KR20070120594A - Systems, methods, and catalysts for producing a crude product - Google Patents

Abstract

Methods and systems for contacting of a crude feed with one or more catalysts to produce a total product that includes a crude product are described. The crude product is a liquid mixture at 25 °C and 0.101 MPa. The crude product may have a total content of alkali metal and alkaline-earth metal in metal salts of organic acids of at most 90% of the total content of alkali metal and alkaline-earth metal in metal salts of organic acids of the crude feed. One or more other properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed.

Description

Systems, methods and catalysts for preparing crude oil products {SYSTEMS, METHODS, AND CATALYSTS FOR PRODUCING A CRUDE PRODUCT}

The present invention typically relates to systems, methods and catalysts for processing crude oil feeds. More specifically, certain embodiments described herein relate to systems, methods and catalysts for converting crude oil feeds to total products wherein the total product is a liquid mixture at 25 ° C., 0.101 MPa Crude oil products having one or more properties modified for each property of the crude oil feed.

Crude oil with one or more unsuitable characteristics that cannot be transported economically or cannot be processed using conventional facilities is usually referred to as "lower crude oil".

Lower crude oil may contain acidic components that contribute to the total acid number (TAN) of the crude feed. Low grade crude oil with a relatively high TAN causes corrosion of the metal fittings during its transport and / or processing. Removing acidic components from lower crude oil may involve a process of chemically neutralizing the acidic components with various bases. Alternatively, corrosion resistant metals may be used in the transfer device and / or the processing device. Since the use of corrosion resistant metals often involves significant expense, the use of corrosion resistant metals in existing installations may be undesirable. Another way to prevent corrosion is to add a corrosion inhibitor for the lower crude oil prior to transportation and / or treatment of the lower crude oil. The use of corrosion inhibitors can adversely affect the quality of the apparatus and / or the products produced from the crude oil used in the processing of the crude oil.

Low grade crude oil often contains relatively high levels of residue. Low-grade crude oil containing these high levels of residues will be difficult and costly to transfer and / or process using existing plants.

Lower crude oil often contains organic bonded heteroatoms (eg sulfur, oxygen and nitrogen). Organic bonded heteroatoms, in some cases, have a negative effect on the catalyst used to process lower crude oil.

Lower crude oils have a relatively high content of metal impurities, such as nickel, vanadium, and / or iron, for example. During processing of such crude oil, metal impurities and / or compounds of metal impurities may be deposited on the surface of the catalyst or within the void volume of the catalyst. This deposition can lower the catalytic activity.

Lower crude oil may have coke and / or ingredients that cause thermal degradation of this lower crude oil. Coke and / or thermally degraded components may rapidly form and / or deposit on the catalyst surface during processing of lower crude oil. There is a significant cost to regenerate the catalytic activity of catalysts contaminated with coke and / or thermally degraded crude oil. In addition, the high temperature used during regeneration of the catalyst can lead to a decrease in catalyst activity and / or deterioration of the catalyst.

Lower crude oil may include metals (eg calcium, potassium and / or sodium) in organic acid metal salts. Typically, the metal in the organic acid metal salt is separated from the lower crude oil by conventional product treatment, such as, for example, desalting and / or acid washing.

The presence of metals in organic acid metal salts has often led to problems in conventional catalytic treatment of crude oil. Nickel and vanadium are usually deposited near the outer surface of the catalyst, but the metal in the organic acid metal salt may preferentially be deposited in the volume of the pores between the catalyst particles, in particular on top of the catalyst bed. On top of the catalyst bed, deposits of contaminants, for example metals in organic acid metal salts, typically increase the pressure drop over the catalyst bed, causing the catalyst bed to actually occlude. In addition, the metal in the organic acid metal salt can lead to rapid deactivation of the catalyst.

Lower crude oil may include organic oxygen compounds. Treatment plants that process lower crude oil with an oxygen content of at least 0.002 grams per gram of lower crude oil may encounter difficulties during processing. If the organic oxygen compounds are heated during the treatment process, they are difficult to remove from the treated crude oil and / or corrode / contaminate the equipment during the treatment process, resulting in higher order oxidizing compounds (e.g., Acids formed by oxidation of ketones and / or alcohols and / or acids formed by oxidation of ethers).

Lower crude oil may include hydrogen deficient hydrocarbons. In the case of treating hydrogen deficient hydrocarbons, in particular in the case of the production of unsaturated content from the cracking process, a certain amount of hydrogen should usually be added. Hydrogenation during treatment, which typically involves the use of an active hydrogenation catalyst, may be necessary to prevent the unsaturated content from forming coke. Hydrogen is costly to transport to its manufacturing and / or processing facilities.

Lower crude oil shows instability during processing at conventional facilities. Crude oil instability leads to phase separation of components during processing and / or formation of undesirable byproducts (eg hydrogen sulfide, water, carbon dioxide).

Conventional treatment processes for processing lower crude oil can reduce the amount of components contributing to the higher viscosity, thermal degradation and / or coke of the lower crude oil. However, the removal of these components can lead to instability of the crude oil, leading to separation of the crude oil during transportation. In conventional processing, components contributing to high viscosity and / or coke are typically removed when treating crude oil with catalysts having large pore size, large surface area and low hydroprocessing activity. The final crude oil can then be further processed to remove other unwanted components in the crude oil.

Some treatments to improve the quality of crude oil include adding diluents to the lower crude oil to lower the weight percentage of ingredients contributing to undesirable properties. However, adding a diluent generally increases the cost of processing the lower crude oil due to the cost of entering the diluent and / or the increasing cost of handling the lower crude oil. Adding a diluent to lower crude oil may, in some cases, reduce the stability of the crude oil.

US Pat. No. 6,547,957 to Sudhakar et al., US Pat. No. 6,277,269 to Myers et al., US Pat. No. 6,203,695 to Harle et al., Grande et al. US Patent No. 6,063,266, US Patent No. 5,928,502 to Bearden et al., US Patent No. 5,914,030 to Beerden et al., US Patent No. 5,897,769 to Trachte et al. , US Pat. No. 5,744,025 to Boon et al., US Pat. No. 4,212,729 to Hensley, Jr., and US Pat. No. 4,048,060 to Riley, and Schulz. U.S. Patent Application 2004/0106516 to U.S. et al. Describes various processing processes, systems, and catalysts for processing crude oil, which are incorporated herein by reference. However, the treatment processes, systems and catalysts described in these patent documents have limitations in their application due to the many technical problems described above.

In short, lower crude oils typically have undesirable properties (eg, relatively high TAN, a tendency to become unstable during treatment, and / or a tendency to consume relatively large amounts of hydrogen during treatment). Lower crude oils may include relatively large amounts of undesirable components (eg, components that contribute to thermal degradation, residues, organic bond heteroatoms, metal impurities, metals in organic acid metal salts and / or organic oxygen compounds). . These properties and components cause problems such as increased corrosion, shortened catalyst life, process blockages, and / or increased hydrogen consumption during processing in conventional transport and / or treatment facilities. Therefore, there is a significant economic and technical need for improved systems, methods and / or catalysts for converting lower crude oil into crude oil products having more desirable properties. There is also a significant economic and technical need for systems, methods and / or catalysts that can alter selected properties of the lower crude oil while minimizing other properties of the lower crude oil.

In some embodiments, the present invention provides a process for producing a crude oil product, the process comprising contacting the crude oil feed with at least one catalyst to produce a total product comprising the crude oil product, wherein the crude oil The product is a liquid mixture at 25 ° C., 0.101 MPa, the crude feed having a micro residual carbon content (MCR) content of at least 0.0001 gram per gram of this crude feed, and the at least one catalyst is at least one metal in Group 6 on the periodic table. And / or a Group 6 metal catalyst comprising at least one compound of at least one metal in Group 6 on the periodic table, having a pore size distribution having a median pore diameter of at least 110 μs, and a pore having a pore diameter of at least 350 μs being the maximum of the pore volume. The contacting step having a pore volume occupying 10%, the pore volume and pore diameter measured by ASTM method D4282; And a controlling step of controlling the contact conditions such that the crude product has an MCR content of up to 90% of the MCR content of the crude feed, wherein the MCR content is measured by ASTM method D4530.

In some embodiments, the present invention provides a catalyst, the catalyst comprising: a carrier; And at least one compound of at least one metal in Group 6 on the periodic table and / or at least one compound of at least one metal in Group 6 on the periodic table, the catalyst having a pore size distribution having a median pore diameter of at least 110 Pa and a pore diameter of at least 350 Pa The pores have a pore volume that accounts for up to 10% of the pore volume, and the pore diameter and pore volume are measured by ASTM method D4282.

In some embodiments, the present invention also provides a process for the preparation of a catalyst, wherein the process comprises at least one compound of at least one metal in Group 6 on the periodic table and / or at least one compound in Group 6 on the periodic table. And a blending step, wherein the carrier has a pore volume in which pores having an average pore diameter of at least 90 mm 3 and a pore diameter of at least 350 mm 3 occupy up to 15% of the pore volume of the carrier, wherein the pore diameter and pore volume are ASTM method D4282. Is measured.

