NL2000053C2 - Systems, methods and catalysts for producing a crude product. - Google Patents

Description

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

FIELD OF THE INVENTION

The present invention relates generally to systems, methods and catalysts for treating crude feed. More specifically, certain embodiments described herein relate to systems, methods, and catalysts for converting a crude feed into a total product, the total product including a crude product containing at 25 ° C and 0.101. 10 MPa is a liquid mixture and which has one or more properties that are changed with respect to the respective property of the crude feed.

DESCRIPTION OF THE RELATED ART 15 Crude-containing raw materials that have one or more unsuitable properties that prevent crude-containing raw materials from being economically transported or processed with conventional facilities are commonly referred to as "disadvantaged crudes": 20 crude-containing raw materials with adverse shelves.

Disadvantaged crudes may include acidic components that contribute to the total acid value ("TAN") of the crude feed.

Disadvantaged crudes with a relatively high TAN can contribute to corrosion of metal components during transport and / or processing of the disadvantaged crudes. The removal of acid components from disadvantaged - 2 - crudes may include chemically neutralizing acid components with various bases.

Corrosion-resistant metals can also be used in transport and / or processing equipment. The use of corrosion-resistant metal often involves considerable costs, so that the use of corrosion-resistant metal in existing equipment may not be desirable. Another method of counteracting corrosion may involve adding corrosion inhibitors to disadvantaged crudes prior to transportation and / or processing of the disadvantaged crudes. The use of corrosion inhibitors can adversely affect equipment used for processing the crude oil raw materials and / or the quality of products produced from the crude oil raw materials.

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

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

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

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

Disadvantaged crudes may contain components that contribute coke and / or contribute to thermal degradation of the disadvantaged crude. During the processing of disadvantaged crudes, the coke and / or thermally degraded components can form and / or deposit rapidly on catalyst surfaces. Regenerating the catalytic activity of a catalyst contaminated with coke and / or thermally degraded crude feedstock can be a costly affair. Moreover, high temperatures used during the regeneration of a catalyst can also reduce the activity of the catalyst and / or degrade the catalyst.

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

In conventional catalytic processing of crude oils, problems are often encountered when metals are present in metal salts of organic acids. In contrast to nickel and vanadium, which usually settle near the outer surface of the catalyst, metals in metal salts of organic acids can preferentially deposit in empty volumes between catalyst particles, in particular at the top of the catalyst bed. Deposition of contaminants, for example metals in metal salts of organic acids, at the top of the catalyst bed generally leads to an increase in pressure drop through the bed and can actually clog the bed. In addition, the metals in metal salts of organic acids can cause rapid deactivation of catalysts.

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

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

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

Conventional treatment processes for disadvantaged crudes can reduce the amount of components that contribute to high viscosity, thermal degradation of the disadvantaged crude and / or coke formation. However, removal of these components can cause instability in the crude feedstock and thereby separation during transport. In conventional processing, components that contribute to high viscosity and / or coke formation are usually removed when the crude feedstock is treated with a catalyst with a large pore size, a large surface area and a low hydrogenation treatment activity. The crude-containing raw material thus obtained can then be further treated to remove other undesirable components in the crude-containing raw material.

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

U.S. Patent Nos. 6,547,957 to Sudhakar et al., 6,277,269 to Myers et al., 6,203,695 to Harle et al., 6,063,266 to

Grande et al., 5,928,502 to Bearden et al., 5,914,030 to Bearden et al., 5,897,769 to Trachte et al., 5,744,025 to Boon et al., 4,212 .729 in the name of Hensley. Jr. and 4,048,060 to Riley, 10, and U.S. Patent Application Publication No. ÜS 2004/0106516 in the name of Schulz et al. Describe various processes, systems and catalysts for the processing of crude oil-containing raw materials. However, due to many of the technical problems outlined above, the processes, systems and catalysts described in these patents have limited applicability.

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

SUMMARY OF THE INVENTION

In some embodiments, the invention provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product which includes the crude-oil product wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture; Wherein the crude feed has a micro carbon residue level ("MCR content") of at least 0.0001 grams per gram of crude feed; and wherein at least one of the catalysts is a column 6 metal catalyst comprising: one or more metals from Column 6 of the Periodic Table and / or one or more compounds of one or more metals from Column 6 of the Periodic Table ; a pore size distribution with a median pore diameter of more than 110 A; and a pore volume wherein pores with a pore diameter of at least 350 A make up at most 10% of the pore volume, wherein pore volume and pore diameter are as determined by ASTM method D4282; and controlling the contact conditions such that the crude-8 product has an MCR content of at most 90% of the MCR content of the crude feed, wherein MCR content is as determined by ASTM method D4530 .

In some embodiments, the invention also provides a catalyst, comprising: a support and one or more metals from Column 6 of the Periodic Table and / or one or more compounds of one or more metals from Column 6 of the Periodic Table, wherein the catalyst has a pore size distribution with a median pore diameter 10 of more than 110 A and a pore volume in which pores with a pore diameter of at least 350 A make up at most 10% of the pore volume, wherein pore diameter and pore volume are as determined by ASTM method D4282.

In some embodiments, the invention also provides a method for making a catalyst, comprising: combining a support with a metal solution containing one or more metals from Column 6 of the Periodic System and / or one or more compounds of one or more comprises metals from Column 6 of the Periodic System 20, wherein the support has an average pore diameter of at least 90 A and a pore volume in which pores with a pore diameter of at least 350 A constitute at most 15% of the pore volume of the support, pore diameter and pore volume are as determined by ASTM method D4282.

In some embodiments, the invention also provides a method for producing a crude oil-containing product, comprising: contacting a crude oil-containing feed with one or more catalysts to form a total product that includes the crude oil-containing product wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein the crude feed has an MCR content of at least 0.0001 grams per gram of crude feed, and wherein at least at least one of the catalysts is a catalyst from Columns 6-10 which per gram of catalyst comprises at least 0.3 gram of one or more metals from Columns 6-10 of the Periodic Table and / or one or more compounds of one or more metals contains from Columns 6-10 of the Periodic System and a binder; and controlling the contact conditions such that the crude product has an MCR-10 content of at most 90% of the MCR content of the crude feed, wherein MCR content is as determined by ASTM method D4530 .

In some embodiments, the invention also provides a method for producing a crude oil-containing product, comprising: contacting a crude oil-containing feed with one or more catalysts to form a total product that includes the crude oil-containing product wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed comprising one or more alkali metal salts of one or more organic acids, alkaline earth metal salts of one or more organic acids or mixtures thereof, the crude feed has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at least 0.00001 grams per gram of crude feed, and wherein at least one of the catalysts is a metal catalyst from Columns 5-10 is comprising: a carrier, which carrier comprises theta alumina; and one or more metals from Columns 5-10 of the

Periodic Table and / or one or more compounds of one or more metals from Columns 5-10 of the Periodic Table; and controlling the contact conditions such that the crude product contains a total alkali metal and alkaline earth metal content in metal salts of organic acids of at most 90% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the has a crude feed, wherein the content of alkali metal and alkaline earth metal in metal salts of organic acids is as determined by ASTM method D1318.

In some embodiments, the invention also provides a method for producing a crude-oil product, comprising: contacting a crude-oil feed with one or more catalysts to form a total product that includes the crude-oil product wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture; wherein the crude feed has a nitrogen content of at least 0.0001 grams per gram of crude feed; and wherein at least one of the catalysts is a column 6 metal catalyst comprising: one or more metals from Column 6 of the Periodic Table and / or one or more compounds of one or more metals from Column 6 of the Periodic Table ; a pore size distribution with a median pore diameter greater than 110 A; and a pore volume in which pores with a pore diameter of at least 350 A make up at most 10% of the pore volume, wherein pore diameter and pore volume are as determined by ASTM method D4282; and controlling the contact conditions such that the crude product has a nitrogen content of at most 90% of the nitrogen content of the crude feed, wherein nitrogen content is as determined by ASTM method D5762.

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In some embodiments, the invention also provides a method for producing a crude oil-containing product, comprising: contacting a crude oil-containing feed with one or more catalysts to form a total product that includes the crude oil-containing product wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture; wherein the crude feed has a nitrogen content of at least 0.0001 grams per gram of crude feed; wherein at least one of the catalysts is a column 6 metal catalyst that can be obtained by heating a column 6 metal catalyst precursor in the presence of one or more sulfur-containing compounds at a temperature below about 500 ° C, the column precursor of metal from Column 6 comprises one or more metals from Column 6 of the Periodic Table and / or one or more compounds of one or more metals from Column 6 of the Periodic Table and a support; and controlling the contact conditions such that the crude product has a nitrogen content of at most 90% of the nitrogen content of the crude feed, wherein nitrogen content is as determined by ASTM method D5762.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, the metal catalyst from Column 6: (a) wherein pores with a pore diameter of at least 350 A at most 5%, at most 3%, not more than 1%, or not more than 0.5% of the pore volume; (b) having a pore size distribution with a median pore diameter of at least 120 A, at least 130 A, at least 150 A, at least 180 A, at least 200 A, at least 250 A, or at most - 12 - at most 300 A, wherein pore size spread is as determined by ASTM method D4282; and / or (c) having a pore size distribution such that at least 60% of the total number of pores within the pore size spread is within about 45 A, about 35 A, or about 25 A of the median pore size of the pore size spread.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, the metal catalyst

Column 6: (a) per gram of catalyst from about 0.0001 grams to about 0.3 grams, about 0.005 grams to about 0.2 grams, or about 0.01 grams to about 0.1 grams of one or more of the metals from Column 6 and / or one or more of the metal compounds from Column 6, calculated as the total weight of metal from Column 6; (b) comprises one or more metals from Columns 7-10 of the Periodic Table and / or one or more compounds of one or more metals from Columns 7-10 of the Periodic Table; and per 20 grams of catalyst about 0.001 grams to about 0.1 grams, or about 0.01 grams to about 0.05 grams of one or more of the metals from Columns 7-10 and / or one or more of the metal compounds from Columns 7-10, calculated as the total weight of metals from Columns 7-10; (c) one or more metals from Column 10 of the

Periodic Table and / or one or more compounds of one or more metals from Column 10 of the Periodic Table; (d) molybdenum and / or tungsten; (e) comprises nickel and / or cobalt; (f) comprises nickel and / or iron; (g) comprises one or more elements from Column 15 of the Periodic Table and / or one or more connections of one or more elements from Column 15 of the Periodic Table; and per gram of catalyst from about 0.000001 grams to about 0.1 grams, about 0.00001 grams to about 0.06 grams, about 0.00005 grams to about 0.03 grams, or about 0.0001 grams to contains about 0.001 grams of one or more of the elements from Column 15 and / or one or more compounds of 5 of the elements from Column 15, calculated as the total weight of elements from Column 15; (h) comprises phosphorus; and / or (i) contains no more than 0.001 gram of one or more metals from Column 5 of the Periodic Table and / or one or more compounds of one or more metals from Column 5 of the Periodic Table, calculated as the total weight of metal from Column 5.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, the metal catalyst

Column 6 or solution of metal from Column 6 per gram of catalyst or solution of metal from Column 6 contains: (a) about 0.01 grams to about 0.15 grams of molybdenum and / or one or more compounds of molybdenum, calculated as the total weight of molybdenum; and from about 0.001 grams to about 0.05 grams of nickel and / or one or more nickel compounds, calculated as the total nickel weight; and (b) optionally from about 0.001 grams to about 0.05 grams of iron and / or one or more compounds of iron, calculated as the total weight of iron; and (c) optionally from about 0.0001 grams to about 0.05 grams of phosphorus and / or one or more compounds of phosphorus, calculated as the total weight of phosphorus.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, that the metal catalyst of Columns 5-10 comprises: (a) molybdenum; (b) comprises tungsten; (c) comprises vanadium; (d) per gram of catalyst about - 14 - 0.001 gram to about 0.1 gram, or about 0.01 gram to about 0.05 gram of one or more metals from Columns 7-10 of the Periodic Table and / or one or contains more compounds of one or more metals from Columns 7-10 of the Periodic System; (e) comprises one or more elements from Column 15 of the Periodic Table and / or one or more connections of one or more elements from Column 15 of the Periodic Table; (f) comprises phosphorus; and / or (g) has a pore size distribution with a median pore diameter of at least 180 A, at least 200 A, at least 230 A, at least 250 A, or at least 300 A.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, the metal catalyst

