CN101166810A - Systems, methods, and catalysts for producing a crude product - Google Patents

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

Info

Publication number
CN101166810A
CN101166810A CNA2006800146558A CN200680014655A CN101166810A CN 101166810 A CN101166810 A CN 101166810A CN A2006800146558 A CNA2006800146558 A CN A2006800146558A CN 200680014655 A CN200680014655 A CN 200680014655A CN 101166810 A CN101166810 A CN 101166810A
Authority
CN
China
Prior art keywords
crude oil
gram
metal
content
catalyzer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2006800146558A
Other languages
Chinese (zh)
Inventor
欧平德·契斯汉·班
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of CN101166810A publication Critical patent/CN101166810A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining 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
    • C10G45/04—Refining 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining 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
    • C10G45/04—Refining 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
    • C10G45/06—Refining 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 containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining 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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G71/00—Treatment by methods not otherwise provided for of hydrocarbon oils or fatty oils for lubricating purposes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A method of producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product that includes the crude product, wherein at least one of the catalysts comprises:a support, the support comprising theta alumina; and one or more metals from Columns 5-10 of the Periodic Table. The crude product is a liquid mixture at 25 DEG C and 0.101 MPa. The crude product may have a total content of alkali metal and alkaline-earth metal in metal salts of organic acids of at most 90% of the total content of alkali metal and alkaline-earth metal in metal salts of organic acids of the crude feed. 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