In some embodiments, the present invention provides a process for producing a crude oil product, the process comprising contacting the crude oil feed with at least one catalyst to produce a total product comprising the crude oil product, wherein the crude oil The product is a liquid mixture at 25 ° C., 0.101 MPa, the crude feed having an MCR content of at least 0.0001 gram per gram of this crude feed, and at least one catalyst, in groups 6 to 10 on the periodic table, per gram of catalyst. Said contacting step having a Group 6-10 catalyst and a binder having at least 0.3 grams of at least one compound of at least one metal and / or at least one compound of at least one metal in Groups 6-10 on the periodic table; And a controlling step of controlling the contact conditions such that the crude product has an MCR content of up to 90% of the MCR content of the crude feed, wherein the MCR content is measured by ASTM method D4530.

In some embodiments, the present invention provides a process for producing a crude oil product, the process comprising contacting the crude oil feed with at least one catalyst to produce a total product comprising the crude oil product, wherein the crude oil The product is a liquid mixture at 25 ° C., 0.101 MPa and the crude oil feed comprises at least one alkali metal salt of at least one organic acid, at least one alkaline earth metal salt of at least one organic acid, or a mixture thereof, wherein the crude feed is crude oil Having a total content of alkali metals and alkaline earth metals in an organic acid metal salt of at least 0.00001 grams per gram of feed, the at least one catalyst being a Group 5-10 metal catalyst, the catalyst comprising a theta alumina and a Group 5-10 on the periodic table At least one metal of and / or at least one compound of at least one metal of groups 5 to 10 of the periodic table Is the contact step; And controlling the contacting conditions such that the crude oil product has a total content of alkali metals and alkaline earth metals in the organic acid metal salt of up to 90% of the content of alkali metals and alkaline earth metals in the organic acid metal salts of the crude feed. The content of alkali metals and alkaline earth metals in the organic acid metal salts includes the control step measured by ASTM method D1318.

In some embodiments, the present invention provides a process for producing a crude oil product, the process comprising contacting the crude oil feed with at least one catalyst to produce a total product comprising the crude oil product, wherein the crude oil The product is a liquid mixture at 25 ° C., 0.101 MPa, wherein the crude feed has a nitrogen content of at least 0.0001 gram per gram of the crude feed, and the at least one catalyst is at least one metal in Group 6 on the periodic table and / or 6 on the periodic table. A Group 6 metal catalyst comprising at least one compound of at least one metal in the group, having a pore size distribution of median pore diameter of at least 110 mm 3, and having a pore diameter of at least 350 mm 3, a pore volume of up to 10% of the pore volume; The pore diameter and pore volume are measured by ASTM method D4282; And a controlling step of controlling the contact conditions such that the crude product has a nitrogen content of up to 90% of the nitrogen content of the crude feed, wherein the nitrogen content comprises a controlling step measured by ASTM method D5762.

In some embodiments, the present invention also provides a process for producing a crude oil product, the process comprising contacting the crude oil feed with at least one catalyst to produce a total product comprising the crude product. The crude product is a liquid mixture at 25 ° C., 0.101 MPa, the crude feed having a nitrogen content of at least 0.0001 gram per gram of the crude feed, and the at least one catalyst is capable of reducing the Group 6 metal precursor in the presence of at least one sulfur containing compound. A Group 6 metal catalyst obtainable by heating to a temperature of 500 ° C. or less, wherein the Group 6 metal catalyst precursor is at least one metal of Group 6 on the periodic table and / or at least one compound of one or more metals in Group 6 on the periodic table And a contacting step comprising a carrier; And a controlling step of controlling the contact conditions such that the crude product has a nitrogen content of up to 90% of the nitrogen content of the crude feed, wherein the nitrogen content comprises a controlling step measured by ASTM method D5762.

In some embodiments, the present invention also provides a Group 6 metal catalyst in combination with one or more of the foregoing embodiments, wherein (a) pores having a pore diameter of at least 350 mm 3 have a maximum of 5%, maximum 3%, Occupies up to 1%, or up to 0.5%, and (b) has a pore size distribution with a median pore diameter of at least 120 mm, at least 130 mm, at least 150 mm, at least 180 mm, at least 200 mm, at least 250 mm, or at most 300 mm; The distribution is measured by ASTM method D4282 and / or (c) at least 60% of the total number of voids in the pore size distribution is within about 45 mm, about 35 mm, or about 25 mm of the median pore diameter in the pore size distribution.

In some embodiments, the invention also provides a Group 6 metal catalyst in combination with one or more of the foregoing embodiments, wherein (a) about 0.0001 gram to about 0.3, calculated as the total weight of Group 6 metal per gram of catalyst Gram, about 0.005 grams to about 0.2 grams, or about 0.01 grams to about 0.1 grams of at least one Group 6 metal and / or at least one Group 6 metal compound, and (b) at least one metal in Groups 7-10 on the periodic table. And / or from about 0.001 grams to about 0.1 grams or from about 0.01 grams to about one or more compounds of at least one metal in Groups 7 to 10 on the periodic table, calculated as the total weight of the Groups 7 to 10 metals per gram of catalyst 0.05 grams of at least one Group 7-10 metal and / or at least one Group 7-10 metal compound, and (c) at least one metal in Group 10 of the periodic table and / or one or more metals in Group 10 of the periodic table Containing the above compounds (d) at least one element comprising molybdenum and / or tungsten, (e) including nickel and / or cobalt, (f) including nickel and / or iron, and (g) in Group 15 on the periodic table; and From about 0.000001 grams to about 0.1 grams, from about 0.00001 grams to about 0.06 grams, about 0.00005 grams, comprising at least one compound of at least one element from group 15 of the periodic table and calculated as the total weight of the elements of group 15 per gram of catalyst To about 0.03 grams, or about 0.0001 grams to about 0.001 grams of at least one Group 15 element and / or at least one Group 15 elemental compound, comprising (h) phosphorus, and / or (i) Group 5 per gram catalyst At least one metal in Group 5 on the periodic table and / or one or more metals in Group 5 on the periodic table, calculated as the total weight of the metal.

In some embodiments, the present invention also provides a combination of one or more of the foregoing embodiments, wherein the Group 6 metal catalyst or Group 6 metal solution is calculated as the total weight of (a) molybdenum per gram of the Group 6 metal solution or catalyst. Grams to about 0.15 grams of molybdenum and / or one or more molybdenum compounds, and about 0.001 grams to about 0.05 grams of nickel and / or one or more nickel compounds calculated as the total weight of nickel, and (b) optionally, a total of iron From about 0.001 grams to about 0.05 grams of iron and / or one or more iron compounds calculated by weight, and (c) optionally from about 0.0001 grams to about 0.05 grams of phosphorus and / or one or more phosphorus compounds Provide to have.

In some embodiments, the present invention also provides a Group 5-10 metal catalyst in combination with one or more of the foregoing embodiments, comprising (a) molybdenum, (b) tungsten, (c) vanadium (D) from about 0.001 to about 0.1 grams per gram of catalyst or from about 0.01 to about 0.05 grams of one or more metals in Groups 7 to 10 on the periodic table and / or of one or more metals in Groups 7 to 10 on the periodic table At least one compound of (e) at least one element of group 15 on the periodic table and / or at least one compound of at least one element of group 15 on the periodic table, (f) comprising phosphorus, and / or ( g) has a pore size distribution having an intermediate pore diameter of at least 180 mm, at least 200 mm, at least 230 mm, at least 250 mm, or at least 300 mm.

In some embodiments, the present invention also provides a combination of one or more of the foregoing embodiments to provide a Group 6 metal catalyst which is a carrier catalyst, wherein the carrier comprises (a) at least 0.8 grams, at least 0.9 grams or at least 0.95 grams per gram of carrier. Or more gamma alumina, (b) at most 0.1 grams, at most 0.08 grams, at most 0.06 grams, at most 0.04 grams or at most 0.02 grams of silica, or (c) at least 0.3 grams or at least 0.5 grams of theta alumina.

In some embodiments, the present invention also provides a contacting step of contacting the crude oil feed with at least one catalyst in combination with at least one of the foregoing embodiments, wherein at least one catalyst comprises a mixture with at least one Group 6 metal and And / or a Group 6 metal catalyst obtainable by blending one or more Group 6 metal compounds, the mixture comprising one or more metals in Groups 7 to 10 on the periodic table and / or one or more metals in Groups 7 to 10 on the periodic table At least one compound and a carrier. In some embodiments, in combination with one or more of the foregoing embodiments, the one or more Group 7-10 metals include nickel, cobalt, iron, or mixtures thereof.

In some embodiments, the present invention also provides a crude oil feed in combination with one or more of the foregoing embodiments, wherein the crude feed comprises (a) from about 0.0001 grams to about 0.5 grams, about 0.005 per gram of crude oil feed Gram to about 0.1 grams, or about 0.01 grams to about 0.05 grams of MCR, (b) 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 oil feed And / or (c) 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 metals and alkaline earth metals of organic acid metal salts per gram of crude oil feed.