Column 6 is a supported catalyst, wherein the support: (a) is at least 0.8 grams, at least 0.9 grams, or at least 0.95 grams of gamma alumina; (b) no more than 0.1 grams, no more than 0.08 grams, no more than 0.06 grams, no more than 0.04 grams or no more than 0.02 grams of silica, or (c) no less than 0.3 grams or contains at least 0.5 grams of theta alumina per gram of carrier.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, contacting the crude feed with one or more catalysts in which at least one or more of the catalysts is a column 6 metal catalyst is that can be obtained by combining a mixture with one or more of the metals from Column 6 and / or one or more of the metal compounds from Column 6, and wherein the mixture is one or more metals from Columns 7-10 of the Periodic System and / or one or more compounds of one or more metals from Columns 7-10 of the Periodic Table and a support. In some embodiments, in combination with one or more of the above embodiments, at least one of the metals from Columns 7-10 comprises nickel, cobalt, iron, or mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, a crude feed containing: (a) about 0.0001 grams to about 0.5 grams, about 0.005 grams to about 0.1 grams, or about 0.01 grams to about 0.05 grams of MCR per gram of crude feed; (b) from about 0.0001 grams to about 0.1 grams, about 0.001 grams to about 0.05 grams, or about 0.005 grams to about 0.01 grams of nitrogen per gram of crude feed; and / or (c) from about 0.00001 grams to about 0.005 grams, about 0.00005 grams to about 0.05 grams, or about 0.0001 grams to about 0.01 grams of alkali metal and alkaline earth metal in metal salts of organic acids per gram of crude-oiled food.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, a crude product containing: (a) an MCR content of at most 80%, at most 50%, at most 30% or at least maximum 10% of the MCR content of the crude feed; (b) a nitrogen content of at most 80%, at most 50%, at most 30% or at most 10% of the nitrogen content of the crude-oiled feed; (c) a total alkali metal and alkaline earth metal content in metal salts of organic acids in the crude oil product of up to 80%, up to 50%, up to 30% or up to 16 - up to 10% of the alkali metal content, and alkaline earth metal, in metal salts of organic acids in the crude feed; (d) an MCR content in a range of from about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9% of the MCR content of the crude feed; (e) a nitrogen content in a range of from about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9% of the nitrogen content of the crude feed; (f) a total content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude product in a range of from about 0.1% to about 75%, about 0 * 5% to about 45%, about 1% to about 25%, or about 2% to about 9% of the alkali metal and alkaline earth metal content in metal salts of organic acids in the crude feed; (g) about 0.00001 grams to about 0.1 grams, about 0.0001 grams to about 0.05 grams, or about 0.001 grams to about 0.005 grams of MCR per gram of crude product; (h) from about 0.00001 grams to about 0.05 grams, about 0.0001 grams to about 0.01 grams, or about 0.0005 grams to about 0.001 grams of nitrogen per gram of crude product; (i) about 1 x 10 "^ gram to about 5 x 10" 5 gram, about 5 x 10 "^ gram to about 1 x 10" ^ gram, or about 1 x 10 "® gram to about 5 x 10" ® grams of alkali metal and alkaline earth metal in metal salts of 30 organic acids per gram of crude product (j) a viscosity at 37.8 ° C (100 ° F) of at most 90%, at most 80%, at most 70%, at at most 50%, at most 30% or at most 10% of the viscosity at - 17 - 37/8 ° C (100 ° F) of the crude feed, where viscosity is as determined by ASTM method D445; (k) a C5 asphaltenes content of at most 90%, at most 80%, at most 70%, at most 50%, at most 30% or at most 10% of the C5 asphaltenes content of the crude feed, where C5 asphaltenes content is as determined by ASTM method D2007, (1) a residual content of not more than 90%, not more than 80%, not more than 70%, not more than 50%, not more than 30% or not more than 10% of the residual content of the crude feed, where residue is as determined by ASTM method D5307; and / or (m) a sulfur content of at most 90%, at most 80%, at most 70%, at most 50%, at most 30% or at most 10% of the sulfur content of the crude feed, wherein sulfur content is as determined by ASTM method D4294.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, contacting the crude feed with one or more catalysts and one or more additional catalysts, wherein at least one of the catalysts is the catalyst is of column 6 metal, and wherein one or more of the additional catalysts has a median pore diameter of at least 60 A, at least 90 A, at least 110 A, at least 180 A, at least 200 A, or at least 250 A; and wherein the metal catalyst from Column 6 is contacted with the crude feed prior to and / or after contacting the crude feed with at least one of the additional catalysts.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, contacting the crude-containing feed with one or more catalysts and one or more additional catalysts, wherein at least one of the catalysts the metal catalyst is from Columns 5-10 and the additional catalyst has a median pore diameter of at least 60 A, and wherein the additional catalyst after contacting the crude feed with the metal from Columns 5-10 catalyst with the crude -oil container is brought into contact with the food.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, contacting the crude feed with one or more catalysts to produce a total product in which a mixture of crude feed and total product has a P value of at least 1.5 during contact.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, contact in the presence of a hydrogen source.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, the touch conditions that include: (a) a temperature in the range of about 50 ° C to about 500 ° C; (b) a temperature of at most 430 ° C, at most 420 ° C, or at most 410 ° C; (c) a total pressure in a range of from about 0.1 MPa to about 20 MPa; (d) a total pressure of at most 18 MPa, at most 16 MPa, or at most 14 MPa; (e) a specific liquid flow rate per hour of at least 0.05 h -1; and / or (f) a ratio of a gaseous hydrogen source to the crude-containing feed - 19 - in a range of about 0.1 Nm3 / m3 to about 100,000 Nm3 / m3.

In some embodiments, the invention also provides, in combination with one or more of the above embodiments, a method which involves contacting one or more catalysts with a crude-containing feed to form a total product comprising inter alia a crude-containing product, which method further comprises combining the crude-containing product with a crude-containing raw material which may or may not differ from the crude-containing feed to form a mixture suitable for transport.

In some embodiments, the invention, in combination with one or more of the above embodiments, provides a method of making a catalyst that includes combining a support with a solution of metal from Column 6: (a) having a pH to about 3; (b) which has a pH in a range of about 1 to about 3; (c) wherein an amount of metal from Column 6 in the metal solution is selected such that the catalyst is from about 0.0001 grams to about 0.3 grams, about 0.005 grams to about 0.2 grams, or about 0.01 grams to about 0.1 gram of one or more of the metals

Column 6 and / or one or more of the metal compounds from Column 6 per gram of catalyst, calculated as the total weight of metal from Column 6; (d) comprising one or more metals from Columns 7-10 of the Periodic Table and / or one or more compounds of one or more metals from Columns 7-10 of the Periodic Table; and wherein an amount of metals from Columns 7-10 is selected such that the catalyst is from about 0.001 grams to about 0.1 grams, or about 0.01 grams to about 0.05 grams of one or more of the metals from Columns 7-10 and / or one or more of the metal compounds from Columns 7-10 per gram of catalyst, calculated as the total weight of metals from Columns 7-10; (e) comprising one or more metals from Column 10 of the Periodic Table and / or one or more compounds of one or more metals from Column 10 of the Periodic Table; (f) comprising molybdenum and / or tungsten; (g) comprising nickel and / or cobalt; (h) which comprises nickel and iron; (i) comprising one or more elements from Column 15 of the Periodic Table and / or one or more connections of one or more elements from Column 15 of the Periodic Table; and wherein an amount of elements from Column 15 is selected such that the catalyst is from about 0.000001 grams to about 0.1 grams, about 0.00001 grams to about 0.06 grams, about 0.00005 grams to about 0.03 grams or about 0.0001 grams to about 0.001 grams of one or more of the elements from Column 15 and / or one or more compounds of the elements from Column 15 per gram of catalyst, calculated as the total weight of elements from Column 15 ; (j) comprising phosphorus; (k) which comprises one or more mineral acids; (1) comprising one or more organic acids; (m) comprising hydrogen peroxide; And / or (n) comprising an amine.

In some embodiments, the invention, in combination with one or more of the above embodiments, provides a method for making a catalyst that includes: heat treatment of the supported metal at a temperature in a range of from about 40 ° C to about 400 ° C, about 60 ° C to about 300 ° C or about 100 ° C to about 200 ° C and any further heat treatment of the supported metal at a temperature of at least 400 ° C.

In some embodiments, the invention, in combination with one or more of the above embodiments, provides a metal catalyst

Columns 6-10: (a) comprising one or more metals from Column 6 of the Periodic Table and / or one or more compounds of one or more metals from Column 6 of the Periodic Table; (b) comprising one or more metals from Columns 7-10 of the Periodic Table and / or one or more compounds of one or more metals from Columns 7-10 of the Periodic Table; (c) comprising molybdenum and / or tungsten; (d) which comprises nickel and / or cobalt; (e) wherein the binder comprises silica, alumina, silica / alumina, titanium oxide, zirconium oxide or mixtures thereof; and / or (f) which is amorphous.

In further embodiments, features of specific embodiments may be combined with features of other embodiments. For example, features of a particular embodiment can be combined with features of any of the other embodiments.

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

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

In further embodiments, transport fuels, fuel, lubricants, or chemicals can be obtained from a crude product or a mixture obtained by any of the methods and systems described herein.

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BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of the present invention will be apparent to those skilled in the art from the following detailed description and with reference to the accompanying drawings, in which: FIG. 1 is a schematic representation of an embodiment of a touch system.

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

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

FIG. 4 is a schematic representation of an embodiment of a separation zone in combination with a touch system.

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

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

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

DETAILED DESCRIPTION

The above problems can be addressed using the systems, methods and catalysts described herein. For example, the crude oil product with a reduced MCR content and / or a reduced nitrogen content relative to the MCR content and / or the nitrogen content of the crude feed 10 is produced by contacting the crude feed with the catalyst having a pore size distribution with a median pore diameter greater than 110 Å and a pore volume in which pores with a pore diameter of at least 350 Å make up at most 10% of the pore volume. Crude oil product with a reduced nitrogen content relative to the nitrogen content of the crude oil feed is produced by contacting the crude oil feed with the unnealed catalyst. Crude oil product with a reduced metal content in metal salts of organic acids relative to the metal content in metal salts of organic acids of the crude feed is produced by contacting the crude feed with the catalyst which include metal / (metals) from Columns 5-10 and theta alumina. Crude oil product with a reduced MCR content relative to the MCR content of the crude feed is produced by contacting the crude feed with the bulk metal catalyst.

In U.S. Application Serial Nos. 11 / 014,335, 11 / 013,553, 11 / 014,386, 11 / 013,554, 11 / 013,629, - 24 - 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, 5 11 / 014.132, 11/0 014,363, 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, and 11 / 013,622, systems, methods and catalysts are also discussed that address the above problems, albeit with regard to crude feeds that may differ in some respects from the crude feeds treated according to the inventions described herein.

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

"ASTM" refers to American Standard Testing and Materials.

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

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

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

"Binder" refers to a substrate in which smaller particles are combined with each other to form larger substances (e.g., blocks or grains).

- 25 - "Bulk metal catalyst" refers to a catalyst that comprises at least one metal and that does not require a support.

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

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

System.

"Element (s) from Column X" refers to one or more elements from Column X of the Periodic Table and / or one or more connections of one or more elements from Column X of the Periodic Table, where X with a column number ( for example 13-18) of the Periodic System. For example, "element (s) from Column 15" refers to one or more elements from Column 15 of the Periodic Table and / or one or more connections of one or more elements from Column 15 of the Periodic Table.

Within the scope of this application, weight of a metal from the Periodic Table, weight of a compound of a metal from the Periodic Table, weight of an element from the Periodic Table

System or weight of a connection of an element from the Periodic System calculated as the weight of metal or the weight of element. For example, if 0.1 gram of MoO 3 is used per gram of catalyst, the calculated weight of the molybdenum metal in the catalyst is 0.067 gram per gram of catalyst.

"Content" refers to the weight of a component in a substrate (for example, a crude-containing feed, a total product or a crude-containing product), expressed as a weight fraction or weight percentage based on the total weight of the substrate. "Wtppm" refers to parts by weight of 10 per million.

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

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

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

Basic nitrogen ("bn") is as determined by ASTM method D2896.

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

"Flat plate breaking strength" refers to the compressive force required to break a catalyst. Flat plate breaking strength is D4179 as determined by ASTM method 10.

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

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

"Periodic Table" refers to the Periodic Table as specified by the

International Union of Pure and Applied Chemistry (IUPAC), November 2003.

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

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

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

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

"Ni / V / Fe content" refers to the content of nickel, vanadium, iron or combinations thereof. The Ni / V / Fe content is as determined by ASTM method D5708.

"Nm3 / m3" refers to normal cubic meters of gas per cubic meter of crude feed.

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

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

are gases.

"P (eptization) value", or "P value", refers to a numerical value that represents the flocculation of asphaltenes in the crude feed 30. The determination of the P value is described by J. J. Heithaus in "Measurement and Significance of Asphaltene Peptization", Journal of - 29 -

Institute of Petroleum, Vol. 48, Number 458, February 1962, pp. 45-53.

"Pore diameter", "average pore diameter", "median pore diameter" and "pore volume" refer to pore diameter, average pore diameter, median pore diameter and pore volume, as determined by ASTM method D4284 (mercury porosimetry at a contact angle equal to 140 °). A micromeritics® A9220 instrument (Micromeritics Ine., Norcross, Georgia, U.S.A.) can be used to determine these values. Pore volume means the volume of all pores in the catalyst. Median pore diameter refers to the pore diameter where 50% of the total number of pores has a pore diameter above the median pore diameter and 50% of the total number of pores has a pore diameter below the median pore diameter. The average pore diameter, expressed in units of Angstrom (A), is determined with the following equation:

Average pore diameter = (40,000 x total pore volume in cm 3 / g) / (area in m2 / g).

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

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

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

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

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

- 30 - (10000F) at 0.101 MPa. The VGO content is as determined by ASTM method D5307.

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

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

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

Stabilized crude oil raw materials include crude oil raw materials that have not been distilled and / or fractionally distilled in a treatment facility to produce multiple components with a specific coke spread (e.g. naphtha, distillates, VGO and / or lubricating oils).

Distillation includes, but is not limited to, atmospheric distillation methods and / or vacuum distillation methods. Non-distilled and / or non-fractionated, stabilized crude oil raw materials may include components that have a carbon number greater than 4 in amounts of at least 0.5 grams of such components per gram of crude oil raw material. Stabilized raw oil-containing raw materials also include crude-containing raw materials from distillation processes on the earth's surface. For example, Canadian tar sands can be extracted by mining and then treated in a distillation process at the surface of the earth.

The crude-containing raw material produced from such distillation at the earth's surface can be a stabilized crude-containing raw material. Examples of stabilized crude oil raw materials include crude oil raw materials as a whole, topped crude oil raw materials, desalinated crude oil raw materials, desalinated topped crude oil raw materials, distilled crude oil raw materials or mixtures thereof. "Capped" refers to a crude feedstock that has been treated such that at least some of the components having a boiling point below 35 ° C at 0.101 MPa (about 95 ° F at 1 atm) have been removed. Capped crude-containing raw materials generally have a content of at most 0.1 grams, at most 0.05 grams or at most 0.02 grams of such components per gram of capped crude-containing raw material.

Some stabilized crude-containing raw materials have properties that make it possible to transport the stabilized crude-containing raw materials with conveyors (for example, pipelines, trucks or ships) to conventional treatment facilities - 32 - Other crude-containing raw materials have one or more unsuitable properties that make them "disadvantaged" (giving adverse properties). Such "disadvantaged crudes" may be unacceptable for a means of transport and / or a treatment facility, which gives the disadvantaged crude a low economic value. The economic value can be such that a reservoir that includes, among other things, the disadvantaged crude is considered too expensive to produce, transport and / or treat.