Produce system, method and the catalyzer of crude oil products
Technical field
The present invention relates generally to system, method and the catalyzer of handling crude oil material.More specifically, some embodiment described herein relates to system, method and the catalyzer that makes crude oil material change into total product, and wherein total product is included under 25 ℃ and the 0.101MPa crude oil products that to be liquid mixture and one or more performances changed with respect to each performance of crude oil material.
Background technology
Have one or more crude oil that are not suitable for performance that do not allow to use conventional facility to transport economically or process crude oil and be commonly referred to " unfavorable crude oil ".
Unfavorable crude oil can comprise the contributive acidic components of total acid value (" TAN ") to crude oil material.Unfavorable crude oil with high relatively TAN can cause the transportation of unfavorable crude oil and/or handle during the corrosion of metal component.Removing acidic components from unfavorable crude oil can relate to the various alkalization of employing and acidic components.Alternatively, corrosion resistant metal can be used for transportation equipment and/or treatment facility.The use of corrosion resistant metal is usually directed to bigger expenditure and therefore may wish to use corrosion resistant metal in existing installation.Inhibition corrosive another kind method can relate in the transportation of unfavorable crude oil and/or before handling and add inhibitor in unfavorable crude oil.The use of inhibitor can negatively influence the equipment that is used to handle crude oil and/or from the quality of the product of crude production.
Unfavorable crude oil comprises high-load relatively residual oil usually.The unfavorable crude oil that uses conventional facility transportation and/or processing to have high residual oil content tends to comparatively difficulty and expensive.
Unfavorable crude oil comprises organic bonded heteroatoms (for example sulphur, oxygen and nitrogen) usually.Organically combine heteroatoms and can have disadvantageous effect to the catalyzer that is used to handle unfavorable crude oil in some cases.
The metal pollutant that unfavorable crude oil can comprise high relatively quantity is nickel, vanadium and/or iron for example.During the processing of this crude oil, the compound of metal pollutant and/or metal pollutant may deposit in deposition on the surface of catalyzer or the void volume at catalyzer.This settling can cause the decline of catalyst activity.
Unfavorable crude oil can contain the component that causes unfavorable crude oil coking and/or thermal destruction.The component of coking and/or thermal destruction may form on catalyst surface and/or deposition during the processing of unfavorable crude oil apace.Comparatively expensively regenerate possibly by the catalytic activity of the catalyzer of coke and/or thermal destruction crude oil pollution.The high temperature that uses during catalyst regeneration in addition also may reduce activity of such catalysts and/or make catalyst degradation.
Unfavorable crude oil may comprise the metal (for example calcium, potassium and/or sodium) in the metal salts of organic acids.Typically do not handle for example desalination and/or acid elution metal in the separating organic acid metal-salt from unfavorable crude oil by routine production.
During metal in having metal salts of organic acids, in the conventional catalytic treatment of crude oil, encounter problems usually.Form contrast with nickel and the vanadium near the outside deposition of catalyzer typically, the metal in the metal salts of organic acids preferentially in the void volume between granules of catalyst, deposit at the top of beds especially.The pollutent for example deposition of metal at the beds top in the metal salts of organic acids causes increasing and may stopping up bed effectively by bed pressure drop usually.In addition, the metal in the metal salts of organic acids can cause the rapid deactivation of catalyzer.
Unfavorable crude oil can comprise organic oxygen compound.Handling oxygen level is that the treatment facility that the unfavorable crude oil at least 0.002 of every gram restrains the unfavorable crude oil of oxygen may encounter problems during handling.Organic oxygen compound can form the compound (for example ketone that is formed by the oxidation of alcohol and/or acid and/or the acid that formed by the oxidation of ether) of higher degree oxidation when being heated during handling, and these compounds are difficult to remove from the crude oil of handling and/or may corrode during handling/contaminated equipment and cause obstruction in the transport line.
Unfavorable crude oil can comprise hydrogen deficient hydrocarbon.When handling hydrogen deficient hydrocarbon, need usually to add the consistent hydrogen of measuring, if when particularly generation is from the unsaturated segment of cracking technology.May need typically to relate to the hydrogenation during the processing of using active hydrofining catalyst, form coke to suppress unsaturated segment.The production of hydrogen and/or to be transported to treatment facility expensive.
Unfavorable crude oil also tends to show unstable during the processing in conventional facility.Component was separated and/or forms undesirable byproduct (for example hydrogen sulfide, water and carbonic acid gas) during the crude oil unstable was tended to cause handling.
The common process of handling unfavorable crude oil can reduce the thermal destruction that causes high viscosity, unfavorable crude oil and/or the quantity of pyrogenic component.But these components remove the unstable that can cause in the crude oil, therefore cause the separation of crude oil during transportation.During conventional processing, when employing has the active catalyst treatment crude oil of wide aperture, high surface area and low hydrotreatment, typically remove and cause high viscosity and/or pyrogenic component.The crude oil that can further handle acquisition then is to remove other undesirable component in the crude oil.
The certain methods of improving crude quality comprises add thinner causes the component of unfavorable performance with reduction weight percent in unfavorable crude oil.But add thinner usually because the cost of thinner and/or the cost of handling unfavorable crude oil increase the cost of the unfavorable crude oil of processing.In unfavorable crude oil, add the stability that thinner may reduce this crude oil in some cases.
People's such as Sudhakar U.S. patent No.6,547,957, people's such as Myers U.S. patent 6,277,269, people's such as Harle U.S. patent 6,203,695, people's such as Grande U.S. patent 6,063,266, people's such as Bearden U.S. patent 5,928,502, people's such as Bearden U.S. patent 5,914,030, people's such as Trachte U.S. patent 5,897,769, people's such as Boon U.S. patent 5,744,025, Hensley, Jr. U.S. patent 4,212,729 and the U.S. patent 4,048 of Riley, 060, open No.US 2004/0106516 has described the whole bag of tricks of handling crude oil with people's such as Schulz U.S. patent application, system and catalyzer, all these disclosures are herein incorporated by reference.But the method for describing in these patents, system and catalyzer are owing to above-described technical problem has limited applicability.
Generally speaking, unfavorable crude oil has undesirable performance (for example high relatively TAN, the tendency that becomes unsettled tendency and/or consume a large amount of relatively hydrogen during handling during handling) usually.What unfavorable crude oil also can comprise high relatively quantity does not wish component (for example causing metal and/or organic oxygen compound in the component, residual oil, combination heteroatoms, metal pollutant, metal salts of organic acids of thermal destruction).These performances and component tend to cause problem that in routine transportation and/or treatment facility the catalyst life that the burn into that comprising increases during the processing reduces, technology are stopped up and/or the consumption of hydrogen increases.Therefore at economical and technical special needs unfavorable crude oil is changed into and have more improvement system, method and/or the catalyzer of the crude oil products of the performance of hope.Also economical and technical special needs can change the performance of selecting in the unfavorable crude oil minimize unfavorable crude oil simultaneously in system, method and/or the catalyzer of change of other performance.
Summary of the invention
In some embodiments, the invention provides a kind of method of producing crude oil products, described method comprises: make crude oil material contact the total product that comprises crude oil products with generation with one or more catalyzer, wherein said crude oil products is a liquid mixture under 25 ℃ and 0.101MPa; Little carbon residue of described crude oil material (" MCR ") content is every gram crude oil material at least 0.0001 gram; With at least a catalyzer be the 6th row metal catalyst, its mean pore sizes that comprises one or more compounds, the pore size distribution of one or more metals of one or more metals of periodictable the 6th row and/or periodictable the 6th row provides 10% pore volume at the most greater than aperture in 110  and its pore volume for the hole of at least 350 , and its mesopore volume and aperture are measured by ASTM method D4282; Make that with the control contact conditions MCR content of described crude oil products is at the most 90% of described crude oil material MCR content, wherein MCR content is measured by ASTM method D4530.
In some embodiments, the present invention also provides a kind of catalyzer, and described catalyzer comprises: carrier; One or more compounds with one or more metals of one or more metals of periodictable the 6th row and/or periodictable the 6th row; Wherein said catalyzer has mean pore sizes provides 10% pore volume at the most greater than aperture in the pore size distribution of 110  and its pore volume for the hole of at least 350 , and wherein aperture and pore volume are measured by ASTM method D4282.
In some embodiments, the present invention also provides a kind of method for preparing catalyzer, described method comprises the metallic solution of one or more compounds of one or more metals that mixed carrier and one or more metals that comprise periodictable the 6th row and/or periodictable the 6th are listed as, the mean pore size of wherein said carrier provides 15% described pore volume at the most for aperture at least 90  and its pore volume for the hole of at least 350 , and wherein aperture and pore volume are measured by ASTM method D4282.
In some embodiments, the present invention also provides a kind of method of producing crude oil products, described method comprises: make crude oil material contact the total product that comprises crude oil products with generation with one or more catalyzer, wherein said crude oil products is a liquid mixture under 25 ℃ and 0.101MPa; The MCR content of described crude oil material is every gram crude oil material at least 0.0001 gram, with at least a catalyzer be 6-10 row catalyzer, it contains one or more compounds and the binding agent of one or more metals of one or more metals of every gram catalyzer at least 0.3 gram periodictable 6-10 row and/or periodictable 6-10 row; Make that with the control contact conditions MCR content of described crude oil products is at the most 90% of described crude oil material MCR content, wherein MCR content is measured by ASTM method D4530.
In some embodiments, the present invention also provides a kind of method of producing crude oil products, described method comprises: make crude oil material contact the total product that comprises crude oil products with generation with one or more catalyzer, wherein said crude oil products is a liquid mixture under 25 ℃ and 0.101MPa, described crude oil material comprises one or more an alkali metal salts of one or more organic acids, one or more organic acid alkaline earth salts or its mixture, crude oil material has basic metal and the alkaline-earth metal total content in the metal salts of organic acids of every gram crude oil material at least 0.00001 gram, with at least a catalyzer be 5-10 row metal catalysts, it comprises one or more compounds of one or more metals of one or more metals of carrier (described carrier comprises the θ aluminum oxide) and periodictable 5-10 row and/or periodictable 5-10 row; With the control contact conditions make basic metal in the metal salts of organic acids of crude oil products and alkaline-earth metal total content be in the crude oil material basic metal in the metal salts of organic acids and alkaline earth metal content at the most 90%, wherein the content of basic metal in the metal salts of organic acids and alkaline-earth metal is measured by ASTM method D1318.
In some embodiments, the present invention also provides a kind of method of producing crude oil products, described method comprises: make crude oil material contact the total product that comprises crude oil products with generation with one or more catalyzer, wherein said crude oil products is a liquid mixture under 25 ℃ and 0.101MPa; The nitrogen content of crude oil material is every gram crude oil material at least 0.0001 gram; With at least a catalyzer be the 6th row metal catalyst, its mean pore sizes that comprises one or more compounds, the pore size distribution of one or more metals of one or more metals of periodictable the 6th row and/or periodictable the 6th row provides 10% pore volume at the most greater than aperture in 110  and its pore volume for the hole of at least 350 , and wherein aperture and pore volume are measured by ASTM method D4282; Make that with the control contact conditions nitrogen content of crude oil products is at the most 90% of a crude oil material nitrogen content, wherein nitrogen content is measured by ASTM method D5762.
In some embodiments, the present invention also provides a kind of method of producing crude oil products, described method comprises: make crude oil material contact the total product that comprises crude oil products with generation with one or more catalyzer, wherein said crude oil products is a liquid mixture under 25 ℃ and 0.101MPa; The nitrogen content of crude oil material is every gram crude oil material at least 0.0001 gram; Wherein at least a catalyzer is can be lower than in the presence of one or more sulfocompounds under about 500 ℃ temperature by heating the 6th row metal catalyst that the 6th row metal catalysts precursors obtains, and wherein the 6th row metal catalysts precursors comprises: one or more compounds of one or more metals of one or more metals of periodictable the 6th row and/or periodictable the 6th row; And carrier; Make that with the control contact conditions nitrogen content of crude oil products is at the most 90% of a crude oil material nitrogen content, wherein nitrogen content is measured by ASTM method D5762.
In some embodiments, the present invention that combines with one or more above embodiments also provides the 6th row metal catalyst: (a) wherein the aperture provides 5%, at the most 3%, at the most 1% or at the most 0.5% pore volume at the most for the hole of at least 350 ; (b) have mean pore sizes and be at least 120 , at least 130 , at least 150 , at least 180 , at least 200 , at least 250  or the pore size distribution of 300  at the most, wherein pore size distribution is measured by ASTM method D4282; And/or (c) its pore size distribution make pore size distribution hole sum at least 60% within about 45 , about 35  or about 25  of the mean pore sizes of pore size distribution.
In some embodiments, the present invention that combines with one or more above embodiments also provides the 6th row metal catalyst: (a) contain the about 0.0001-0.3 gram of every gram catalyzer, about 0.005-0.2 gram or about 0.01-0.1 and restrain one or more the 6th row metals and/or one or more the 6th row metallic compounds, as the total weight of the 6th row metal; (b) comprise one or more metals of periodictable 7-10 row and/or one or more compounds of one or more metals that periodictable 7-10 is listed as; With contain the about 0.001-0.1 of every gram catalyzer gram or about 0.01-0.05 and restrain one or more 7-10 row metals and/or one or more 7-10 row metallic compounds, as the total weight of 7-10 row metal; (c) comprise one or more metals of periodictable the 10th row and/or one or more compounds of one or more metals that periodictable the 10th is listed as; (d) comprise molybdenum and/or tungsten; (e) comprise nickel and/or cobalt; (f) comprise nickel and/or iron; (g) comprise one or more elements of periodictable the 15th row and/or one or more compounds of one or more elements that periodictable the 15th is listed as; The about 0.000001-0.1 of every gram catalyzer restrains, about 0.00001-0.06 restrains, about 0.00005-0.03 restrains or about 0.0001-0.001 restrains one or more the 15th column elements and/or one or more the 15th column element compounds, as the total weight of the 15th column element with containing; (h) comprise phosphorus; And/or (i) contain every gram catalyzer one or more compounds of one or more metals of one or more metals of 0.001 gram periodictable the 5th row and/or periodictable the 5th row at the most, as the total weight of the 5th row metal.
In some embodiments, the present invention that combines with one or more above embodiments also provides the 6th row metal catalyst or the 6th row metallic solution, every gram catalyzer or the 6th row metallic solution contain: (a) about 0.01-0.15 gram molybdenum and/or one or more molybdenum compounds, as the total weight of molybdenum; With about 0.001-0.05 gram nickel and/or one or more nickel compounds, as the total weight of nickel; (b) randomly about 0.001-0.05 gram iron and/or one or more iron cpds are as the total weight of iron; (c) randomly about 0.0001-0.05 gram phosphorus and/or one or more phosphorus compounds are as the total weight of phosphorus.
In some embodiments, the present invention that combines with one or more above embodiments also provides 5-10 row metal catalyst: (a) comprise molybdenum; (b) comprise tungsten; (c) comprise vanadium; (d) contain one or more metals of the about 0.001-0.1 gram of every gram catalyzer or about 0.01-0.05 gram periodictable 7-10 row and/or one or more compounds of one or more metals that periodictable 7-10 is listed as; (e) comprise one or more elements of periodictable the 15th row and/or one or more compounds of one or more elements that periodictable the 15th is listed as; (f) comprise phosphorus; And/or (g) have mean pore sizes and be the pore size distribution of at least 180 , at least 200 , at least 230 , at least 250  or at least 300 .
In some embodiments, the present invention that combines with one or more above embodiments also is provided as the 6th row metal catalyst of supported catalyst, and wherein carrier contains every gram carrier: (a) at least 0.8 gram, at least 0.9 gram or at least 0.95 gram gamma-alumina; (b) at the most 0.1 the gram, at the most 0.08 the gram, at the most 0.06 the gram, at the most 0.04 the gram or at the most 0.02 the gram silicon-dioxide; Or (c) at least 0.3 gram or at least 0.5 gram θ aluminum oxide.
In some embodiments, provide also with the present invention that combines of one or more above embodiments that to make crude oil material and at least a or multiple catalyzer wherein be that one or more catalyzer of the 6th row metal catalyst contact, described the 6th row metal catalyst can by blend mixture and one or more the 6th row metals and/or one or more the 6th row metallic compounds obtain and described mixture comprises: one or more compounds of one or more metals of one or more metals of periodictable 7-10 row and/or periodictable 7-10 row; And carrier.In some embodiments, combine with one or more above embodiments, at least a 7-10 row metal comprises nickel, cobalt, iron or its mixture.
In some embodiments, the present invention that combines with one or more above embodiments also provides the crude oil material with following character: (a) the about 0.0001-0.5 gram of every gram crude oil material, about 0.005-0.1 gram or about 0.01-0.05 restrain MCR; (b) the about 0.0001-0.1 gram of every gram crude oil material, about 0.001-0.05 gram or about 0.005-0.01 gram nitrogen; And/or (c) the about 0.00001-0.005 of every gram crude oil material gram, about 0.00005-0.05 gram or about 0.0001-0.01 restrain basic metal and alkaline-earth metal in the metal salts of organic acids.
In some embodiments, the present invention that combines with one or more above embodiments also provides the crude oil products with following character: (a) MCR content is at the most 80%, at the most 50%, at the most 30% or at the most 10% of crude oil material MCR content; (b) nitrogen content is at the most 80%, at the most 50%, at the most 30% or at the most 10% of a crude oil material nitrogen content; (c) in the crude oil products total content of basic metal in the metal salts of organic acids and alkaline-earth metal be in the crude oil material basic metal in the metal salts of organic acids and alkaline earth metal content at the most 80%, at the most 50%, at the most 30% or at the most 10%; (d) MCR content is about 0.1-75% of crude oil material MCR content, about 0.5-45%, about 1-25% or about 2-9%; (e) nitrogen content is about 0.1-75% of crude oil material nitrogen content, about 0.5-45%, about 1-25% or about 2-9%; (f) total content of basic metal in the metal salts of organic acids and alkaline-earth metal is the basic metal in the metal salts of organic acids and about 0.1-75% of alkaline earth metal content, about 0.5-45%, about 1-25% or about 2-9% in the crude oil material in the crude oil products; (g) the about 0.00001-0.1 gram of every gram crude oil products, about 0.0001-0.05 gram or about 0.001-0.005 gram MCR; (h) the about 0.00001-0.05 gram of every gram crude oil products, about 0.0001-0.01 gram or about 0.0005-0.001 gram nitrogen; (i) every gram crude oil products about 1 * 10 -7-5 * 10 -5Gram, about 5 * 10 -7-1 * 10 -5Gram or about 1 * 10 -6-5 * 10 -6Basic metal and alkaline-earth metal in the gram metal salts of organic acids; (j) viscosity under 37.8 ℃ (100 ) be crude oil material 37.8 ℃ (100 ) down viscosity at the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10%, its medium viscosity is measured by ASTM method D445; (k) C 5Asphalt content is the C of crude oil material 5At the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of asphalt content, wherein C 5Asphalt content is measured by ASTM method D2007; (1) residual oil content is at the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of crude oil material residual oil content, and wherein residual oil content is measured by ASTM method D5307; And/or (m) sulphur content is at the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of a crude oil material sulphur content, and wherein sulphur content is measured by ASTM method D4294.
In some embodiments, also provide crude oil material is contacted with one or more additional catalysts with one or more catalyzer with the present invention that combines of one or more above embodiments, at least a catalyzer is that the mean pore sizes of the 6th row metal catalyst and one or more additional catalysts is at least 60 , at least 90 , at least 110 , at least 180 , at least 200  or at least 250 ; With at crude oil material with before at least a additional catalyst contacts and/or the 6th row metal catalyst is contacted with crude oil material.
In some embodiments, combine with one or more above embodiments that also to provide at least a catalyzer be 5-10 row metal catalysts in the present invention; Contact with the additional catalyst that makes crude oil material and mean pore sizes at least 60 , and after crude oil material and 5-10 row metal catalyst, additional catalyst is contacted with crude oil material.
In some embodiments, also provide crude oil material is contacted with one or more catalyzer to produce total product with the present invention that combines of one or more above embodiments, wherein the P-value at period of contact crude oil material/total product mixture is at least 1.5.
In some embodiments, also be provided at hydrogen source contacting under existing with the present invention that combines of one or more above embodiments.
In some embodiments, the present invention that combines with one or more above embodiments also provides contact conditions, and described contact conditions comprises: (a) about 50-500 ℃ temperature; (b) 430 ℃, 420 ℃ or 410 ℃ temperature at the most at the most at the most; (c) total pressure of about 0.1-20MPa; (d) 18MPa, 16MPa or the total pressure of 14MPa at the most at the most at the most; (e) 0.05h at least -1Liquid hourly space velocity; And/or (f) about 0.1-100,000Nm 3/ m 3The gas hydrogen source and the ratio of crude oil material.
In some embodiments, the present invention that combines with one or more above embodiments also provides a kind of method, described method comprises makes crude oil material contact the total product that comprises crude oil products with generation with one or more catalyzer, and described method also comprises making with the identical or different crude oil of described crude oil material mixes the blend that is suitable for transporting with formation with crude oil products.
In some embodiments, combining with one or more above embodiments the invention provides a kind of method for preparing catalyzer, and described method comprises mixed carrier and the 6th row metallic solution, described the 6th row metallic solution: (a) have about at the most 3 pH; (b) has the pH of about 1-3; (c) wherein select the amount of the 6th row metal in the metallic solution, make catalyzer contain the about 0.0001-0.3 gram of every gram catalyzer, about 0.005-0.2 gram or about 0.01-0.1 and restrain one or more the 6th row metals and/or one or more the 6th row metallic compounds, as the total weight of the 6th row metal; (d) comprise one or more metals of periodictable 7-10 row and/or one or more compounds of one or more metals that periodictable 7-10 is listed as; Wherein select the amount of 7-10 row metal, make catalyzer contain the about 0.001-0.1 of every gram catalyzer gram or about 0.01-0.05 restrains one or more 7-10 row metals and/or one or more 7-10 row metallic compounds, as the total weight of 7-10 row metal; (e) comprise one or more metals of periodictable the 10th row and/or one or more compounds of one or more metals that periodictable the 10th is listed as; (f) comprise molybdenum and/or tungsten; (g) comprise nickel and/or cobalt; (h) comprise nickel and iron; (i) comprise one or more elements of periodictable the 15th row and/or one or more compounds of one or more elements that periodictable the 15th is listed as; Wherein select the amount of the 15th column element, make catalyzer contain the about 0.000001-0.1 gram of every gram catalyzer, about 0.00001-0.06 gram, about 0.00005-0.03 gram or about 0.0001-0.001 and restrain one or more the 15th column elements and/or one or more the 15th column element compounds, as the total weight of the 15th column element; (j) comprise phosphorus; (k) comprise one or more mineral acids; (l) comprise one or more organic acids; (m) comprise hydrogen peroxide; And/or (n) comprise amine.
