the average TAN is less than 4% of the crude feed and the average total Ni / V content is equal to the total Ni / V content of the crude feed. It was 61% or less. The average residue content of each crude product was 88-90% of the crude feed residue content. The average VGO content of each crude product was 115-117% of the VGO content of the crude feed. The average API specific gravity of each crude product was 110-117% of the API specific gravity of the crude feed, while the viscosity of each crude product was 45% or less of the crude feed viscosity.

Examples 12-14: Contact of crude oil feedstock with minimum hydrogen consumption with catalyst having pore size distribution with median pore diameter of 180 mm or more In Examples 12-14, each reactor (number and content of contact zones) The catalyst sulfurization method, the separation method of each total product, and the analysis method of each crude product are the same as in Example 5. All catalysts were mixed with an equal volume of silicon carbide. The crude feed stream in each reactor is from the top to the bottom. Silicon carbide was placed at the bottom of each reactor in order to serve as a bottom support. Each reactor has one contact zone. After the catalyst / silicon carbide mixture was placed in the contact zone of each reactor, silicon carbide was placed on the top contact zone in each reactor to fill the dead space and serve as a preheating zone. Each reactor was loaded into a Lindberg furnace having three heating zones corresponding to a preheating zone, a contact zone, and a bottom support. The crude feed was contacted with each catalyst in the presence of hydrogen gas.

A catalyst / silicon carbide mixture (40 cm 3 ) was placed on the silicon carbide to form a contact zone. In Example 12, the catalyst is the vanadium catalyst prepared in Example 2. In Example 13, the catalyst is the molybdenum catalyst prepared in Example 3. In Example 14, the catalyst is the molybdenum / vanadium catalyst prepared in Example 4.
The contact conditions of Examples 12 to 14 are as follows. The hydrogen to crude feed ratio fed to the reactor is 160 Nm 3 / m 3 (1000 SCFB), LHSV is 1 h −1 , and the pressure is 6.9 MPa (1014.7 psi). The contact zone was gradually heated to 343 ° C. (650 ° F.) over a period of time and maintained at this temperature for 120 hours and a total operating time of 360 hours.

All products exiting the reactor were separated as in Example 5. The total hydrogen absorption during contact was measured for each catalyst system. In Example 12, the total hydrogen absorption was −10.7 Nm 3 / m 3 (−65 SCFB), and the TAN of the crude product was 6.75. In Example 13, the total hydrogen absorption was in the range of 2.2 to 3.0 Nm 3 / m 3 (13.9 to 18.7 SCFB), and the TAN of the crude product was in the range of 0.3 to 0.5. It was. In Example 14, the total hydrogen absorption is in the range of −0.05 Nm 3 / m 3 to 0.6 Nm 3 / m 3 (−0.36 SCFB to 4.0 SCFB) during the contact between the crude feed and the molybdenum / vanadium catalyst. The TAN of the crude product ranged from 0.2 to 0.5.

From the total hydrogen absorption value during contact, hydrogen was estimated to be generated at a rate of 10.7 Nm 3 / m 3 (65SCFB) during the contact between the crude material and the vanadium catalyst. Due to the generation of hydrogen during the contact, this process can use less hydrogen than is conventionally used to improve the disadvantageous properties of the crude oil. Since a small amount of hydrogen is required during contact, it is easy to reduce the cost of processing crude oil.
Furthermore, contact of the crude feed with the molybdenum / vanadium catalyst produced a crude product with a TAN lower than that of the crude product produced with the individual molybdenum catalyst.

Examples 15 to 18: Contact of crude raw material with vanadium catalyst and additional catalyst Reactors (excluding the number and contents of contact zones), catalyst sulfidation methods, separation methods of all products, and production of crude oils The method for analyzing the product is the same as in Example 5. Unless otherwise indicated, all catalysts were mixed with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part catalyst. The crude feed stream in each reactor is from the top to the bottom. Silicon carbide was placed at the bottom of each reactor in order to serve as a bottom support. Each reactor has a bottom contact zone and a top contact zone. After the catalyst / silicon carbide mixture was placed in the contact zone of each reactor, silicon carbide was placed on the top contact zone in each reactor to fill the dead space and serve as a preheating zone. Each reactor was loaded into a Lindberg furnace having a preheating zone, two contact zones, and four heating zones corresponding to the bottom support.