Features of disadvantaged crudes may include but are not limited to: a) a TAN of at least 0.1 or at least 0.3; b) a viscosity of at least 10 cSt; c) an API density of at most 19; D) a total Ni / V / Fe content of at least 0.00002 grams or at least 0.0001 grams of Ni / V / Fe per gram of disadvantaged crude; e) a total heteroatom content of at least 0.005 grams of heteroatoms per gram of disadvantaged crude; f) a residue content of heteroatoms of at least 0.0001 grams of residue per gram of disadvantaged crude; g) a C5 asphaltenes content of at least 0.04 grams of C5 asphaltenes per gram of disadvantaged crude; h) an MCR content of at least 0.0001 grams of MCR per gram of disadvantaged crude; i) a metal content in metal salts of organic acids of at least 0.00001 grams of metals per gram of disadvantaged crude; or j) combinations thereof. In some embodiments, disadvantaged crudes include at least 0.2 grams of residue, at least 0.3 grams of residue, at least 0.5 grams of residue, or at least 0.9 grams of residue per gram of disadvantaged crude.

In some embodiments, disadvantaged crudes have a TAN in a range of from about 0.1 to about 20, about 0.3 to about 10, or about - 33 - 0.4 to about 5. In certain embodiments, disadvantaged crudes have a sulfur content of at least ten at least 0.005, at least 0.01 or at least 0.02 grams per gram of disadvantaged crude.

In some forms, disadvantaged crudes have an MCR content of at least 0.0001 grams, at least 0.001 grams, at least 0.003 grams, at least 0.005 grams, at least 0.01 grams, at least 0.1 grams or at least 0.5 grams per gram of disadvantaged crude.

Disadvantaged crudes can have an MCR content in a range of from about 0.0001 grams to about 0.5 grams, about 0.005 grams to about 0.1 grams, or about 0.01 grams to about 0.05 grams per gram of disadvantaged crude to have.

In some embodiments, disadvantaged crudes have a nitrogen content of at least 0.0001 grams, at least 0.001 grams, at least 0.01 grams, at least 0.05 grams or at least 0.1 grams per gram of disadvantaged crude. Disadvantaged crudes can have a nitrogen content in a range of from about 0.0001 grams to about 0.1 grams, about 0.001 grams to about 0.05 grams, or about 0.005 grams to about 0.01 grams per gram of disadvantaged crude.

In some forms, disadvantaged crudes contain at least 0.00001 grams, at least 0.0001 grams, at least 0.001 grams, or at least 0.01 grams of alkali and alkaline earth metals in metal salts of organic acids. Disadvantaged crudes can include a metal content in metal salts of organic acids in a range of from about 0.00001 grams to about 0.003 grams, about 0.00005 grams to about 0.005 grams, or about 0.0001 grams to about 0.01 grams of alkali metal - 34 - and alkaline earth metal in metal salts of organic acids.

In some forms, disadvantaged crudes have features including, but not limited to: a) 5 a TAN of at least 0.5; b) an oxygen content of at least 0.005 grams of oxygen per gram of crude feed; c) a C5 asphaltenes content of at least 0.04 grams of C5 asphaltenes per gram of crude feed; d) a viscosity higher than desired (for example, higher than or equal to 10 cSt with a crude feed with an API density of at least 10. e) a metal content in metal salts of organic acids of at least 0, 00001 grams of alkali and alkaline earth metals per gram of crude feed; or f) combinations thereof.

Disadvantaged crudes can include per gram of disadvantaged crude, inter alia: at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a coke spread between approximately 95 ° C and approximately 200 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between approximately 200 ° C and approximately 300 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between approximately 300 ° C and approximately 400 ° C at 0.101 MPa and at least 0.001 gram, at least 0.005 gram or at least 0.01 grams of hydrocarbons with a boiling range spread between approximately 400 ° C and 650 ° C at 0.101 MPa.

Disadvantaged crudes can include per gram of disadvantaged crude: at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread of at most 100 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between approximately 100 ° C and approximately 200 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between approximately 200 ° C and approximately 300 ° C at 0.101 MPa; at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between approximately 300 ° C and approximately 400 ° C at 0.101 MPa; and at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread between approximately 400 ° C and 650 ° C at 0.101 MPa.

Some disadvantaged crudes may include per gram of disadvantaged crude, inter alia: at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range spread of at most 100 ° C at 0.101 MPa, in addition to higher-boiling components. Usually the disadvantaged crude has such a hydrocarbon content of at most 0.2 grams or at most 0.1 grams per gram of disadvantaged crude.

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

In certain forms, disadvantaged crudes include up to 0.9 grams, or up to 0.99 grams, of hydrocarbons with a boiling range spread above 300 ° C per gram of disadvantaged crude. In certain forms, disadvantaged crudes also include at least 0.001 grams of hydrocarbons with a boiling range spread above 650 ° C per gram of disadvantaged crude. In certain forms, disadvantaged crudes include up to about 0.9 grams> or 5 to about 0.99 grams of hydrocarbons with a boiling range spread between about 300 ° C and about 1000 ° C per gram of disadvantaged crude.

Examples of disadvantaged crudes that can be treated using the processes described herein include but are not limited to crude oil resources from the following regions of the world: the US Gulf Coast, southern California, the "north slope" of Alaska, the Canadian tar sands, the Canadian Alberta region, the Mexican 15 Campeche bay, the Argentinian San Jorge basin, the

Brazilian Santos and Campos basins, the Egyptian Gulf of Suez, Chad, the British sector of the North Sea, the Angolan Offshore, the Chinese Bohai Bay, the Chinese Karamay area, the Iraqi Zagros area, the 20 Kazakh sector of the Caspian Sea, the Nigerian

Offshore, northwestern Madagascar, Oman, Schoonebeek, the Venezuelan Zulia region, Malaysia and Sumatra. Treatment of disadvantaged crudes can improve the properties of the disadvantaged crudes such that the crude-containing raw materials are acceptable for transportation and / or handling. A crude oil raw material to be treated and / or disadvantaged crude is referred to herein as a "crude oil feed." The crude feed may be topped as described herein. The crude feed can be obtained by methods as described herein, but not exclusively therewith. The crude-oil product obtained from treatment of the crude feed, as described herein, is generally suitable for transport and / or handling. Properties of the crude oil product produced as described herein are closer to the corresponding properties of crude West Texas Intermediate oil than those of the crude oil feed or closer to the corresponding properties of Brent crude oil than those of the crude oil oil-based food, which increases the economic value of the crude-oiled food. Such a crude-containing product can be refined with less pre-treatment than other crude-containing products or without pre-treatment from disadvantaged crude feeds, which increases refining efficiency. Pre-treatment may include desulfurization * demetallization and / or atmospheric distillation to remove impurities.

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

- FIG. 1 is a schematic representation of touch system 100, which includes an upstream touch zone 102. The crude-containing feed enters upstream contact zone 102 via crude-containing feed line 104. A contact zone can be a reactor, a part of a reactor, multiple parts of a reactor or combinations thereof. Examples of a contact zone include a stacked bed reactor, a fixed bed reactor, a bubbling bed reactor, a continuously stirred tank reactor ("CSTR"), a fluidized bed reactor, a spray reactor and a liquid / liquid contactor. In certain embodiments, the touch system is located at or connected to an offshore facility. The contact of the crude feed with the catalyst (s) in contact system 100 can be a continuous process or a batch process.

The contact zone may include one or more catalysts (e.g., two catalysts). In some embodiments, contacting the crude feed with a first catalyst of the two catalysts can reduce the metals in metal salts of organic acids of the crude feed. Subsequent contact of the crude feed containing fewer metal salts with the second catalyst can reduce the MCR content and / or the heteroatoms content. In other embodiments, TAN, viscosity, Ni / V / Fe content, hetero atom content, residue content, API density or combinations of these properties of the crude product change by at least 10% relative to the same properties of the crude - oil-based feed - 39 - after contacting the crude-oiled feed with one or more catalysts.

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

The contact conditions in the contact zone may include, but are not limited to: temperature, pressure, flow of the hydrogen source, flow of the crude feed or combinations thereof. In some embodiments, the contact conditions are controlled to produce a crude product with specific properties. The temperature in the contact zone may range from about 50 ° C to about 500 ° C, about 60 ° C to about 440 ° C, about 70 ° C to about 430 ° C, or about 80 ° C to about 420 ° C. The pressure in a contact zone can range from about 0.1 MPa to about 20 MPa, about 1 MPa to about 12 MPa, about 4 MPa to about 10 MPa, or about 6 MPa to about 8 MPa. The LHSV of the crude feed 30 will generally range from about 0.05 h -1 to about 30 h -1, about 0.5 h -1 to about 25 h -1, about 1 h -1 to about 20 h -1, about 1.5 h -1 to about 15 h -1, or about 2 h -1 to about 10 h -1.

- 40 -

In some embodiments, the LHSV is at least 5 h -1, at least 11 h -1, at least 15 h -1, or at least 20 h -1. In some embodiments, the total pressure is at most 18 MPa, at most 16 MPa, maximum 14 MPa, 5 maximum 12 MPa, maximum 10 MPa, or maximum 8 MPa. In certain embodiments, the temperature is at most 430 ° C, at most 420 ° C, at most 410 ° C, or at most 400 ° C.

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

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

In downstream separation zone 108, the crude product and the gas can be separated from the total product using well-known separation techniques, for example gas-liquid separation. The crude-containing product can leave downstream separation zone 108 via crude-containing product line 112 and then be transported to transport means, pipelines, storage vessels, refineries, other processing zones or a combination thereof. The gas may include gas formed during processing (e.g. hydrogen sulfide, carbon dioxide and / or carbon monoxide), excess hydrogen source and / or carrier gas. The excess gas can be recirculated to touch system 100, purified and transported to other processing zones, storage vessels or combinations thereof.

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

- FIG. 2-3 are schematic representations of embodiments of touch system 100, which includes two or three touch zones. In FIG. 2A and 2B include touch system 100, including upstream touch zone 102 and downstream touch zone 114.

FIG. 3A and 3B include, for example, touch zones 102, 114, 116. In FIG. 2A and 3A, touch zones 102, 114, 116 are depicted as separate touch zones in one reactor. The crude-containing feed enters upstream contact zone 102 via crude-containing feed line 104.

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

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

-43-

Touch zones 102, 114, 116 may include one or more catalysts. As shown in FIG. 2B, leaves the feed stream upstream touch zone 102 via feed stream line 118 and enters downstream touch zone 114. As shown in FIG. 3B, leaves the feed stream downstream touch zone 114 via line 118 and enters additional downstream touch zone 116.

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

FIG. 4 is a schematic representation of an embodiment of a separation zone upstream of touch system 100. The (whether or not capped) disadvantaged crude enters upstream separation zone 120 via disadvantaged crude line 122. In upstream separation zone 120, at least a portion of the disadvantaged crude is cleaved using techniques known in the art (e.g., spraying, membrane separation, pressure reduction, filtering, or combinations thereof) to produce the crude feed. For example, water can be split off at least partially from the disadvantaged crude into upstream separation zone 120. In another example, components having a boiling range spread below 95 ° C or below 100 ° C can be at least partially 5 in upstream separation zone 120. from the disadvantaged crude are split off to produce the crude feed. In some embodiments, at least a portion of naphtha and compounds that are more volatile than naphtha are cleaved from the disadvantaged crude. In some embodiments, at least a portion of the spliced components leave upstream separation zone 120 via conduit 124.

In some embodiments, the crude oil-containing feedstock obtained from upstream separation zone 120 includes a mixture of components with a coke gap spread of at least 100 ° C or, in some embodiments, a coke trail spread of at least 120 ° C. Typically, the cleaved crude feed includes a mixture of ingredients with a boiling range spread between about 100 ° C to about 1000 ° C, about 120 ° C to about 900 ° C, or about 200 ° C to about 800 ° C. At least a portion of the crude feed leaves upstream separation zone 120 and enters touch system 100 via additional crude feed line 126 (see, for example, the touch zones in FIGS. 1-3) to be further processed to form a rough feed. oil-containing product. In some embodiments, upstream separation zone 120 may be located upstream or downstream of a desalination unit. In certain embodiments, upstream separation zone 120 may be located downstream of a distillation process for bitumen, shale oil and / or tar sands. After processing, the crude product leaves touch system 100 via crude product line 112.

In some embodiments, the crude oil product is mixed with a crude oil raw material that may or may not be the same as the crude oil feed. For example, the crude-oil product can be combined with a crude-oil raw material with a different viscosity, which yields a mixed product with a viscosity that lies between the viscosity of the crude-oil product and the viscosity of the crude-oil raw material. In another example, the crude product 15 may be mixed with crude raw material that has a TAN and / or an MCR content that is different, yielding a product that has a TAN and / or an MCR content that is between the TAN and / or MCR content of the crude product and that of the crude feedstock. The mixed product can be suitable for transport and / or handling.

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

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

In some embodiments, the crude product and / or the blended product is (are) transported to a refinery and distilled and / or fractionally distilled to form one or more distillate fractions. The distillate fractions can be processed to produce commercial products such as transport fuel, lubricants or chemical products.

In some embodiments, after contacting the crude feed with the catalyst, the crude product has a TAN of at most 90%, at most 50%, at most 30% or at most 10% of the TAN of the crude oil feed. In certain embodiments, the crude product has a TAN of at most 1, at most 0.5, at most 0.3, at most 0.2, at most 0.1 or at most 0.05. The TAN of the crude product will often be at least 0.0001 and more often at least 0.001. In some embodiments, the TAN of the crude product may be in a range of from about 0.001 to about. 0.5, about 0.01 to about 0.2, or about 0.05 to about 0.1.

In some embodiments, the crude product has a total Ni / V / Fe content of at most 90%, at most 50%, at most 30%, at most 10%, at most 5% or at most 3% of the Ni / V / Fe content of the crude feed. In certain embodiments, the crude product has a total Ni / V / Fe content in a range from about 1 x 10 "7 grams to about 5 x 10" 5 grams, about 3 x 10 "7 grams to about 2 x 10 "5 grams, or about 1 x 10-6 grams to about 1 x 10" 5 grams per 30 grams of crude product. In certain embodiments, the crude product has a maximum of 2 x 10 "5 grams of Ni / V / Fe per gram of crude product. In some embodiments, a total Ni / V / Fe content of the crude product is about 70% to about 130%, about 80% to about 120%, or about 90% to about 110% of the Ni / V / Fe content of the crude feed.