In some embodiments, the present invention also provides a crude oil product in combination with one or more of the foregoing embodiments, wherein the crude oil product is (a) at most 80%, at most 50%, at most 30% of the MCR content of the crude oil feed. Or MCR content of up to 10%, (b) up to 80%, up to 50%, up to 30%, or up to 10% nitrogen content of the crude oil feed, (c) alkali metals of organic acid metal salts of the crude feed and Up to 80%, up to 50%, up to 30%, or up to 10% of the alkaline earth metal in the crude oil product, the total content of alkali and alkaline earth metals of the organic acid metal salt, (d) from about 0.1% to about the MCR content of the crude feed MCR content in the range of about 75%, about 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9%, (e) about 0.1% to 75% of the nitrogen content of the crude oil feed, about Nitrogen content in the range of 0.5% to about 45%, about 1% to about 25%, or about 2% to about 9%, (f) alkali metals of organic acid metal salts of crude oil feeds, and Alkali and alkaline earth metals of organic acid metal salts in crude oil products ranging 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 alkaline earth metals. Total content, (g) about 0.00001 grams to about 0.1 grams per gram of crude oil product, about 0.0001 grams to about 0.05 grams, or about 0.001 grams to about 0.005 grams of MCR, (h) about 0.00001 grams per gram of crude oil product 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, (i) about 1 × 10 ^-7 grams to about 5 × 10 ^-5 grams, about 5 per gram of crude oil product Alkali metals and alkaline earth metals in an organic acid metal salt of from about 10 ⁻⁷ grams to about 1 × 10 ⁻⁵ grams, or about 1 × 10 ⁻⁶ grams to about 5 × 10 ⁻⁶ grams, (j) 37.8 ° C. in a crude oil feed Viscosity of up to 90%, up to 80%, up to 70%, up to 50%, up to 30%, or up to 10% of the viscosity at (100 ° F.) (viscosity measured by ASTM method D445), (k) crude oil C ₅ asphaltene content of up to 90%, up to 80%, up to 70%, up to 50%, up to 30%, or up to 10% of the C ₅ asphaltene content of the feed (C ₅ asphaltene content is measured by ASTM method D2007 ), (L) residue content of up to 90%, up to 80%, up to 70%, up to 50%, up to 30%, or up to 10% of the residue content of the crude oil feed (residue content is determined by ASTM method D5307). Measured), and / or (m) sulfur content of up to 90%, up to 80%, up to 70%, up to 50%, up to 30%, or up to 10% of the sulfur content of the crude oil feed (the sulfur content is ASTM method D4294 Measured as.

In some embodiments, the present invention provides a contacting step of combining at least one of the foregoing embodiments to contact a crude oil feed with at least one catalyst and at least one additional catalyst, wherein the at least one catalyst is a Group 6 metal catalyst, The at least one additional catalyst has a median pore diameter of at least 60 kPa, at least 90 kPa, at least 110 kPa, at least 180 kPa, at least 200 kPa, or at least 250 kPa, and the Group 6 metal catalyst is before and / or after contacting the crude oil feed with at least one additional catalyst. Contact with the crude feed.

In some embodiments, the present invention provides a combination of one or more of the foregoing embodiments to provide at least one catalyst that is a Group 5-10 metal catalyst and to contact the crude oil feed with an additional catalyst having a median pore diameter of at least 60 mm 3. Providing a step, wherein the additional catalyst is contacted with the crude oil feed and subsequently the crude feed is contacted with a Group 5-10 metal catalyst.

In some embodiments, the present invention also provides a contacting step of contacting the crude oil feed with the at least one catalyst to combine one or more of the foregoing embodiments to produce a total product, and upon contacting the crude oil feed / total product mixture Has a P-value greater than 1.5.

In some embodiments, the invention also provides a contacting step in which one or more of the foregoing embodiments are combined to contact in the presence of a hydrogen source.

In some embodiments, the present invention also provides a combination of one or more of the foregoing embodiments of (a) a temperature in the range of about 50 ° C to about 500 ° C, (b) a maximum of 430 ° C, a maximum of 420 ° C, or a maximum of 410 ° C. Temperature, (c) total pressure in the range of about 0.1 MPa to about 20 MPa, (d) total pressure of up to 18 MPa, up to 16 MPa, or up to 14 MPa, (e) liquid space velocity per hour above 0.05 h ⁻¹ , and And / or (f) contact conditions including the ratio of gaseous hydrogen source to crude oil feed in the range of about 0.1 Nm ³ / m ³ to about 100,000 Nm ³ / m ³ .

In some embodiments, the present invention also provides a mixture suitable for conveying in a manner comprising combining one or more of the aforementioned embodiments to contact the crude feed with at least one catalyst to produce a total product comprising the crude product. It further provides a compounding step of combining the crude product with the same or different crude oil to form a crude feed.

In some embodiments, the invention also provides a method for preparing a catalyst comprising a compounding step of combining one or more of the foregoing embodiments to combine a carrier and a Group 6 metal solution, the solution comprising (a) at most about 3 (B) a pH in the range of about 1 to about 3, and (c) the amount of Group 6 metal in the metal solution is about 0.0001 where the catalyst is calculated as the total weight of Group 6 metal per gram of this catalyst. From grams to about 0.3 grams, from about 0.005 grams to about 0.2 grams, or from about 0.01 grams to about 0.1 grams of at least one Group 6 metal and / or at least one Group 6 metal compound, and (d) 7- on the periodic table. At least one compound of at least one metal in Group 10 and / or at least one metal in Groups 7 to 10 on the Periodic Table, wherein the amount of Group 7 to 10 metal is determined by the catalyst being a Group 7 to 10 metal per gram of Calculated as the total weight of about 0.001 grams to about 0.1 RAM or about 0.01 grams to about 0.05 grams of at least one Group 7-10 metal and / or at least one Group 7-10 metal compound, and (e) at least one metal and / or periodic table in Group 10 of the periodic table. At least one compound of at least one metal in Group 10 of phase 10, (f) comprises molybdenum and / or tungsten, (g) comprises nickel and / or cobalt, (h) comprises nickel and iron, (i) at least one element of group 15 on the periodic table and / or at least one compound of at least one element on group 15 of the periodic table, wherein the amount of the group 15 element is determined by the catalyst of the Group 15 element per gram of From about 0.000001 grams to about 0.1 grams, from about 0.00001 grams to about 0.06 grams, from about 0.00005 grams to about 0.03 grams, or from about 0.0001 grams to about 0.001 grams, calculated as total weight Add compound of element Selected to contain (j) phosphorus, (k) at least one mineral acid, (l) at least one organic acid, (m) hydrogen peroxide, and / or (n) amines do.

In some embodiments, the present invention also provides a method of preparing a catalyst in combination with one or more of the foregoing embodiments, wherein the method for preparing a catalyst comprises a carrier metal of about 40 ° C. to about 400 ° C., about 60 ° C. to about 300 Heat treating at a temperature in the range of about 100 ° C. to about 200 ° C., and optionally further heat treating the carrier metal at a temperature of 400 ° C. or higher.

In some embodiments, the present invention provides a Group 6-10 metal catalyst in combination with one or more of the foregoing embodiments, which catalyst comprises (a) one or more metals in Group 6 on the periodic table and / or six on the periodic table. At least one compound of at least one metal in a group, (b) at least one compound of at least one metal in groups 7 to 10 on the periodic table and / or at least one compound of at least one metal in groups 7 to 10 on a periodic table, (c) molybdenum and / or tungsten, (d) nickel and / or cobalt, (e) binders include silica, alumina, silica / alumina, titanium oxide, zirconium oxide, or combinations thereof And / or (f) they are amorphous.

In other embodiments, features of certain embodiments of the invention can be combined with features of other embodiments of the invention. For example, features from one embodiment of the present invention can be combined with any of the other embodiments.

In other embodiments, the crude oil product can be obtained by any of the methods and systems described herein.

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

In other embodiments, the transfer fuel, heating fuel, lubricating oil or chemicals may be obtained from crude oil products or mixtures obtained by any of the methods and systems described herein.

Those skilled in the art will appreciate the advantages of the present invention with reference to the following detailed description and accompanying drawings.

1 is a schematic view showing one embodiment of a contact system;

2A and 2B are schematic diagrams showing embodiments of a contact system comprising two contact regions;

3A and 3B are schematic diagrams showing embodiments of a contact system comprising three contact regions,

4 is a schematic view showing one embodiment of a separation zone in combination with a contact system;

5 is a schematic diagram showing one embodiment of a blending region in combination with a contact system, and

6 is a schematic diagram showing one embodiment of a combination of separation zone, contact system, and blending zone.

The invention can accommodate various modifications and variations, and specific embodiments thereof are shown in the drawings by way of example. The drawings may not be drawn to scale. The drawings and detailed description are not intended to limit the invention to the particular forms disclosed above, and on the contrary, all changes, equivalents, and substitutions within the spirit and scope of the invention as defined by the appended claims. It is intended to include.

The foregoing problems will be addressed using the systems, methods and catalysts described herein. For example, the MCR content of a crude oil feed may be brought into contact with a crude feed with a pore size distribution having a median pore diameter of at least 110 mm 3 and a pore volume with a pore diameter of at least 350 mm 3 having a pore volume of up to 10% of the pore volume. Crude oil products are produced that have a reduced MCR content and / or a reduced nitrogen content relative to the nitrogen content. By contacting the crude feed with the uncalcined catalyst, a crude oil product with reduced nitrogen content relative to the nitrogen content of the crude feed is produced. By contacting the crude oil feed with a catalyst comprising Group 5-10 metal (s) and theta alumina, a crude oil product is produced in which the metal content in the organic acid metal salt is reduced compared to the metal content in the organic acid metal salt of the crude feed. By contacting the crude oil feed with the bulk metal catalyst, a crude oil product with reduced MCR content relative to the MCR content of the crude oil feed is produced.