In each example, a vanadium catalyst was prepared in the same manner as in Example 2 and used in combination with an additional catalyst.
In Example 15, an additional catalyst / silicon carbide mixture (45 cm 3 ) was placed in the bottom contact zone. This additional catalyst is a molybdenum catalyst prepared as in Example 3. A vanadium catalyst / silicon carbide mixture (15 cm 3 ) was placed in the top contact zone.
In Example 16, an additional catalyst / silicon carbide mixture (30 cm 3 ) was placed in the bottom contact zone. This additional catalyst is a molybdenum catalyst prepared as in Example 3. A vanadium catalyst / silicon carbide mixture (30 cm 3 ) was disposed in the top contact zone.

In Example 17, an additional catalyst / silicon carbide mixture (30 cm 3 ) was placed in the bottom contact zone. This additional catalyst is a molybdenum / vanadium catalyst prepared as in Example 4. A vanadium catalyst / silicon carbide mixture (30 cm 3 ) was disposed in the top contact zone.
In Example 18, Pyrex (Glass Works Corporation, New York, USA) beads (30 cm 3 ) were placed in each contact zone.

In Examples 15-18, crude oil (Santo Basin, Brazil) having the characteristics summarized in Table 5 of FIG. 17 was fed to the top of the reactor. Crude oil feed flowed to the preheating zone, tower top contact zone, tower bottom contact zone and tower bottom support. The crude feed contacted each catalyst in the presence of hydrogen gas. The contact conditions for each example are as follows. Was fed to the reactor, the ratio of hydrogen gas to crude feed is in the first 86 hours 160Nm 3 / m 3 (1000SCFB) , 80Nm 3 / m 3 for the remaining time (500SCFB), LHSV is 1h -1, The pressure is 6.9 MPa (1014.7 psi). These contact zones were gradually heated to 343 ° C. (650 ° F.) over a predetermined time and maintained at this temperature for a total operating time of 1400 hours.

  These examples show a pore size with a median pore size of 350 liters, which combines a crude feed in the presence of a hydrogen source with an additional catalyst having a pore size distribution with a median pore size in the range of 250-300 liters. Crude product in which the selected properties vary greatly compared to the same properties of the crude feed, while other properties vary only slightly compared to the same properties of the crude feed due to contact with the column 5 metal catalyst having a distribution Indicates that is manufactured. Further, during contact, it was observed that hydrogen absorption by the crude feed was relatively low.

  Specifically, as shown in Table 5 in FIG. 17, in Examples 15 to 17, the TAN of the crude product was 15% or less of the TAN of the crude raw material. The total Ni / V / Fe content of the crude products produced in Examples 15-17 are each 44% or less of the total Ni / V / Fe content of the crude feed, and the oxygen content is the same property of the crude feed The viscosity was 50% or less, and the viscosity was also 75% or less. Furthermore, the API specific gravity of the crude product produced in Examples 15 to 17 was 100 to 103% of the API specific gravity of the crude raw material.

  In contrast, the viscosity and API specific gravity of the crude product produced under non-contact conditions (Example 18) increased compared to the viscosity of the crude feed and decreased compared to the API specific gravity of the crude feed. From the increase in viscosity and the decrease in API specific gravity, it can be presumed that coke generation and / or polymerization of the crude raw material has started.

Example 19: Contacting crude feed with different LHSV The contact system and catalyst are the same as in Example 6. The characteristics of the crude oil raw material are shown in Table 6 of FIG. The contact conditions are as follows. The hydrogen gas to crude feed ratio fed to the reactor was 160 Nm 3 / m 3 (1000 SCFB), the pressure was 6.9 MPa (1014.7 psi), and the temperature in the contact zone was 371 ° C. (700 ° F.) during the total operating time. ). LHSV during contacting in example 19, increased from 1h -1 for a predetermined time to 12h -1, it was maintained at 12h -1 48 hours, raised to 20.7H -1, and maintained at this LHSV 96 h.
In Example 19, TAN, viscosity in LHSV is 12h -1 and the operating time 20.7H -1, density, VGO content, residue content, heteroatoms content, and content of metals in metal salts of organic acids The crude product was analyzed to determine the amount. The average values of the characteristics of these crude products are shown in Table 6 of FIG.