In some embodiments, the crude product has a total metal content in metal salts of organic acids of at most 90%, at most 50%, at most 30%, at most 10% or at most 5% of the total content of metals in metal salts of organic acids in the crude-oiled feed. In some embodiments, the total metal content in metal salts of organic acids is in a range of about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25%, or about 2 % to about 9% of the metal content in metal salts of organic acids from the crude feed. Organic acids that generally form metal salts include, but are not limited to, carboxylic acids, thiols, imides, sulfonic acids, and sulfonates. Examples of carboxylic acids include, but are not limited to, naphthenic acids, phenanthrene acids, and benzoic acid. The metal part of the metal salts may include alkali metals (e.g. lithium, sodium and potassium), alkaline earth metals (e.g. magnesium, calcium and barium), metals from Column 12 (e.g. zinc and cadmium), metals from Column 15 (e.g. arsenic), metals from Column 6 (e.g. chromium) or mixtures thereof.

In some embodiments, the crude product has a total alkali metal and alkaline earth metal content in metal salts of organic acids of at most 90%, at most 80%, at most 50%, at most 30%, at most 10% or at most 5% of the content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude feed. In some embodiments, the total content of alkali metal and alkaline earth metal in metal salts of organic acids in the crude product is in a range of about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9% of the total content of alkali metal and alkaline earth metal salts of 10 organic acids in the crude feed.

In certain embodiments, the crude product has a total zinc salts content of one or more organic acids of at most 90%, at most 80%, at most 50%, at most 30%, at most 10% or at most 5 % of the zinc salts content of one or more organic acids in the crude feed. In some embodiments, the total zinc salts content of organic acids in the crude product is in a range of from about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25% or about 2% to about 9% of the total zinc salts content of organic acids in the crude feed.

In some embodiments, the crude product has a total content of chromium and / or arsenic in metal salts of organic acids of up to 90% of the content of chromium and / or arsenic in metal salts of organic acids in the crude feed.

In certain embodiments, the crude product contains about 1 x 10-7 grams to about 5 x 10 ~ 5 grams, about 5 x 10 7 grams to about 1 x 10 "5 grams, or about 1 x 10" grams. to about - 50 - 5 x 10 "6 grams of alkali metal and alkaline earth metal in metal salts of organic acids per gram of crude product.

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

In certain embodiments, the crude product has a viscosity of at most 90%, at most 80%, at most 70%, at most 50%, at most 30%, at most 10% or at most 5% of the viscosity of the crude feed. In some embodiments, the viscosity of the crude product is at most 90% of the viscosity of the crude feed while the API density of the crude product is about 70% to about 130%, about 80% to about 120%, or about 90% to about 110% of the API density is the crude feed.

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

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

In some embodiments, the total nitrogen content of the crude product may be at most 90%, at most 80%, at most 70%, at most 50%, at most 30% or at most 10% or at most 5% of a total nitrogen content of the crude feed. In certain embodiments, the crude product has a total nitrogen content of at least 1%, at least 30%, at least 80%, or at least 99% of the total nitrogen content of the crude feed. In certain embodiments, the crude product has a total nitrogen content in a range of from about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9% of the total nitrogen content of the crude feed. In some embodiments, the crude product has a total nitrogen content in a range of from about 0.00001 grams to about 0.05 grams, about 0.0001 grams to about 0.01 grams, or about 0.0005 grams to about 0.001 grams per gram of crude product.

- 52 -

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

In some embodiments, the oxygen content of the crude product may be at most 90%, at most 50%, at most 30%, at most 10% or at most 5% of the oxygen content of the crude feed. In certain embodiments, the oxygen content of the crude product may be at least 1%, at least 30%, at least 80%, or at least 99% of the oxygen content of the crude feed. In some embodiments, the total content of carboxylic acid compounds of the crude product can be at most 90%, at most 50%, at most 30%, at most 10% or at most 5% of the content of carboxylic acid compounds in the crude nutrition. In certain embodiments, the total carboxylic acid compound content of the crude product may be at least 1%, at least 30%, at least 80%, or at least 99% of the total carboxylic acid compound content in the crude feed.

In some embodiments, selected organic oxygen compounds can be reduced in the crude feed. In some embodiments, carboxylic acids and / or metal salts of carboxylic acids may be chemically reduced prior to non-carboxyl-containing organic oxygen compounds. Carboxylic acids and non-carboxyl-containing organic oxygen compounds in a crude product may be differentiated by analysis of the crude product using well-known spectroscopy methods (e.g., infrared analysis, mass spectrometry, and / or gas chromatography).

In certain embodiments, the crude product has an oxygen content of at most 90% f at most 80% r at most 70% or at most 50% of the oxygen content of the crude feed and the TAN of the crude product is at most 90%, at most 70%, at most 50%, at most 30% or at most 40% of the TAN of the crude feed. In certain embodiments, the oxygen content of the crude product can be at least 1%, at least 30%, at least 80% or at least 99% of the oxygen content of the crude feed and the crude product has one TAN of at least 1%, at least 30%, at least 80% or at least 99% of the TAN of the crude feed.

In addition, the crude product may contain a content of carboxylic acids and / or metal salts of carboxylic acids of at most 90%, at most 70%, at most 50% or at most 40% of the crude feed and a content of non- carboxylic organic oxygen compounds within about 70% to about 130%, about 80% to about 120%, or about 90% to about 110% of the non-carboxylic organic oxygen compounds of the crude feed.

- 54 -

In some embodiments, the crude product in its molecular structure includes from about 0.05 grams to about 0.15 grams, or from about 0.09 grams to about 0.13 grams of hydrogen per gram of crude product. The crude product may include in its molecular structure inter alia about 0.8 grams to about 0.9 grams, or about 0.82 grams to about 0.88 grams of carbon per gram of crude product. A ratio of atomic hydrogen to atomic carbon (H / C) of the crude product may be within about 70% to about 130%, about 80% to about 120%, or about 90% to about 110% of the H / C atomic ratio of the crude feed. An H / C atomic ratio of the crude product that is within about 10% to about 30% of the H / C atomic ratio of the crude feed indicates that hydrogen uptake and / or consumption in the process is relatively is low and / or that hydrogen is produced in situ.

The crude-containing product includes components with various boiling points. In some embodiments, the crude product per gram of crude product includes: at least 0.001 gram, or about 0.001 gram to about 0.5 gram of hydrocarbons with a boiling range of at most 100 ° C at 0.101 MPa; at least 0.001 grams, or about 0.001 grams to about 0.5 grams of hydrocarbons with a boiling range spread between about 100 ° C and about 200 ° C at 0.101 MPa; at least 0.001 30 grams, or about 0.001 grams to about 0.5 grams of hydrocarbons with a boiling range spread between about 200 ° C and about 300 ° C at 0.101 MPa; at least 0.001 gram, or about 0.001 gram to about - 55 -

0.5 grams of hydrocarbons with a coke spread between about 300 ° C and about 400 ° C at 0.101 MPa; and at least 0.001 grams, or about 0.001 grams to about 0.5 grams of hydrocarbons with a boiling range spread between about 400 ° C and about 538 ° C

at 0.101 MPa.

In some embodiments, the crude product includes at least 0.001 grams of hydrocarbons with a coke spread of at most 100 ° C at 0.101 MPa and / or at least 0.001 grams of hydrocarbons with a coke spread between about 100 ° C and about 200 ° C at 0.101 MPa per gram of crude product.

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

In some embodiments, the crude product has a distillate content in a range of from about 0.00001 grams to about 0.5 grams, about 0.001 grams to about 0.3 grams, or about 0.002 grams to about 0.2 grams per gram crude product.

In certain embodiments, the crude product has a VGO content in a range of from about 0.00001 grams to about 0.8 grams, about 0.001 grams to about 0.5 grams, about 0.005 grams to about 0.4 grams, or from about 0.01 grams to about 0.3 grams per gram of crude product.

In some embodiments, the crude product has a residual content of at most - 56 - 90%, at most 70%, at most 50%, at most 30% or at most 10% of the residual content of the crude feed. In certain embodiments, the crude product has a residual content of about 70% to about 130%, about 80% to about 120%, or about 90% to about 110% of the residual content of the crude feed. The crude product can have a residual content per gram of crude product in a range of from about 0.00001 grams to about 0.8 grams, about 0.0001 grams to about 0.5 grams, about 0.0005 grams to about 0.4 grams, about 0.001 grams to about 0.3 grams, about 0.005 grams to about 0.2 grams, or about 0.01 grams to about 0.1 grams.

In some embodiments, the C5 asphaltenes content is at most 90%, at most 80%, at most 70%, at most 50%, at most 30% or at most 10% of the C5 asphaltenes content of the crude nutrition. In certain embodiments, the C5-20 asphaltenes content of the crude oil product is at least 10%, at least 60% or at least 70% of the C5 asphaltenes content of the crude feed. The crude product may have a C5 asphaltenes content in a range of about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9 % of the C5 asphaltenes content of the crude feed. The crude product in some embodiments contains about 0.0001 grams to about 0.1 grams, about 0.005 grams to about 0.08 grams, or about 0.01 grams to about 0.05 grams of C5 asphaltenes per gram of crude oil product.

- 57 -

In certain embodiments, the crude product has an MCR content that is at most 90%, at most 80%, at most 50%, at most 30% or at most 10% of the MCR content of the crude feed is. In some embodiments, the crude product has an MCR content in a range of about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9% of the MCR content of the crude oil-containing feed. The crude product in some embodiments contains about 0.00001 grams to about 0.1 grams, about 0.0001 grams to about 0.05 grams, or about 0.001 grams to about 0.005 grams of MCR per gram of crude product.

In some embodiments, the C5 asphaltene content and the MCR content can be combined to obtain a mathematical relationship between the highly viscous components in the crude oil product and the highly viscous components in the crude oil feed. For example, a sum of a C5 asphaltenes content in a crude oil feed and an MCR content in a crude oil feed can be represented as S. A sum of a C5 asphaltenes content in a crude oil product and an MCR content content in a crude product can be represented as S '. The sums can be compared with each other (S 'with S) to assess the net reduction in highly viscous components in the crude feed. S 'of the crude product may be in a range of about 1% to about 99%, about 10% to about 90%, or about 20% to about 80% of S. In some embodiments, a ratio of the MCR content of the crude product to the C5 asphaltenes content is in a range of about 1.0 to about 3.0, about 1.2 to about 2.0, or about 1.3 to about 1.9.

In some embodiments, the crude product includes, among other things, more than 0 grams but less than 0.01 grams, about 0.000001 grams to about 0.001 grams, or about 0.00001 grams to about 0.0001 grams total catalyst per gram of crude product. The catalyst can help to stabilize the crude product during transport and / or handling. The catalyst can prevent corrosion, prevent friction, and / or increase water separation capabilities of the crude product. Methods described herein can be configured to add one or more catalysts described herein to the crude product during treatment.

The crude-containing product produced from touch system 100 (as shown in FIGS. 1-6) has properties other than the characteristics of the crude-containing feed. Such properties may include but are not limited to: a) reduced TAN; b) reduced viscosity; c) reduced total Ni / V / Fe content; d) reduced sulfur, oxygen, nitrogen or combinations thereof; e) reduced residue level; f) reduced C5 asphaltenes content; g) reduced MCR content; h) increased API density; i) reduced metal content in metal salts of organic acids; j) increased stability with respect to the crude feed; or k) combinations thereof.

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

Examples of commercially available catalysts contemplated for use as described herein include 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, RN5010, RN5010, RN5010, RN5010 Z603, Z623, Z673, Z703, Z713, Z723, Z753 and Z763 available from CRI International, Inc. (Houston, Texas, U.A.).

In some embodiments, catalysts used to alter crude-oil feed properties include one or more metals from Columns 5-10 on a support. Metal (s) from Columns 5-10 include but not limited to vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum or mixtures thereof. Compounds of metal / (metals) from Columns 5-10 include but are not limited to oxides, nitrates, ammonium salts and carbonates of the metal / (metals) from Columns 5-10. Examples of compounds of metals from Columns 5-10 include but are not limited to molybdenum trioxide, molybdenum ammonium oxide, molybdenum carbonate, tungsten trioxide, nickel oxide, nickel carbonate, nickel nitrate, cobalt carbonate and cobalt oxide.

The catalyst can have a total metal / (metals) content from Columns 5-10 in a range of at least 0.0001 grams, at least 0.001 grams, at least 0.01 grams, at least 0.3 grams, at least 0.5 grams, at least 0.6 grams, at least 0.8 grams, or at least 0.9 grams per gram of catalyst. A total metal / (metal) content from Columns 5-10 can be in a range of from about 0.0001 grams to about 0.99 grams, about 0.0005 grams to about 0.5 grams, about 0.001 grams to about 0, 3 grams, about 0.005 grams to about 0.2 grams, or about 0.01 grams to about 0.1 grams per gram of catalyst. In some embodiments, in addition to the metal (s) from Columns 5-10, the catalyst includes, among others, element (s) from Column 15. An example of an element from Column 15 is phosphorus. The catalyst can have a total content of element from Column 15 in the range of about 0.000001 grams to about 0.1 grams, about 0.00001 grams to about 0.06 grams, about 0.00005 grams to about 0.03 grams, or about 0.0001 grams to about 0.001 grams per gram of catalyst. In other embodiments, the catalyst does not include a column 15 element.

In some embodiments, the catalyst includes a combination of metal / (metals) from Column 6 with one or more metals from Column 5 and / or Columns 7-30 10. A molar ratio of metal from Column 6 to metal from Column 5 may are in a range of about 0.1 to about 20, about 1 to about 10, or about 2 to about 5. A molar ratio of metal from · 1 - 61 -

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

In certain embodiments, the catalyst includes, inter alia, metal / (metals) from Column 6. The catalyst can have a total metal / (metal) content from Column 6 of at least 0.00001 grams, at least 0.01 grams, at least 0.02 grams and / or in a range of about 0.0001 to about 0.6 grams, about 0.001 to about 0.3 grams, about 0.005 to about 0.2 grams, or about 0.01 to about 0, Have 1 gram per gram of catalyst.