In some embodiments, combining with one or more above embodiments the invention provides a kind of method for preparing catalyzer, and described method is included in the metal of thermal treatment load under the temperature of about 40-400 ℃, about 60-300 ℃ or about 100-200 ℃; The further metal of thermal treatment load under at least 400 ℃ temperature randomly.
In some embodiments, combine with one or more above embodiments and the invention provides 6-10 row metal catalyst, described 6-10 row metal catalyst: one or more compounds that (a) comprise one or more metals of one or more metals of periodictable the 6th row and/or periodictable the 6th row; (b) comprise one or more metals of periodictable 7-10 row and/or one or more compounds of one or more metals that periodictable 7-10 is listed as; (c) comprise molybdenum and/or tungsten; (d) comprise nickel and/or cobalt; (e) wherein binding agent comprises silicon-dioxide, aluminum oxide, silica/alumina, titanium oxide, zirconium white or its mixture; And/or (f) be unbodied.
In further embodiment, the feature of specific embodiments is combined with the feature of other embodiment.The feature of an embodiment is combined with the feature of any other embodiment.
In further embodiment, can obtain crude oil products by any method and system described herein.
In further embodiment, can increase additional features to specific embodiments described herein.
In further embodiment, transport fuel, heating fuel, lubricant or chemical can be obtained by crude oil products or the blend that any method and system described herein obtains.
Description of drawings
Have benefited from following detailed description and with reference to the accompanying drawings the time, advantage of the present invention is obvious to those skilled in the art, wherein:
Fig. 1 is the sketch of the embodiment of contact system.
Fig. 2 A and 2B are the sketches of embodiment that comprises the contact system of two zone of action.
Fig. 3 A and 3B are the sketches of embodiment that comprises the contact system of three zone of action.
Fig. 4 is the sketch with the embodiment of contact system bonded disengaging zone.
Fig. 5 is the sketch with the embodiment in contact system bonded blend district.
Fig. 6 is the sketch of embodiment of the combination in disengaging zone, contact system and blend district.
Although the present invention allows various improvement and alternative form, provide its specific embodiments by embodiment in the accompanying drawings.The accompanying drawing not to scale (NTS).Be to be understood that accompanying drawing and its detailed description is not wished to limit the invention to disclosed particular form, opposite all improvement, equivalent scheme and the replacement scheme of wishing to cover by in the spirit and scope of the present invention of claims definition.
Embodiment
Above problem can use system described herein, method and catalyzer to solve.For example by crude oil material being contacted produce MCR content and/or nitrogen content with respect to crude oil material to have the crude oil products that reduces MCR content and/or reduce nitrogen content with catalyzer, described catalyzer has mean pore sizes provides 10% pore volume at the most greater than aperture in the pore size distribution of 110  and its pore volume for the hole of at least 350 .Has the crude oil products that reduces nitrogen content by making crude oil material contact the nitrogen content of producing with respect to crude oil material with incinerating catalyzer not.By crude oil material is contacted produce the crude oil products that has the metal content in the metal salts of organic acids of reduction with respect to the metal content in the metal salts of organic acids of crude oil material with the catalyzer that comprises 5-10 row metal and θ aluminum oxide.By being contacted with bulk metal catalyst, crude oil material produces the crude oil products that has reduction MCR content with respect to the MCR content of crude oil material.
U.S. apply for serial Nos.11/014,335,11/013,553,11/014,386,11/013,554,11/013,629,11/014,318,11/013,576,11/013,835,11/014,362,11/014,011,11/013,747,11/013,918,11/014,275,11/014,060,11/014,272,11/014,380,11/014,005,11/013,998,11/014,406,11/014,365,11/013,545,11/014,132,11/014,363,11/014,251,11/013,632,11/014,009,11/014,297,11/014,004,11/013,999,11/014,281,11/013,995,11/013,904,11/013,952,11/014,299,11/014,381,11/014,346,11/014,028,11/013,826, with 11/013,622 the system that overcomes the above problems has been discussed also, method and catalyzer are though the crude oil material that relates to may be different in some aspects with the said crude oil material of handling according to the present invention.
At this certain embodiments of the present invention are described in more detail.Term definition is as follows as used herein.
" ASTM " refers to USS test and material.
" api gravity " refers to the api gravity under 15.5 ℃ (60 ).Api gravity is measured by ASTM method D6822.
The atomic hydrogen per-cent of crude oil material and crude oil products and atoms carbon per-cent are measured by ASTM method D5291.
Unless otherwise mentioned, the boiling Range Distribution Analysis of crude oil material, total product and/or crude oil products is measured by ASTM method D5307.
" binding agent " refers to small-particle more is combined together to form the matrix of bigger material (for example block or pellet).
The catalyzer that " bulk metal catalyst " refers to comprise at least a metal and do not require supporting body or carrier.
" C 5Bituminous matter " refers to be insoluble to the bituminous matter of pentane.C 5Asphalt content is measured by ASTM method D2007.
" X row metal " refers to one or more metals of periodictable X row and/or one or more compounds of one or more metals that periodictable X is listed as, and wherein X is corresponding to the columns (for example 1-12) of periodictable.For example " the 6th row metal " refers to one or more metals of periodictable the 6th row and/or one or more compounds of one or more metals that periodictable the 6th is listed as.
" X column element " refers to one or more elements of periodictable X row and/or one or more compounds of one or more elements that periodictable X is listed as, and wherein X is corresponding to the columns (for example 13-18) of periodictable.For example " the 15th column element " refers to one or more elements of periodictable the 15th row and/or one or more compounds of one or more elements that periodictable the 15th is listed as.
In the application's scope, the weight of the compound of the element of the weight of the element of the weight of the compound of the metal of the weight of the metal of periodictable, periodictable, periodictable or periodictable is calculated as the weight of metal or the weight of element.If for example every gram catalyzer uses 0.1 gram MoO 3, the weight of molybdenum is every gram catalyzer 0.067 gram in the catalyzer of calculating.
" content " refers to the gross weight based on matrix, is expressed as the weight of the middle component of matrix (for example crude oil material, total product or crude oil products) of weight fraction or weight percent." ppmw " refers to 1,000,000/portion by weight.
" crude oil material/total product mixture " refers to the mixture of contact catalyst during handling.
" overhead product " refers to the hydrocarbon of boiling Range Distribution Analysis between 204 ℃ (400 ) and 343 ℃ (650 ) under 0.101MPa.Overhead product content is measured by ASTM method D5307.
" heteroatoms " refers to the oxygen, nitrogen and/or the sulphur that comprise in the molecular structure of hydrocarbon.Content of heteroatoms is measured by the ASTM method E385 that is used for oxygen, the D4294 that is used for the D5762 of total nitrogen and is used for sulphur." total basic nitrogen " refers to that pKa is less than 40 nitrogen compound.Basic nitrogen (" bn ") is measured by ASTM method D2896.
" hydrogen source " refers to hydrogen and/or when reacting so that a kind of compound and/or the multiple compound of hydrogen compound in the crude oil material to be provided in the presence of crude oil material and catalyzer.Hydrogen source can include but not limited to hydrocarbon (C for example 1To C 4Hydrocarbon such as methane, ethane, propane, butane), water or its mixture.The net quantity that can the implementation quality balance be provided to the hydrogen of compound in the crude oil material with evaluation.
The pressure that the broken catalyzer of " dull and stereotyped shatter strength " finger pressure needs.Dull and stereotyped shatter strength is measured by ASTM method D4179.
" LHSV " refers to the liquid volume feed rate of unit catalyzer cumulative volume and with a hour (h -1) express.The cumulative volume of catalyzer is calculated by the summation of all catalyst volumes in the zone of action, as said.
" liquid mixture " refer to comprise one or more in standard temperature and pressure (STP) (25 ℃, 0.101MPa are hereinafter referred to as " STP ") down for the compound compositions of liquid or comprise one or more and under STP, under STP, be the composition of solid combination of compounds for the compound of liquid and one or more.
" periodictable " refers to the periodictable by International Union of Pure and Applied Chemistry (IUPAC) in November, 2003 regulation.
" metal in the metal salts of organic acids " refers to basic metal, alkaline-earth metal, zinc, arsenic, chromium or its combination.Metal content in the metal salts of organic acids is measured by ASTM method D1318.
" MCR " content refers to remaining remaining carbon after matrix evaporation and pyrolysis.MCR content is measured by ASTM method D4530.
" petroleum naphtha " refers to the hydrocarbon component of boiling Range Distribution Analysis between 38 ℃ (100 ) and 200 ℃ (392 ) under 0.101MPa.Petroleum naphtha content is measured by ASTM method D5307.
" Ni/V/Fe " refers to Ni-V-Fe or its combination.
" Ni/V/Fe content " refers to the content of Ni-V-Fe or its combination.Ni/V/Fe content is measured by ASTM method D5708.
" Nm 3/ m 3" the gas standard cubic meter number that refers to every cubic metre of crude oil material.
" non-carboxylic organic oxygen compound " refers to not contain carboxyl (CO 2-) organic oxygen compound.Non-carboxylic organic oxygen compound includes but not limited to not contain ether, cyclic ethers, alcohol, aromatic alcohol, ketone, aldehyde or its combination of carboxyl.
" not condensable gases " refers to be the component of gas and/or component mixture under STP.
" P (peptization) value " or " P-value " refer to the numerical value of the tendency of flocculation of table crude oil material medium pitch matter.The mensuration of P-value by J.J.Heithaus at " Measurement and Significanceof Asphaltene Peptization ", Journal of Institute of Petroleum, Vol.48 No. 458, in February, 1962, describes among the pp.45-53.
" aperture ", " mean pore size ", " mean pore sizes " and " pore volume " refer to aperture, mean pore size, mean pore sizes and the pore volume measured by ASTM method D4284 (in the mercury porosimetry that equals under 140 ° the contact angle).Micromeritics (Georgia U.S.A.) can be used for measuring these numerical value to the A9220 instrument for Micromeritics Inc., Norcross.Pore volume comprises institute's foraminous volume in the catalyzer.The aperture in 50% hole that mean pore sizes is represented aperture mesopore sum greater than the aperture in 50% hole of mean pore sizes and hole sum less than mean pore sizes.Use following formula to determine with the mean pore size that atomic meter () expresses:
Mean pore size=(40,000 * with cm 3The total pore volume of/g meter)/(with m 2The surface-area of/g meter).
" residual oil " refers to the boiling Range Distribution Analysis measured by the ASTM method D5307 component greater than 538 ℃ (1000 ).
" SCFB " refers to the standard cubic foot gas of every barrel of crude oil material.
" surface-area " of catalyzer measured by ASTM method D3663.
" TAN " refers to the total acid value with milligram (" mg ") KOH expression of every gram (" g ") sample.TAN is measured by ASTM method D664.
" VGO " refers to the hydrocarbon of boiling Range Distribution Analysis between 343 ℃ (650 ) and 538 ℃ (1000 ) under 0.101MPa.VGO content is measured by ASTM method D5307.
" viscosity " refers to the kinematic viscosity under 37.8 ℃ (100 ).Viscosity uses ASTM method D445 to measure.
All methods that relate to are herein incorporated by reference.In the application's context,, can make testing method improve and/or calibrate again to test this performance if should understand numerical value that the substrate performance for test obtains beyond the boundary of testing method.
Can be with crude oil from hydrocarbon containing formation production and/or destructive distillation and stable then.Crude oil is solid, semisolid and/or liquid normally.Crude oil can comprise crude oil (crude oil).Stable can including but not limited to removes not condensable gases, water, salt, solid or its combination to form stable crude oil from crude oil.This stabilization can be usually being produced and/or destructive distillation position or near producing and/or carry out the destructive distillation position.
Stable crude oil comprises the crude oil that also distillation and/or fractionation do not have the various ingredients (for example petroleum naphtha, overhead product, VGO and/or lubricating oil) of concrete boiling Range Distribution Analysis with production in treatment facility.Distillation includes but not limited to air distillation method and/or vacuum distillation method.Not distillation and/or not fractionated stable crude oil can comprise every gram crude oil quantity for the carbonatoms of at least 0.5 gram greater than 4 component.Stable crude oil also comprises the crude oil from surperficial distillation process.For example also Canadian tar sand can be exploited out and in surperficial distillation process, handle then.The crude oil of producing from this surperficial destructive distillation can be stable crude oil.The example of stable crude oil comprises whole crude, dials top crude oil, desalted crude, desalination are dialled top crude oil, destructive distillation crude oil or its mixture." dial top " thus refer to processed removed at least a portion under 0.101MPa boiling point less than the crude oil of the component of 35 ℃ (about 95  under the 1atm).Typically, dial top crude oil will have every gram dial top crude oil at the most 0.1 the gram, at the most 0.05 the gram or at the most 0.02 the gram this components contents.
Some stable crude oil have the performance that allows stable crude oil to be transported to the conventional processing facility by transportation means (for example pipeline, truck or boats and ships).Other crude oil has one or more makes their disadvantageous improper performances.Unfavorable crude oil may be unacceptable for transportation means and/or treatment facility, therefore gives low economic value to unfavorable crude oil.Economic worth may make exploitation, transportation and/or the processing of the storage layer that comprises unfavorable crude oil be considered to too expensive.
The performance of unfavorable crude oil can include but not limited to: a) at least 0.1 or at least 0.3 TAN; B) viscosity of 10cSt at least; C) 19 api gravity at the most; D) total N i/V/Fe content of unfavorable crude oil at least 0.00002 gram of every gram or at least 0.0001 gram Ni/V/Fe; E) the heteroatomic total content of heteroatoms of unfavorable crude oil at least 0.005 gram of every gram; F) the residual oil content of the unfavorable crude oil at least 0.01 gram residual oil of every gram; G) the unfavorable crude oil at least 0.04 gram C of every gram 5Bitum C 5Asphalt content; H) the MCR content of the unfavorable crude oil at least 0.0001 gram MCR of every gram; I) metal content in the metal salts of organic acids of the unfavorable crude oil at least 0.00001 gram metal of every gram; Or j) its combination.In some embodiments, unfavorable crude oil comprises the unfavorable crude oil at least 0.2 gram residual oil of every gram, at least 0.3 gram residual oil, at least 0.5 gram residual oil or at least 0.9 gram residual oil.In some embodiments, the TAN of unfavorable crude oil is about 0.1-20, about 0.3-10 or about 0.4-5.In some embodiments, the sulphur content of unfavorable crude oil is unfavorable crude oil at least 0.005, at least 0.01 of every gram or at least 0.02 gram.
In some embodiments, the MCR content of unfavorable crude oil is unfavorable crude oil at least 0.0001 gram of every gram, at least 0.001 gram, at least 0.003 gram, at least 0.005 gram, at least 0.01 gram, at least 0.1 gram or at least 0.5 gram.The MCR content of unfavorable crude oil can be the about 0.0001-0.5 gram of the unfavorable crude oil of every gram, about 0.005-0.1 gram or about 0.01-0.05 gram.
In some embodiments, the nitrogen content of unfavorable crude oil is unfavorable crude oil at least 0.0001 gram of every gram, at least 0.001 gram, at least 0.01 gram, at least 0.05 gram or at least 0.1 gram.The nitrogen content of unfavorable crude oil can be the about 0.0001-0.1 gram of the unfavorable crude oil of every gram, about 0.001-0.05 gram or about 0.005-0.01 gram.
In some embodiments, unfavorable crude oil contains basic metal and the alkaline-earth metal at least 0.00001 gram, at least 0.0001 gram, at least 0.001 gram or at least 0.01 gram metal salts of organic acids.The content of the metal in the metal salts of organic acids of unfavorable crude oil can be basic metal and the alkaline-earth metal in about 0.00001-0.003 gram, about 0.00005-0.005 gram or the about 0.0001-0.01 gram metal salts of organic acids.
In some embodiments, the performance that has of unfavorable crude oil includes but not limited to: a) at least 0.5 TAN; B) oxygen level of every gram crude oil material at least 0.005 gram oxygen; C) every gram crude oil material at least 0.04 gram C 5Bitum C 5Asphalt content; D) be higher than required viscosity (for example for api gravity at least 10 crude oil material more than or equal to 10cSt); E) content of the metal in the metal salts of organic acids of every gram crude oil at least 0.00001 gram basic metal and alkaline-earth metal; Or f) its combination.
Unfavorable crude oil can comprise the unfavorable crude oil of every gram: at least 0.001 gram, at least 0.005 gram or boiling Range Distribution Analysis the hydrocarbon about 95 ℃ and about 200 ℃ between of at least 0.01 gram under 0.101MPa; At least 0.001 gram, at least 0.005 gram or boiling Range Distribution Analysis the hydrocarbon about 200 ℃ and about 300 ℃ between of at least 0.01 gram under 0.101MPa; At least 0.001 gram, at least 0.005 gram or boiling Range Distribution Analysis the hydrocarbon about 300 ℃ and about 400 ℃ between of at least 0.01 gram under 0.101MPa; At least 0.001 gram, at least 0.005 gram or boiling Range Distribution Analysis the hydrocarbon about 400 ℃ and about 650 ℃ between of at least 0.01 gram under 0.101MPa.
Unfavorable crude oil can comprise the unfavorable crude oil of every gram: at least 0.001 gram, at least 0.005 gram or the boiling Range Distribution Analysis of at least 0.01 gram under 0.101MPa are 100 ℃ hydrocarbon at the most; At least 0.001 gram, at least 0.005 gram or boiling Range Distribution Analysis the hydrocarbon about 100 ℃ and about 200 ℃ between of at least 0.01 gram under 0.101MPa; At least 0.001 gram, at least 0.005 gram or boiling Range Distribution Analysis the hydrocarbon about 200 ℃ and about 300 ℃ between of at least 0.01 gram under 0.101MPa; At least 0.001 gram, at least 0.005 gram or boiling Range Distribution Analysis the hydrocarbon about 300 ℃ and about 400 ℃ between of at least 0.01 gram under 0.101MPa; At least 0.001 gram, at least 0.005 gram or boiling Range Distribution Analysis the hydrocarbon about 400 ℃ and about 650 ℃ between of at least 0.01 gram under 0.101MPa.
Except that high boiling component, some unfavorable crude oil can comprise the unfavorable crude oil of every gram at least 0.001 gram, at least 0.005 gram or the boiling Range Distribution Analysis of at least 0.01 gram under 0.101MPa and be 100 ℃ hydrocarbon at the most.Typically, the content of these hydrocarbon of unfavorable crude oil is that the unfavorable crude oil of every gram 0.2 restrains or 0.1 restrains at the most at the most.
Some unfavorable crude oil can comprise the unfavorable crude oil of every gram at least 0.001 gram, at least 0.005 gram or the boiling Range Distribution Analysis of at least 0.01 gram under 0.101MPa less than 200 ℃ hydrocarbon.
In some embodiments, unfavorable crude oil comprise the unfavorable crude oil of every gram at the most 0.9 gram or at the most 0.99 gram boiling Range Distribution Analysis greater than 300 ℃ hydrocarbon.In some embodiments, unfavorable crude oil also comprises the unfavorable crude oil of every gram at least 0.001 gram boiling Range Distribution Analysis greater than 650 ℃ hydrocarbon.In some embodiments, unfavorable crude oil comprises about at the most 0.9 gram of the unfavorable crude oil of every gram or the hydrocarbon of about at the most 0.99 gram boiling Range Distribution Analysis between about 300 ℃ and about 1000 ℃.
Can use the example of the unfavorable crude oil of art breading described herein to include but not limited to: U.S.Gulf Coast from following geographic crude oil in the world, south, California (southern California), Alaska north slope (north slope of Alaska), Canada's tar sand, Canada alberta zone (Canadian Alberta region), Mexico's Campeche (Mexico Bay of Campeche), Ah root moves San Jorge basin (Argentinean San Jorge basin), Brazil Sang Tuosi and Campos basin (Brazilian Santos and Campos basins), Egyptian bay, Suez (EgyptianGulf of Suez), Chad (Chad), the Britain North Sea (United Kingdom North Sea), Angola coastal waters (Angola Off shore), China Bohai Sea Gulf (China Bohai Bay), China Kelamayi (China Karamay), Iraq Zagros (Iraq Zagros), Kazakhstan the Caspian Sea (Kazakhstan Caspian), Nigeria coastal waters (NigeriaOff shore), the Madagascar northwestward (Madagascar northwest), Oman (Oman), Holland Schoonebek (Netherlands Schoonebek), Venezuela Zulia (Venezuelan Zulia), Malaysia (Malaysia) and Indonesia Sumatera (Indonesia Sumatra).The performance that the processing of unfavorable crude oil can improve unfavorable crude oil makes that crude oil is acceptable for transportation and/or processing.The crude oil that will manage herein and/or unfavorable crude oil are called " crude oil material ".Crude oil material can be as the said top of dialling.Crude oil material can obtain by method described herein, but is not limited to method described herein.The crude oil products of handling from crude oil material described herein is suitable for transportation usually and/or handles.As the performance of the crude oil products of said production than crude oil material more near the respective performances of West Texas medium crude oil or than crude oil material more near the respective performances of Brent crude oil, therefore improve the economic worth of crude oil material.Can with this crude oil products utilization with compare less pre-treatment or do not have pre-treatment and refining from other crude oil products of unfavorable crude oil material, therefore improve refining efficiency.Pre-treatment can comprise that desulfurization, demetalization and/or air distillation are to remove impurity.
The processing of crude oil material of the present invention described herein can be included in the combination of zone of action and/or two or more zone of action crude oil material is contacted with catalyzer.In the zone of action, can be by crude oil material and the contact of one or more catalyzer with respect at least a performance of the identical performance change crude oil material of crude oil material.In some embodiments, contact is implemented in the presence of hydrogen source.In some embodiments, the hydrogen source reaction that is one or more under certain contact conditions is to provide the hydrocarbon of relatively small amount hydrogen compound in the crude oil material.
Fig. 1 is the sketch that comprises the contact system 100 of upstream contacting zone 102.Crude oil material enters upstream contacting zone 102 by crude oil material pipeline 104.The zone of action can be the part of reactor, reactor, a plurality of parts or its combination of reactor.The example of zone of action comprises stacked bed bioreactor, fixed-bed reactor, ebullated bed reactor, continuous stirred tank reactor (" CSTR "), fluidized-bed reactor, spray reactor and liquid/liquid-liquid contactor.In some embodiments, make contact system on offshore installation or be connected to offshore installation.Crude oil material can be continuous processing or batch technology with catalyzer contacting in contact system 100.
The zone of action can comprise one or more catalyzer (for example two kinds of catalyzer).In some embodiments, first catalyzer of crude oil material and two kinds of catalyzer contacts metal in the metal salts of organic acids that can reduce crude oil material.Have the crude oil material that reduces metal-salt and can reduce MCR content and/or content of heteroatoms with contacting subsequently of second catalyzer.In other embodiments, with after one or more catalyzer contact, the combination of the TAN of crude oil products, viscosity, Ni/V/Fe content, content of heteroatoms, residual oil content, api gravity or these performances is changed to few 10% with respect to the identical performance of crude oil material at crude oil material.
In some embodiments, the volume of catalyzer is about 10-60vol% of crude oil material cumulative volume in the zone of action, about 20-50vol% or about 30-40vol% in the zone of action.In some embodiments, the slurry of catalyzer and crude oil material can comprise the about 0.001-10 gram of crude oil material, about 0.005-5 gram or the about 0.01-3 gram catalyzer in per 100 gram zone of action.
Contact conditions in the zone of action can include but not limited to temperature, pressure, hydrogen source flow, crude oil material flow or its combination.Control the contact conditions in some embodiments has specific performance with production crude oil products.Temperature in the zone of action can be about 50-500 ℃, about 60-440 ℃, about 70-430 ℃ or about 80-420 ℃.The pressure of zone of action can be about 0.1-20MPa, about 1-12MPa, about 4-10MPa or about 6-8MPa.The LHSV of crude oil material is generally about 0.05-30h -1, about 0.5-25h -1, about 1-20h -1, about 1.5-15h -1Or about 2-10h -1In some embodiments, LHSV is 5h at least -1, 11h at least -1, 15h at least -1Or 20h at least -1In some embodiments, total pressure is 18MPa at the most, 16MPa, 14MPa, 12MPa, 10MPa or 8MPa at the most at the most at the most at the most at the most.In some embodiments, temperature is 430 ℃ at the most, 420 ℃ at the most, 410 ℃ or 400 ℃ at the most at the most.
In the embodiment that hydrogen source is provided as gas (for example hydrogen), the gas hydrogen source that contacts with catalyzer and the ratio of crude oil material typically are about 0.1-100,000Nm therein 3/ m 3, about 0.5-10,000Nm 3/ m 3, about 1-8,000Nm 3/ m 3, about 2-5,000Nm 3/ m 3, about 5-3,000Nm 3/ m 3Or about 10-800Nm 3/ m 3In some embodiments, hydrogen source is mixed with carrier gas and pass through zone of action recirculation.Carrier gas can be for example nitrogen, helium and/or argon gas.Carrier gas can promote flowing of crude oil material and/or flowing of hydrogen source in the zone of action.Carrier gas also can strengthen the mixing in the zone of action.In some embodiments, can make hydrogen source (for example hydrogen, methane or ethane) as carrier gas with by zone of action recirculation.