As shown in Table 6 of FIG. 18, the TAN and viscosity of the crude product of Example 19 are reduced compared to the TAN and viscosity of the crude feed, while the API specific gravity of the crude feed is the API specific gravity of the crude feed. 104-110%. The weight ratio of MCR content vs. C 5 asphaltenes content was at least 1.5. Total MCR content and C 5 asphaltenes content was reduced relative to the sum of the MCR content and C 5 asphaltenes content of the crude feed. From the reduction in the total amount of the MCR content vs. C 5 weight ratio of asphaltenes content and MCR content and C 5 asphaltenes content can presumed to be reduced asphaltenes rather than generated easily ingredients coke. The content of potassium, sodium, zinc and calcium in the crude product was 60% or less of the same metal content in the crude raw material. The sulfur content of the crude product was 80-90% of the sulfur content of the crude feed.

Examples 6 and 19, for producing a crude product having similar characteristics, during the contacting, LHSV is compared to treatment with LHSV of 1h -1, it can be controlled contacting conditions to exceed 10h -1 Indicates. The ability to selectively change one property of the crude feed at LHSV (liquid space velocity per hour) greater than 10 h −1 allows this contact method to be performed in smaller containers than commercially available containers. Due to the smaller size of the container, it may be possible to process unfavorable crude oil on production sites with limited size (eg offshore facilities).

Example 20: Contacting crude feed at various contact temperatures The contact system and catalyst are the same as in Example 6. A crude product having the characteristics shown in Table 7 of 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 product. The two contact zones were operated at different temperatures.

The contact conditions in the tower top contact zone are as follows. LHSV is 1 h −1 , the temperature in the bottom contact zone is 260 ° C. (500 ° F.), the ratio of hydrogen to crude oil feed is 160 Nm 3 / m 3 (1000 SCFB), and the pressure is 6.9 MPa (1014.7 psi).
The contact conditions in the tower bottom contact zone are as follows. The LHSV is 1 h −1 , the temperature in the bottom contact zone is 315 ° C. (600 ° F.), the ratio of hydrogen to crude oil feed is 160 Nm 3 / m 3 (1000 SCFB), and the pressure is 6.9 MPa (1014.7 psi).
The crude product exiting the bottom contact zone was introduced into a gas-liquid phase separator. In the gas-liquid phase separator, the entire product was separated into crude product and gas. To measure the TAN and C 5 asphaltenes content, periodically analyzing the crude product.

The average characteristic values of the crude product obtained during operation are shown in Table 7 of FIG. TAN of the crude feed is 9.3, C 5 asphaltenes content was 0.055g per crude feed 1g. Average TAN of the crude product 0.7, C 5 asphaltenes content was 0.039g per 1g of crude product. C 5 asphaltenes content of the crude product was less than 71% of C 5 asphaltenes content of the crude product.

The total potassium and sodium content in the crude product was 53% or less of the total content of the same metals in the crude feed. The TAN of the crude product was 10% or less of the TAN of the crude feed. During contact, the P value was maintained above 1.5.
As shown in Examples 6 and 20, the second contacting zone in (this bottom contacting zone If) 50 ° C. lower first contacting zone than the temperature (top contacting zone in this case) temperature, C 5 in the crude feed compared to asphaltenes content, it tends to enhance the reduction of C 5 asphaltenes content in the crude product.

  Furthermore, the reduction of the metal content in the organic acid metal salt was improved by using a controlled temperature difference. In each case, the stability of the crude feed / total product mixture was relatively constant from the P value measurement, but the total potassium and sodium content of the crude product obtained in Example 20 was obtained in Example 6. Reduced compared to the total potassium and sodium content of the crude product obtained.