In some embodiments, the catalyst includes inter alia about 0.0001 grams to about 0.2 grams, about 0.001 grams to about 0.08 grams, or about 0.01 grams to 0.06 grams of metal (s) from Column 6 per gram of catalyst. In some embodiments, in addition to the metal (s) from Column 6, the - 62 - catalyst includes, among others, element (s) from Column 15.

In some embodiments, the catalyst includes a combination of metal / (metals) from Column 5 with one or more metals from Columns 7-10. The catalyst can have a total metal / (metals) content from Columns 7-10 in a range of about 0.0001 grams to about 0.1 grams, about 0.001 grams to about 0.05 grams, or about 0.01 grams to about 0.03 grams per gram of catalyst. In certain embodiments, the catalyst comprises, inter alia, about 0.01 grams to about 0.15 grams of molybdenum and about 0.001 grams to about 0.05 grams of nickel per gram of catalyst. The catalyst in some embodiments also includes, among others, about 0.001 grams to about 0.05 grams of iron per gram of catalyst.

In some embodiments, the catalyst includes, for example, from about 0.01 grams to about 0.15 grams of molybdenum, about 0.001 grams to about 0.05 grams of nickel, about 0.001 grams to about 0.05 grams of iron, and about 0.0001 grams to about 0.05 grams of phosphorus per gram of catalyst.

In some embodiments, metal / (metals) from Columns 5-10 is (are) incorporated into or deposited on a support to form the catalyst. In certain embodiments, metal / (metals) from Columns 5-10 in combination with one or more elements from Column 15 is / are incorporated in or deposited on the support to form the catalyst.

In embodiments in which the metal (s) and / or element (s) are supported, the weight of the catalyst comprises the entire support, all metal (s) and all element (s). The support may be porous and may include heat-resistant oxides, porous carbon-based materials, zeolites, or combinations thereof. Heat-resistant oxides may include, but are not limited to, alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof.

Carriers can be obtained from a commercial manufacturer, such as Criterion Catalysts and Technologies LP (Houston, Texas, U.S.A.). Porous materials based on carbon include, but are not limited to, activated carbon and / or porous graphite. Examples of zeolites include Y zeolites, beta zeolites, mordenite zeolites, ZSM-5 zeolites, and ferrierite zeolites. Zeolites can be obtained from a commercial manufacturer, such as Zeolyst (Valley Forge, Pennsylvania, U.S.A.). The carrier can be prepared and / or selected on the basis of various or desired properties. Examples of properties include, but are not limited to, pore volume, average pore diameter, pore volume spread, area and pore percentage above or within a certain pore diameter range.

In some embodiments, the support is prepared such that the support has an average pore diameter of at least 90 A, at least 110 A, at least 130 A, at least 150 A, at least 170 A, or at least 180 A.

In certain embodiments, the carrier is prepared by combining water with the carrier to form a paste. In some embodiments, an acid is added to the paste to facilitate extrusion of the paste. The water and the dilute acid are added in such amounts and by such methods as are necessary to give the extrudable paste a desired consistency. Examples of acids include, but are not limited to, nitric acid, acetic acid, sulfuric acid and hydrochloric acid.

To form extrudates, the paste can be extruded and cut using well-known catalyst extrusion methods and catalyst cutting methods. The extrudates can be thermally treated at a temperature in a range of from about 65 ° C to about 260 ° C or from about 85 ° C to about 235 ° C for a certain period of time (e.g., for about 0.5 hours to about 8 hours ) and / or until the moisture content of the extrudate has reached a desired level. The thermally treated extrudate can further be thermally treated at a temperature in a range of from about 800 ° C to about 1200 ° C or about 900 ° C to about 120 ° C to form a support with an average pore diameter of at least 150 A . The carriers have a pore volume spread over a range of pore diameters. In some embodiments, the carrier contains pores with a pore diameter of at least 350 A, at least 400 A, at least 500 A, or at least 1000 A, or in a range of from about 350 A to about 5000 A, about 400 A to about 1000 A or about 500 A to about 900 A, which is at most 15%, at most 10%, at most 5% at most 3%, at most 1% or at most 0.5% of the total pore volume of the carrier to shape.

In certain embodiments, the carrier includes gamma alumina, theta alumina, delta alumina, alpha alumina, or combinations thereof. The amount of gamma-30 alumina, delta-alumina, alpha-alumina or combinations thereof can be in a range of from about 0.0001 grams to about 0.99 grams, about 0.001 grams to about 0.5 grams, about 0.01 grams to approximately 0.1 grams, or at most 65 - 0.1 grams per gram of catalyst support, as determined by X-ray diffraction. In some embodiments, the carrier includes at least 0.5 grams, at least 0.8 grams, at least 0.9 grams, or at least 0.95 grams of gamma alumina per gram of carrier. In certain embodiments, the carrier contains from about 0.5 grams to about 0.99 grams, about 0.6 grams to about 0.9 grams, or about 0.7 grams to about 0.8 grams of gamma-alumina per gram of carrier. In certain embodiments, the carrier itself or in combination with other forms of alumina has a theta alumina content in a range of from about 0.1 grams to about 0.99 grams, about 0.5 grams to about 0.9 grams, or about 0.6 grams to about 0.8 grams per gram of carrier, as determined by X-ray diffraction. In some embodiments, the carrier may have at least 0.1 grams, at least 0.3 grams, at least 0.5 grams, or at least 0.8 grams of theta alumina per gram of carrier, as determined by X-ray diffraction.

In certain embodiments, the carrier comprises, inter alia, at most 0.2 grams, at most 0.1 grams, at most 0.08 grams, at most 0.06 grams, at most 0.05 grams, at most 0.04 grams , at most 0.03 grams, at most 0.02 grams or at most 0.01 grams of silica per gram of carrier. In certain embodiments, the support has from about 0.001 grams to about 0.2 grams, or about 0.01 grams to about 0.1 grams of silica per gram of support. In some embodiments, the support includes a combination of silica and alumina.

Supported catalysts can be prepared by well-known catalyst preparation techniques. For images of catalyst preparations, U.S. Patent Nos. 6,218,333 to Gabrielov et al., 6,290,841 to Gabrielov et al.

66 and 5,744,025, to Boon et al. And U.S. Patent Application Publication No. US 2003/0111391, to Bhan.

In some embodiments, the support can be combined with metal to form a catalyst. In certain embodiments, prior to the combination with a metal, the support is thermally treated at temperatures in the range of from about 400 ° C to about 1200 ° C, about 450 ° C to about 1000 ° C, or about 600 ° C to about 900 ° C. In some embodiments, impregnation aids may be used during the preparation of the catalyst. Examples of impregnation aids include hydrogen peroxide, organic acids, amines, ethylene diamine tetraacetic acid (EDTA), ammonia or mixtures thereof. Examples of amines include, but are not limited to, alkanolamines, ammonia, alkylamines, aromatic amines, and substituted ammonium compounds. Organic acids include, but are not limited to, citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, or mixtures thereof.

In certain embodiments, the support may be combined with a metal solution having a pH of up to about 3. The pH of the metal solution may range from about 1 to about 3 or from about 1.5 to about 2.5. Control of the pH of the metal solution can facilitate dispersion of metals in the support. A dispersed or substantially dispersed metal catalyst prepared using such pH controlled conditions can, compared to the life of a conventional catalyst, have a longer catalyst life when under the same touch conditions for the processing of a raw material. oil feed is used.

The metal solution may include, among others, metal / (metals) from Column 6. In some embodiments, the metal solution includes inter alia metal / (metals) from Column 6 in combination with metal / (metals) from Columns 7-10.

In certain embodiments, the metal solution includes one or more elements from Column 15 in combination with metal / (metals) from Column 6 or in combination with metal / (metals) from Column 6 and metal / (metals) from Columns 7-10 .

In some embodiments, the pH of the metal solution can be adjusted to the desired pH of up to pH 3 using mineral acids and / or organic acid components. Mineral acids include, but are not limited to, phosphoric acid, nitric acid, sulfuric acid or mixtures thereof.

In certain embodiments, the metal solution is prepared by combining one or more solutions of metals from Columns 6-10 with different pH values. A solution of metals from Columns 6-10 with a pH in a range of about 4 to about 7, or from about 5 to about 6, can be combined with other solutions of metals from Columns 6-10 with a pH in a range from about 0.1 to about 4, or about 1 to about 3. In some embodiments, the solutions of metals from Columns 6-10 include impregnation aids, mineral acids, organic acids, element (s) from Column 30, or mixtures thereof.

In certain embodiments, a catalyst can be formed by successively adding or incorporating multiple metals from Columns 5-10 to / on a 68-carrier. Overlaying a metal on a support that includes a substantially uniform metal concentration, among other things, often gives the catalyst favorable catalytic properties. Thermal treatment of the support after each metal overlay tends to improve the catalytic activity of the catalyst. Methods to prepare a catalyst using overlay methods are described in U.S. Patent Application Publication No.

10, US 2003/0111391 to Bhan.

In some embodiments, a mixture of a support and metal / (metals) from Columns 7-10 is prepared by combining a support with one or more metals from Columns 7-10. In a particular embodiment, the mixture thus obtained comprises, inter alia, from about 0.01 grams to about 0.1 grams of metal / (metals) from Columns 7-10 per gram of carrier and metal / (metals) from Columns 7- 10. The mixture of support and metal / (metals) from Columns 7-10 can be thermally treated for a few hours at a temperature in a range of about 50 ° C to about 100 ° C or about 60 ° C to about 90 ° C, and then being thermally treated for about 2 hours at a temperature in a range of from about 400 ° C to about 700 ° C, about 450 ° C to about 650 ° C, or about 500 ° C to about 600 ° C. The metal-containing support thus obtained can be combined with one or more metals from Column 6 and optionally an additional amount of metal / (metals) from Columns 7-10, so that the finished catalyst per 30 grams of catalyst is at least 0.3 grams, at least 0 Contains 1 gram or at least 0.08 gram of the metal / (s) from Column 6 and a total metal / (s) from Columns 7-10 in a range of about 0.01 gram to - 69 - about 0.2 grams, or about 0.05 grams to about 0.1 grams per gram of catalyst. The catalyst thus obtained can be thermally treated for a few hours at a temperature in a range of from about 50 ° C to about 100 ° C or from about 60 ° C to about 90 ° C, and then thermally treated for about 2 hours at a temperature in a range of from about 350 ° C to about 500 ° C, or 400 ° C to about 450 ° C. In some embodiments, one or more elements from Column 10 can be combined with the mixture of support and metal / (metals) from Columns 7-10 and / or with the metal / (metals) from Column 6.

The metal (s) from (Columns 5-10) and the support can usually be mixed with suitable mixing equipment to form a mixture of metal (s) from Columns 5-10 and support. Examples of suitable mixing equipment include tumbling equipment, stationary trays or gutters, Muller mixers (e.g. batch type or continuous type), impact mixers and any other well-known mixer or device that suitably mixes the metal / (metals) mixture. from Columns 5-10 and support.

In certain embodiments, the materials are mixed until the metal (s) from (Columns 5-10) is / are dispersed substantially homogeneously in the support.

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

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

In other embodiments, however, the catalyst can be thermally treated in the presence of air for a period in a range of 1-3 hours at temperatures in a range of from about 35 ° C to about 500 ° C to remove the majority of the volatile components. practically without the / (the) metal / (metals)

Convert columns 5-10 to metal oxide / oxides. Catalysts prepared by such a method are generally referred to as "non-annealed" catalysts. When catalysts are prepared in this way in combination with a sulfidation method, the active metals can be substantially dispersed on the support. Preparations of such catalysts are described in U.S. Patent Nos.

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

In certain embodiments, a theta-alumina support may be combined with metal / (metals) from Columns 5-10 to form a mixture of theta-alumina support and metal / (metals) from Columns 5-25. The mixture of theta-alumina support and metal / (metals) from Columns 5-10 can be thermally treated at a temperature of at least 400 ° C to form a catalyst that has a pore size distribution with a median pore diameter of at least 230 A. Such a thermal treatment is usually carried out at temperatures of at most 1200 ° C.

In some embodiments, bulk metal catalysts used to change crude-oil feed properties include one or more metals from Columns 6-10. The bulk metal catalyst may have a total metal / (metals) content of Columns 6-10 of at least 0.3 grams, at least 0.5 grams, at least 0.6 grams, at least 0.8 grams, or at least 0 Have 9 grams per gram of catalyst. The total metal / (metals) content of Columns 6-10 can be in a range of from about 0.3 grams to about 0.99 grams, about 0.5 grams to about 0.9 grams, or about 0.6 grams to Lie approximately 0.8 grams per gram of catalyst.

In some embodiments, in addition to the metal (s) from Columns 6-10, the catalyst includes one or more elements from Column 15. The bulk metal catalyst may have a total content of elements from Column 15 in the range of about 0.000001 grams to 0.1 grams, about 0.00001 grams to about 0.06 grams, about 0.00005 grams to about 0.03 grams, or about 0.0001 grams to about 0.001 grams per gram of catalyst.

The bulk metal catalyst may in some embodiments include a binder. The binder can be silica, alumina oxide, zinc oxide, oxides of the metal (s) from Columns 6-10, carbon, zeolites or mixtures thereof. In certain embodiments, the catalyst includes inter alia a maximum of 0.2 g, a maximum of 0.1 g, a maximum of 0.05 g, a maximum of 0.01 g or a maximum of 0.005 g of binder per gram of catalyst.

The bulk metal catalyst can be prepared as described in U.S. Patent Nos. 4,937,218 to Aqudelo et al., 6,162,350 to Soled et al., And 6,783,663 to Riley et al.,

US patent applications with Publications no.

US 2004/0182749 to Domokos et al. And - 72 - US 2004/0235653 to Domokos et al .; and by Landau et al. in "Hydrosulfurization of Methyl-Substituted Dibenzothiophenes: Fundamental Study of Routes to Deep Desulfurization, Journal of Catalysis, 1996, Vol. 159, pages 236-235.