Hydrogen source can also flow with crude oil material in crude oil material pipeline 104 or enter upstream contacting zone 102 by gas pipeline 106 individually.In upstream contacting zone 102, crude oil material produces the total product that comprises crude oil products and gas in some embodiments with contacting of catalyzer.In some embodiments, carrier gas is mixed in pipeline 106 with crude oil material and/or hydrogen source.Total product can leave upstream contacting zone 102 and enter downstream separation district 108 by total product pipeline 110.
In downstream separation district 108, can use common known separation techniques for example gas-liquid separation crude oil products is separated from total product with gas.Can make crude oil products leave downstream separation district 108 and be transported to transportation means, pipeline, storage vessel, refinery, other treatment zone or its combination then by crude oil products pipeline 112.Gas can comprise gas (for example hydrogen sulfide, carbonic acid gas and/or carbon monoxide), excess air hydrogen source and/or the carrier gas that forms during the processing.Can make excess air be recycled to contact system 100, purifying, be transported to other treatment zone, storage vessel or its combination.
In some embodiments, crude oil material is contacted to produce total product implements in two or more zone of action with catalyzer.Total product is separated to form crude oil products and gas.
Fig. 2-the 3rd comprises the sketch of embodiment of the contact system 100 of two or three zone of action.In Fig. 2 A and 2B, contact system 100 comprises upstream contacting zone 102 and downstream contacting zone 114.Fig. 3 A and 3B comprise zone of action 102,114,116.In Fig. 2 A and 3A, zone of action 102,114,116 is described as independent zone of action in the reactor.Crude oil material enters upstream contacting zone 102 by crude oil material pipeline 104.
In some embodiments, carrier gas is mixed in gas pipeline 106 with hydrogen source and introduce the zone of action as mixture.In some embodiment shown in Fig. 1,3A and the 3B, hydrogen source and/or carrier gas can with crude oil material separate by gas pipeline 106 and/or against crude oil material mobile direction by the one or more zone of action of for example gas pipeline 106 ' enter.Can improve the mixing of crude oil material and catalyzer with the adding of the hydrogen source of crude oil material adverse current and/or carrier gas and/or contact.
Crude oil material forms feed stream with catalyzer contacting in upstream contacting zone 102.Feed stream flow to downstream contacting zone 114 from upstream contacting zone 102.In Fig. 3 A and 3B, feed stream flow to other downstream contacting zone 116 from downstream contacting zone 114.
Zone of action 102,114,116 can comprise one or more catalyzer.Shown in Fig. 2 B, feed stream leaves upstream contacting zone 102 and enters downstream contacting zone 114 by feed stream pipeline 118.Shown in Fig. 3 B, feed stream leaves downstream contacting zone 114 and enters other downstream contacting zone 116 by pipeline 118.
Feed stream and other catalyzer are contacted to form total product in downstream contacting zone 114 and/or other downstream contacting zone 116.Total product leaves downstream contacting zone 114 and/or other downstream contacting zone 116 and enters downstream separation district 108 by total product pipeline 110.Crude oil products and/or gas are separated from total product.Crude oil products leaves downstream separation district 108 by crude oil products pipeline 112.
Fig. 4 is the sketch in the embodiment of the disengaging zone of contact system 100 upstreams.(dial the top or do not dial top) unfavorable crude oil enters disengaging zone, upstream 120 by crude oil pipeline 122.In disengaging zone, upstream 120, use technology known in the art (for example injection, membrane sepn, decompression, filtration or its combination) to separate the unfavorable crude oil of at least a portion to produce crude oil material.For example can water be separated at least in part from unfavorable crude oil.In another example, can in disengaging zone, upstream 120, make boiling Range Distribution Analysis less than 95 ℃ or from unfavorable crude oil, separate to produce crude oil material at least in part less than 100 ℃ component.In some embodiments, at least a portion petroleum naphtha is separated from unfavorable crude oil with the compound of volatility greater than petroleum naphtha.In some embodiments, the isolating component of at least a portion is left disengaging zone, upstream 120 by pipeline 124.
120 crude oil materials that obtain comprise the mixture of boiling Range Distribution Analysis at least 100 ℃ component in some embodiments from the disengaging zone, upstream, or comprise the mixture of boiling Range Distribution Analysis at least 120 ℃ component in some embodiments.Typically, isolating crude oil material comprises the mixture of boiling Range Distribution Analysis for the component of about 100-1000 ℃, about 120-900 ℃ or about 200-800 ℃.At least a portion crude oil material leave disengaging zone, upstream 120 by other crude oil material pipeline 126 and enter contact system 100 (referring to the zone of action among for example Fig. 1-3) thus form crude oil products with further processing.In some embodiments, disengaging zone, upstream 120 can be positioned at the upstream or the downstream of desalination unit.In some embodiments, disengaging zone, upstream 120 can be positioned at the downstream of the distillation process of pitch, resinous shale and/or tar sand.After handling, crude oil products leaves contact system 100 by crude oil products pipeline 112.
In some embodiments, make crude oil and the crude oil products blend identical or different with crude oil material.Crude oil products is mixed with the crude oil with different viscosity, therefore obtain the blend product of viscosity between crude oil products viscosity and viscosity of crude.In another example, can make crude oil products and crude oil blend with different TAN and/or MCR content, therefore produce TAN and/or MCR content at the TAN of crude oil products and crude oil and/or the product between the MCR content.The product of blend can be suitable for transportation and/or handle.
As shown in Figure 5, in some embodiments, crude oil material enters contact system 100 by crude oil material pipeline 104 and makes at least a portion crude oil products leave contact system 100 and introduce blend district 130 by pipeline 128.In blend district 130, at least a portion crude oil products and one or more process-streams (for example hydrocarbon stream is as the petroleum naphtha by the separation of produced of one or more crude oil materials), crude oil, crude oil material or its mixture are mixed with the production blend product.Process-stream, crude oil material, crude oil or its mixture are directly introduced blend district 130 or passed through the upstream that logistics pipeline 132 is introduced these blend districts.Mixing system can be arranged in blend district 130 or near blend district 130.Blend product can satisfy by refinery and/or the specified product specification of transportation means.Product specification includes but not limited to the scope or the boundary of api gravity, TAN, viscosity or its combination.Make blend product leave blend district 130 with transportation or processing by blend pipeline 134.
In Fig. 6, unfavorable crude oil enters disengaging zone, upstream 120 by crude oil pipeline 122, and makes that unfavorable crude oil is as discussed previously to be separated to form crude oil material.Crude oil material enters contact system 100 by other crude oil material pipeline 126 then.At least a portion component from unfavorable crude oil is left disengaging zone 120 by pipeline 124.At least a portion crude oil products leaves contact system 100 and enters blend district 130 by crude oil products pipeline 128.Make other process-stream and/or crude oil directly or by logistics pipeline 132 enter blend district 130 and mixes with the formation blend product with crude oil products.Blend product is left blend district 130 by blend pipeline 134.
In some embodiments, crude oil products and/or blend product are transported to refinery and distillation and/or fractionation to produce one or more overhead product cuts.Can handle the overhead product cut to produce commodity such as transport fuel, lubricant or chemical.
In some embodiments, at crude oil material with after catalyzer contacts, the TAN of crude oil products be crude oil material TAN at the most 90%, at the most 50%, at the most 30% or at the most 10%.In some embodiments, the TAN of crude oil products is at the most 1, at the most 0.5, at the most 0.3, at the most 0.2, at the most 0.1 or at the most 0.05.The TAN of crude oil products is generally at least 0.0001 and more generally at least 0.001.In some embodiments, the TAN of crude oil products can be about 0.001-0.5, about 0.01-0.2 or about 0.05-0.1.
In some embodiments, at the most 90%, at the most 50%, at the most 30%, at the most 10%, at the most 5% or at the most 3% of total Ni/V/Fe content of crude oil products Ni/V/Fe content that is crude oil material.In some embodiments, total Ni/V/Fe content of crude oil products is every gram crude oil products about 1 * 10 -7-5 * 10 -5Gram, about 3 * 10 -7-2 * 10 -5Gram or about 1 * 10 -6-1 * 10 -5Gram.In some embodiments, crude oil products contains every gram crude oil products at the most 2 * 10 -5Gram Ni/V/Fe.In some embodiments, about 70-130%, about 80-120% or about 90-110% of total Ni/V/Fe content of crude oil products Ni/V/Fe content that is crude oil material.
In some embodiments, the total metal content in the metal salts of organic acids of crude oil products be in the crude oil material total metal content in the metal salts of organic acids at the most 90%, at the most 50%, at the most 30%, at the most 10% or at the most 5%.In some embodiments, the total content of the metal in the metal salts of organic acids is about 0.1-75%, about 0.5-45%, about 1-25% or about 2-9% of the metal content in the metal salts of organic acids of crude oil material.Usually the organic acid that forms metal-salt includes but not limited to carboxylic acid, mercaptan, imide, sulfonic acid and sulphonate.The example of carboxylic acid includes but not limited to naphthenic acid, phenanthrenecarboxylic acid (phenanthrenic acids) and phenylformic acid.The metal part of metal-salt can comprise basic metal (for example lithium, sodium and potassium), alkaline-earth metal (for example magnesium, calcium and barium), the 12nd row metal (for example zinc and cadmium), the 15th row metal (for example arsenic), the 6th row metal (for example chromium) or its mixture.
In some embodiments, basic metal in the metal salts of organic acids of crude oil products and alkaline-earth metal total content be in the crude oil material basic metal in the metal salts of organic acids and alkaline earth metal content at the most 90%, at the most 80%, at the most 50%, at the most 30%, at the most 10% or at the most 5%.In some embodiments, basic metal in the metal salts of organic acids and alkaline-earth metal total content are organic acid basic metal and about 0.1-75% of alkaline earth salt total content, about 0.5-45%, about 1-25% or about 2-9% in the crude oil material in the crude oil products.
In some embodiments, one or more organic acid zinc salt total contents of crude oil products be in the crude oil material one or more organic acid zinc salt content at the most 90%, at the most 80%, at the most 50%, at the most 30%, at the most 10% or at the most 5%.In some embodiments, the total content of organic acid zinc salt is about 0.1-75% of organic acid zinc salt total content in the crude oil material, about 0.5-45%, about 1-25% or about 2-9% in the crude oil products.
In some embodiments, the chromium in the metal salts of organic acids of crude oil products and or the arsenic total content be in the crude oil material chromium in the metal salts of organic acids and or arsenic content at the most 90%.
In some embodiments, crude oil products contains every gram crude oil products about 1 * 10 -7-5 * 10 -5Gram, about 5 * 10 -7-1 * 10 -5Gram or about 1 * 10 -6-5 * 10- 6 gramsBasic metal in the metal salts of organic acids and alkaline-earth metal.
In some embodiments, the api gravity that contacts the crude oil products of producing from crude oil material and catalyzer is about 70-130% of the api gravity of crude oil material, about 80-120%, about 90-110% or about 100-130% under contact conditions.In some embodiments, the api gravity of crude oil products is about 14-40, about 15-30 or about 16-25.
In some embodiments, the viscosity of crude oil products is at the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30%, at the most 10% or at the most 5% of crude oil material viscosity.In some embodiments, the viscosity of crude oil products be crude oil material viscosity at the most 90%, and the api gravity of crude oil products is about 70-130% of crude oil material api gravity, about 80-120% or about 90-110%.
In some embodiments, total content of heteroatoms of crude oil products be crude oil material total content of heteroatoms at the most 90%, at the most 50%, at the most 30%, at the most 10% or at the most 5%.In some embodiments, total content of heteroatoms of crude oil products be crude oil material total content of heteroatoms at least 1%, at least 30%, at least 80% or at least 99%.
In some embodiments, the sulphur content of crude oil products can be at the most 90%, at the most 50%, at the most 30%, at the most 10% or at the most 5% of crude oil material sulphur content.In some embodiments, the sulphur content of crude oil products is at least 1%, at least 30%, at least 80% or at least 99% of a crude oil material sulphur content.
In some embodiments, the total nitrogen content of crude oil products can be at the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% or at the most 5% of crude oil material total nitrogen content.In some embodiments, the total nitrogen content of crude oil products is at least 1%, at least 30%, at least 80% or at least 99% of a crude oil material total nitrogen content.In some embodiments, the total nitrogen content of crude oil products is about 0.1-75% of crude oil material total nitrogen content, about 0.5-45%, about 1-25% or about 2-9%.In some embodiments, the total nitrogen content of crude oil products is the about 0.00001-0.05 gram of every gram crude oil products, about 0.0001-0.01 gram or about 0.0005-0.001 gram.
In some embodiments, the basic n content of crude oil products can be at the most 95%, at the most 90%, at the most 50%, at the most 30%, at the most 10% or at the most 5% of crude oil material basic n content.In some embodiments, the basic n content of crude oil products is at least 1%, at least 30%, at least 80% or at least 99% of a crude oil material basic n content.
In some embodiments, the oxygen level of crude oil products can be at the most 90%, at the most 50%, at the most 30%, at the most 10% or at the most 5% of crude oil material oxygen level.In some embodiments, the oxygen level of crude oil products can be at least 1%, at least 30%, at least 80% or at least 99% of crude oil material oxygen level.In some embodiments, the carboxylic acid cpd total content of crude oil products can be at the most 90%, at the most 50%, at the most 30%, at the most 10% or at the most 5% of carboxylic acid cpd content in the crude oil material.In some embodiments, the carboxylic acid cpd total content of crude oil products can be at least 1%, at least 30%, at least 80% or at least 99% of carboxylic acid cpd total content in the crude oil material.
In some embodiments, can reduce the organic oxygen compound of selecting in the crude oil material.In some embodiments, carboxylic acid and/or carboxylic metallic salt chemistry before non-carboxylic organic oxygen compound is reduced.Can use common known spectrographic technique (for example infrared analysis, mass spectrum and/or gas-chromatography) to distinguish carboxylic acid and non-carboxylic organic oxygen compound in the crude oil products by the analysis of crude oil products.
Crude oil products oxygen level in some embodiments be the crude oil material oxygen level at the most 90%, at the most 80%, at the most 70% or at the most 50% and the TAN of crude oil products be at the most 90%, at the most 70%, at the most 50%, at the most 30% or at the most 40% of crude oil material TAN.In some embodiments, the oxygen level of crude oil products can for the crude oil material oxygen level at least 1%, at least 30%, at least 80% or at least 99% and the TAN of crude oil products be at least 1%, at least 30%, at least 80% or at least 99% of crude oil material TAN.
In addition, the carboxylic acid of crude oil products and/or carboxylic acid metal's salts contg can for crude oil material at the most 90%, at the most 70%, at the most 50% or at the most 40% and the non-content that contains the organic oxygen compound of carboxylic acid contain within about 70-130% of the organic oxygen compound of carboxylic acid, about 80-120% or the about 90-110% the non-of crude oil material.
In some embodiments, crude oil products comprises the about 0.05-0.15 gram of every gram crude oil products or about 0.09-0.13 gram hydrogen in its molecular structure.Crude oil products can comprise the about 0.8-0.9 gram of every gram crude oil products or about 0.82-0.88 gram carbon in its molecular structure.The crude oil products atomic hydrogen can be within about 70-130% of the atom H/C of crude oil material ratio, about 80-120% or about 90-110% to the ratio of atoms carbon (H/C).Crude oil products atom H/C ratio shows the absorption of hydrogen in the technology and/or consumes relatively little and/or original position generation hydrogen within about 10-30% of crude oil material atom H/C ratio.
Crude oil products comprises the component with boiling spread.In some embodiments, crude oil products comprises every gram crude oil products: at least 0.001 gram or about 0.001-0.5 gram are 100 ℃ hydrocarbon at the most in the boiling Range Distribution Analysis of 0.101MPa; At least 0.001 gram or about 0.001-0.5 gram are at the hydrocarbon of boiling Range Distribution Analysis between about 100 ℃ and about 200 ℃ of 0.101MPa; At least 0.001 gram or about 0.001-0.5 gram are at the hydrocarbon of boiling Range Distribution Analysis between about 200 ℃ and about 300 ℃ of 0.101MPa; At least 0.001 gram or about 0.001-0.5 gram are at the hydrocarbon of boiling Range Distribution Analysis between about 300 ℃ and about 400 ℃ of 0.101MPa; At least 0.001 gram or about 0.001-0.5 gram are at the hydrocarbon of boiling Range Distribution Analysis between about 400 ℃ and about 538 ℃ of 0.101MPa.
In some embodiments, crude oil products comprise every gram crude oil products at least 0.001 gram the boiling Range Distribution Analysis of 0.101MPa for 100 ℃ hydrocarbon and/or at least 0.001 gram at the most at the hydrocarbon of boiling Range Distribution Analysis between about 100 ℃ and about 200 ℃ of 0.101MPa.
In some embodiments, crude oil products can contain every gram crude oil products at least 0.001 gram or at least 0.01 gram petroleum naphtha.In other embodiments, the petroleum naphtha content of crude oil products can for every gram crude oil products at the most 0.6 the gram or at the most 0.8 the gram petroleum naphtha.
In some embodiments, the overhead product content of crude oil products is the about 0.00001-0.5 gram of every gram crude oil products, about 0.001-0.3 gram or about 0.002-0.2 gram.
In some embodiments, the VGO content of crude oil products is the about 0.00001-0.8 gram of every gram crude oil products, about 0.001-0.5 gram, about 0.005-0.4 gram or about 0.01-0.3 gram.
In some embodiments, the residual oil content of crude oil products is at the most 90%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of crude oil material residual oil content.In some embodiments, the residual oil content of crude oil products is about 70-130% of crude oil material residual oil content, about 80-120% or about 90-110%.The residual oil content of crude oil products can be the about 0.00001-0.8 gram of every gram crude oil products, about 0.0001-0.5 gram, about 0.0005-0.4 gram, about 0.001-0.3 gram, about 0.005-0.2 gram or about 0.01-0.1 gram.
In some embodiments, C 5Asphalt content is crude oil material C 5At the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of asphalt content.In some embodiments, the C of crude oil products 5Asphalt content is crude oil material C 5At least 10%, at least 60% or at least 70% of asphalt content.The C of crude oil products 5Asphalt content can be crude oil material C 5About 0.1-75% of asphalt content, about 0.5-45%, about 1-25% or about 2-9%.In some embodiments, crude oil products contains the about 0.0001-0.1 gram of every gram crude oil products, about 0.005-0.08 gram or about 0.01-0.05 gram C 5Bituminous matter.
In some embodiments, the MCR content of crude oil products is at the most 90%, at the most 80%, at the most 50%, at the most 30% or at the most 10% of crude oil material MCR content.In some embodiments, the MCR content of crude oil products is about 0.1-75% of crude oil material MCR content, about 0.5-45%, about 1-25% or about 2-9%.In some embodiments, crude oil products contains the about 0.00001-0.1 gram of every gram crude oil products, about 0.0001-0.05 gram or about 0.001-0.005 gram MCR.
In some embodiments, can be in conjunction with C 5Asphalt content and MCR content are with respect to producing mathematical relation between the high viscosity component of the high viscosity component in the crude oil material in crude oil products.Crude oil material C for example 5The summation of asphalt content and crude oil material MCR content can be represented by S.Crude oil products C 5The summation of asphalt content and crude oil products MCR content can be by S ' expression.Can compare the clean minimizing of summation (S ' to S) with evaluation crude oil material medium-high viscosity component.The S ' of crude oil products can be about 1-99% of S, about 10-90% or about 20-80%.In some embodiments, crude oil products MCR content is to C 5The ratio of asphalt content is about 1.0-3.0, about 1.2-2.0 or about 1.3-1.9.
In some embodiments, crude oil products comprises every gram crude oil products greater than 0 gram but less than 0.01 gram, about 0.000001-0.001 gram or about 0.00001-0.0001 gram total catalyst.Catalyzer helps the stable crude product during can and/or handling in transportation.But the water sepn ability of the friction of the burn into crude oil for inhibiting product of catalyzer crude oil for inhibiting product and/or increase crude oil products.Can dispose method described herein during handling, to add one or more catalyzer described herein to crude oil products.
The performance of the crude oil products of producing from contact system 100 (shown in Fig. 1-6) is different from the performance of crude oil material.These performances can include but not limited to: a) TAN of Jiang Diing; B) viscosity of Jiang Diing; C) total Ni/V/Fe content of Jiang Diing; D) content of the sulphur of Jiang Diing, oxygen, nitrogen or its combination; E) the residual oil content of Jiang Diing; F) C of Jiang Diing 5Asphalt content; G) the MCR content of Jiang Diing; H) api gravity of Zeng Jiaing; I) metal content in the metal salts of organic acids of Jiang Diing; J) stability with respect to crude oil material of Zeng Jiaing; Or k) its combination.
The catalyzer that is used for one or more embodiments of the present invention can comprise one or more metals on one or more base metals and/or the carrier.Metal can or be the form of metallic compound for element form.Can make catalyzer described herein as precursor introduce the zone of action with in the zone of action, become then active with as catalyzer (for example when the crude oil material that makes sulphur and/or sulfur-bearing contacts with precursor).Can be commercial catalysts or can not be commercial catalysts as the catalyzer of said use or the combination of catalyzer.The example of the commercial catalysts of imagination as said use comprises HDS22, HDN60, C234, C311, C344, C411, C424, C344, C444, C447, C454, C448, C524, C534, DN120, DN140, DN190, DN200, DN800, DC2118, DC2318, DN3100, DN3110, DN3300, DN3310, RC400, RC410, RN412, RN400, RN410, RN420, RN440, RN450, RN650, RN5210, RN5610, RN5650, RM430, RM5030, Z603, Z623, Z673, Z703, Z713, Z723, Z753 and Z763, they are available from CRI International, Inc. (Houston, the Texas, U.S.A.).
In some embodiments, the catalyst pack that is used to change the crude oil material performance is contained in one or more 5-10 row metals on the carrier.5-10 row metal includes but not limited to vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, starves, iridium, platinum or its mixture.The compound of 5-10 row metal includes but not limited to oxide compound, nitrate, ammonium salt and the carbonate of 5-10 row metal.The example of 5-10 row metallic compound includes but not limited to molybdic oxide, molybdenum oxide ammonium, carbonic acid molybdenum, tungstic oxide, nickel oxide, nickelous carbonate, nickelous nitrate, cobaltous carbonate and cobalt oxide.
The 5-10 row total metal content of catalyzer can be every gram catalyzer at least 0.0001 gram, at least 0.001 gram, at least 0.01 gram, at least 0.3 gram, at least 0.5 gram, at least 0.6 gram, at least 0.8 gram or at least 0.9 gram.5-10 row total metal content can be the about 0.0001-0.99 gram of every gram catalyzer, about 0.0005-0.5 gram, about 0.001-0.3 gram, about 0.005-0.2 gram or about 0.01-0.1 gram.In some embodiments, except that 5-10 row metal, catalyzer comprises the 15th column element.The example of the 15th column element is a phosphorus.The 15th column element total content of catalyzer can be the about 0.000001-0.1 gram of every gram catalyzer, about 0.00001-0.06 gram, about 0.00005-0.03 gram or about 0.0001-0.001 gram.In other embodiments, catalyzer does not comprise the 15th column element.
In some embodiments, catalyzer comprises the 6th row metal and one or more combinations from the metal of the 5th row and/or 7-10 row.The mol ratio of the 6th row metal pair the 5th row metal can be about 0.1-20, about 1-10 or about 2-5.The mol ratio of the 6th row metal pair 7-10 row metal can be about 0.1-20, about 1-10 or about 2-5.In some embodiments, except that the 6th row metal and one or more combinations from the metal of the 5th row and/or 7-10 row, catalyzer comprises the 15th column element.In other embodiments, catalyzer comprises the 6th row metal and the 10th row metal.The mol ratio of whole the 6th row metals of whole the 10th row metal pairs can be about 1-10 or about 2-5 in the catalyzer.In some embodiments, catalyzer comprises the 5th row metal and the 10th row metal.The mol ratio of whole the 5th row metals of whole the 10th row metal pairs can be about 1-10 or about 2-5 in the catalyzer.
In some embodiments, catalyzer comprises the 6th row metal.The 6th row total metal content of catalyzer can be every gram catalyzer at least 0.00001 gram, at least 0.01 gram, at least 0.02 gram and/or about 0.0001-0.6 gram, about 0.001-0.3 gram, about 0.005-0.2 gram or about 0.01-0.1 gram.In some embodiments, catalyzer comprises the about 0.0001-0.2 gram of every gram catalyzer, about 0.001-0.08 restrains or about 0.01-0.06 restrains the 6th row metal.In some embodiments, except that the 6th row metal, catalyzer comprises the 15th column element.