United States Patent Application Nos. 11 / 014,335, 11 / 013,553, 11 / 014,386, 11 / 013,554, 11 / 013,629, 11 / 014,318, 11 / 013,5779, 11 / 014,362, 11 / 014,011, 11 / 013,747, 11 / 013,918, 11 / 014,275, 11 / 014,060, 11 / 014,272, 11 / 014,380, 11 / 014,005 11 / 013,998, 11 / 014,406, 11 / 014,365, 11 / 013,545, 11 / 014,132, 11 / 014,363, 11 / 014,251, 11 / 013,632, 1 11 / 014,009, 11 / 014,297, 11 / 014,004, 11 / 013,999, 11 / 014,281, 11 / 031,995, 11 / 013,904, 11 / 013,952, 11/11 014,299, 11 / 014,381, 11 / 014,346, 11 / 014,028, 11 / 013,826, and 11 / 013,622 differ somewhat from crude oil feeds treated in accordance with the invention described herein. For systems, methods, and catalysts that address this problem for crude oil feedstock, As described.

Herein, certain embodiments of the present invention are described in more detail. Definitions of terms used herein are as follows.

"ASTM" means US Standard Tests and Materials.

"API gravity" refers to API gravity at 15.5 ° C (60 ° F). API specific gravity is measured by ASTM method D6822.

The atomic hydrogen percentage and atomic carbon percentage of crude oil feed and crude oil product are measured by ASTM method D5291.

Boiling range distributions for crude oil feed, total product, and / or crude oil product are measured by ASTM method D5307, unless otherwise noted.

"Binder" refers to a substrate that binds smaller materials together to form larger materials (eg, blocks or pellets).

"Bulk metal catalyst" refers to a catalyst that contains one or more metals and does not require a carrier or carrier.

"C ₅ Asphaltenes "refers to asphaltenes that do not dissolve in pentane. C ₅ The asphaltene content is measured by ASTM method D2007.

"Group X metal (s)" refers to one or more compounds of one or more metals of Group X on the periodic table and / or one or more metals of one or more metals of Group X on the periodic table, where X is a group number (eg, 1 to 12) For example, “Group 6 metal (s)” refers to one or more compounds of one or more metals in Group 6 on the periodic table and / or one or more metals in Group 6 on the periodic table.

"Group X element (s)" refers to one or more compounds of one or more elements of group X on the periodic table and / or one or more elements of one or more elements of group X on the periodic table, where X is a group number (eg, 13 to 18) For example, "Group 15 element (s)" refers to one or more compounds of one or more elements in Group 15 of the Periodic Table and / or one or more elements in Group 15 of the Periodic Table.

Within the scope of the present application, the weight of the metal from the periodic table, the weight of the compound of the metal from the periodic table, the weight of the element from the periodic table or the weight of the compound of the element from the periodic table are calculated according to the weight of the metal or the weight of the element. . For example, using 0.1 grams of MoO ₃ per gram of catalyst, the resulting weight of molybdenum metal in the catalyst is 0.067 grams per gram of catalyst.

"Content" refers to the weight of one component in a substrate, expressed in parts by weight or weight percentage relative to the total weight of the substrate (eg, crude oil feed, total product, or crude product). "Wtppm" refers to 1 million parts by weight.

"Crude oil feed / total product mixture" refers to a mixture that comes into contact with the catalyst during processing.

"Distillate" refers to a hydrocarbon having a boiling range distribution between 204 ° C. (400 ° F.) and 343 ° C. (650 ° F.) at 0.101 MPa. Distillate content is measured by ASTM method D5307.

"Heteroatoms" refer to oxygen, nitrogen, and / or sulfur included in the molecular structure of a hydrocarbon. The heteroatom content is measured by ASTM method E385 for oxygen, D5762 for total nitrogen, and D4294 for sulfur. "Total basic nitrogen" refers to a nitrogen compound having a pKa of less than 40. Base nitrogen (“bn”) is measured by ASTM method D2896.

"Hydrogen source" refers to hydrogen, and / or compounds and / or compounds that, if present, provide hydrogen to the compound (s) in the crude feed, when present. Hydrogen sources can include, but are not limited to, hydrocarbons (eg, C ₁ -C ₄ hydrocarbons such as methane, ethane, propane, butane), water, or mixtures thereof. Mass balance can be analyzed to estimate the net amount of hydrogen provided to the compound (s) in the crude oil feed.

"Flat plate crush strength" refers to the compressive force required to break the catalyst. Plate break strength is measured by ASTM method D4179.

"LHSV" refers to the ratio of the supplied liquid volume to the total volume of the catalyst, expressed in hours (h ^-1 ). The total volume of catalyst is calculated by summing all catalyst volumes in the contacting zones, as described herein.

"Liquid mixture" refers to a composition comprising at least one compound in a liquid phase at standard temperature and standard pressure (25 ° C., 0.101 Mpa, hereinafter referred to as “STP”), or a solid phase in STP and at least one compound in liquid phase in STP Refers to a composition comprising a combination of one or more compounds of.

"Periodic Table" means the Periodic Table established by the International Union of Pure and Applied Chemistry in November 2003.

"Metal in organic acid metal salt" refers to alkali metal, alkaline earth metal, zinc, arsenic, chromium or combinations thereof. The content of metals in organic acid metal salts is measured by ASTM method D1318.

"MCR" content refers to the amount of residual carbon remaining after evaporation and pyrolysis of the substrate. MCR content is measured by ASTM method D4530.

“Naphtha” refers to hydrocarbon components having a boiling range distribution between 38 ° C. (100 ° F.) and 200 ° C. (392 ° F.), at 0.101 MPa. Naphtha content is measured by ASTM method D5307.

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

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

"Nm ³ / m ³ " refers to the normal cubic meter of gas per cubic meter of crude oil feed.

"Non-carboxyl group-containing organic oxygen compound" refers to organic oxygen compounds that do not have a carboxy (-CO _2- ) group. Non-carboxyl group-containing organic oxygen compounds include, but are not limited to, ethers, cyclic ethers, alcohols, aromatic alcohols, ketones, aldehydes, or combinations thereof that do not have a carboxyl group.

"Non-condensable gas" refers to components and / or mixtures of components that are gases in STP.

"P (peptization) value", ie, "P-value", refers to a numerical value representing the aggregation of asphaltenes in a crude oil feed. The method of determining this P-value is J. J. "Measurement and Importance of Asphalt Bridges" by J.J.Heithaus, Journal of Institute of Petroleum, Vol. 48, 458, February 1962, pages 45-53.

"Pore diameter", "average pore diameter", "medium pore diameter" and "pore volume" are measured by ASTM method D4284 (mercury porosimetry using mercury infiltration at a contact angle equivalent to 140 °). It refers to the same pore diameter, average pore diameter, middle pore diameter and pore volume. To obtain these values, the Micromeritics ^® A9220 instrument (Micromeritics Inc., Norcross, Georgia, USA) can be used. Pore volume includes all pore volumes of the catalyst. The middle pore diameter refers to the pore diameter where 50% of the total pore number has a pore diameter of at least the middle pore diameter and 50% of the total pore number has a pore diameter of less than or equal to the mid pore diameter. The average pore diameter is expressed in angstrom units (kPa) and is determined using the following formula.

Average pore diameter = (40,000 × total pore volume (cm 3 / g)) / (surface area (m 2 / g))

“Residue” refers to components that have a boiling range distribution of temperature higher than 538 ° C. (1000 ° F.), as measured by ASTM method D5307.

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

The "surface area" of the catalyst is measured by ASTM method D3663.

"TAN" refers to the total acid value expressed in milligrams ("mg") of KOH per gram of sample ("g"). TAN is measured by ASTM method D664.

"VGO" refers to a hydrocarbon having a boiling range distribution between 343 ° C (650 ° F) and 538 ° C (1000 ° F) at 0.101 MPa. VGO content is measured by ASTM method D5307.

"Viscosity" refers to kinematic viscosity at 37 ° C (100 ° F). Viscosity is measured using ASTM method D445.

All the methods mentioned are referenced herein. In the present application, if the values obtained for the properties of the substrate being tested are outside the limits of the test method, those properties can be tested by modifying and / or recalibrating the test method.

Crudes may be prepared and / or distilled from hydrocarbon-containing formations and then stabilized. Typically the crude is a solid, semi-solid, and / or liquid. The crude includes crude oil. Stabilization treatment includes, but is not limited to, removing non-condensable gases, water, salts, solids, or combinations thereof from crude oil to form stabilized crude oil. This stabilization can usually be done at or near the site of manufacture and / or distillation.

Stabilized crude oil includes crude oil that has not been distilled and / or fractionally distilled at a processing facility for producing a number of components (eg, naphtha, distillate, VGO, and / or lubricants) having a specific boiling range distribution. do. Distillation includes an atmospheric distillation method and / or a vacuum distillation method, but is not limited only to these methods. Undistilled and / or fractionated stabilized crude oil may comprise components having more than four carbons in an amount of at least 0.5 grams per gram of crude oil. Stabilized crude oil also includes crude oil from a surface distillation process. For example, Canadian tar sands can be mined and treated in a surface distillation process. The crude oil produced by the surface distillation may be a stabilized crude oil. Examples of stabilized crude oils include whole crudes, topped crudes, desalted crudes, desalted topped crudes, or combinations thereof. “Topped” refers to crude oil that has been treated to remove at least some of the components having a boiling point of less than 35 ° C. (less than about 95 ° F. at 1 atm) at 0.101 MPa. Typically, atmospheric distillate crude oil will have such components in an amount of up to 0.1 grams, up to 0.05 grams, or up to 0.02 grams per gram of the atmospheric distillation crude oil.