In some embodiments, one or more slurries of metal from Columns 6-10 in water or other protic liquids are contacted at a temperature in a range of about 25 ° C to about 95 ° C with a slurry of water, alkali compound and a binder to form a slurry of columns from Columns 6-10 and binder. The slurries of metal from Columns 6-10 can include 0.01 gram to 0.8 gram, 0.02 gram to 0.5 gram, or 0.05 gram to 0.3 gram of metal / (metals) from Columns 6-10 per gram of slurry. In some embodiments, the alkali compound is ammonia. An amount of alkali compound can be at least 0.5 mole, at least 0.7 mole, at least 0.8 mole, at least 0.9 mole or at most 2 mole per mole of metal / metals from Columns 6-10 , based on the oxide form of the metal (s) from Columns 6-10. In some embodiments, the binder can be silica, alumina, silica / alumina, titanium oxide, zirconium oxide, or mixtures thereof.

The metal slurry from Columns 6-10 and binder can be kept at ambient and / or slurry temperature for a certain time (for example, at least 10 minutes, at least 30 minutes or at least 240 minutes) and then, if necessary, cooled down. The bulk metal catalyst can be isolated from the slurry using general isolation techniques (e.g., filtering, spray drying, evaporative drying, evaporation, and vacuum distillation). The bulk metal catalyst may be thermally treated in a range of about 25 ° C to 95 ° C, about 55 ° C to about 90 ° C, or about 70 ° C to about 80 ° C. In some embodiments, the bulk metal catalyst is further thermally treated at a temperature in a range of about 100 ° C to about 600 ° C, about 120 ° C to about 400 ° C, or at most 300 ° C. In certain embodiments, the bulk metal catalyst can be pulverized, shaped and / or combined with other materials. The bulk metal catalyst can be characterized using powder X-ray diffraction methods.

In some embodiments, the bulk metal catalyst cannot exhibit significant reflection attributable to the metal components of Columns 6-10. No significant reflection as observed with X-ray diffraction methods may indicate that the bulk metal catalyst is substantially amorphous or amorphous.

In some embodiments, the support (a commercial support or a support prepared as described herein) may be combined with a supported catalyst and / or a bulk metal catalyst. In some embodiments, the supported catalyst may include one or more elements from Column 15. For example, the supported catalyst and / or the bulk metal catalyst can be converted to a powder with an average particle size of about 1 micron to about 50 microns, about 2 microns to about 45 microns, or about 5 microns to about 40 microns. The powder can be combined with carrier to form an embedded metal catalyst. In some embodiments, the powder may be combined with the support and then extruded using standard techniques to form a catalyst with a pore size distribution with a median pore diameter in a range of about 80 A to about 200 A or about 90 A to about 180 A, or about 120 A to about 130 A. By combining the catalyst 5 with the support, in some embodiments at least a portion of the metal may remain below the surface of the embedded metal catalyst thus obtained, leading to less metal on the surface would otherwise be the case in the non-embedded metal catalyst. In some embodiments, having less metal on the catalyst surface extends the service life and / or catalytic activity of the catalyst by allowing at least a portion of the metal to go to the catalyst surface during use. The metals can move to the catalyst surface through erosion of the catalyst surface during the contact of the catalyst with a crude feed.

In some embodiments, catalysts can be characterized by pore structure.

Various pore structure parameters include, but are not limited to, pore diameter, pore volume, surfaces or combinations thereof. The catalyst can have a total pore size distribution relative to pore diameter. The median pore diameter of the pore size distribution can be in a range of about 30 A to about 1000 A, about 50 A to about 500 A, or about 60 A to about 300 A. In some embodiments, catalysts that include at least 0.5 grams of gamma alumina per gram of catalyst have a pore size distribution with a median pore diameter in a range of about 50 A to about 500 A, about 60 A to about 200 A, - 75 - about 90 A to about 180 A, about 100 A to about 140 A, or about 120 A to about 130 A. In other embodiments, catalysts that include at least 0.1 grams of theta alumina per gram of catalyst have a pore size distribution with a median pore diameter in a range of about 180 A to about 500 A, about 200 A to about 300 A, or about 230 A to about 250 A. Such median pore diameters are typically at most 1000 A.

In certain embodiments, the median pore diameter of the pore size spread is greater than 110 A, at least 120 A, at least 130 A, at least 140 A, at least 150 A, at least 200 A, or at least 250 A. Such median pore diameters are usually at most 300 A. The median pore diameter of the pore size distribution may be in a range of from about 115 A to about 290 A, about 120 A to about 190 A, about 130 A to about 180 A, or about 140 A to about 160 A.

In some embodiments, the pore size spread catalyst has at least 60% of a total number of pores within the pore size spread with a pore diameter within about 45 A, about 35 A, about 30 A, about 25 A, or about 20 A of the median pore diameter of the pore distribution. In embodiments where the median pore diameter of the pore size spread is at least 180 A, at least 200 A, or at least 230 A, more than 60% of a total number of pores in the pore size spread have a pore diameter within about 50 A, about 70 A or about

90 A of the median pore diameter. In some embodiments, the catalyst has a pore size distribution with a median pore diameter in a range of about 180 A

- 76 - to about 500 A, about 200 A to about 400 A, or about 230 A to about 300 A, with at least 60% of a total number of pores in the pore size spread having a pore diameter within about 50 A, about 70 A or 5 approximately 90 A of the median pore diameter.

In some embodiments, the pore volume of pores can be at least 0.3 cm 3 / g, at least 0.7 cm 3 / g or at least 0.9 cm 3 / g. In certain embodiments, the pore volume of pores can range from about 0.3 cm 3 / g to about 0.99 cm 3 / g, about 0.4 cm 3 / g to about 0.8 cm 3 / g, or about 0.5 cm 3 / g g to about 0.7 cm 3 / g. In some embodiments, pores with a pore diameter of at least 350 A, at least 400 A, at least 500 A, at least 1000 A, at least 3000 A, or at least 5000 A, constitute at most 10%, at most 5%, at least at most 3%, at most 1% or at most 0.5% of the total pore volume of the catalyst. Such pore diameters can be in a range of from about 350 A to about 5000 A, about 400 A to about 1000 A, or about 500 A to about 900 A. The total pore volume formed by pores with such pore diameters can be in a range of about 0% to about 9%, about 0.1% to about 5%, or about 0.5% to about 1%.

The catalyst having a pore size distribution with a median pore diameter in a range of from about 60 A to about 500 A may in some embodiments have an area of at least 100 m2 / g, at least 120 m2 / g, at least 170 m2 / g, at least 220 m2 / g or at least 270 m2 / g. Such an area can be in a range of from about 100 m2 / g to about 300 m2 / g, about 120 m2 / g to about 270 m2 / g, about 130 m2 / g to about 250 m2 / g, or about 170 m2 / g up to - 77 - approximately 220 m2 / g. In certain embodiments, a surface area of a bulk metal catalyst formed is at least 30 m2 / g, at least 60 m2 / g or is in a range of about 10 m2 / g to about 350 m2 / g.

In some embodiments, the bulk metal catalyst, the supported catalyst and / or the catalyst precursor (prior to use) is sulfidated using techniques known in the art (e.g., the ACTICAT ™ process, CRI International, Ine.) To form metal sulfides. In some embodiments, the catalyst (s) and / or catalyst precursor can be dried and then sulfided. Alternatively, the catalyst (s) or catalyst precursor can be sulfided in situ by contacting the catalyst with a crude feed containing, inter alia, sulfur-containing compounds. In situ sulfurization, use can be made of gaseous hydrogen sulfide in the presence of hydrogen or of sulfurizing agents in liquid phase, such as organic sulfur compounds (including alkyl sulfides, polysulfides, thiols and sulfoxides). Ex-situ sulfurization processes are described in U.S. Patent Nos. 5,468,372 to Seamans et al. And 5,688,736 to Seamans et al.

In certain embodiments, a first type of catalyst ("first catalyst") includes inter alia metal / (metals) from Columns 5-10 in combination with a theta-alumina support. The first catalyst has a pore size distribution with a median pore diameter of at least 180 A, at least 220 A, at least 230 A, at least 250 A, at least 300 A or at most 500 A. The support may include at least 0, 1 gram, at least 0.5 gram or at least 0.9 gram, or at most 0.999 gram * theta alumina per gram of carrier. In some embodiments, the carrier has an alpha alumina content of less than 0.1 grams of alpha alumina per gram of catalyst. In some embodiments, the catalyst comprises, inter alia, at most 0.1 gram of metal / (metals) from Column 6 per gram of catalyst and at least 0.0001 gram of metal / (metals) from Column 6 per gram of catalyst. In some embodiments, the (s) is / (the) metal / (s) from Column 6 is molybdenum and / or tungsten. In some embodiments, a first catalyst may include metal / (metals) from Column 5. The first catalyst can permit removal of alkali metals and alkaline earth metals in metal salts of organic acids. The first catalyst can generally remove at least a portion of the alkali metals and / or alkaline earth metal salts of organic acids, which can lower the viscosity and / or surface tension of the crude feed. As a result, the crude-containing feed thus obtained can more easily be brought into contact with catalysts arranged after the first catalyst.

In certain embodiments, a second type of catalyst ("second catalyst") includes metal / (metals) from Columns 6-10 in combination with a support.

The second catalyst has a median pore diameter of more than 110 A. The second catalyst has pores with a pore diameter of at least 350 A that make up at most 10% of the pore volume of the second catalyst. The second catalyst in some embodiments has a total metal / (metal) content from Column 6 per gram of second catalyst in a range of about 0.0001 gram to about 0.3 gram, a total content of - 79 - metal / ( metals) from Columns 7-10 in a range of about 0.0001 grams to about 0.1 grams, and a total content of element (s) from Column 15 in a range of about 0.00001 grams to about 0.1 grams . In certain embodiments, the second catalyst support has at least 0.9 grams of gamma alumina per gram of support. The second catalyst is generally capable of: removing at least a portion of the components from the crude feed that contribute to thermal degradation as measured by MCR; removing at least a portion of organic nitrogenous compounds; and removing at least a portion of the C5 asphaltenes from the crude feed. In some embodiments, the second catalyst also removes at least a portion of the residue, at least a portion of the Ni / Fe / V, at least a portion of the components that contribute to high viscosity values, and / or at least a portion of the components that contribute to a low API density.

In some embodiments, a third type of catalyst ("third catalyst") may have a median pore diameter of about 250 A. The third catalyst has pores with a pore diameter of at least 350 A, which forms at most 10% of the pore volume of the third catalyst. The third catalyst is generally capable of: removing at least a portion of the components from the crude feed that contribute to thermal degradation, as measured by MCR; removing a portion of compounds containing heteroatoms; and / or removing part of the C5 asphaltenes from the crude feed. In some embodiments, the third catalyst - 80 - also removes components that contribute to high viscosity values and / or a low API density.

In some embodiments, the second catalyst (s) and third catalyst (s) have selected median pore diameters and pores with selected pore diameters that constitute at most 10%, at most 5%, at most 3% or at most 1% of the pore volume. These catalysts provide greater reduction of the C5 asphaltenes content in the crude feed and / or reduction of at least a portion of the components that contribute to thermal degradation of the crude feed, as measured by MCR. By reducing these compounds using catalysts with a selected median pore diameter and a selected pore volume, the number of catalysts can be reduced to the minimum. Typically, the crude feed is first treated with a conventional catalyst with a relatively low catalytic activity to remove C5-20 asphaltenes and / or components that contribute to thermal degradation. These types of conventional catalysts generally remove the C5 asphaltenes and / or other components by allowing a relatively large portion of the C5 asphaltenes and / or other components to enter the pores of the catalysts and fill the pores.

While the pores are being filled, the C5 asphaltenes and / or other components can be physically removed from the crude feed. As soon as the pores are full and / or clogged, the life of the conventional catalyst decreases. Catalysts with a selected median pore diameter and selected pore volumes remove C5 asphaltenes and / or other components that contribute to thermal degradation by limiting any portion of C5 asphaltenes and / or other components that enter the pores of the catalyst. As such, the life of the catalyst need not be reduced due to contact of the catalyst with C5 asphaltenes and / or other components.

In some embodiments, the second catalyst (s) and / or the third catalyst (s) can remove at least a portion of the alkali metals and alkaline earth metals in metal salts of organic acids. In certain embodiments, the second catalyst (s) and / or the third catalyst (s) are capable of removing at least a portion of the alkali metals and / or alkaline earth metal salts from organic acids that contribute to the formation of compounds that have viscosity and / or increase the surface tension of the crude feed. In some embodiments, the second catalyst (s) and / or the third catalyst (s) are capable of removing at least a portion of the components that contribute to a relatively high viscosity of the crude feed.

In some embodiments, a fourth type or catalyst ("fourth catalyst") can be obtained by combining a support with metal / (metals) from

Column 6 to form a catalyst precursor. Typically, the catalyst precursor is heated to at least 100 ° C for about 2 hours. In certain embodiments, the fourth catalyst (s) can have a content of one or more elements from Column 15 in a range of from about 0.001 grams to about 0.03 grams, 0.005 grams to about 0.02 grams, or 0.008 grams to about 0.01 grams per gram of fourth catalyst (s). The fourth catalyst (s) can exhibit significant activity and stability when used to treat the crude feed described herein. In some embodiments, the catalyst precursor is heated at temperatures below 500 ° C in the presence of one or more sulfur compounds. The fourth catalyst (s) is / are generally capable of removing a portion of nitrogenous compounds from the crude feed. Removal of nitrogen-containing compounds reduces the corrosive properties of the crude-oil product compared to the corrosive properties of the crude-oil feed. The fourth catalyst (s) can remove at least a portion of the components that contribute to the TAN from the crude feed, remove at least a portion of the metals in metal salts of organic acids, at least a portion of the Remove Ni / V / Fe, and / or remove at least part of components that contribute to a high viscosity of the crude feed.

In some embodiments, the fourth catalyst (s) may also reduce at least a portion of the MCR content of the crude feed, while maintaining the stability of the crude feed / total product. In certain embodiments, the fourth catalyst (s) can have a metal / (metal) content from Column 6 in a range of about 0.0001 grams to about 0.1 grams, about 0.005 grams to about 0.05 grams, or about 0.001 grams to about 0.01 grams and a metal / (metals) content of Column 10 in a range of about 0.0001 grams to about 0.05 grams, about 0.005 grams - 83 - to about 0.03 grams, or from about 0.001 grams to about 0.01 grams per gram of fourth catalyst (s) The fourth catalyst (s) may promote reduction of at least a portion of the components that contribute to MCR in the crude feed at temperatures in a range of from about 300 ° C to about 500 ° C or about 350 ° C to about 450 ° C and pressure values in a range from about 0.1 MPa to about 20 MPa, about 1 MPa to about 10 MPa, or 10 about 2 MPa to about 8 MPa.