In some embodiments, catalyzer comprises the combination of the metal of the 6th row metal and one or more 7-10 row.The 7-10 row total metal content of catalyzer can be the about 0.0001-0.1 gram of every gram catalyzer, about 0.001-0.05 gram or about 0.01-0.03 gram.In some embodiments, catalyzer comprises the about 0.01-0.15 gram molybdenum of every gram catalyzer and about 0.001-0.05 gram nickel.In some embodiments, catalyzer also comprises the about 0.001-0.05 gram of every gram catalyzer iron.
In some embodiments, catalyzer comprises the about 0.01-0.15 gram of every gram catalyzer molybdenum, about 0.001-0.05 gram nickel, about 0.001-0.05 gram iron and about 0.0001-0.05 gram phosphorus.
In some embodiments, 5-10 row metal is introduced in the carrier or on carrier deposition to form catalyzer.In some embodiments, introduce the combination of 5-10 row metal and the 15th column element in the carrier or formation of deposits catalyzer on carrier.In the embodiment of loaded metal and/or element, the weight of catalyzer comprises all carriers, all metals and all elements therein.Carrier can be porous and can comprise refractory oxide, porous carbon sill, zeolite or its combination.Refractory oxide can include but not limited to aluminum oxide, silicon-dioxide, silica-alumina, titanium oxide, zirconium white, magnesium oxide or its mixture.Carrier can be from commercial manufacturers such as Criterion Catalysts and Technologies LP (Houston, Texas, U.S.A.) acquisition.The porous carbon sill includes but not limited to gac and/or porous graphite.The example of zeolite comprises Y-zeolite, β zeolite, mordenite, ZSM-5 zeolite and ferrierite.Zeolite can be from commercial manufacturers such as Zeolyst (Valley Forge, Pennsylvania, U.S.A.) acquisition.Can and/or select carrier based on various required characteristic preparations.The example of described characteristic include but not limited to pore volume, mean pore size, pore volume distribution, surface-area and on the certain pore size scope or among the per-cent in hole.
In some embodiments, the preparation carrier makes the mean pore size of carrier be at least 90 , at least 110 , at least 130 , at least 150 , at least 170  or at least 180 .In some embodiments, form paste by mixing water and carrier and prepare carrier.In some embodiments, in paste, add acid to help extruding of paste.Add entry and diluted acid has required denseness so that can extrude paste with certain quantity with by the method that requires.The example of acid includes but not limited to nitric acid, acetate, sulfuric acid and hydrochloric acid.
Can use common known catalyzer extrusion method and catalyzer cutting method to extrude and cut paste to form extrudate.Can be with extrudate thermal treatment certain hour (for example about 0.5-8 hour) and/or reach required level under the temperature of about 65-260 ℃ or about 85-235 ℃ up to the moisture content of extrudate.Can with heat treated extrudate under the temperature of about 800-1200 ℃ or about 900-1100 ℃ further thermal treatment be the carrier of at least 150  to form mean pore size.The pore volume distribution of carrier is on pore diameter range.In some embodiments, carrier comprises the aperture and is at least 350 , at least 400 , at least 500  or at least 1000  or be the hole of about 350-5000 , about 400-1000  or about 500-900 , and described hole provides at the most 15%, at the most 10%, at the most 5% at the most 3%, at the most 1% or at the most 0.5% of carrier total pore volume.
In some embodiments, carrier comprises gamma-alumina, θ aluminum oxide, δ aluminum oxide, αYang Hualv or its combination.By the amount of gamma-alumina, δ aluminum oxide, αYang Hualv or its combination of every gram support of the catalyst of x ray diffraction determination can be for about 0.0001-0.99 gram, about 0.001-0.5 gram, about 0.01-0.1 restrains or 0.1 restrain at the most.In some embodiments, carrier comprises every gram carrier at least 0.5 gram, at least 0.8 gram, at least 0.9 gram or at least 0.95 gram gamma-alumina.In some embodiments, carrier comprises the about 0.5-0.99 gram of every gram carrier, about 0.6-0.9 gram or about 0.7-0.8 gram gamma-alumina.In some embodiments, by the carrier of x ray diffraction determination separately or with the θ alumina content of other form aluminum oxide combination be the about 0.1-0.99 gram of every gram carrier, about 0.5-0.9 restrains or about 0.6-0.8 restrains.In some embodiments, carrier can contain every gram carrier at least 0.1 gram, at least 0.3 gram, at least 0.5 gram or at least 0.8 gram θ aluminum oxide by the x ray diffraction determination.
In some embodiments, carrier contain every gram carrier at the most 0.2 the gram, at the most 0.1 the gram, at the most 0.08 the gram, at the most 0.06 the gram, at the most 0.05 the gram, at the most 0.04 the gram, at the most 0.03 the gram, at the most 0.02 the gram or at the most 0.01 the gram silicon-dioxide.In some embodiments, carrier contains the about 0.001-0.2 gram of every gram carrier or about 0.01-0.1 gram silicon-dioxide.In some embodiments, carrier comprises the combination of silicon-dioxide and aluminum oxide.
The catalyzer of load can use common known catalyst preparation technology preparation.The example of Preparation of Catalyst is described in people's such as Gabrielov U.S. patent Nos.6,218,333; People such as Gabrielov 6,290,841, among the open No.US 2003/0111391 of U.S. patent application of people's such as Boon 5,744,025 and Bhan, all these disclosures are herein incorporated by reference.
In some embodiments, can be with carrier and melts combine to form catalyzer.In some embodiments, with carrier with melts combine before thermal treatment under the temperature about 400-1200 ℃, about 450-1000 ℃ or about 600-900 ℃.In some embodiments, can during Preparation of catalysts, use the dipping auxiliary agent.The example of dipping auxiliary agent comprises hydrogen peroxide, organic acid, amine, ethylenediamine tetraacetic acid (EDTA) (EDTA), ammonia or its mixture.The example of amine includes but not limited to alkanolamine, ammonia, alkylamine, aromatic amine and substituted ammonium compound.Organic acid includes but not limited to citric acid, tartrate, oxalic acid, propanedioic acid, oxysuccinic acid or its mixture.
In some embodiments, can be that about 3 metallic solution combines at the most with pH with carrier.The pH of metallic solution can be about 1-3 or about 1.5-2.5.The pH of control metallic solution can promote that metal is dispensed in the carrier.When under identical contact conditions, being used to handle crude oil material, compare with the life-span of conventional catalyst, use the dispersive of this pH controlled condition preparation or the catalyst life that basic dispersive metal catalyst can have increase.
Metallic solution can comprise the 6th row metal.In some embodiments, metallic solution comprises the combination of the 6th row metal and 7-10 row metal.In some embodiments, metallic solution comprise the 15th column element and the 6th row metal combination or with the combination of the 6th row metal and 7-10 row metal.
In some embodiments, can use mineral acid and/or organic acid composition that the pH regulator of metallic solution is arrived the required pH of pH3 at the most.Mineral acid includes but not limited to phosphoric acid, nitric acid, sulfuric acid or its mixture.
In some embodiments, prepare metallic solution by mixing one or more 6-10 row metallic solutions with different pH values.PH can be mixed for the different 6-10 row metallic solutions of about 0.1-4 or about 1-3 with pH for the 6-10 row metallic solution of about 4-7 or about 5-6.In some embodiments, 6-10 row metallic solution comprises dipping auxiliary agent, mineral acid, organic acid, the 15th column element or its mixture.
In some embodiments, can form catalyzer by in carrier, being sequentially added into or introducing multiple 5-10 row metal (" covering ").On the carrier top of the metal that comprises basic uniform concentration, cover the useful catalytic performance that metal provides catalyzer usually.The thermal treatment carrier tends to improve the catalytic activity of catalyzer after each covering of metal.The method of using covering method to prepare catalyzer is described in the open No.US2003/0111391 of U.S. patent application of Bhan.
In some embodiments, by preparing carrier/7-10 row metal mixture in conjunction with carrier and one or more 7-10 row metals.In embodiments, the mixture of acquisition comprises every gram carrier/about 0.01-0.1 of 7-10 row metal mixture and restrains 7-10 row metal.Can be with carrier/7-10 row metal mixture in thermal treatment several hours under the temperature of about 50-100 ℃ or about 60-90 ℃ and about 2 hours of thermal treatment under the temperature about 400-700 ℃, about 450-650 ℃ or about 500-600 ℃ then.Can be with the metallic carrier that obtains and the 7-10 row melts combine of the 6th row metal and optional additional content, make that finished catalyst comprises every gram catalyzer at least 0.3 gram, at least 0.1 gram or at least 0.08 restrains the 6th row metal and the whole 7-10 row of every gram catalyzer metal is about 0.01-0.2 gram or about 0.05-0.1 gram.Can be with the catalyzer that obtains in thermal treatment several hours under the temperature of about 50-100 ℃ or about 60-90 ℃ and about 2 hours of thermal treatment under the temperature about 350-500 ℃ or 400-450 ℃ then.In some embodiments, can with the 15th column element and carrier/7-10 row metal mixture and/or with the 6th row melts combine.
Typically, can adopt suitable mixing equipment to mix on 5-10 row metal and carrier to form 5-10 row metal/carrier mixture.The example of suitable mixing equipment comprises cylinder, set casing or groove, Muller mixing machine (for example batch type or type continuously), impact mixing machine and any other common known mixing machine or equipment of 5-10 row metal/carrier mixture is provided suitably.In some embodiments, with material mixing up to 5-10 row metal is disperseed in carrier substantially equably.
In some embodiments, after in conjunction with carrier and metal, with catalyzer thermal treatment under the temperature of about 150-750 ℃, about 200-740 ℃ or about 400-730 ℃.
In some embodiments, can with catalyzer in the presence of warm air and/or the oxygen-rich air under about 400-1000 ℃ temperature thermal treatment make at least a portion 5-10 row metal changed into corresponding metal oxide to remove volatile matter.
But in other embodiments, can with catalyzer in the presence of the air under about 35-500 ℃ temperature thermal treatment 1-3 hour time can obviously not transform 5-10 row metal to remove most of volatile constituent and become metal oxide.Zhi Bei catalyzer is called " not incinerating " catalyzer by this method.When adopting this mode to prepare catalyzer, combine with vulcanization process, can be on carrier basic dispersed active metal.This Preparation of catalysts is described in people's such as Gabrielov U.S. patent No.6, in 218,333 and people's such as Gabrielov U.S. patent No.6,290,841.
In some embodiments, can be with θ alumina supporter and 5-10 row melts combine to form θ alumina supporter/5-10 row metal mixture.Can be the catalyzer of at least 230  with the mean pore sizes that forms pore size distribution with the thermal treatment under at least 400 ℃ temperature of θ alumina supporter/5-10 row metal mixture.Typically, this thermal treatment is being implemented under 1200 ℃ the temperature at the most.
In some embodiments, the bulk metal catalyst that is used to change the crude oil material performance comprises one or more 6-10 row metals.The 6-10 row total metal content of bulk metal catalyst can be every gram catalyzer at least 0.3 gram, at least 0.5 gram, at least 0.6 gram, at least 0.8 gram or at least 0.9 gram.6-10 row total metal content can be the about 0.3-0.99 gram of every gram catalyzer, about 0.5-0.9 gram or about 0.6-0.8 gram.
In some embodiments, except that 6-10 row metal, catalyzer comprises the 15th column element.The 15th column element total content of bulk metal catalyst can be the about 0.000001-0.1 gram of every gram catalyzer, about 0.00001-0.06 gram, about 0.00005-0.03 gram or about 0.0001-0.001 gram.
In some embodiments, bulk metal catalyst can comprise binding agent.Binding agent can be oxide compound, carbon, zeolite or its mixture of silicon-dioxide, aluminum oxide oxide compound, zinc oxide, 6-10 row metal.In some embodiments, catalyzer comprise every gram catalyzer at the most 0.2 the gram, at the most 0.1 the gram, at the most 0.05 the gram, at the most 0.01 the gram or at the most 0.005 the gram binding agent.
Bulk metal catalyst can be according to described in the following document and prepare: people's such as Aqudelo U.S. patent No.4,937,218; People's such as Soled 6,162,350; With people's such as Riley 6,783,663; People's such as open Nos.US2004/0182749 of people's such as Domokos U.S. patent application and Domokos US 2004/0235653; Existing with people such as Landau, " Hydrosulfurization of Methyl-Substituted Dibenzothiophenes:Fundamental Study of Routes to Deep Desulfurization; Journalof Catalysis; 1996; Vol.159; described in the pp.236-235, all these disclosures are herein incorporated by reference.
In some embodiments, the slurry of one or more 6-10 row metals in water or other protic liquid contacted to form 6-10 row metal/binding agent slurry with the slurry of water, basic cpd and binding agent under about 25-95 ℃ temperature.6-10 row metal paste can comprise every gram slurry 0.01-0.8 gram, 0.02-0.5 gram or 0.05-0.3 and restrain 6-10 row metal.In some embodiments, basic cpd is an ammonia.The amount of basic cpd can be at least 0.5 mole, at least 0.7 mole, at least 0.8 mole, at least 0.9 mole on every mole of 6-10 row metal or 2 moles at the most, based on the oxide form meter of 6-10 row metal.In some embodiments, binding agent can be silicon-dioxide, aluminum oxide, silica/alumina, titanium oxide, zirconium white or its mixture.
Can with 6-10 row metal/binding agent slurry at ambient temperature and/or under slurry temperature, keep certain hour (for example at least 10 minutes, at least 30 minutes or at least 240 minutes) and as needs cool off then.Bulk metal catalyst can be used general isolation technique (for example filtration, spraying drying, expansion drying, evaporation and underpressure distillation) and pulp separation.Can be with bulk metal catalyst in about 25-95 ℃, about 55-90 ℃ or about 70-80 ℃ of following thermal treatment.In some embodiments, with bulk metal catalyst in about 100-600 ℃, about 120-400 ℃ or further thermal treatment under 300 ℃ the temperature at the most.In some embodiments, bulk metal catalyst can powdered, moulding and/or combine with other material.
Bulk metal catalyst can use the X-ray diffraction method to characterize.In some embodiments, bulk metal catalyst can not show the obvious reflection that is attributable to 6-10 row metal component.May not show that by the detected obvious reflection of X-ray diffraction method bulk metal catalyst is essentially amorphous or unbodied.
In some embodiments, carrier (commercial carrier or as the carrier of said preparation) can be combined with the catalyzer and/or the bulk metal catalyst of load.In some embodiments, the catalyzer of load can comprise the 15th column element.For example the catalyzer and/or the bulk metal catalyst of load can be changed into the powder of mean particle size for about 1-50 micron, about 2-45 micron or about 5-40 micron.Powder can be combined with carrier to form and embed metal catalyst.In some embodiments, the mean pore sizes that powder can be combined and use then standard technique to extrude with the formation pore size distribution with carrier is the catalyzer of about 80-200  or about 90-180  or about 120-130 .Catalyzer is combined with carrier allow at least a portion metal under the surface of the embedding metal catalyst that obtains, to exist in some embodiments, make less with the metal of comparing from the teeth outwards that in not embedding metal catalyst, occurs in addition.In some embodiments, on catalyst surface, have less metal and prolong receiving the order of catalyzer and/or catalytic activity by allowing at least a portion metal to move to catalyst surface during use.Metal can move to the surface of catalyzer at the period of contact of catalyzer and crude oil material by the erosion of catalyst surface.
In some embodiments, catalyzer can characterize by pore structure.Various pore structure parameters include but not limited to aperture, pore volume, surface-area or its combination.Catalyzer can have the distribution of aperture total amount to the aperture.The mean pore sizes of pore size distribution can be about 30-1000 , about 50-500  or about 60-300 .In some embodiments, every gram catalyzer comprises the mean pore sizes of pore size distribution of catalyzer of at least 0.5 gram gamma-alumina for about 50-500 , about 60-200 , about 90-180 , about 100-140  or about 120-130 .In other embodiments, the every gram catalyzer mean pore sizes of pore size distribution that comprises the catalyzer of at least 0.1 gram θ aluminum oxide is about 180-500 , about 200-300  or about 230-250 .This mean pore sizes typically is 1000  at the most.
In some embodiments, the mean pore sizes of pore size distribution is greater than 110 , at least 120 , at least 130 , at least 140 , at least 150 , at least 200  or at least 250 .This mean pore sizes typically is 300  at the most.The mean pore sizes of pore size distribution can be about 115-290 , about 120-190 , about 130-180  or about 140-160 .
In some embodiments, has at least 60% the aperture of pore size distribution mesopore sum of catalyzer of pore size distribution within about 45  of the mean pore sizes of pore size distribution, about 35 , about 30 , about 25  or about 20 .The mean pore sizes of pore size distribution is in the embodiment of at least 180 , at least 200  or at least 230  therein, in the pore size distribution total hole count greater than 60% aperture within about 50  of mean pore sizes, about 70  or about 90 .In some embodiments, catalyzer has mean pore sizes and is the pore size distribution of about 180-500 , about 200-400  or about 230-300 , always reaches in the pore size distribution at least 60% of hole count aperture within about 50  of mean pore sizes, about 70  or about 90 .
In some embodiments, the pore volume in hole can be 0.3cm at least 3/ g, 0.7cm at least 3/ g or 0.9cm at least 3/ g.In some embodiments, the pore volume in hole can be about 0.3-0.99cm 3/ g, about 0.4-0.8cm 3/ g or about 0.5-0.7cm 3/ g.In some embodiments, the aperture provides at the most 10%, at the most 5%, at the most 3%, at the most 1% or at the most 0.5% of catalyzer total pore volume for the hole of at least 350 , at least 400 , at least 500 , at least 1000 , at least 3000  or at least 5000 .This aperture can be about 350-5000 , about 400-1000  or about 500-900 .The total pore volume that is provided by the hole with this aperture can be about 0-9%, about 0.1-5% or about 0.5-1%.
In some embodiments, have mean pore sizes and be 100m at least for the surface-area of the catalyzer of the pore size distribution of about 60-500  2/ g, 120m at least 2/ g, 170m at least 2/ g, 220m at least 2/ g or 270m at least 2/ g.This surface-area can be about 100-300m 2/ g, about 120-270m 2/ g, about 130-250m 2/ g or about 170-220m 2/ g.In some embodiments, the surface-area of contoured body metal catalyst is 30m at least 2/ g, 60m at least 2/ g or for about 10-350m 2/ g.
In some embodiments, (before using) uses technology known in the art (ACTICA for example TMTechnology, CRI International, Inc.) catalyzer and/or the catalyst precursor with bulk metal catalyst, load vulcanizes to form metallic sulfide.In some embodiments, catalyzer and/or catalyst precursor drying can be vulcanized then.Alternatively, can contact and original position sulphurized catalyst or catalyst precursor with the crude oil material that comprises sulfocompound by catalyzer or catalyst precursor.The original position sulfuration can utilize gas vulcanization hydrogen or liquid phase vulcanizing agent such as the organosulfur compound (comprising alkyl sulfur compounds, polysulfide, mercaptan and sulfoxide) under the hydrogen existence.The sulfuration process of offing normal is described in people's such as Seamans U.S. patent Nos.5,468,372 and people such as Seamans 5,688,736 in, all these disclosures are herein incorporated by reference.
In some embodiments, first type catalyzer (" first catalyzer ") comprises the combination of 5-10 row metal and θ alumina supporter.First catalyzer has mean pore sizes and is at least 180 , at least 220 , at least 230 , at least 250 , at least 300  or the pore size distribution of 500  at the most.Carrier can comprise every gram carrier at least 0.1 gram, at least 0.5 gram or at least 0.9 gram or 0.999 restrain the θ aluminum oxide at the most.In some embodiments, the αYang Hualv content of carrier is less than every gram catalyzer 0.1 gram αYang Hualv.In some embodiments, catalyzer comprises every gram catalyzer 0.1 gram the 6th row metal and every gram catalyzer at least 0.0001 gram the 6th row metal at the most.In some embodiments, the 6th row metal is molybdenum and/or tungsten.In some embodiments, first catalyzer can comprise the 5th row metal.The first catalyzer tolerable removes basic metal and the alkaline-earth metal in the metal salts of organic acids.First catalyzer can remove at least a portion organic acid basic metal and/or alkaline earth salt usually, and it can reduce the viscosity and/or the surface tension of crude oil material.This can make, and the crude oil material that obtains is easier to be contacted with the catalyzer that is positioned at after first catalyzer.
In some embodiments, second type catalyzer (" second catalyzer ") comprises the combination of 6-10 row metal and carrier.The mean pore sizes of second catalyzer is greater than 110 .Second catalyzer contains the aperture and is the hole of at least 350 , and they provide at the most 10% of second catalyst pore volume.In some embodiments, by every gram second catalyzer, the 6th row total metal content of second catalyzer restrains for about 0.0001-0.1 for about 0.0001-0.3 gram, 7-10 row total metal content and the 15th column element total content is about 0.00001-0.1 gram.In some embodiments, second support of the catalyst contains every gram carrier at least 0.9 gram gamma-alumina.Second catalyzer usually can: remove the component that at least a portion causes the thermal destruction of being measured by MCR from crude oil material; Remove at least a portion nitrogen-containing organic compound; With remove at least a portion C from crude oil material 5Bituminous matter.In some embodiments, second catalyzer also removes at least a portion residual oil, removes at least a portion Ni/Fe/V, removes at least a portion and causes full-bodied component, and/or remove the component that at least a portion causes low api gravity.
In some embodiments, the mean pore sizes of the catalyzer of the third type (" the 3rd catalyzer ") can be about 250 .The 3rd catalyzer contains the aperture and is the hole of at least 350 , and they provide at the most 10% of the 3rd catalyst pore volume.The 3rd catalyzer usually can: remove the component that at least a portion causes the thermal destruction of being measured by MCR from crude oil material; Remove a part and contain heteroatomic compound; And/or remove a part of C from crude oil material 5Bituminous matter.In some embodiments, the 3rd catalyzer also removes the component that causes high viscosity and/or low api gravity.
In some embodiments, second catalyzer and the 3rd catalyzer have the mean pore sizes of selection and have the hole of selecting the aperture provides at the most 10%, at the most 5%, at the most 3% or at the most 1% of pore volume.These catalyzer are strengthened C in the crude oil material 5The minimizing of asphalt content and/or at least a portion cause the reduction of the component of the crude oil material thermal destruction of being measured by MCR.But use has the catalyzer of the mean pore sizes of selection and selecting hole volume to reduce the number of these compound minimum catalyst.Typically, crude oil material is at first adopted conventional catalyst handle to remove C with low relatively catalytic activity 5Bituminous matter and/or cause the component of thermal destruction.By allowing most relatively C 5Bituminous matter and/or other component enter the hole and the filling orifice of catalyzer, and the conventional catalyst of these types removes C usually 5Bituminous matter and/or other component.Because the hole is filled, can be with C 5Bituminous matter and/or other component remove from crude oil material physics.In case the hole is filled and/or stops up, the lost of life of conventional catalyst.Enter the C of catalyst pores by restriction 5The part of bituminous matter and/or other component (if any) has the catalyst removal C that selects mean pore sizes and selecting hole volume 5Bituminous matter and/or cause other component of thermal destruction.Like this, life of catalyst can be owing to catalyzer and C 5Bituminous matter and/or other component contact and shorten.
In some embodiments, second catalyzer and/or the 3rd catalyzer can remove basic metal and the alkaline-earth metal at least a portion metal salts of organic acids.In some embodiments, second catalyzer and/or the 3rd catalyzer can remove at least a portion organic acid basic metal and/or alkaline earth salt, and these salt cause forming increase crude oil material viscosity and/or capillary compound.In some embodiments, second catalyzer and/or the 3rd catalyzer can remove at least a portion and cause the full-bodied relatively component of crude oil material.
In some embodiments, the 4th type catalyzer (" the 4th catalyzer ") can be by obtaining to produce catalyst precursor in conjunction with carrier and the 6th row metal.Typically, catalyst precursor is heated at least 100 ℃ about 2 hours.In some embodiments, the 15th column element content of the 4th catalyzer can be the about 0.001-0.03 gram of every gram the 4th catalyzer, 0.005-0.02 gram or 0.008-0.01 gram.When as said when being used to handle crude oil material, the 4th catalyzer can show tangible activity and stability.In some embodiments, catalyst precursor is heated in the presence of one or more sulphur compounds under less than 500 ℃ temperature.The 4th catalyzer can remove a part of nitrogenous compound from crude oil material usually.With respect to the corrosive nature of crude oil material, remove the corrosive nature that nitrogenous compound has reduced crude oil products.The 4th catalyzer can remove the component that at least a portion causes crude oil material TAN, removes the metal at least a portion metal salts of organic acids, removes at least a portion Ni/V/Fe, and/or removes at least a portion and cause the full-bodied component of crude oil material.