Certain stabilized crude oils have the property of allowing the stabilized crude oil to be transferred to conventional processing facilities by transfer carriers (eg, pipelines, trucks, or ships). Other crude oils have one or more ineligible properties that impede barriers. Lower crude oils may not be suitable for transfer carriers and / or processing facilities, resulting in lower economic value of the lower crude oils. Its economic value is the same in reservoirs containing lower crude oil, which are expensive to manufacture, transport and / or process.

Properties of lower crude oils include a) a TAN of at least 0.1 or at least 0.3, b) a viscosity of at least 10 cSt, c) a specific gravity of API of at most 19, d) a total Ni / V / Fe content of at least 0.00002 grams per gram of lower crude oil. Or at least 0.0001 grams of Ni / V / Fe, e) total heteroatomic content, including at least 0.005 grams of heteroatoms per gram of crude oil, f) residue content, including at least 0.01 grams of residue per gram of crude oil, g A) C ₅ asphaltene content comprising at least 0.04 grams of C ₅ asphaltenes per gram of crude oil; h) MCR content comprising at least 0.0001 grams of MCR per gram of crude crude oil; i) at least 0.00001 grams of metal per gram of crude crude oil Metal content in the organic acid metal salt comprising, or j) combinations thereof, but is not limited thereto. In some embodiments, the lower crude oil comprises at least 0.2 grams residue, at least 0.3 grams residue, at least 0.5 grams residue, or at least 0.9 grams residue per gram of crude oil. In some embodiments, the lower crude oil has a TAN in the range of about 0.1 to about 20, about 0.3 to about 10, or about 0.4 to about 5. In some embodiments, the lower crude oil has a sulfur content of at least 0.005 grams, at least 0.01 grams, or at least 0.02 grams per gram of this lower crude oil.

In some embodiments, the lower crude oil has 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 this lower crude oil. Lower crude oil may have an MCR content in the range of about 0.0001 to about 0.5 grams, about 0.005 to about 0.1 grams, or about 0.01 to about 0.05 grams per gram of this lower crude oil.

In some embodiments, the lower crude oil has 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 this lower crude oil. Lower crude oil may have a nitrogen content in the range of about 0.0001 to about 0.1 grams, about 0.001 to about 0.05 grams, or about 0.005 to about 0.01 grams per gram of this lower crude oil.

In some embodiments, the lower crude oil has an alkali metal and an alkaline earth metal in at least 0.00001 gram, at least 0.0001 gram, at least 0.001 gram or at least 0.01 gram of organic acid metal salt. Lower crude oil may have an alkali metal and an alkaline earth metal in about 0.00001 to about 0.003 grams, about 0.00005 to about 0.005 grams, or about 0.0001 to about 0.01 grams of organic acid metal salt.

In some embodiments, the lower crude oil has a) a TAN of at least 0.5, b) an oxygen content comprising at least 0.005 grams of oxygen per gram of crude oil feed, c) a minimum of 0.04 grams C ₅ per gram of crude oil feed C ₅ containing asphaltenes Asphaltene content, d) viscosity higher than the required viscosity (e.g., at least 10 cSt for crude oil feed with an API gravity of at least 10), e) metal content in organic acid metal salts of at least 0.00001 grams per gram of crude oil, or f) having characteristics including a combination thereof, but not limited thereto.

Low crude oil contains at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams, and at least 0.01 grams of hydrocarbons having a boiling range distribution from 0.101 MPa to about 95 ° C. to about 200 ° C. per gram of this lower crude oil. At least 0.001 gram, at least 0.005 gram, or at least 0.01 gram of hydrocarbon having a boiling range distribution of ℃, at least 0.001 gram, at least 0.005 gram, or minimum of hydrocarbon having a boiling range distribution of about 300 ° C. to about 400 ° C. at 0.101 MPa. And at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams of hydrocarbons having a boiling range distribution of from about 400 grams to about 650 degrees Celsius at 0.01 grams and 0.101 MPa.

Lower crude oils have a boiling range of at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams, 0.101 MPa at about 100 ° C. to about 200 ° C. for hydrocarbons having a boiling range distribution of 0.101 MPa up to 100 ° C. per gram of this lower crude oil. A hydrocarbon having a distribution of at least 0.001 grams, a minimum of 0.005 grams, or at least 0.01 grams, a hydrocarbon having a boiling range distribution from 0.101 MPa to about 200 ° C. to about 300 ° C., at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams, Hydrocarbons having a boiling range distribution of from about 300 ° C. to about 400 ° C. at 0.101 MPa are at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams, and hydrocarbons having a boiling range distribution of from about 400 ° C. to about 650 ° C. at 0.101 MPa And at least 0.001 gram, at least 0.005 gram, or at least 0.01 gram.

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

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

In some embodiments, the lower crude oil comprises hydrocarbons having a boiling range distribution of at least 300 ° C. up to 0.9 grams or up to 0.99 grams per gram of lower crude oil. In some embodiments, certain lower crude oils may also comprise a minimum of 0.001 grams per gram of lower crude oil with hydrocarbons having a boiling range distribution of at least 650 ° C. In some embodiments, the lower crude oil comprises a hydrocarbon having a boiling range distribution of about 300 ° C. to about 1000 ° C. up to about 0.9 grams or up to about 0.99 grams per gram of lower crude oil.

Examples of lower crude oils that can be processed using the treatment processes described herein include the following regions of the world, the US Gulf Coast and Southern California, the northern slopes of Alaska, the Canadian Tar Sands, the Alberta Region of Canada, the Gulf of Campeche, and the Argentine Coral. Le Basin, Brazil Santos and Campos Basin, Suezman, Egypt, Chad, North England, offshore Angola, Bohai Bay, China, Karamay, Iraq, Zagros, Kazakhstan Caspian Sea, Nigeria, Offshore, Madagascar, Northwest, Oman, Netherlands Crude oil from Nebec, Zulia, Venezuela, Malaysia, and Sumatra, Indonesia. Processing lower crude oil can improve the properties of the lower crude oil to be suitable for transport and / or processing. Crude oil and / or lower crude oil processed herein is referred to as a "crude oil feed." This crude oil feed may be atmospheric distilled as described herein. Crude oil feeds can be obtained by the methods described herein and are not limited to these methods. Crude oil products obtained by treating crude oil feeds are typically suitable for transport and / or treatment, as described herein. The properties of crude oil products prepared as described herein are closer to the corresponding properties of West Texas heavy or bran oil than their crude feed, thereby enhancing the economic value of the crude feed. Such crude oil products can be purified with less pretreatment or without any pretreatment than other crude oil products from lower crude oil feeds, thereby improving the purification efficiency. Pretreatment may include desulfurization, demetallization and / or atmospheric distillation to remove impurities.

Treatment of the crude oil feed according to the invention described herein may include contacting the crude feed with the catalyst (s) in one contacting zone and / or in a combination of two or more contacting zones. In the contacting zone, one or more properties of the crude oil feed can be altered by contacting the crude feed with one or more catalysts for the same properties of the crude oil feed. In some embodiments, the contact is carried out in the presence of a hydrogen source. In some embodiments, the hydrogen source is one or more hydrocarbons that react under predetermined contact conditions to supply relatively small amounts of hydrogen to the compound (s) in the crude oil feed.

1 is a schematic diagram of a contact system 100 including an upstream contact region 102. The crude feed enters the upstream contacting region 102 through the crude feed conduit 104. The contact region may be a reactor, a part of the reactor, a plurality of parts of the reactor or a combination thereof. Examples of contact areas include stacked bed reactors, fixed bed reactors, ebullating bed reactors, continuous stirred tank reactors ("CSTR"), fluidized bed reactors, spray reactors And liquid / liquid contactors. In some embodiments, the contact system is at or connected to an offshore facility. The contact between the crude oil feed and the catalyst (s) in the contact system 100 may be a continuous process or a batch process.

The contacting zone may comprise one or more catalysts (eg two catalysts). In some embodiments, contacting the first of the two catalysts with the crude oil feed can reduce the metal in the organic acid metal salt of the crude feed. Subsequent contact of the crude oil feed with reduced metal salts to the second catalyst can lower the MCR content and / or heteroatomic content. In another embodiment, combinations of these properties of TAN, viscosity, Ni / V / Fe content, heteroatomic content, residue content, API specific gravity, or crude oil product may be obtained after the crude oil feed has contacted one or more catalysts. And at least 10% of the same characteristics of the crude oil feed.

In some embodiments, the volume of catalyst in the contacting zone is from about 10 to about 60 volume percent, from about 20 to about 50 volume percent, or from about 30 to about 40 volume percent of the total volume of the crude oil feed at the contacting zone. Is in the range of. In some embodiments, the slurry of catalyst and crude oil feed may comprise from about 0.001 to about 10 grams, from about 0.005 to about 5 grams, or from about 0.01 to about 3 grams of catalyst per 100 grams of crude oil feed in the contacting zone. .