In certain embodiments, a fifth type of catalyst ("fifth catalyst") can be a bulk metal catalyst. The fifth catalyst (s) include at least 0.3 grams of metal (s) from 15 Columns 6-10 per gram of fifth catalyst (s). In certain embodiments, the fifth catalyst (s) also include the binder, among others. In some embodiments, the fifth catalyst (s) comprises metal / (metals) from Column 6 in combination with metal / (metals) from Column 9 and / or metal / (metals) from Column 10. The fifth catalyst (s) is / are generally capable of removing at least a portion of the components that contribute to thermal degradation as measured by MCR. In some embodiments, the fifth catalyst (s) is also capable of removing at least a portion of C5 asphaltenes, at least a portion of organic compounds containing heteroatoms, at least a portion of the total Ni / V / Fe content, at least a part of the components that contribute to high viscosity and / or at least a part of the components that contribute to a low API density.

- 84 -

The first catalyst (s), second catalyst (s), third catalyst (s), fourth catalyst (s), and fifth catalyst (s) may be at temperatures of at least 5 370 ° C during contact with the crude feed. at least 380 ° C, at least 390 ° C, at least 400 ° C or at least 420 ° C and pressure values of at least 8 Nm3 / m3, at least 10 Nm3 / m3 or at least 14 Nm3 / m3 at least 3 months, stable for at least 6 months or at least 1 year.

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

Other embodiments of the first catalyst (s), second catalyst (s), third catalyst (s), fourth catalyst (s) and fifth catalyst (s) can also be made and / or used as otherwise described herein.

By choosing the catalyst (s) according to this application and controlling the operating conditions, a crude-containing product can be produced that has an MCR content, a nitrogen content, a metal content in metal salts of organic acids and / or selected properties that compared to the crude oil feed. The crude-containing product thus obtained may have improved properties over the crude-containing feed and therefore be more acceptable for transport and / or refining.

- 85 -

By arranging two or more catalysts in a selected order, the order of property improvements of the crude feed can be controlled. For example, metals in metal salts of organic acids in the crude feed can be lowered before at least a portion of the components that contribute to MCR and / or heteroatoms in the crude feed is reduced.

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

A catalyst life can be determined by measuring the temperature change of the touch zone over a certain period (for example, a month, two months, three months, six months and / or a year), while other touch conditions remain relatively constant, so that certain product specifications are maintained. If it is necessary to raise the temperature by about 15 ° C, about 13 ° C, or about 10 ° C above the temperature initially required for processing, it may indicate that the effectiveness of the catalyst has decreased.

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

The first catalyst allows in some embodiments removal of at least a portion of metals in metal salts of organic acids from the crude feed. For example, removal of at least a portion of the metals in metal salts of organic acids in the crude-oil feed and total product mixture relative to the crude oil feed inhibits clogging of other downstream catalysts and thus extends the time during which the touch system can be operated without catalyst replacement.

Removal of at least a portion of the metals in metal salts of organic acids from the crude feed may, in some embodiments, extend the service life of one or more catalysts disposed after the first catalyst.

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

In some embodiments, the fifth catalyst (s) can be arranged downstream of commercially available catalysts. The commercially available catalysts can be used to remove at least a portion of the Ni / V / Fe in a crude feed. Further contact of the crude feed / total product mixture 20 with the fifth catalyst (s) can lower the MCR content, lower the sulfur content, lower the nitrogen content and / or lower the oxygen content.

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

At certain times during the contact period, the concentration of crude feed and / or total product in the mixture of crude feed and total product may change. As the concentration of the total product in the mixture of crude oil feed and total product changes due to the formation of the crude oil product, the solubility of the components of the crude oil feed and / or components of the total product also has in the mixture of crude-oiled food and total product the tendency to change. The crude feed may, for example, contain components that are soluble in the crude feed at the start of processing. As properties of the crude feed change (e.g., TAN, MCR, C5 asphaltenes, P value or combinations thereof), the components may tend to become less soluble in the crude feed and total product mixture. In some cases, the crude feed and the total product can form two phases and / or become insoluble in each other.

- 89 -

Changes in solubility can also cause the mixture of crude-oiled food and total product to form two or more phases. Formation of two phases by flocculation of asphaltenes, change in the concentration of crude feed and total product and / or precipitation of components tends to shorten the life of one or more of the catalysts. Moreover, it can reduce the efficiency of the process. For example, repeated treatment of the crude feed and total product mixture may be required to produce a crude oil product with desired properties.

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

The catalysts described herein can promote reduction of the MCR content and the viscosity at elevated temperature and pressure values while maintaining the stability of the mixture of crude feed and total product and / or maintaining the life of the catalysts.

In some embodiments, the touch conditions are controlled such that temperatures in one or more touch zones may be different. Operating at different temperatures allows selective modification of the properties of the crude feed while maintaining the stability of the mixture of crude feed and total product. The crude feed enters a first touch zone at the start of a process.

A first contact temperature is the temperature in the first touch zone. Other contact temperatures (e.g., second temperature, third temperature, fourth temperature, etc.) are the temperatures in touch zones arranged after the first touch zone. A first contact temperature can be in a range of about 100 ° C to about 420 ° C and a second contact temperature can be in a range that is about 20 ° C to about 100 ° C, about 30 ° C to about 90 ° C, or about 40 ° C to about 60 ° C deviates from the first contact temperature. In some embodiments, the second contact temperature is higher than the first contact temperature. Having different contact temperatures can lower the TAN and / or C5 asphaltenes content in a crude-containing product more strongly than the TAN and / or the C5-91 asphaltenes content of the crude feed than the extent of any TAN and / or C5 asphaltene reduction that is obtained when the first and second contact temperatures are the same or within 10 ° C of each other.

EXAMPLES

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

Example 1. Preparation of a catalyst support. An alumina / silica support was prepared by triturating 550 grams of an alumina / silica mixture for 35 minutes with 26 grams of calcined fine alumina particles, 585 grams of water and 8 grams of 16M nitric acid. The alumina / silica blend was prepared by combining at least 0.98 grams of alumina / silica blend (Criterion Catalysts and Technologies LP) per gram of support with at most 0.02 grams of silica (Criterion Catalysts and Technologies LP) per gram of alumina / silica blend. The finely ground mixture was extruded through 1.94 mm and 3.28 mm diameter die plates and then thermally treated at a temperature in the range of 93 ° C (200 ° F) to 121 ° C (250 ° F) to a loss after annealing in a range from 27% to 30% by weight, based on initial extrudate weight. Loss after annealing was performed by heating the extrudates to 540 ° C for 15 to 50 minutes and then determining the relative amount of weight lost by the extrudates. The extrudates were further thermally treated at 918 ° C (1685 ° F) for 1 hour. The support had an average pore diameter of 125 A, a surface area of 281 m2 / g, a pore volume of 0.875 cm 3 / g, and pores with> • -.¾ · - 92 -

a diameter of at least 350 A, which represented 0.9% of the total pore volume of the support. Example 1 demonstrates the preparation of a carrier that has an average pore diameter of at least 90 A and 5 of which pores with a pore diameter of at least 350 A

constitute at most 15% of the pore volume of the support.

Example 2. Preparation of a catalyst with a median pore diameter of 115 A and a selected pore volume spread. A catalyst was prepared as follows. An alumina / silica support prepared as described in Example 1 was impregnated with a molybdenum / nickel / phosphorus impregnation solution prepared as follows. A first solution was made by combining 62.34 grams of (NH 4) 2 Mo 2 O 7, 17.49 grams of MoO 3, 12.22 grams of 30% H 2 O 2 and 50.47 grams of deionized water to form a slurry.

MEA (3.0 grams) was added to the slurry at a rate sufficient to control the solution exotherm.

The slurry was heated to 64 ° C (147 ° F) until the solids dissolved and then cooled to room temperature. The pH of the first solution was 5.34.

A second solution was made by combining 8.2 grams of Ni (NO 3) 2 · 6H 2 O and 5.47 grams of NiCO 3 with 30.46 grams of deionized water and then adding 29.69 grams of 85 wt.% H 3 PO 4 . The pH of the second solution was 0.29. The first and the second solution were combined with one another and sufficient deionized water was added to bring the combined solution volume to 218.75 ml, yielding the molybdenum / nickel / phosphorus impregnation solution.

The pH of the impregnation solution was 2.02.

The carrier (200.0 grams) was combined with the impregnation solution and aged for a few hours with occasional stirring. The thus-obtained mixture of support and metal was thermally treated at 125 ° C for a few hours and then thermally treated at 482 ° C (900 ° F) for 2 hours. The catalyst thus obtained contained 0.13 grams of molybdenum, 0.03 grams of nickel and 0.03 grams of phosphorus per gram of catalyst, with the remainder being supported. The catalyst had a pore size distribution with a median pore diameter of 115 A, with 66.7% of the total number of pores with a pore diameter within 28 A of the median pore diameter. The surface area of the catalyst was 179 m2 / g. The pore volume of the catalyst was 0.5 cm 3 / g. Table 1 contains an overview of the pore volume distribution.

- 94 Table 1

Range, A ~% pore volume of catalyst <7.0 3.07 70-100 16.21 100-130 69.36 130-150 7.81 150-180 0.86 180-200 0.37 200-240 0.47 240 -300 0.39 300-350 0.23 350-450 0.27 "450-600 0.23 600-1000 0.27 1000-3000 0.22 3000-5000 0.72> 5000 Ö

As Table 1 shows, the pores of the catalyst with a pore diameter of at least 350 A formed 1.71% of the total pore volume of the catalyst.

Example 2 shows the preparation of a metal catalyst from Column 6 with a pore size distribution with a median pore diameter greater than 110 A and a pore volume in which pores with a pore diameter of at least 350 A constitute at most 10% of the total pore volume. This example also shows the preparation of a metal catalyst from

Column 6 from a support with an average pore diameter of at least 90 A and a pore volume in which pores with a pore diameter of at least 350 A make up at most 15% of the total pore volume.

- 95 -

Example 3. Touch of a crude oil feed with two catalysts.

A tubular reactor with a centrally positioned thermometer tube was equipped with thermocouples to measure temperatures throughout an entire catalyst bed.

The catalyst bed was formed by filling the space between the thermometer tube and an inner wall of the reactor with catalysts and silicon carbide (20-grid, Stanford Materials; Aliso Viejo, CA). It is believed that such silicon carbide has low, if not catalytic, properties under the process conditions described herein. All catalysts were mixed with silicon carbide in a volume ratio of 2 parts of silicon carbide to 1 part of catalyst before placing the mixture in the contact zone parts of the reactor.

The flow of the crude feed to. the reactor was from the top of the reactor to the reactor bottom. Silicon carbide 20 was placed at the bottom of the reactor to serve as the lower support. A mixture of lower catalyst and silicon carbide (81 cm 3) was placed on top of the silicon carbide to form a lower touch zone. The bottom catalyst was prepared as described in Example 2.

A mixture of upper catalyst and silicon carbide (9 cm 3) was placed on top of the lower touch zone to form an upper touch zone. The top catalyst was a molybdenum / vanadium catalyst on a support of theta alumina prepared as follows. A carrier was prepared by 576 grams of alumina (Criterion Catalysts and Technologies LP,

Michigan City, Michigan, U.S.A.) for 35 minutes finely rub with 585 grams of water and 8 grams of ice nitrate II.

- 96 - acid. The thus-obtained finely rubbed mixture was extruded through a 13 mm die plate, heat-treated between 90 ° C and about 125 ° C and further heat-treated at 918 ° C, yielding 650 grams of a support with a median pore diameter of 182 A.

The thermally treated support was placed in a Lindberg stove. The furnace temperature was raised to about 1000 ° C to about 1100 ° C in 1.5 hours and was then maintained at that area for 2 hours to produce the support. The support was impregnated with a molybdenum / vanadium impregnation solution prepared as follows. A first solution was made by combining 2.14 grams (NH 4) 2 Mo 2 O 7, 3.21 grams of MoO 3, 0.56 grams of 30% H 2 O 2, 0.14 grams of monoethanolamine and 3.28 grams of deionized water to form a slurry. The slurry was heated to 65 ° C until solids dissolved and then cooled to room temperature. A second solution was made by combining 3.57 grams of VOSO 4 * xH 2 O (x = 3 to 5) with 40 grams of deionized water. The first and the second solution were combined with each other and sufficient deionized water was added to bring the combined solution volume to 82 ml, yielding the molybdenum / vanadium impregnation solution. The support was impregnated with the molybdenum / vanadium impregnation solution and aged for 2 hours with occasional stirring. The mixture of support and metal thus obtained was thermally treated at 125 ° C for several hours and then thermally treated at 480 ° C for 2 hours. The catalyst thus obtained contained 0.02 grams of vanadium and 0.02 grams of molybdenum per gram of catalyst and the remainder of the support.

- 97 -

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

The catalysts were sulfided by introducing into the contact zones a gaseous mixture of 5 vol.% Hydrogen sulfide and 95 vol.% Hydrogen gas at a rate of about 1.5 liters of gaseous mixture per volume (ml) of total catalyst (silicon carbide was not counted as part of the catalyst volume) during the following periods. The reactor pressure was approximately 1.9 MPa (279.7 psi). The temperature of the touch zones were gradually increased to 204 ° C (400 ° F) in 1 hour and then kept at 204 ° C for 2 hours. After holding at 204 ° C, the temperature of the touch zones was at a rate of about 10 ° C (about 50 ° F) per hour gradually increased to 316 ° C (600 ° F). The touch zones were kept at 316 ° C for one hour, after which the temperature was gradually increased to 370 ° C in 1 hour (700 ° F) and then held at 370 ° C for two hours, then the touch zones were allowed to cool to ambient temperature.