In some embodiments, the 4th catalyzer also can reduce at least a portion MCR content of crude oil material, keeps crude oil material/total product stability simultaneously.In some embodiments, the 6th row metal content of the 4th catalyzer can for the about 0.0001-0.1 gram of every gram the 4th catalyzer, about 0.005-0.05 gram or about 0.001-0.01 restrains and the 10th row metal content is the about 0.0001-0.05 gram of every gram the 4th catalyzer, about 0.005-0.03 gram or about 0.001-0.01 gram.Under the pressure of the temperature of about 300-500 ℃ or about 350-450 ℃ and about 0.1-20MPa, about 1-10MPa or about 2-8MPa, the 4th catalyzer can promote at least a portion in the crude oil material to cause the reduction of the component of MCR.
In some embodiments, the 5th type catalyzer (" the 5th catalyzer ") can be bulk metal catalyst.The 5th catalyzer comprises every gram the 5th catalyzer at least 0.3 gram 6-10 row metal.In some embodiments, the 5th catalyzer also comprises binding agent.In some embodiments, the 5th catalyzer comprises the combination of the 6th row metal and the 9th row metal and/or the 10th row metal.The 5th catalyzer can take off the component that at least a portion causes the thermal destruction of being measured by MCR usually.In some embodiments, the 5th catalyzer also can remove at least a portion C 5Bituminous matter, at least a portion contain heteroatomic organic compound, the total Ni/V/Fe content of at least a portion, at least a portion and cause that full-bodied component and/or at least a portion cause the component of low api gravity.
With the crude oil material period of contact, at the temperature of at least 370 ℃, at least 380 ℃, at least 390 ℃, at least 400 ℃ or at least 420 ℃ and 8Nm at least 3/ m 3, 10Nm at least 3/ m 3Or 14Nm at least 3/ m 3Pressure under, first catalyzer, second catalyzer, the 3rd catalyzer, the 4th catalyzer and the 5th catalyzer can be stablized 3 months, 6 months or 1 year at least at least at least.
In some embodiments, crude oil material can with contact with other catalyzer after first catalyzer contacts.Other catalyzer can be one or more following materials: second catalyzer, the 3rd catalyzer, the 4th catalyzer, the 5th catalyzer, commercial catalysts described herein or its combination.
Other embodiment of first catalyzer, second catalyzer, the 3rd catalyzer, the 4th catalyzer and the 5th catalyzer also can with different preparations described herein and/or use.
Select the application's catalyzer and red-tape operati condition can produce the crude oil products that has the performance of metal content in the MCR content, nitrogen content, metal salts of organic acids of change and/or selection with respect to crude oil material.The crude oil products that obtains can have with respect to the crude oil material augmented performance, is acceptable more for transportation and/or refining therefore.
The improvement in performance of the arrangement may command crude oil material of two or more catalyzer order in the order of selecting.For example can reduce the metal in the metal salts of organic acids in the crude oil material before causing in the crude oil material MCR and/or heteroatomic component reducing at least a portion.
In some embodiments, the arrangement of catalyzer and/or selection can improve the stability of life of catalyst and/or crude oil material/total product mixture.During handling, improve catalyst life and/or crude oil material/total product stabilized with mixture can make contact system operation at least 3 months, at least 6 months or at least 1 year and do not change catalyzer in the zone of action.Life of catalyst can be measured by following mode: measure the temperature variation of the interior zone of action of certain hour (for example month, two months, three months, six months and/or a year), other contact conditions keeps constant relatively some product specification of feasible maintenance simultaneously.About 15 ℃, about 13 ℃ or about 10 ℃ temperature rising requirement can show that the effectiveness of catalyzer reduces more than the initial temperature of processing requirements.
The catalyst combination of selecting can allow to reduce at least a portion MCR content, at least a portion Ni/V/Fe, at least a portion C from crude oil material before other performance that changes crude oil material 5Metal in the metal salts of organic acids of bituminous matter, at least a portion, at least a portion cause component, at least a portion residual oil or its combination of TAN, the stability (for example keeping the crude oil material P-value greater than 1.5) of crude oil material/total product mixture during keeping simultaneously handling.Alternatively, can contact with the catalyzer of selection by crude oil material and reduce C cumulatively 5Bituminous matter, TAN and/or api gravity.Cumulative ground and/or the ability that optionally changes the crude oil material performance can keep the stability of crude oil material/total product mixture during handling.
In some embodiments, first catalyzer can remove metal at least a portion metal salts of organic acids from crude oil material.For example with respect to crude oil material reduce the metal at least a portion metal salts of organic acids in crude oil material/total product mixture suppress to be positioned at the downstream other catalyzer obstruction and therefore increase and can operate contact system and the time span of make-up catalyst not.In some embodiments, remove metal at least a portion metal salts of organic acids from crude oil material and can increase one or more life of catalyst that are positioned at after first catalyzer.
Second catalyzer, the 3rd catalyzer and/or the 4th catalyzer can be positioned at the downstream of first catalyzer.Crude oil material/total product mixture and second catalyzer, the 3rd catalyzer and/or the 4th catalyzer further contacts can reduce MCR content, reduce Ni/V/Fe content, reduce sulphur content, reduce oxygen level, reduce viscosity and/or further reduce the content of the metal in the metal salts of organic acids.
In some embodiments, the 5th catalyzer can be positioned at the downstream of commercial catalysts.Commercial catalysts can be used for removing at least a portion Ni/V/Fe in the crude oil material.Crude oil material/total product mixture can reduce MCR content, reduces sulphur content, reduces nitrogen content and/or reduce oxygen level with further contact of the 5th catalyzer.
In some embodiments, select with the catalyzer of controlled contact conditions (for example temperature and/or crude oil material flow) combination and/or hydrogen that the order of catalyzer can help to reduce crude oil material absorbs, crude oil material/total product stabilized with mixture during keep handling and with respect to one or more performances of each performance change crude oil products of crude oil material.The stability of crude oil material/total product mixture may be subjected to be separated and to influence from the crude oil material/difference of total product mixture.Being separated can insoluble, the bituminous matter in crude oil material/total product mixture be flocculated from crude oil material/total product mixture by for example crude oil material and/or crude oil products, component precipitates from crude oil material/total product mixture or its combination and causing.
Some time during period of contact, can change crude oil material and/or the total product concentration in crude oil material/total product mixture.When the formation owing to crude oil products changed the concentration of total product in crude oil material/total product mixture, the component of crude oil material and/or the component of the total product solubleness in crude oil material/total product mixture was tended to change.For example crude oil material can comprise the component that is insoluble to crude oil material when handling beginning.(for example TAN, MCR, C because the performance of crude oil material 5Bituminous matter, P-value or its combination) change, described component can be tended at crude oil material/total product mixture more indissoluble that becomes.In some cases, crude oil material and total product can form two mutually and/or insoluble each other.Changes in solubility also can cause forming the crude oil material/total product mixture of two or more phases.Variation by bitum flocculation, crude oil material and total product concentration and/or component precipitation form two and tend to shorten one or more life of catalyst mutually.In addition, may reduce the efficient of technology.The crude oil products that for example may must re-treatment crude oil material/total product mixture have desired properties with production.
During handling, can monitor the P-value and the stability that can evaluate technology, crude oil material and/or crude oil material/total product mixture of crude oil material/total product mixture.Typically, 1.5 P-value shows that common generation bituminous matter flocculates from crude oil material at the most.If the P-value be initially at least 1.5 and this P-value in period of contact increase or relatively stable, then this shows that crude oil material is metastable at period of contact.Can be by controlling contact conditions, selecting, control crude oil material/total product stabilized with mixture of evaluating by the P-value by catalyst selectivity ordering or its combination by catalyzer.This control of contact conditions can comprise control LHSV, temperature, pressure, hydrogen absorption, crude oil material flow or its combination.
Catalyzer described herein can promote the reduction of MCR content and viscosity and keep the stability of crude oil material/total product mixture simultaneously and keep life of catalyst under high temperature and high pressure.
In some embodiments, the control contact conditions makes that the temperature in one or more zone of action can be different.Operation allows the selectivity of crude oil material performance to change under differing temps, keeps the stability of crude oil material/total product mixture simultaneously.Crude oil material enters first zone of action when technology begins.The first contact temperature is the temperature in first zone of action.Other contact temperature (for example second temperature, the 3rd temperature, the 4th temperature etc.) is the temperature that is arranged in zone of action afterwards, first zone of action.The first contact temperature can be about 100-420 ℃, and contacting temperature with second can be for being different from first scope that contacts about 20-100 ℃ of temperature, about 30-90 ℃ or about 40-60 ℃.In some embodiments, the second contact temperature is greater than the first contact temperature.Having different contact temperature can be with respect to the TAN and/or the C of crude oil material 5Asphalt content reduces TAN and/or the C in the crude oil products 5Asphalt content is if the reduction degree of this moment contacts TAN and/or the C that temperature are identical or have each other within 10 ℃ the time than first and second 5Bitum reduction degree is bigger.
Embodiment
Below provide preparing carriers, Preparation of Catalyst and have that selection of catalysts is arranged and the non-limiting example of the system of controlled contact conditions.
Embodiment 1. preparation support of the catalyst(Michigan is U.S.A.) with 585 gram water and 8 gram ice nitric acid preparation in 35 minutes carrier for CriterionCatalysts and Technologies LP, Michigan City by grinding 576 gram aluminum oxide.The grinding mixture that obtains is extruded by the 1.3mm die plate, thermal treatment and further thermal treatments under 918 ℃ between 90 ℃ and about 125 ℃, obtaining 650 gram mean pore sizes like this is the carrier of 182 .Heat treated carrier is put into the Lindberg stove.Furnace temperature was elevated to about 1000-1100 ℃ and keep 2 hours to produce carrier in this scope in 1.5 hours.Carrier comprises by every gram carrier 0.0003 gram gamma-alumina of x ray diffraction determination, 0.0008 gram αYang Hualv, 0.0208 gram δ aluminum oxide and 0.9781 gram θ aluminum oxide.The surface-area of carrier is 110m 2/ g and total pore volume are 0.821cm 3/ g.Carrier has the pore size distribution that mean pore sizes is 232 , and the aperture in 66.7% hole of pore size distribution mesopore sum is within 85  of mean pore sizes.
Embodiment 1 shows how to prepare the carrier that every gram carrier comprises at least 0.1 gram θ aluminum oxide.
Embodiment 2. preparations comprise the molybdenum catalyst of θ aluminum oxidePrepare molybdenum catalyst in the following way.To mix with the molybdenum dipping solution by the alumina supporter of the preparation of method described in the embodiment 1.By mixing 4.26 gram (NH 4) 2Mo 2O 7, 6.38 the gram MoO 3, 1.12 the gram 30%H 2O 2, 0.27 gram monoethanolamine (" MEA ") and 6.51 gram deionized waters formation slurries and prepare the molybdenum dipping solution.Slurry is heated to 65 ℃ up to solid dissolving and cool to room temperature then.The pH of solution is 5.36.Liquor capacity is adjusted to 82mL with deionized water.
Alumina supporter (100 gram) is mixed with dipping solution and adopts irregular stirring to wear out 2 hours, 125 ℃ of following thermal treatments several hours with then 480 ℃ of following thermal treatments 2 hours.The catalyzer that obtains comprises every gram catalyzer 0.04 gram molybdenum and surplus is a carrier.Molybdenum catalyst has the pore size distribution that mean pore sizes is 250 , and pore volume is 0.77cm 3/ g and surface-area are 116m 2/ g.In addition, the aperture in 66.7% of the pore size distribution mesopore sum of molybdenum catalyst hole is within 86  of mean pore sizes.
Embodiment 2 has shown that preparation comprises the 6th row metal catalyst of θ alumina supporter.
Embodiment 3. preparations comprise the molybdenum/vanadium catalyst of θ aluminum oxidePrepare molybdenum/vanadium catalyst in the following way.To adopt the molybdenum/vanadium dipping solution dipping of preparation in the following way by the alumina supporter of the preparation of method described in the embodiment 1.By mixing 2.14 gram (NH 4) 2Mo 2O 7, 3.21 the gram MoO 3, 0.56 the gram 30%H 2O 2, 0.14 gram MEA and 3.28 gram deionized waters form slurries and prepare first solution.Slurry is heated to 65 ℃ up to solid dissolving and cool to room temperature then.
By mixing 3.57 gram VOSO 4XH 2O (x=3-5) prepares second solution with 40 gram deionized waters.First solution and second solution mixed and add enough deionized waters make mixed liquor volume reach 82mL to obtain molybdenum/vanadium dipping solution.Aluminum oxide was irregularly stirred aging 2 hours by dipping solution dipping and employing.With carrier/metal mixture of obtaining 125 ℃ of following thermal treatments several hours with then 480 ℃ of following thermal treatments 2 hours.It is carrier that the catalyzer that obtains comprises every gram catalyzer 0.02 gram vanadium and 0.02 gram molybdenum and surplus.Molybdenum/vanadium catalyst has the pore size distribution that mean pore sizes is 300 .
This embodiment shows and has prepared the 6th row metal/the 5th row metal catalyst that comprises the θ alumina supporter.
Embodiment 4. crude oil materials contact with two kinds of catalyzerThe tubular reactor that will have the thermocouple sheath of center arrangement assembles thermopair to measure the temperature of whole beds.By using catalyzer and silicon carbide (20-lattice, Stanford Materials; Aliso Viejo CA) is filled in the space between thermocouple sheath and the reactor wall and forms beds.It is believed that under the described herein processing condition of this silicon carbide to have low catalytic performance, if catalytic performance exists.Before the zone of action part of mixture being put into reactor, all catalyzer are mixed the volume ratio of 1 part of catalyzer by 2 parts of silicon carbide with silicon carbide.The crude oil material stream that enters reactor is to the bottom of reactor from the top of reactor.
The bottom that silicon carbide is arranged in reactor is to be used as bottom carrier.With bottom catalyst/carbon silicon mixture (81cm 3) be arranged in silicon carbide the top to form the zone of action, bottom, wherein the bottom catalyzer is the molybdenum/nickel/phosphorus catalyst of load.By mixed carrier and molybdenum/nickel/phosphorus soaking solution preparation bottom catalyzer.By grinding 550 gram alumina/silica mixtures, 26 gram incinerating aluminum oxide particulates, 585 gram water and 8 gram 16M nitric acid preparation in 35 minutes carrier.By mix every gram carrier at least 0.98 gram alumina/silica mixture (Criterion Catalysts andTechnologies LP) and every gram alumina/silica mixture at the most 0.02 gram silicon-dioxide (Criterion Catalysts and Technologies LP) prepare the alumina/silica mixture.The mixture that grinds extruded by 1.94mm and 3.28mm diameter die plate and then 93 ℃ (200 ) to the temperature of 121 ℃ (250 ) thermal treatment up to the loss on ignition that obtains 27-30wt%, based on initial extrudate weight meter.By heating extrudate to 540 ℃ following 15-50 minute and measuring then by the relative weight of extrudate loss and determine loss on ignition.Extrudate is descended further thermal treatment 1 hour at 918 ℃ (1685 ).Molybdenum/nickel/phosphorus soaking solution prepares as follows.By mixing 62.34 gram (NH 4) 2Mo 2O 7, 17.49 the gram MoO 3, 12.22 the gram 30%H 2O 2Form slurry and prepare first solution with 50.47 gram deionized waters.MEA (3.0 gram) is added in the slurry under being enough to control the speed of exothermic dissolution.Slurry is heated to 64 ℃ (147 ) up to solid dissolving and cool to room temperature then.The pH of first solution is 5.34.By mixing 8.2 gram Ni (NO 3) 26H 2O and 5.47 gram NiCO 3With 30.46 gram deionized waters with add 29.69 then and restrain 85wt%H 3PO 4And prepare second solution.The pH of second solution is 0.29.Mixing first solution and second solution and adding enough deionized waters makes mixed liquor volume reach 218.75mL to obtain molybdenum/nickel/phosphorus soaking solution.The pH of dipping solution is 2.02.Carrier (200.0 gram) is mixed with dipping solution and adopts irregular stirring to wear out several hours.With carrier/metal mixture of obtaining 125 ℃ of following thermal treatments several hours with then at 482 ℃ (900 ) 2 hours molybdenum/nickel/phosphorus catalysts of thermal treatment down with the formation load.
With top catalyst/carbon silicon mixture (9cm 3) be arranged in the top of zone of action, bottom to form the zone of action, top.Prepare the top catalyzer as described in example 3 above.
The top that silicon carbide is arranged in the zone of action, top is to fill the dead band and to be used as the preheating zone.Beds is written into the Lindberg stove that comprises corresponding to four heating zone of preheating zone, top and zone of action, bottom and bottom carrier.
The sulphurized catalyst by the time of the gaseous mixture (silicon carbide is not counted the part of catalyst volume) under the flow of about 1.5 liters of every volumes of gaseous mixture (mL) total catalyst of 5vol% hydrogen sulfide and 95vol% hydrogen being introduced the zone of action following provisions.Reactor pressure is about 1.9MPa (279.7psi).The temperature of zone of action was increased to 204 ℃ (400 ) and descended maintenance 2 hours at 204 ℃ then from envrionment temperature in 1 hour.After 204 ℃ keep down, the zone of action is increased to 316 ℃ (600 ) cumulatively under about 10 ℃ (about 50 ) speed hourly.The zone of action 316 ℃ of following maintenances one hour, was elevated to 370 ℃ (700 ) cumulatively and descends maintenance two hours at 370 ℃ then in 1 hour.Allow the zone of action to be cooled to envrionment temperature then.
After sulfuration, then the zone of action is fed to the top of reactor at 2 hours internal heating to 204 ℃ and the crude oil material (BC-10, Brazil) that performance is as shown in table 1.Crude oil material flows through preheating zone, zone of action, top, zone of action, bottom and the bottom carrier of reactor.Crude oil material is contacted in the presence of hydrogen with every kind of catalyzer.Contact conditions is as follows: being provided to the hydrogen of reactor and the ratio of crude oil material is 656Nm 3/ m 3(4000SCFB), LHSV is 0.5h -1With pressure be 13.8MPa (2014.7psi).Two zone of action are heated to 390 ℃ and kept 311 hours down at 390 ℃ then from 204 ℃ cumulatively under 0.1-10 ℃/hour speed.The temperature of beds is elevated to 400 ℃ and kept 352 hours down at 400 ℃ cumulatively.
Total product (being crude oil products and gas) leaves beds.Total product is introduced gas-liquid phase separator.In gas-liquid separator, with total product atomization oil production and gas.Enter the gas input of system by the mass flow controller measurement.With the gas cooling of leaving system to being enough to from the temperature of gas removal carbon number for any liquid ingredient of at least 5.Use wet testing instrument to measure gas separated.The periodic analysis crude oil products is with the weight percent of the component of definite crude oil products.The crude oil products performance is summarized in table 1.
Table 1
Performance Crude oil material Crude oil products
TAN 3.6 ≤0.05
Api gravity 15.1 20
The density under ℃ 15.56 (60 ), g/cm 3 0.9651 0.9306
Hydrogen, wt% 11.4 12.1
Carbon, wt% 87.1 87.4
Sulphur, wt% 0.433 0.05
Oxygen, wt% 0.42 0.01
Nitrogen, wt% 0.52 0.24
Basic nitrogen, wt% 0.16 0.08
Calcium, ppmw 3.5 0.6
Potassium, ppmw 1.8 1.3
Sodium, ppmw 5.3 0.6
Nickel, ppmw 12.4 7.3
Vanadium, ppmw 19.2 6.4
Iron, ppmw 10 0.4
Little carbon residue, wt% 8.5 4.6
C 5Bituminous matter, wt% 7.5 4.3
Petroleum naphtha, wt% 0 4.1
Overhead product, wt% 17.5 26.6
VGO，wt％ 39.2 40.9
Residual oil, wt% 43.3 28.4
The P-value 5 3.6
The viscosity under ℃ 37.8 (100 ), cSt 1705 156
As shown in table 1, every gram crude oil products nitrogen content of crude oil products is that 0.0024 gram, MCR content are 0.046 gram and C 5Asphalt content is 0.043 gram.The calcium contents of crude oil products is that 0.6ppmw, potassium content are that 1.3ppmw and sodium content are 0.6ppmw in addition.
Embodiment 4 shows that crude oil material is contacted with one or more catalyzer produces the total product that comprises crude oil products.At least a catalyzer is the 5-10 row metal catalyst that comprises the θ alumina supporter.As what measured by the P-value, the stability of crude oil material/total product mixture is maintained.With respect to crude oil material, crude oil products has basic metal in the organic acid of MCR, reduction of reduction and alkaline earth salt, the Ni/V/Fe content of reduction, the sulphur content of reduction, the nitrogen content of reduction, the C of reduction 5The oxygen level of bituminous matter and reduction.
Embodiment 5. crude oil materials contact with two kinds of catalyzerIdentical with described in the embodiment 4 of reactor apparatus (except the content of zone of action), crude oil material, catalyst vulcanization method, total product separation method, contact conditions, duration of contact and crude oil products analysis.Crude oil material flows to the bottom of reactor from the top of reactor.
Molybdenum/cobalt/phosphorus catalyst/silicon carbide mixture (81cm with load 3) be arranged in the zone of action, bottom.Molybdenum/cobalt/the phosphorus catalyst for preparing load by mixed carrier and molybdenum/cobalt/phosphorus soaking solution.Prepared carrier in 35 minutes by grinding 550 gram alumina powders (Criterion Catalysts andTechnologies LP), 26 gram incinerating aluminum oxide particulates, 585 gram water and 8 gram 16M nitric acid.The mixture that grinds is extruded by 1.94mm and 3.28mm diameter die plate, descend thermal treatment and descend thermal treatment up to the loss on ignition that obtains 27-30wt%, based on initial extrudate weight meter at 121 ℃ (250 ) then at 93 ℃ (200 ), 107 ℃ (225 ).Loss on ignition is determined as described in embodiment 4.With extrudate 918 ℃ (1685 ) down further thermal treatment 1 hour to form carrier.Preparation molybdenum/cobalt as described below/phosphorus soaking solution.With MoO 3(22.95 gram) and 85wt%H 3PO 4(12.67 gram) mixes and is heated to 82 ℃ (180 ) to form molybdenum/phosphorus solution.With Co (OH) 2Be heated to 100 ℃ in (29.83 gram) adding molybdenum/phosphorus solution and with the molybdenum/cobalt/phosphorus solution that obtains.Citric acid monohydrate compound (21.5 gram) is added molybdenum/cobalt/phosphorus solution, be heated to 100 ℃ and kept 1 hour down at 100 ℃.The liquor capacity that obtains is reduced to 252mL to produce molybdenum/cobalt/phosphorus soaking solution.The pH of dipping solution is 3.22.Alumina supporter (300.0 gram) is mixed with dipping solution, adopt and irregularly stirred aging several hours.With carrier/metal mixture of obtaining 120 ℃ of following thermal treatments several hours with then at 426 ℃ (800 ) thermal treatment 2 hours and 2 hours molybdenum/cobalt/phosphorus catalysts of further thermal treatment under 593 ℃ (1100 ) then down so that load to be provided.
To mix with silicon carbide as the molybdenum/vanadium catalyst of preparation as described in the embodiment 3.With molybdenum/vanadium catalyst/silicon carbide mixture (9cm 3) in the zone of action, top, arrange.
The crude oil products performance is summarized in table 2.
Table 2
Performance Crude oil material Crude oil products
TAN 3.6 ≤0.05
Api gravity 15.1 19.2
The density under ℃ 15.56 (60 ), g/cm 3 0.9651 0.9554
Hydrogen, wt% 11.4 11.6
Carbon, wt% 87.1 87.6
Sulphur, wt% 0.43 0.16
Oxygen, wt% 0.42 0.11
Nitrogen, wt% 0.52 0.47
Calcium, ppmw 5.4 0.5
Potassium, ppmw 46 1.5
Sodium, ppmw 117 0.6
Nickel, ppmw 12.4 7.5
Vanadium, ppmw 19.2 6.2
Iron, ppmw 10.4 0.9
Little carbon residue, wt% 8.5 7.2
C 5Bituminous matter, wt% 7.5 5.0
Petroleum naphtha, wt% 0 2.3
Overhead product, wt% 17.5 20.3
VGO，wt％ 39.2 42.0
Residual oil, wt% 43.3 35.4
The P-value 5 4.2
The viscosity under ℃ 37.8 (100 ), cSt 1705 698
As shown in table 2, every gram crude oil products nitrogen content of crude oil products is that 0.0047 gram, MCR content are 0.072 gram and C 5Asphalt content is 0.05 gram.Crude oil products contains 0.5ppmw calcium, 1.5ppmw potassium and 0.6ppmw sodium in addition.
Embodiment 5 shows that adopting controlled contact conditions that crude oil material is contacted with one or more catalyzer produces the total product that comprises crude oil products.At least a catalyzer is the 5-10 row metal catalyst that comprises the θ alumina supporter.With respect to crude oil material, crude oil products has basic metal in the organic acid of MCR, reduction of reduction and alkaline earth salt, the Ni/V/Fe content of reduction, the sulphur content of reduction, the nitrogen content of reduction, the C of reduction 5The oxygen level of bituminous matter and reduction.
Consider foregoing description, the further improvement of each side of the present invention and alternate embodiment are tangible to those skilled in the art.Therefore, described description only is to instruct those skilled in the art to implement general mode of the present invention for illustrative and its purpose.Should understand in this form of the present invention that provides and describe and only be the embodiment of embodiment.Can be substituted in those elements and the material of this explanation and description, parts and technology can be reversed and some feature of the present invention can adopt independently, after having benefited from description of the invention, this is tangible to those skilled in the art.Can change key element described herein and not deviate from the spirit and scope of the present invention that following claim is described.