Contact conditions in the contacting zone may include, but are not limited to, temperature, pressure, hydrogen source flow, crude oil feed flow, or combinations thereof. In some embodiments, the contact conditions are controlled to produce crude oil products having specific properties. The temperature in the contact region may range from about 50 ° C. to about 500 ° C., from about 60 ° C. to about 440 ° C., from about 70 ° C. to about 430 ° C., or from about 80 ° C. to about 420 ° C. The pressure in the contact region can range from about 0.1 MPa to 20 MPa, about 1 MPa to about 12 MPa, about 4 MPa to about 10 MPa, or about 6 MPa to about 8 MPa. LHSV of crude oil feed is typically about 0.05h ^-1 to about 30h ^-1 , about 0.5h ^-1 to about 25h ^-1 , about 1h ^-1 to about 20h ^-1 , about 1.5h ^-1 to about 15h ^-1 , or about 2h ^-1 ~ about 10h ^- it may be in the range of ^1. In some embodiments, the LHSV is at least 5h- ¹ , at least 11h- ¹ , at least 15h- ¹ , or at least 20h ^{- 1} . In some embodiments, the total pressure is at most 18 MPa, at most 16 MPa, at most 14 MPa, at most 12 MPa, at most 10 MPa, or at most 8 MPa. In some embodiments, the temperature is at most 430 ° C, at most 420 ° C, at most 410 ° C, or at most 400 ° C.

In embodiments in which the hydrogen source is supplied as a gas (eg hydrogen gas), the ratio of the gaseous hydrogen source to the crude oil feed in contact with the catalyst (s) is typically from about 0.1 Nm ³ / m ³ to about 100,000 Nm ³ / m ³ , about 0.5 Nm ³ / m ³ to about 10,000 Nm ³ / m ³ , about 1 Nm ³ / m ³ to about 8,000 Nm ³ / m ³ , about 2 Nm ³ / m ³ to about 5,000 Nm ³ / m ³ , about 5 Nm ³ / m ³ to about 3,000 Nm ³ / m ³ , or about 10 Nm ³ / m ³ to about 800 Nm ³ / m ³ . The hydrogen source, in some embodiments, is combined with the carrier gas (s) to recycle the contact area. The carrier gas can be, for example, nitrogen, helium, and / or argon. This carrier gas may promote the flow of crude oil feed and / or the flow of hydrogen source in the contacting zone (s). This carrier gas may enhance mixing at the contacting region (s). In some embodiments, a hydrogen source (eg, hydrogen, methane, or ethane) may be used as the carrier gas to recycle the contacting zone.

The hydrogen source may enter the upstream contacting region 102 co-currently with the crude oil feed in the crude oil feed conduit 104 or separately through the gas conduit 106. In the upstream contacting region 102, contact of the catalyst with the crude oil feed produces a crude product, and in some embodiments a total product comprising gas. In some embodiments, the carrier gas is combined with the crude oil feed and / or the hydrogen source in the conduit 106. The total product may exit the upstream contacting region 102 and enter the downstream separation region 108 via the total product conduit 110.

In the downstream separation zone 108, generally known separation techniques, such as gas-liquid separation, can be used to separate the crude product and the gas from the total product. The crude product may exit the downstream separation zone 108 and pass through the product conduit 112 and then be transferred to a transfer carrier, transport conduit, storage vessel, refinery, other processing area, or combination thereof. have. The gas may include gases formed during the treatment process (eg, hydrogen sulfide, carbon dioxide, and / or carbon monoxide), excess gaseous hydrogen source, and / or carrier gas. Excess gas may be refluxed into the contact system 100, purified, and transferred to other process areas, storage vessels, or a combination thereof.

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

2 and 3 are schematic diagrams showing embodiments of a contact system 100 that includes two or three contact regions. 2A and 2B, the contact system 100 includes an upstream contact region 102 and a downstream contact region 114. 3A and 3B include contact regions 102, 114, and 116. 2A and 3A, contact regions 102, 114, 116 are shown as independent contact regions within a reactor. The crude feed enters the upstream contacting region 102 via the crude feed conduit 104.

In some embodiments, the carrier gas is combined with the hydrogen source in gas conduit 106 and introduced into the contacting region as a mixture. In some embodiments, as shown in FIGS. 1, 3A, and 3B, the hydrogen source and / or carrier gas may separately enter one or more contacting zones along with the crude oil feed via a gas conduit 106 and / or For example, it may enter into one or more contacting regions via a gas conduit 106 'in a direction opposite to the flow of the crude oil feed. The addition of a hydrogen source and / or carrier gas to oppose the flow of the crude oil feed may enhance the mixing and / or contact of the crude oil feed with the catalyst.

Crude feed is contacted with the catalyst (s) in the upstream contacting zone 102 to form a feed stream. This feed stream flows from the upstream contact region 102 to the downstream contact region 114. 3A and 3B, the feed stream flows from the downstream contact region 114 to another downstream contact region 116.

Contact regions 102, 114, 116 may include one or more catalysts. As shown in FIG. 2B, the feed stream exits the upstream contact region 102 and enters the downstream contact region 114 via the crude oil feed conduit 118. As shown in FIG. 3B, the feed stream exits the downstream contact region 114 and enters the other downstream contact region 116 via the conduit 118.

The feed stream may contact additional catalyst (s) in the downstream contacting region 114 and / or other downstream contacting region 116 and may form the total product. Total product exits downstream contact region 114 and / or other downstream contact region 116 and enters downstream separation region 108 via total product conduit 110. Crude oil product and / or gas (s) are separated from the total product. The crude product exits downstream separation zone 108 through crude product conduit 112.

4 is a schematic diagram showing one embodiment of an upstream separation region of the contact system 100. Lower crude oil (with or without atmospheric distillation) enters the upstream separation zone 120 via the crude oil conduit 122. In the upstream separation zone 120, at least a portion of the lower crude oil uses techniques known in the art (eg, sparging, membrane separation, reduced pressure, filtration, or a combination thereof). To separate and produce a crude oil feed. For example, water can be at least partially separated from the lower crude oil in the upstream separation zone 120. In another embodiment, components having a boiling range distribution below 95 ° C. or 100 ° C. may be at least partially separated from the lower crude oil in upstream separation zone 120 to produce a crude oil feed. In some embodiments, naphtha and at least some of the more volatile compounds than naphtha can be separated from lower crude oil. In some embodiments, at least some of the separated components exit the upstream separation region 120 through the conduit 124.

The crude oil feed obtained from the upstream separation zone 120, in some embodiments, comprises a mixture of components having a boiling range distribution of at least 100 ° C., or in some embodiments, a boiling range of at least 120 ° C. A mixture of components having a distribution. Typically, the separated crude oil feed comprises a mixture of components having a boiling range distribution of about 100 ° C. to about 1,000 ° C., about 120 ° C. to about 900 ° C., or about 200 ° C. to about 800 ° C. At least a portion of the crude feed exits the upstream separation zone 120 and enters the contact system 100 via the crude feed conduit 126 (see, for example, the contact zones of FIGS. 1-3) for further processing. To form a crude product. In some embodiments, upstream separation zone 120 may be located upstream or downstream of the desalination unit. In some embodiments, the upstream separation zone 120 may be located downstream of the distillation process of bitumen, oil shale, and / or tar sands. After the treatment, the crude product exits the contact system 100 through the crude product conduit 112.

In some embodiments, the crude oil product is combined with crude oil that is the same as or different from the crude oil feed. For example, the crude oil product can be combined with crude oil of different viscosity, thus obtaining a blended product having a viscosity between the viscosity of the crude oil product and the viscosity of the crude oil. In another embodiment, the crude oil product may be blended with crude oil having a different TAN and / or MCR content, and thus TAN between the TAN and / or MCR content of the crude oil product and the TAN and / or MCR content of the crude oil. And / or a product having an MCR content can be obtained. The blended product may be suitable for transport and / or processing.

As shown in FIG. 5, in some embodiments, the crude feed enters the contact system 100 through the crude feed conduit 104 and at least a portion of the crude product passes through the conduit 128. 100 is exited and introduced into the blending region 130. In blending zone 130, at least a portion of the crude oil product is at least one process stream (eg, a hydrocarbon stream such as naphtha produced by separating one or more crude feeds), crude oil, crude feed, or mixtures thereof These are combined to obtain a blended product. The process stream, crude feed, crude oil, or mixtures thereof are introduced directly into blending zone 130 or directly upstream of the blending zone via stream conduit 132. The mixing system can be disposed in or near the blending region 130. The blended product may meet product specifications and / or requirements of transfer carriers as defined by the refinery. Product specifications include, but are not limited to, API specific gravity, TAN, viscosity, or ranges or combinations thereof. The blended product is conveyed or processed out of blended zone 130 through blended conduit 134.

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

In some embodiments, the crude oil and / or blended product is sent to a refining plant for distillation and / or partial distillation to produce one or more distillation fractions. This distillation fraction can be processed to produce commercially available products such as conveying fuels, lubricants or chemicals.