After sulfidation, the contact zones were then heated to 204 ° C in 2 hours and crude feed (BC-10, Brazil) was added to the top of the reactor. The crude feed passed through the pre-heating zone, the upper touch zone, the lower touch zone, and the lower support of the reactor. The crude feed was contacted in the presence of hydrogen gas with each of the catalysts from 5 to 98. The contact conditions were as follows: the ratio of hydrogen gas to the crude feed fed to the reactor was 656 Nm3 / m3 (4000 SCFB), the LHSV was 0.5 h -1 and the pressure was 13.8 MPa 5 (2014.7 psi). The two touch zones were gradually heated from 204 ° C to 390 ° C at a rate in the range of 0.1 ° C per hour to 10 ° C per hour and then kept at 390 ° C for 311 hours. The temperature of the catalyst bed was gradually raised to 400 ° C and kept at 400 ° C for 352 hours.

The total product (i.e., the crude product and the gas) left the catalyst bed. The total product was fed into a gas-liquid phase separator. In the gas-liquid separator, the total product was split into the crude product and gas. The gas input to the system was measured with a mass flow controller. Gas exiting the system was cooled to a temperature sufficient to remove any liquid components with a carbon number of at least 5 from the gas. The split gas was measured with a "wet test" meter. The crude product was analyzed periodically to determine a weight percentage of components of the crude product. The properties of the crude product and the crude feed are listed in Table 2.

- 99 Table 2

Property Crude-crude oil-containing food product TAN 3Γβ '^ 0.05, API density 15.1 20

Density at 15.56 ° C 0.9651 0.9306 (60 ° F), g / cm3

Hydrogen, weight% 11/4 12.1

Carbon, wt% 87.1 87.4

Sulfur, wt% 0.433 0.05

Oxygen, wt% 0.42 0.01

Nitrogen, wt% 0.52 0.24

Basic nitrogen, 0.16 0.08% by weight

Calcium, wtppm 3.5 0.6

Potassium, wtppm 1.8 1.3

Sodium, wtppm 5.3 0.6

Nickel, wtppm 12.4 7.3

Vanadium, wtppm 19.2 6.4 Iron, wtppm 10 0.4

Micro carbon residue, 8.5 4.6 wt. % C5 asphaltenes,% 7.5 by weight 4.3

Naphtha,% w / w 4.1

Distillate, weight% 17.5 26.6 VGO, weight% 39.2 40.9

Residue, weight% 43.3 28.4 P-value 5 3.6

Viscosity at 37.8 ° C 1705 156 (100 ° F), cSt - 100 -

As Table 2 shows, the crude product had a nitrogen content of 0.0024 grams, an MCR content of 0.046 grams, and a C5 asphaltenes content of 0.043 grams per gram of crude product. The crude product also had a calcium content of 0.6 wtppm, a potassium content of 1.3 wtppm and a sodium content of 0.6 wtppm.

Example 3 shows that contacting the crude feed with one or more catalysts under controlled contact conditions yielded a total product comprising inter alia the crude feed. At least one of the catalysts was a column 6 metal catalyst comprising: (a) including metal / (metals) from Column 6; (B) had a pore size distribution with a median pore diameter greater than 110 Å; and (c) had a pore volume in which pores with a pore diameter of at least 350 A constituted at most 10% of the pore volume. As measured on the basis of the P value, the stability of the mixture of crude feed and total product was maintained. Compared to the crude feed, the crude product had a lowered MCR, fewer alkali metal and alkaline earth metal salts in organic acids, a lower 25 Ni / V / Fe content, a lower sulfur content, a lower nitrogen content, fewer C5 asphaltenes and a lower oxygen content.

Example 4. Preparation of a catalyst support.

An alumina carrier was prepared by finely rubbing 550 grams of alumina powder (Criterion Catalysts and Technologies LP) for 35 minutes with 26 grams of calcined fine alumina particles, 585 grams of water and 8 grams of 16M nitric acid. The finely ground mixture was extruded through 1.94 iran and 3.28 mm diameter die plates, heat treated at 93 ° C (200 ° F), 107 ° C (225 ° F) and then heat treated at 121 ° C ( 250 ° F) until a loss after annealing in a range of 27% by weight to 30% by weight, based on initial extrudate weight, was obtained. Loss after annealing was performed as described in Example 1. The extrudates were further thermally treated at 918 ° C (1685 ° F) for 1 hour. The support had an average pore diameter of 186.4 Å, a pore volume of 0.868 cm 3 / ml and pores with a diameter of at least 350 Å that constituted 13.3% of the total pore volume of the support. Example 4 shows the preparation of a support that has an average pore diameter of at least 90 A and a pore volume in which pores with a pore diameter of at least 350 A constitute at most 15% of the pore volume of the support.

Example 5. Preparation of a catalyst with a median pore diameter of 250 A and a selected pore volume spread.

The alumina support prepared as described in Example 4 was impregnated with a molybdenum / cobalt / phosphorus impregnation solution prepared as follows. MoO 3 (22.95 grams) was combined with 85 wt% H 3 PO 4 (12.67 grams) and heated to 82 ° C (180 ° F) to form a molybdenum / phosphorus solution. Co (OH) 2 (29.83 grams) was added to the molybdenum / phosphorus solution and the molybdenum / cobalt / phosphorus solution thus obtained was heated to 100 ° C. Citric acid monohydrate (21.5 grams) was added to the molybdenum / cobalt / phosphorus solution, after which it was heated to 100 ° C and held at 100 ° C for 1 hour. The volume of the solution thus obtained was reduced to 252 ml to pirate the molybdenum / cobalt / phosphorus impregnation solution. The impregnation solution had a pH of 3.22.

The alumina carrier (300.0 grams) was combined with the impregnation solution and aged for a few 5 hours with occasional stirring. The thus-obtained mixture of support and metal was thermally treated at 120 ° C for a few hours and then thermally treated at 426 ° C (800 ° F) for 2 hours. The catalyst thus obtained was further thermally treated for 2 hours at 593 ° C (1100 ° F). The catalyst

contained 0.153 grams of molybdenum, 0.043 grams of cobalt and 0.008 grams of phosphorus per gram of catalyst, with the remainder being supported. The catalyst had a pore size distribution with a median pore diameter of 250 A, with 67% of the total number of pores with a pore diameter within 58 A

of the median pore diameter. The surface area of the catalyst was 98 m2 / g. The pore volume distribution is shown in Table 3.

- 103 - Table 3

Range, A% pore volume of catalyst <70 Ö 70-100 Ö 100-130 0.15 130-150 075 150-180 275 '180-200 4.25 200-240 22.66 240-300 63.77 300-350 3.36 350-450 0798 "450-600 0746 600-1000 Ö4 1000-3000 0746 3000-5000 0.46> 5000 Ö

As Table 3 shows, pores with a pore diameter of at least 350 A formed 2.8% of the total pore volume of the catalyst.

Example 5 shows the preparation of the metal catalyst from Column 6 which has a pore size distribution with a median pore diameter greater than 110 Å and a pore volume in which pores of at least 350 Å make up at most 10% of the total pore volume. This example also shows the preparation of the column 6 metal catalyst from a support with an average pore diameter of at least 90 A and a pore volume in which pores with a pore diameter of at least 350 A make up at least 15% of the total pore volume .

- 104 -

Example 6. Touch of a crude oil feed with two catalysts.

The reactor apparatus (excluding contents of the contact zones), the crude-containing feed, the catalyst sulfiding method, the cleavage method of the total product, the contact conditions, the contact time and the analysis of the crude-containing product were the same as described in Example 3.

The crude feed fed from the upper part of the reactor to the reactor bottom. A molybdenum / cobalt / phosphorus catalyst as described in Example 5 was mixed with silicon carbide (81 cm 3) and the mixture was placed in the lower touch zone. The molybdenum / vanadium catalyst on a theta-alumina support prepared as described in Example 3 was mixed with silicon carbide. The mixture of molybdenum / vanadium catalyst and silicon carbide (9 cm 3) was placed in the upper touch zone.

The properties of the crude product 20 are listed in Table 4.

- 105 - Table 4

Property Crude-crude oil-containing food product TAN 3Të '£ 0.05' API density 15.1 19.2

Density at 15.56 ° C 0.9651 0.9554 (60 ° F), g / cm3

Hydrogen, weight% 11/4 11.6

Carbon, wt% 87.1 87.6

Sulfur, wt% 0.43 0.16

Oxygen, wt% 0.42 0.11

Nitrogen, wt% 0.52 0.47

Calcium, wtppm 5.4 0.5

Potassium, wtppm 46 1.5

Sodium, wtppm 117 0.6

Nickel, wtppm 12.4 7.5

Vanadium, wtppm 19.2 6.2 Iron, wtppm 10.4 0.9

Micro carbon residue, 8.5 7.2 wt.% C5 asphaltenes, wt.% 7.5 5.0

Naphtha, wt% 0 2.3

Distillate, weight% 17.5 20.3 VGO, weight% 39.2 42.0

Residue,% by weight 43.3 35.4 P value 5 4.2

Viscosity at 1705 698, 37.8 ° C (100 ° F), cSt

As shown in Table 4, the crude product had a nitrogen content of 0.0047 grams, a MCR content of 0.072 grams, and a C5 asphaltenes content of 0.05 grams per gram of crude product. The crude product also had 0.5 wtppm of calcium, 1.5 wtppm of potassium and 0.6 wtppm of sodium.

Example 6 shows that contacting the crude feed with one or more catalysts under controlled contact conditions yielded a total product comprising inter alia the crude feed. At least one of the 10 catalysts was a column 6 metal catalyst comprising: (a) including metal / (metals) from Column 6; (b) had a pore size distribution with a median pore diameter greater than 110 Å; and (c) had a pore volume in which pores with a pore diameter of at least 350 A formed at most 10% of the pore volume. Compared to the crude feed, the crude product had a reduced MCR, fewer alkali metal and alkaline earth metal salts of organic acids, a lower Ni / V / Fe content, a lower sulfur content, a lower nitrogen content, fewer C5 asphaltenes and a lower oxygen content.

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

2000053

Claims (18)

A method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to form a total product comprising inter alia the crude oil product, wherein crude oil product at 25 ° C and 0.101 MPa is a liquid mixture; wherein the crude feed has a nitrogen content of at least 0.0001 grams per gram of crude feed; and wherein at least one of the catalysts is a column 6 metal catalyst comprising: one or more metals from Column 6 of the Periodic Table and / or one or more compounds of one or more metals from Column 6 of the Periodic Table; 15 a pore size distribution with a median pore diameter of more than 110 A; and a pore volume wherein pores with a pore diameter of at least 350 A make up at most 10% of the pore volume, wherein pore diameter and pore volume are as determined by ASTM method D4282; and controlling the contact conditions of temperature, pressure, crude oil feed stream, or combinations thereof such that the crude oil product has a nitrogen content of at most 90% of the nitrogen content of the crude oil feed, wherein nitrogen content is such as determined by ASTM method D5762. A method according to claim 1, wherein pores with a pore diameter of at least 350 Å constitute at most 5%, at most 1,00553 - 109 - at most 3%, at most 1%, or at most 0.5% of the pore volume. Method according to claim 1 or 2, wherein the nitrogen content of the crude product is at most 80%, at most 50%, at most 30% or at most 10% of the nitrogen content of the crude feed. The method of any one of claims 1-3, wherein the crude feed contains 0.0001 grams to 0.1 grams, 0.001 grams to 0.05 grams, or 0.005 grams to 0.01 grams of nitrogen per gram of crude has food. 5 Column 15 of the Periodic System. 5. Method as claimed in any of the claims 1-4, wherein the crude product contains 0.00001 grams to 0.05 grams, 0.0001 grams to 0.01 grams, or 0.0005 grams to 0.001 grams of nitrogen per gram of crude oil-containing product. The method of any one of claims 1-5, wherein the column 6 metal catalyst per gram of catalyst is 0.0001 gram to 0.3 gram, 0.005 gram to 0.2 gram, or 0.01 gram to 0.1 gram of one or more of the metals Column 6 and / or one or more of the metal compounds from Column 6, calculated as the total weight of metal from Column 6. 7. A method according to any one of claims 1-6, wherein the catalyst from column 6 metal also comprises one or more metals from Columns 7-10 of the Periodic Table and / or one or more compounds of one or more metals from Columns 7- 10 of the Periodic System. 8. Method according to any of claims 1-7, wherein the column 6 metal from column 6 also comprises one or more metals from Column 10 of the Periodic System and / or one or more compounds of one or more metals from Column 10 of the Periodic System includes. - 110 - A method according to any one of claims 1-8, wherein the metal catalyst from Column 6 also comprises one or more elements from Column 15 of the Periodic Table and / or one or more compounds of one or more elements from The method of any one of claims 1-9, wherein the column 6 metal catalyst has a median pore diameter of at least 120 A, at least 130 A, at least 150 A, at least 180 A, at least 200 A, at least 10 has at least 250 A or at most 300 A, pore size distribution being as determined by ASTM method D4282. 11. A method according to any one of claims 1-10, wherein the column 6 metal catalyst has a pore size distribution such that at least 60% of the total number of pores in the pore size spread within 45 A, 35 A or 25 A of the median pore diameter of the pore size distribution is. 12. A method according to any one of claims 1-11, wherein the metal catalyst from Column 6 also comprises a support, and wherein the support is at least 0.8 grams, at least 0.9 grams or at least 0.95 grams of gamma -alumina per gram of carrier. 13. Method according to any of claims 1-12, wherein the contact is made in the presence of a hydrogen source. The method of any one of claims 1-13, wherein the contacting conditions comprise: a temperature in the range of 50 ° C to 500 ° C; a total pressure in a range 30 from 0.1 MPa to 20 MPa; a specific liquid transfer rate per hour of at least 0.05 h -1; and a ratio of a gaseous hydrogen source to the crude oil-containing feed in a range of 0.1 Nm3 / m3 to 100,000 Nm3 / m3. A method according to any one of claims 1-14, wherein a mixture of crude-oil feed and total product 5 has a P value of at least 1.5 during the contact. The method of any one of claims 1 to 15, which method further comprises combining the crude oil product with a crude oil raw material 10, which may or may not differ from the crude oil feed, to form a mixture. 17. Method according to any of claims 1-16, further comprising the step of processing the crude product or mixture to produce transport fuel, fuel fuel, lubricants or chemicals. The method of any one of claims 1-17, wherein the crude feed is crude oil. 2 00 0 053