When the low temperature first contact zone is used, a high molecular weight compound (for example, C 5 asphaltene and / or a compound and / or a compound (for example, rubber and / or tar)) having a flexible and / or adhesive property is easily formed. Or an organic acid metal salt). In this way, since these compounds can be removed at a low temperature before they clog and coat the catalyst, the life of the catalyst for high temperature operation placed after the first contact zone can be improved.

Example 21: Slurry contact between crude feed and catalyst In some embodiments, a bulk metal catalyst and / or a catalyst of the present application (0.0001-5 g or 0.02-4 g catalyst per 100 g crude feed) is You may make it into a slurry form and make it react in predetermined time on the following conditions. The temperature is in the range of 85-425 ° C. (185-797 ° F.), the pressure is in the range of 0.5-10 MPa, and the hydrogen source to crude oil feed ratio is 16-1600 Nm 3 / m 3 . After reacting for a time sufficient to form a crude product, the crude product is separated using a separation device such as a filter and / or centrifuge. Crude product, TAN compared to crude feed, iron, nickel and / or vanadium content and C 5 asphaltenes content may change or decreased.

  Further modifications and alternative embodiments of the various aspects of the invention will be apparent to those skilled in the art from the foregoing description. Accordingly, the foregoing description is to be construed as illustrative only and is for the purpose of teaching those skilled in the art the general manner of carrying out the invention. The forms of the invention specified and described herein are to be taken as examples of embodiments. The elements and materials may be interchanged with those illustrated and described herein, parts and methods may be interchanged, and certain features of the invention may be used independently, both of which benefit from the description of the invention. Later, it will be apparent to those skilled in the art. The elements described herein may be varied without departing from the scope of the invention as set forth in the claims.

1 is a schematic diagram of one embodiment of a contact system. FIG. 2A and 2B are schematic views of one embodiment of a contact system having two contact zones. 3A and 3B are schematic views of one embodiment of a contact system having three contact zones. 1 is a schematic view of one embodiment of a blending band in combination with a contact system. FIG. 1 is a schematic view of one embodiment of a blending band in combination with a contact system. FIG. 1 is a schematic view of an embodiment combining a separation zone, a contact system, and a blending zone. FIG. 2 is a representative characterization table for crude feed and crude product in one embodiment where the crude feed is contacted with three catalysts. 2 is a graph of loaded average bed temperature versus operating length for one embodiment of contacting a crude feed with one or more catalysts. 2 is a representative characterization table for crude feed and crude product in one embodiment where the crude feed is contacted with two catalysts. FIG. 5 is another exemplary property table for a crude feed and crude product in one embodiment where the crude feed is contacted with two catalysts. FIG. 2 is a table of crude feed and crude product in an embodiment where a crude feed is contacted with four different catalyst systems. 2 is a graph of P value versus operating time for a crude product in an embodiment where the crude feed is contacted with four different catalyst systems. 2 is a graph of total hydrogen uptake by a crude feed versus operating time for an embodiment in which a crude feed is contacted with four different catalyst systems. 2 is a graph of crude product residue content (% by weight) versus operating time for an embodiment in which a crude feed is contacted with four different catalyst systems. FIG. 4 is a graph of change in API specific gravity versus operating time of a crude product in an embodiment in which a crude feed is contacted with four different catalyst systems. 2 is a graph of crude product oxygen content (% by weight) versus operating time for an embodiment in which a crude feed is contacted with four different catalyst systems. Representative of crude feed and crude product in embodiments in which the crude feed is contacted with catalyst systems comprising various amounts of molybdenum and vanadium catalysts; catalyst systems comprising vanadium and molybdenum / vanadium catalysts; and glass beads. It is a characteristic table. 2 is a chart of characteristics of crude feed and crude product in embodiments in which the crude feed is contacted with one or more catalysts at various liquid hourly space velocities. Figure 5 is a chart of characteristics of crude feed and crude product in embodiments where the crude feed is contacted at various contact temperatures.