In some embodiments, after contacting the crude oil feed with the catalyst, the crude oil product has a TAN of at most 90%, at most 50%, at most 30%, or at most 10% of the crude oil feed. In some embodiments, the crude oil 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 0.005. The TAN of the crude product will frequently be at least 0.0001, more frequently at least 0.001. In some embodiments, the TAN of the crude oil product may range 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 total Ni / V / Fe content of the crude oil product is up to 90%, up to 50%, up to 30%, up to 10%, up to 5%, or up to the Ni / V / Fe content of the crude feed. Up to 3%. In some embodiments, the crude oil product is about 1 × 10 ⁻⁷ grams to about 5 × 10 ⁻⁵ grams, about 3 × 10 ⁻⁷ grams to about 2 × 10 ⁻⁵ grams, or about 1 per gram of crude oil product It has a total Ni / V / Fe content in the range of 10 × ⁶ grams to about 1 × 10 ⁻⁵ grams. In some embodiments, the crude oil product has a maximum of 2 × 10 ⁻⁵ grams of Ni / V / Fe per gram of crude oil product. In some embodiments, the total Ni / V / Fe content of the crude oil product is about 70% to about 130%, about 80% to about 120%, or about 90% of the Ni / V / Fe content of the crude feed. To about 110%.

In some embodiments, the crude oil product comprises at most 90%, at most 50%, at most 30%, at most 10%, or at most 5% of the total amount of metals in the organic acid metal salt of the organic acid metal salt of the crude feed. Content. In some embodiments, 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 metals in the organic acid metal salt in the crude oil feed The total content of metals in the organic acid metal salt of the range. In general, organic acids forming metal salts include, but are not limited to, carboxylic acids, thiols, imides, sulfonic acids, sulfonates, and the like. Carboxylic acids include, but are not limited to, naphthenic acid, phenanthrene acid, benzene acid, and the like. The metal parts of the metal salts include alkali metals (eg lithium, sodium, and potassium), alkaline earth metals (eg magnesium, calcium, and barium), group 12 metals (eg zinc and cadmium), Group 15 metals (eg arsenic), group 6 metals (eg chromium), or mixtures thereof.

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

In some embodiments, the crude oil product comprises a total content of up to 90%, up to 80%, up to 50%, up to 30%, up to 10%, or up to 5% of the organic acid zinc salt of the at least one organic acid zinc salt in the crude oil feed. Has In some embodiments, the total content of organic acid zinc salt of the crude oil product is about 0.1% to about 75%, about 0.5% to about 45%, about 1% to about 25%, of the total content of organic acid zinc salt in the crude oil feed, Or about 2% to about 9%.

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

In some embodiments, the crude oil product is about 1 × 10 ⁻⁷ grams to about 5 × 10 ⁻⁵ grams, about 5 × 10 ⁻⁷ grams to about 1 × 10 ⁻⁵ grams, or about per gram of the crude oil product Alkali metals and alkaline earth metals in organic acid metal salts from 1 × 10 ⁻⁶ grams to about 5 × 10 ⁻⁶ grams.

In some embodiments, the API gravity of the crude oil product produced by contacting the crude oil feed with the catalyst at the contacting conditions is about 70% to about 130%, about 80% to about 120% of the API gravity of the crude oil feed. About 90% to about 110%, or about 100% to about 130%. In some embodiments, the API gravity of the crude oil product is about 14 to about 40, about 15 to about 30, or about 16 to about 25.

In some embodiments, the crude oil 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 oil feed. In some embodiments, the viscosity of the crude oil product is at most 90% of the viscosity of the crude oil feed, and the API gravity of the crude oil product is about 70% to about 130%, about 80% to about 120%, Or about 90% to about 110%.

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

In some embodiments, the total nitrogen content of the crude oil product is at most 90%, at most 80%, at most 70%, at most 50%, at most 30%, at most 10%, or at most of the total nitrogen content of the crude oil feed. Can be 5%. In some embodiments, the crude oil product has a total nitrogen content of at least 1%, at least 30%, at least 80%, or at least 99% of the total nitrogen content of the crude feed. In some embodiments, the crude oil product comprises 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 oil feed. Has a total nitrogen content. In some embodiments, the crude product has a total nitrogen content of 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 oil product.

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

In some embodiments, the oxygen content of the crude oil 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 some embodiments, the crude oil product may have an oxygen content of at least 1%, at least 30%, at least 80%, or at least 99% of the oxygen content of the crude feed. In some embodiments, the total content of carboxylic acid compounds of the crude oil product may be at most 90%, at most 50%, at most 30%, at most 10%, at most 5% of the content of the carboxylic acid compounds of the crude feed. In some embodiments, the crude product has a total content of at least 1%, at least 30%, at least 80%, or at least 99% of the carboxylic acid compounds of the carboxylic acid compounds of the crude feed.

In some embodiments, selected organic oxygen compounds may be reduced in the crude oil feed. In some embodiments, the carboxylic acid and / or metal salt of the carboxylic acid may be chemically reduced before the non-carboxyl group containing organic oxygen compounds. Carboxylic acid and non-carboxyl group-containing organic oxygen compounds of crude oil products are commonly described as those of crude oil products using known spectroscopic methods (eg, infrared spectroscopy, mass spectrometry, and / or gas chromatography). Can be identified through analysis.

The crude oil product, in some embodiments, has an oxygen content of at most 90%, at most 80%, at most 70%, or at most 50% of the oxygen content of the crude feed, wherein the TAN of the crude product is the crude oil feed Up to 90%, up to 70%, up to 50%, up to 40% or up to 30% of the TAN of the water. In some embodiments, the crude oil product has an oxygen content of at least 1%, at least 30%, at least 80%, or at least 99% of the oxygen content of the crude feed, wherein the crude product is a TAN of the crude feed Have a TAN of at least 1%, at least 30%, at least 80%, or at least 99%.

Additionally, the crude oil product may contain up to 90%, up to 70%, up to 50%, or up to 40% of the content of metal salts of carboxylic acids and / or carboxylic acids and of non-carboxyl group containing organic oxygen compounds of the crude feed. It may have a content of non-carboxyl group containing organic oxygen compounds in the range of about 70% to about 130%, about 80% to about 120%, or about 90% to about 110%.

In some embodiments, the crude product comprises about 0.05 grams to about 0.15 grams or about 0.09 grams to about 0.13 grams of hydrogen in its own molecular structure per gram of crude oil product. The crude oil product may comprise from about 0.8 grams to about 0.9 grams or from about 0.82 grams to about 0.88 grams of carbon in its own molecular structure per gram of crude oil product. The ratio of atomic hydrogen to atomic carbon of the crude oil product (H / C) is about 70% to about 130%, about 80% to about 120%, or about 90% to about the atomic H / C ratio of the crude oil feed. May range from 110%. Crude product atom H / C ratios range from about 10% to about 30% of the crude feed atom H / C ratio, resulting in relatively low uptake and / or consumption of hydrogen in the treatment process, and / or hydrogen generated in situ. Indicates.

The crude oil product contains components having a boiling range. In some embodiments, the crude oil product comprises at least 0.001 grams or about 0.001 grams to about 0.5 grams of hydrocarbons having a boiling range distribution from 0.101 MPa up to 100 ° C. per gram of the crude oil product, from about 100 ° C. to 0.101 MPa. At least 0.001 gram or about 0.001 gram to about 0.5 gram of hydrocarbon having a boiling range distribution of about 200 ° C., at least 0.001 gram or about 0.001 gram to about 0.001 gram of hydrocarbon having a boiling range distribution of about 200 ° C. to about 300 ° C. at 0.101 MPa A hydrocarbon having a boiling range distribution of about 300 ° C. to about 400 ° C. at 0.5 grams, 0.101 MPa, has a boiling range distribution of at least 0.001 grams or about 0.001 grams to about 0.5 grams, and a boiling range distribution of about 400 ° C. to about 538 ° C. at 0.101 MPa And at least 0.001 gram or about 0.001 gram to about 0.5 gram of hydrocarbon.

In some embodiments, the crude oil product has a boiling range of from about 100 ° C. to about 200 ° C. at least 0.001 gram and / or 0.101 MPa at least 0.001 gram and / or 0.101 MPa per gram of the crude oil product. At least 0.001 gram of hydrocarbon with distribution.

In some embodiments, the crude product may have a minimum of 0.001 grams, or at least 0.01 grams of naphtha, per gram of crude oil product. In another embodiment, the crude oil product may have a naphtha content of up to 0.6 grams, or up to 0.8 grams, per gram of crude oil product.

In some embodiments, the crude oil product has a distillate content in the range of 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 of crude oil product.

In some embodiments, the crude oil product ranges from about 0.00001 grams to about 0.8 grams, from about 0.001 grams to about 0.5 grams, from about 0.005 grams to about 0.4 grams, or from about 0.01 grams to about 0.3 grams per gram of crude oil product. Has a VGO content.

In some embodiments, the crude oil product has a residue content of at most 90%, at most 70%, at most 50%, at most 30%, or at most 10% of the residue content of the crude feed. In some embodiments, the crude product has a residue content of about 70% to about 130%, about 80% to about 120%, or about 90% to about 110% of the residue content of the crude feed. The crude oil product may contain 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, per gram of crude oil product, Or a residue content in the range of about 0.01 gram to about 0.1 gram.