Claims (18)

1. method of producing crude oil products, described method comprises:
Make crude oil material contact the total product that comprises crude oil products with generation with one or more catalyzer, wherein said crude oil products is a liquid mixture under 25 ℃ and 0.101MPa, described crude oil material comprises one or more an alkali metal salts of one or more organic acids, one or more alkaline earth salts of one or more organic acids or its mixture, the total content of basic metal and alkaline-earth metal is every gram crude oil material at least 0.00001 gram in the metal salts of organic acids of described crude oil material, with at least a catalyzer be 5-10 row metal catalysts, described 5-10 row metal catalyst comprises:
Carrier, described carrier comprises the θ aluminum oxide; With
One or more compounds of one or more metals of one or more metals of periodictable 5-10 row and/or periodictable 5-10 row; With
Control contact conditions temperature, pressure, crude oil material flow or its combination, make in the described crude oil products that the total content of basic metal and alkaline-earth metal in the metal salts of organic acids is in the described crude oil material in the metal salts of organic acids at the most 90% of the content of basic metal and alkaline-earth metal, wherein the content of basic metal and alkaline-earth metal is measured by ASTM method D1318 in the metal salts of organic acids.
2. the process of claim 1 wherein in the described crude oil products that the total content of basic metal and alkaline-earth metal in the metal salts of organic acids is in the described crude oil material in the metal salts of organic acids at the most 80%, at the most 50%, at the most 30% or at the most 10% of the content of basic metal and alkaline-earth metal.
3. claim 1 or 2 each methods, wherein said crude oil material has basic metal and alkaline-earth metal in every gram crude oil material 0.00001-0.005 gram, 0.00005-0.05 gram or the 0.0001-0.01 gram metal salts of organic acids.
4. each method of claim 1-3, wherein said crude oil products has every gram crude oil products 1 * 10 -7To 5 * 10 -5Gram, 5 * 10 -7To 1 * 10 -5Gram or 1 * 10 -6To 5 * 10 -6Basic metal and alkaline-earth metal in the gram metal salts of organic acids.
5. each method of claim 1-4, the organic acid zinc salt total content that wherein said crude oil material also comprises one or more zinc salts of one or more organic acids and described crude oil products be in the described crude oil material organic acid zinc salt content at the most 90%, at the most 80%, at the most 50%, at the most 30% or at the most 10%.
6. each method of claim 1-5, wherein said 5-10 row metal catalyst also comprise one or more compounds of one or more elements of one or more elements of periodictable the 15th row and/or periodictable the 15th row.
7. each method of claim 1-6, wherein said carrier contains every gram carrier at least 0.1 gram, at least 0.3 gram, at least 0.5 gram, at least 0.7 gram or at least 0.9 gram θ aluminum oxide.
8. each method of claim 1-7, wherein said 5-10 row metal catalyst has the pore size distribution of mean pore sizes at least 180 , at least 200 , at least 230 , at least 250  or at least 300 , and wherein pore size distribution is measured by ASTM method D4282.
9. each method of claim 1-8, wherein said crude oil material also has C 5The C of asphalt content and described crude oil products 5Asphalt content is crude oil material C 5At the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of asphalt content, wherein C 5Asphalt content is measured by ASTM method D2007.
10. each method of claim 1-9, the viscosity of wherein said crude oil products under 37.8 ℃ (100 ) is at the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of the viscosity of crude oil material under 37.8 ℃, and its medium viscosity is measured by ASTM method D445.
11. each method of claim 1-10, the sulphur content that wherein said crude oil material also has sulphur content and a described crude oil products is at the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of a crude oil material sulphur content, and wherein sulphur content is measured by ASTM method D4294.
12. each method of claim 1-11, the residual oil content that wherein said crude oil material also has residual oil content and a described crude oil products is at the most 90%, at the most 80%, at the most 70%, at the most 50%, at the most 30% or at the most 10% of crude oil material residual oil content, and wherein residual oil content is measured by ASTM method D5307.
13. each method of claim 1-12 is wherein implemented described contact and control contact conditions hydrogen source flow to produce described crude oil products in the presence of hydrogen source.
14. each method of claim 1-13, wherein contact conditions comprises: 50-500 ℃ temperature, the total pressure of 1-20MPa, 0.05h at least -1Liquid hourly space velocity and 0.1-100,000Nm 3/ m 3The gas hydrogen source and the ratio of crude oil material.
15. each method of claim 1-14, wherein the P-value at period of contact crude oil material/total product mixture is at least 1.5.
16. each method of claim 1-15, wherein said crude oil material has at the most 90% of chromium in the metal salts of organic acids that chromium in the metal salts of organic acids of chromium in the metal salts of organic acids and/or arsenic content and described crude oil products and/or arsenic content is crude oil material and/or arsenic content in addition.
17. each method of claim 1-16, wherein said method also comprise making with the identical or different crude oil of described crude oil material and mix with described crude oil products or blend to form blend.
18. each method of claim 1-17 also comprises and handles described crude oil products or the blend step with production and transport fuel, heating fuel, lubricant or chemical.
CNA2006800146558A 2005-04-11 2006-04-07 Systems, methods, and catalysts for producing a crude product Pending CN101166810A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67014705P 2005-04-11 2005-04-11
US60/670,147 2005-04-11