Explanation of symbols

100 Contact system 102 Contact zone 104 Crude feed conduit 106 Hydrogen source and / or carrier gas conduit 106 'Crude feed conduit 108 Separation zone 110 Total product conduit 112 Crude product conduit 114 Contact zone 116 Contact zone 118 Crude feed stream conduit 120 Separation Zone 122 Unfavorable crude oil conduit 126 Crude feed conduit 128 Crude product conduit 130 Blend zone 134 Blend product conduit point 136 Average WABT
Point 140 Crude Product P Value Point 142 in Example 8 Crude Product P Value Point 144 in Example 9 Crude Product P Value Point 146 in Example 10 Crude Product P Value Point 148 in Example 11 Total Hydrogen Absorption Point 150 in Example 8 Total Hydrogen Absorption Point 152 in Example 9 Total Hydrogen Absorption Point 154 in Example 10 Total Hydrogen Absorption Point 156 in Example 11 Crude Product Residue in Example 8 Content point 158 Crude product residue content point 160 in Example 9 Crude product residue content point 162 in Example 10 Crude product residue content point 164 in Example 11 Crude Product API Ratio Priority 166 Crude Product API Ratio Priority in Example 9 168 Crude Product API Ratio Priority in Example 10 170 Crude Product API Ratio Priority in Example 11 172 Crude Oil Production in Example 8 Product Oxygen Content Point 174 Crude Product Oxygen Content Point in Example 9 176 Example Crude product oxygen content point at 178 Crude product oxygen content at Example 11

Claims (27)

  1. A crude oil feedstock having a total acid number (TAN) (measured by ASTM method D664) of 0.3 or more, and a pore size distribution in which at least one of the catalysts has a median pore diameter of 90 mm or more (measured by ASTM method D4282) The catalyst having the pore size distribution is one or more containing 0.0001 to 0.08 g of molybdenum, one or more molybdenum compounds or a mixture thereof, calculated as the weight of molybdenum per 1 g of the catalyst. A step of producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and the TAN of the crude product is 90% or less of the TAN of the crude feed And a method for producing a crude product, comprising a step of controlling contact conditions.
  2.   The method according to claim 1, wherein the TAN of the crude product is 50% or less, 30% or less, or 10% or less with respect to TAN of the crude raw material.
  3.   The process according to claim 1, wherein the crude product has a TAN in the range of 1-80%, 20-70%, 30-60%, or 40-50% of the TAN of the crude feed.
  4.   The method according to any one of claims 1 to 3, wherein the crude product has a TAN in the range of 0.001 to 0.5, 0.01 to 0.2, or 0.05 to 0.1.
  5.   The method according to any one of claims 1 to 4, wherein the crude raw material has a TAN in the range of 0.3 to 20, 0.4 to 10, or 0.5 to 5.
  6. 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 alkali metals in the organic acid metal salts and A crude oil raw material having a total alkaline earth metal content (measured by ASTM method D1318) of 0.00001 g or more per gram of crude oil raw material, and at least one catalyst has a pore size distribution having a median pore diameter of 90 mm or more. (Measured in accordance with ASTM method D4282), the catalyst of the pore size distribution is 0.0001-0. Producing a total product comprising a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, in contact with one or more catalysts containing 3 g, and crude oil The total content of alkali metal and alkaline earth metal in the organic acid metal salt of the product is 90% or less with respect to the total content of alkali metal and alkaline earth metal in the organic acid metal salt of the crude oil raw material. The process of controlling the contact conditions;
    A method for producing a crude product comprising:
  7.   The total content of alkali metal and alkaline earth metal in the organic acid metal salt in the crude product is 50% or less relative to the total content of alkali metal and alkaline earth metal in the organic acid metal salt in the crude material. The method according to claim 6, which is not more than 5% or not more than 5%.
  8.   The total content of alkali metal and alkaline earth metal in the organic acid metal salt in the crude product is 1 to 80% with respect to the total content of alkali metal and alkaline earth metal in the organic acid metal salt in the crude raw material, The method of claim 6, which is in the range of 10-70%, 20-60%, or 30-50%.
  9.   The total content of alkali metal and alkaline earth metal in the organic acid metal salt in the crude product is from 0.0000001 to 0.00005 g, 0.0000003 to 0.00002 g, or 0.000001 to 0 per gram of crude product. The method according to any one of claims 6 to 8, which is in the range of 0.0001 g.
  10. A crude feed having a TAN (measured by ASTM method D664) of 0.3 or more and a total Ni / V / Fe content (measured by ASTM method D5708) of 0.00002 g or more per gram of crude feed is treated with at least one catalyst. The seed has a pore size distribution (measured by ASTM method D4282) having a median pore diameter of 90 mm or more, and the catalyst of the pore size distribution is molybdenum, one or more molybdenum compounds or their compounds per gram of catalyst. Total product, including crude product, which is a liquid mixture at 25 ° C. and 0.101 MPa when the mixture is calculated as the weight of molybdenum and contacted with one or more catalysts containing a total of 0.0001-0.3 g And the crude product TAN is 90% or less of the crude raw material TAN, and the crude product has a total Ni / V / Fe content of N a step of controlling the contact conditions such that the i / V / Fe content is 90% or less,
    Crude product containing.
  11.   The total Ni / V / Fe content of the crude product is 50% or less, 10% or less, 5% or less, or 3% or less with respect to the total Ni / V / Fe content of the crude raw material. the method of.
  12.   The crude product has a total Ni / V / Fe content in the range of 1-80%, 10-70%, 20-60%, or 30-50% of the total Ni / V / Fe content of the crude feed The method according to claim 10.
  13.   The total Ni / V / Fe content of the crude product ranges from 0.0000001 to 0.00005 g, 0.0000005 to 0.00001 g, or 0.000001 to 0.000005 g per gram of crude product. The method of any one of -12.
  14.   The process according to any one of claims 1 to 13, wherein the molybdenum content is in the range of 0.005 to 0.05 g / g molybdenum catalyst.
  15.   The method according to any one of claims 1 to 14, wherein the molybdenum catalyst has a pore size distribution with a median pore diameter of 180 mm or more, or 230 mm or more.
  16.   The pore size distribution of the molybdenum catalyst is a distribution in which 60% or more of the total number of pores in the distribution has a pore diameter within 70, 45, 35, or 25 of the median pore diameter. 16. The method according to any one of 15.
  17.   Molybdenum catalyst is one or more metals in column 5 of the periodic table, one or more compounds of one or more columns 5 metal, one or more metals in columns 7-10 of the periodic table, columns 7-10 The method according to any one of claims 1 to 16, further comprising one or more compounds of one or more metals and / or mixtures thereof.
  18.   The method according to any one of claims 1 to 17, wherein the molybdenum catalyst further comprises one or more elements of the 15th column of the periodic table and / or one or more compounds of the 15th column element. .
  19.   19. The method according to any one of claims 1 to 18, wherein the one or more catalysts further comprise an additional catalyst having a pore size distribution with a median pore diameter of 60 mm or more, or 180 mm or more.
  20.   20. The method of claim 19, wherein the contacting step comprises contacting the crude feed with a metal catalyst in column 6 of the periodic table after contacting the crude feed with an additional catalyst.
  21.   21. A method according to any one of the preceding claims, wherein the crude feed is contacted in a contact zone that is on or connected to the offshore facility.
  22.   The method according to any one of claims 1 to 21, wherein the contacting step comprises a step of contacting in the presence of a hydrogen source.
  23.   23. The method of any one of claims 1-22, further comprising combining the crude product with a crude that is the same as or different from the crude feed to form a blend.
  24.   A crude product or blend obtained by the method of any one of claims 1-23.
  25.   25. A method of manufacturing a transportation fuel, heating fuel, lubricant or chemical comprising the step of processing the crude product or blend of claim 24.
  26.   26. The method of claim 25, wherein the processing step comprises distilling the crude product or blend into one or more distillate fractions.
  27. 27. A method according to claim 25 or 26, wherein the treatment step comprises a hydrotreatment step.

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