Publications (1)

Publication Number Publication Date
CN101166810A true CN101166810A (en) 2008-04-23

Family

ID=37087550

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2006800146558A Pending CN101166810A (en) 2005-04-11 2006-04-07 Systems, methods, and catalysts for producing a crude product

Country Status (9)

Country Link
US (1) US20060231456A1 (en)
EP (1) EP1869143A2 (en)
JP (1) JP2008535999A (en)
KR (1) KR20070120594A (en)
CN (1) CN101166810A (en)
BR (1) BRPI0609410A2 (en)
CA (1) CA2604015C (en)
NL (1) NL2000051C2 (en)
WO (1) WO2006110546A2 (en)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7745369B2 (en) 2003-12-19 2010-06-29 Shell Oil Company Method and catalyst for producing a crude product with minimal hydrogen uptake
US20050167328A1 (en) 2003-12-19 2005-08-04 Bhan Opinder K. Systems, methods, and catalysts for producing a crude product
US20100098602A1 (en) 2003-12-19 2010-04-22 Opinder Kishan Bhan Systems, methods, and catalysts for producing a crude product
CN101166811A (en) 2005-04-11 2008-04-23 国际壳牌研究有限公司 Method and catalyst for producing a crude product having a reduced nitrogen content
US20080085225A1 (en) 2006-10-06 2008-04-10 Bhan Opinder K Systems for treating a hydrocarbon feed
JP5537418B2 (en) 2007-05-03 2014-07-02 オーテラ インコーポレイテッド Products containing titanyl monomers and polymers and methods for their production
US8298404B2 (en) 2010-09-22 2012-10-30 Auterra, Inc. Reaction system and products therefrom
US9061273B2 (en) 2008-03-26 2015-06-23 Auterra, Inc. Sulfoxidation catalysts and methods and systems of using same
US9206359B2 (en) 2008-03-26 2015-12-08 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US8764973B2 (en) 2008-03-26 2014-07-01 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US8894843B2 (en) 2008-03-26 2014-11-25 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US8114806B2 (en) * 2008-04-10 2012-02-14 Shell Oil Company Catalysts having selected pore size distributions, method of making such catalysts, methods of producing a crude product, products obtained from such methods, and uses of products obtained
KR20110018875A (en) * 2008-04-10 2011-02-24 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 Catalyst systems and methods for converting a crude feed with such catalyst systems
US8734634B2 (en) 2008-04-10 2014-05-27 Shell Oil Company Method for producing a crude product, method for preparing a diluted hydrocarbon composition, crude products, diluents and uses of such crude products and diluents
US8637419B2 (en) * 2009-12-06 2014-01-28 Chevron U.S.A. Inc. Method for making a hydroprocessing catalyst
US9828557B2 (en) 2010-09-22 2017-11-28 Auterra, Inc. Reaction system, methods and products therefrom
TWI579043B (en) 2012-02-17 2017-04-21 先進精鍊科技有限公司 Spheroidal catalyst support and preparation method thereof
FR3007415B1 (en) 2013-06-21 2016-05-27 Ifp Energies Now PROCESS FOR REMOVING THE ARSENIC FROM A HYDROCARBON LOAD
US10246647B2 (en) 2015-03-26 2019-04-02 Auterra, Inc. Adsorbents and methods of use
US10450516B2 (en) 2016-03-08 2019-10-22 Auterra, Inc. Catalytic caustic desulfonylation
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil
US20180230389A1 (en) 2017-02-12 2018-08-16 Magēmā Technology, LLC Multi-Stage Process and Device for Reducing Environmental Contaminates in Heavy Marine Fuel Oil

Family Cites Families (102)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2921023A (en) * 1957-05-14 1960-01-12 Pure Oil Co Removal of naphthenic acids by hydrogenation with a molybdenum oxidesilica alumina catalyst
NL267291A (en) * 1959-05-14 1900-01-01
US3025231A (en) * 1959-06-03 1962-03-13 Texaco Inc Catalytic hydrogenation of heavy oils such as shale oil
US3080435A (en) * 1960-07-18 1963-03-05 Shell Oil Co Dehydrogenation process
US3446730A (en) * 1966-06-21 1969-05-27 Gulf Research Development Co Catalytic hydrodenitrogenation of petroleum fractions
US3553279A (en) * 1968-03-29 1971-01-05 Texas Instruments Inc Method of producing ethylene
US3558474A (en) * 1968-09-30 1971-01-26 Universal Oil Prod Co Slurry process for hydrorefining petroleum crude oil
US3576737A (en) * 1969-03-25 1971-04-27 Chevron Res Vanadium removal from hydrocarbons
US3663431A (en) * 1969-10-15 1972-05-16 Union Oil Co Two-phase hydrocarbon conversion system
BE758565A (en) * 1969-11-18 1971-05-06 Shell Int Research PROCEDURE FOR THE CATALYTIC HYDROGENATING CONVERSION OF A RESIDUAL CARBON HYDROGEN OIL
US3713861A (en) * 1969-12-04 1973-01-30 Xerox Corp Inhibitor device
US3716478A (en) * 1970-02-10 1973-02-13 Agency Ind Science Techn Hydrogenation treatment of hydrocarbon oil
US3712861A (en) * 1970-10-19 1973-01-23 Mobil Oil Corp Upgrading a hydrocarbon utilizing a catalyst of metal sulfides dispersed in alumina
US3730876A (en) * 1970-12-18 1973-05-01 A Sequeira Production of naphthenic oils
US3716479A (en) * 1970-12-23 1973-02-13 Mobil Oil Corp Demetalation of hydrocarbon charge stocks
US3812028A (en) * 1971-05-18 1974-05-21 Standard Oil Co Hydrotreatment of fossil fuels
US3786138A (en) * 1971-08-16 1974-01-15 Atlantic Richfield Co Hydrogen generation
JPS5139645B2 (en) * 1972-12-30 1976-10-29
US3876532A (en) * 1973-02-27 1975-04-08 Gulf Research Development Co Method for reducing the total acid number of a middle distillate oil
US3948759A (en) * 1973-03-28 1976-04-06 Exxon Research And Engineering Company Visbreaking a heavy hydrocarbon feedstock in a regenerable molten medium in the presence of hydrogen
US3808122A (en) * 1973-03-29 1974-04-30 Chevron Res Jet fuel by hydrocracking
US3931052A (en) * 1973-08-29 1976-01-06 Mobil Oil Corporation Alumina-supported catalyst for residua demetalation and desulfurization
US3876523A (en) * 1973-08-29 1975-04-08 Mobil Oil Corp Catalyst for residua demetalation and desulfurization
US4016067A (en) * 1975-02-21 1977-04-05 Mobil Oil Corporation Process for demetalation and desulfurization of petroleum oils
JPS51122105A (en) * 1975-04-18 1976-10-26 Toa Nenryo Kogyo Kk Process for hydrofining of hydrocarbon oil
GB1550684A (en) * 1975-08-28 1979-08-15 Mobil Oil Corp Demetalation-desulphurisation catalyst and the preparation and use thereof
US4196102A (en) * 1975-12-09 1980-04-01 Chiyoda Chemical Engineering & Construction Co., Ltd. Catalysts for demetallization treatment of _hydrocarbons supported on sepiolite
GB1561629A (en) * 1975-12-10 1980-02-27 Ici Ltd Catalyst
US4067799A (en) * 1976-07-02 1978-01-10 Exxon Research And Engineering Company Hydroconversion process
US4191635A (en) * 1977-12-21 1980-03-04 Standard Oil Company (Indiana) Process for the cracking of heavy hydrocarbon streams
JPS5579043A (en) * 1978-12-13 1980-06-14 Chiyoda Chem Eng & Constr Co Ltd Hydrogenation catalyst for heavy hydrocarbon oil
US4446244A (en) * 1979-09-26 1984-05-01 Chevron Research Company Hydrocarbons hydroprocessing with imogolite catalyst
JPS595011B2 (en) * 1979-11-27 1984-02-02 千代田化工建設株式会社 Catalyst for hydrotreating heavy hydrocarbon oil and its production method
FI803329L (en) * 1980-10-23 1982-04-24 Farmos Oy VAEXTSUBSTRATBAEDD
US4591426A (en) * 1981-10-08 1986-05-27 Intevep, S.A. Process for hydroconversion and upgrading of heavy crudes of high metal and asphaltene content
US4376037A (en) * 1981-10-16 1983-03-08 Chevron Research Company Hydroprocessing of heavy hydrocarbonaceous oils
US4427535A (en) * 1981-11-02 1984-01-24 Hydrocarbon Research, Inc. Selective operating conditions for high conversion of special petroleum feedstocks
US4431525A (en) * 1982-04-26 1984-02-14 Standard Oil Company (Indiana) Three-catalyst process for the hydrotreating of heavy hydrocarbon streams
US4447314A (en) * 1982-05-05 1984-05-08 Mobil Oil Corporation Demetalation, desulfurization, and decarbonization of petroleum oils by hydrotreatment in a dual bed system prior to cracking
JPS58219293A (en) * 1982-06-15 1983-12-20 Chiyoda Chem Eng & Constr Co Ltd Hydrocracking of heavy oil
FR2528721B1 (en) * 1982-06-17 1986-02-28 Pro Catalyse Ste Fse Prod Cata SUPPORTED CATALYST HAVING INCREASED RESISTANCE TO POISONS AND ITS USE IN PARTICULAR FOR THE HYDROTREATMENT OF OIL FRACTIONS CONTAINING METALS
US4437980A (en) * 1982-07-30 1984-03-20 Rockwell International Corporation Molten salt hydrotreatment process
US4450068A (en) * 1982-12-20 1984-05-22 Phillips Petroleum Company Demetallization of hydrocarbon containing feed streams
US4460707A (en) * 1982-12-28 1984-07-17 Union Oil Company Of California Hydroprocessing catalyst and method for preparing it
FR2538813A1 (en) * 1982-12-31 1984-07-06 Inst Francais Du Petrole HYDROTREATMENT PROCESS CONVERTING IN AT LEAST TWO STEPS A HEAVY FRACTION OF HYDROCARBONS CONTAINING SULFUR IMPURITIES AND METAL IMPURITIES
JPS59132945A (en) * 1983-01-21 1984-07-31 Shokubai Kasei Kogyo Kk Hydro-demetalation catalyst and use thereof
US4498979A (en) * 1983-09-12 1985-02-12 Exxon Research & Engineering Co. Hydrodesulfurization process with conversion of heavy hydrocarbons utilizing a catalyst containing a group IIA metal component
US4587012A (en) * 1983-10-31 1986-05-06 Chevron Research Company Process for upgrading hydrocarbonaceous feedstocks
US4520128A (en) * 1983-12-19 1985-05-28 Intevep, S.A. Catalyst having high metal retention capacity and good stability for use in the demetallization of heavy crudes and method of preparation of same
US4588709A (en) * 1983-12-19 1986-05-13 Intevep, S.A. Catalyst for removing sulfur and metal contaminants from heavy crudes and residues
US4572778A (en) * 1984-01-19 1986-02-25 Union Oil Company Of California Hydroprocessing with a large pore catalyst
US4564439A (en) * 1984-06-29 1986-01-14 Chevron Research Company Two-stage, close-coupled thermal catalytic hydroconversion process
US4659454A (en) * 1984-12-21 1987-04-21 Mobil Oil Corporation Hydrocracking of heavy feeds plus light fractions with dispersed dual function catalyst
US4665261A (en) * 1985-06-21 1987-05-12 Atlantic Richfield Company Hydrocarbon conversion process using a molten salt
US5108581A (en) * 1985-09-09 1992-04-28 Exxon Research And Engineering Company Hydroconversion of heavy feeds by use of both supported and unsupported catalysts
US4661265A (en) * 1985-09-30 1987-04-28 Amoco Corporation Catalyst deoiling process
US4746419A (en) * 1985-12-20 1988-05-24 Amoco Corporation Process for the hydrodemetallation hydrodesulfuration and hydrocracking of a hydrocarbon feedstock
US4729826A (en) * 1986-02-28 1988-03-08 Union Oil Company Of California Temperature controlled catalytic demetallization of hydrocarbons
US4738884A (en) * 1986-03-03 1988-04-19 Owens-Corning Fiberglas Corporation Asphalt adhesives superimposed on asphalt-based roofing sheet
DE3623430A1 (en) * 1986-07-11 1988-01-28 Veba Oel Entwicklungs Gmbh METHOD FOR HYDROGENATING TREATMENT WITH CHLORBIPHENYLENE AND THE LIKE CONTAMINATED MINERAL OILS
US4830736A (en) * 1986-07-28 1989-05-16 Chevron Research Company Graded catalyst system for removal of calcium and sodium from a hydrocarbon feedstock
US4917789A (en) * 1987-02-03 1990-04-17 Fina Technology, Inc. Catalytic dewaxing process
JP2631712B2 (en) * 1988-08-18 1997-07-16 コスモ石油株式会社 Catalyst composition for hydrotreating heavy hydrocarbon oil and hydrotreating method using the same
US4992157A (en) * 1988-08-29 1991-02-12 Uop Process for improving the color and color stability of hydrocarbon fraction
US5089463A (en) * 1988-10-04 1992-02-18 Chevron Research And Technology Company Hydrodemetalation and hydrodesulfurization catalyst of specified macroporosity
US4992163A (en) * 1989-12-13 1991-02-12 Exxon Research And Engineering Company Cat cracking feed preparation
EP0460300A1 (en) * 1990-06-20 1991-12-11 Akzo Nobel N.V. Process for the preparation of a presulphided catalyst; Process for the preparation of a sulphided catalyst, and use of said catalyst
US5089453A (en) * 1990-06-25 1992-02-18 Chevron Research And Technology Company Hydroconversion catalyst and method for making the catalyst
US5089462A (en) * 1990-06-25 1992-02-18 Chevron Research And Technology Company Hydroconversion catalyst and method for making the catalyst
US5200060A (en) * 1991-04-26 1993-04-06 Amoco Corporation Hydrotreating process using carbides and nitrides of group VIB metals
US5171727A (en) * 1991-08-26 1992-12-15 Uop Method of preparing a catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks
US5223472A (en) * 1992-04-14 1993-06-29 Union Oil Company Of California Demetallation catalyst
US5300212A (en) * 1992-10-22 1994-04-05 Exxon Research & Engineering Co. Hydroconversion process with slurry hydrotreating
FR2701270B1 (en) * 1993-02-08 1995-04-14 Inst Francais Du Petrole Process for removing mercury from hydrocarbons by passing over a presulfurized catalyst.
US5397456A (en) * 1993-02-19 1995-03-14 Texaco Inc. Hydroconversion process employing catalyst with specified pore size distribution
US5395536A (en) * 1993-05-07 1995-03-07 Baker Hughes, Inc. Wastewater organic acid removal process
JP3554039B2 (en) * 1993-10-05 2004-08-11 ヒュンダイ エレクトロニクス アメリカ Disk drive device
US5620592A (en) * 1994-07-29 1997-04-15 Chevron U.S.A. Inc. Low macropore resid conversion catalyst
DE19600684A1 (en) * 1995-02-17 1996-08-22 Linde Ag Hydrocarbon splitting method and device
US5885441A (en) * 1997-04-11 1999-03-23 Intevep, S.A. Steam conversion process and catalyst
US5807469A (en) * 1995-09-27 1998-09-15 Intel Corporation Flexible continuous cathode contact circuit for electrolytic plating of C4, tab microbumps, and ultra large scale interconnects
US6210564B1 (en) * 1996-06-04 2001-04-03 Exxon Research And Engineering Company Process for desulfurization of petroleum feeds utilizing sodium metal
US5856609A (en) * 1996-09-12 1999-01-05 Phillips Petroleum Company Aromatic hydrodealkylation process with sulfur oxide containing catalyst
FR2753982B1 (en) * 1996-10-02 1999-05-28 Inst Francais Du Petrole MULTI-STAGE CATALYTIC PROCESS FOR CONVERTING A HEAVY HYDROCARBON FRACTION
EP0848992B1 (en) * 1996-12-17 2002-03-27 Institut Francais Du Petrole Boron and silicon containing catalyst and its application in the hydrotreatment of hydrocarbon feeds
US5744025A (en) * 1997-02-28 1998-04-28 Shell Oil Company Process for hydrotreating metal-contaminated hydrocarbonaceous feedstock
FR2764213B1 (en) * 1997-06-10 1999-07-16 Inst Francais Du Petrole HYDROCARBON CHARGE HYDROTREATMENT CATALYST IN A FIXED BED REACTOR
US5871636A (en) * 1997-08-29 1999-02-16 Exxon Research And Engineering Company Catalytic reduction of acidity of crude oils in the absence of hydrogen
US5897769A (en) * 1997-08-29 1999-04-27 Exxon Research And Engineering Co. Process for selectively removing lower molecular weight naphthenic acids from acidic crudes
US6218333B1 (en) * 1999-02-15 2001-04-17 Shell Oil Company Preparation of a hydrotreating catalyst
US6554994B1 (en) * 1999-04-13 2003-04-29 Chevron U.S.A. Inc. Upflow reactor system with layered catalyst bed for hydrotreating heavy feedstocks
US6509291B2 (en) * 2000-04-11 2003-01-21 Akzo Nobel N.V. Process for sulfiding a catalyst containing an S-containing additive
US6524469B1 (en) * 2000-05-16 2003-02-25 Trans Ionics Corporation Heavy oil upgrading process
US6203313B1 (en) * 2000-06-09 2001-03-20 Rebbecca L. Holmes Candle having reconfigurable shape
US6547957B1 (en) * 2000-10-17 2003-04-15 Texaco, Inc. Process for upgrading a hydrocarbon oil
CA2440452A1 (en) * 2001-04-20 2002-10-31 Exxonmobil Upstream Research Company Heavy oil upgrade method and apparatus
US20030042174A1 (en) * 2001-06-18 2003-03-06 Petronetiics Llc. Method to treat emulsified hydrocarbon mixtures
US6841062B2 (en) * 2001-06-28 2005-01-11 Chevron U.S.A. Inc. Crude oil desulfurization
AU2002326926A1 (en) * 2001-09-17 2003-04-01 Southwest Research Institute Pretreatment processes for heavy oil and carbonaceous materials
US20030070808A1 (en) * 2001-10-15 2003-04-17 Conoco Inc. Use of syngas for the upgrading of heavy crude at the wellhead
US7497943B2 (en) * 2002-08-30 2009-03-03 Baker Hughes Incorporated Additives to enhance metal and amine removal in refinery desalting processes
BRPI0405572A (en) * 2003-12-19 2005-08-30 Shell Int Research Methods of Producing a Transportable Fuel and Crude Petroleum Product, Heating Fuel, Lubricants or Chemicals, and Crude Oil Products

Also Published As

Publication number Publication date
NL2000051A1 (en) 2006-10-12
CA2604015C (en) 2014-02-18
US20060231456A1 (en) 2006-10-19
NL2000051C2 (en) 2007-07-27
EP1869143A2 (en) 2007-12-26
WO2006110546A3 (en) 2007-03-08
WO2006110546A2 (en) 2006-10-19
KR20070120594A (en) 2007-12-24
JP2008535999A (en) 2008-09-04
BRPI0609410A2 (en) 2011-10-11
CA2604015A1 (en) 2006-10-19

Similar Documents

Publication Publication Date Title
CN101166808B (en) Method and catalyst for producing a crude product having a reduced MCR content
CN101166810A (en) Systems, methods, and catalysts for producing a crude product
CN101166811A (en) Method and catalyst for producing a crude product having a reduced nitrogen content
CN101166807A (en) Systems, methods, and catalysts for producing a crude product
CN101166809A (en) Method and catalyst for producing a crude product having a reduced nitrogen content
US8492599B2 (en) Catalysts, preparation of such catalysts, methods of using such catalysts, products obtained in such methods and uses of products obtained
CN101535449A (en) Methods for producing a crude product
AU2004309330A1 (en) Systems, methods, and catalysts for producing a crude product

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20080423