In some embodiments, the C ₅ asphaltene content is at most 90%, at most 80%, at most 70%, at most 50%, at most 30%, or at most 10% of the C ₅ asphaltene content of the crude feed. In some embodiments, C ₅ of the crude oil product The asphaltene content is at least 10%, at least 60%, or at least 70% of the C ₅ asphaltene content of the crude feed. The crude oil product may have a C ₅ in the 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 C ₅ asphaltene content of the crude feed. It can have an asphaltene content. The crude oil product, in some embodiments, has a C ₅ asphaltene content of 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 per gram of crude oil product.

In some embodiments, the crude product has an MCR content of up to 90%, up to 80%, up to 50%, up to 30%, or up to 10% of the MCR content of the crude feed. In some embodiments, the crude oil product comprises MCR in the 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 feed. Has content. The crude oil product, in some embodiments, has an MCR of 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 per gram of crude oil product.

In some embodiments, the C ₅ asphaltene content and the MCR content may be combined to obtain a mathematical relationship between the high viscosity components in the crude product with respect to the high viscosity components in the crude feed. For example, C _{5 of} crude oil feed The sum of the asphaltene content and the MCR content of the crude oil feed can be represented by S. The sum of the C ₅ asphaltene content of the crude product and the MCR content of the crude product can be represented by S '. The sums can be compared (S 'to S) to estimate the net decrease in the high viscosity components in the crude oil feed. S 'of the crude oil product may range from about 1% to about 99%, about 10% to about 90%, or about 20% to about 80% of S. In some embodiments, the ratio of MCR content of the crude oil product to C ₅ asphaltene content is in the 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 oil product comprises more than 0 gram but less than 0.01 gram, about 0.000001 gram to about 0.001 gram, or about 0.00001 gram to about 0.0001 gram total catalyst, per gram of crude oil product. The catalyst helps to stabilize the crude oil product during transportation and / or processing. The catalyst prevents corrosion, prevents friction, and / or increases the water separation ability of the crude oil product. The methods described herein can be configured to add one or more catalysts described herein to the crude oil product during processing.

The crude oil product produced in the contact system 100 (see FIGS. 1-6) has different properties from those of the crude oil feed. These properties include a) reduced TAN, b) reduced viscosity, c) reduced total Ni / V / Fe content, d) reduced sulfur, oxygen, nitrogen, or a combination thereof, e) reduced Residue content, f) reduced C ₅ Asphaltene content, g) reduced MCR content, h) increased API specific gravity, i) reduced metal content of organic acid metal salts, j) increased stability compared to crude oil feed, or k) combinations thereof. Can be, but is not limited to this.

Catalysts used in one or more embodiments of the present invention may include one or more bulk metals and / or one or more metals on a carrier. This metal may be in elemental form or in the form of a compound of a metal. The catalyst described herein may be introduced into the contacting zone as a precursor and then activated as a catalyst in that catalyst zone (eg, when a crude oil feed comprising sulfur and / or sulfur is contacted with the precursor). The catalyst or combination of catalysts used as described herein may or may not be commercially available catalysts. Examples of commercial catalysts expected to be used as described herein include HDS22, available from CRI International, Inc. (Houston, Texas, U.S.A.); HDN60; C234; C311; C344; C411; C424; C344; C444; C447; C454; C448; C524; C534; DN120; DN140; DN190; DN200; DN800; DN2118; DN2318; DN3100; DN3110; DN3300; DN3310; RC400; RC410; RN412; RN400; RN410; RN420; RN440; RN450; RN650; RN5210; RN5610; RN5650; RM430; RM5030; Z603; Z623; Z673; Z703; Z713; Z723; Z753; Includes US Z763.

In some embodiments, the catalyst used to alter the characteristics of the crude oil feed includes one or more Group 5-10 metals on the carrier. Group 5-10 metal (s) include vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum, or mixtures thereof, It is not limited to this. Compounds of Group 5-10 metal (s) include, but are not limited to, oxides, nitrides, ammonium salts and carbonates of Group 5-10 metal (s). Examples of Group 5 to 10 metal compounds include, but are not limited to, molybdenum trioxide, ammonium molybdenum oxide, molybdenum carbonate, tungsten trioxide, nickel oxide, nickel carbonate, nickel nitrate, cobalt carbonate and cobalt oxide.

The catalyst has a total content of Group 5-10 metal (s) of at least 0.0001 gram, at least 0.001 gram, at least 0.01 gram, at least 0.3 gram, at least 0.5 gram, at least 0.6 gram, at least 0.8 gram, or at least 0.9 gram per gram of catalyst. Can have The total content of the Group 5-10 metal (s) is 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 per gram of catalyst. Grams to about 0.1 grams. In some embodiments, the catalyst comprises Group 15 element (s) in addition to Group 5-10 metal (s). Examples of group 15 elements include phosphorus. The catalyst may have a total Group 15 element content 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 another embodiment, the catalyst does not contain a Group 15 element.

In some embodiments, the catalyst comprises a combination of Group 6 metal (s) with one or more metals of Group 5 and / or Groups 7-10. The molar ratio of the Group 6 metal to the Group 5 metal may range from about 0.1 to about 20, about 1 to about 10, or about 2 to about 5. The molar ratio of the Group 6 metal to the Group 7-10 metal may range from about 0.1 to about 20, about 1 to about 10, or about 2 to about 5. In some embodiments, the catalyst comprises Group 15 element (s) in addition to the combination of Group 6 metal (s) and one or more metals of Group 5 and / or Groups 7-10. In other embodiments, the catalyst comprises a Group 6 metal (s) and a Group 10 metal (s). Of the catalysts, the molar ratio of the total Group 10 metal to the total Group 6 metal may range from about 1 to about 10, or from about 2 to about 5. In some embodiments, the catalyst comprises Group 5 metal (s) and Group 10 metal (s). Of these catalysts, the molar ratio of the total Group 10 metal to the total Group 5 metal may range from about 1 to about 10, or from about 2 to about 5.

In some embodiments, the catalyst comprises a Group 6 metal (s). The catalyst may contain at least 0.00001 grams, at least 0.01 grams, at least 0.02 grams and / or about 0.0001 grams to about 0.6 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 per gram of catalyst. May have a total content of Group 6 metal (s) in grams. In some embodiments, the catalyst comprises about 0.0001 grams to about 0.2 grams, about 0.001 grams to about 0.08 grams, or about 0.01 grams to about 0.06 grams of Group 6 metal (s) per gram of catalyst. In some embodiments, the catalyst comprises Group 15 element (s) in addition to the Group 6 metal (s).

In some embodiments, the catalyst comprises a combination of Group 6 metal (s) and one or more metals of Groups 7-10. The catalyst may have a total content of Group 7-10 metal (s) in the 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 some embodiments, the catalyst comprises 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, comprises about 0.001 grams to about 0.05 grams of railway per gram of catalyst.

In some embodiments, the catalyst comprises about 0.01 grams to about 0.15 grams of molybdenum, about 0.001 grams to about 0.005 grams of nickel, about 0.001 grams to about 0.05 grams of iron, and about 0.0001 grams to about 0.05 grams per gram of catalyst. Contains phosphorus.

In some embodiments, the Group 5-10 metal (s) are incorporated into or laminated to a carrier to form a catalyst. In some embodiments, the Group 5-10 metal (s) are combined with the Group 15 element (s) to be incorporated into or deposited on the carrier to form a catalyst. In embodiments in which the metal (s) and / or element (s) are supported, the weight of the catalyst includes all carriers, all metal (s), and all element (s). The carrier may be porous and may also include refractory oxides, porous carbonaceous materials, zeolites, or combinations thereof. The refractory oxide may include, but is not limited to, alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof. Carriers can be obtained from manufacturers such as Criterion Catalysts and Technologies LP (Houston, Texas). Porous carbonaceous materials include, but are not limited to, activated carbon and / or porous graphite. Examples of zeolites include Y-zeolites, beta zeolites, Mordenite zeolites, ZSM-5 zeolites, and ferrierite zeolites. Zeolites are available from manufacturers such as Zeolist (Valley Forge, Pa.). Carriers can be prepared and / or selected according to a variety of desired properties. Examples of such properties include, but are not limited to, pore volume, average pore diameter, pore volume distribution, surface area, and the proportion of pores within or above any pore diameter range.

The carrier is, in some embodiments, made such that the carrier has an average pore diameter of at least 90 kPa, at least 110 kPa, at least 130 kPa, at least 150 kPa, at least 170 kPa, or at least 180 kPa. In some embodiments, the carrier is formed by combining this carrier with water to form a paste. In some embodiments, acid is added to the paste to aid in extrusion of the paste. Water and dilute acid are added in the amounts and methods necessary to impart the required consistency to the extrudable paste. Examples of acids include, but are not limited to, nitric acid, acetic acid, sulfuric acid, and hydrochloric acid.

To form the extrudate, the paste can be extruded and cut using conventionally known catalyst extrusion methods and catalyst cutting methods. The extrudate is either from about 65 ° C. to about 260 ° C. or about 85 ° C. for a period of time (eg, from about 0.5 to about 8 hours) and / or until the water content of the extrudate reaches the required level. Heat treatment can be performed at a temperature in the range of about 235 ° C. This heat treated extrudate can be further heat treated at a temperature in the range of about 800 ° C. to about 1200 ° C. or about 900 ° C. to about 1100 ° C. to form a carrier having an average pore diameter of at least 150 mm 3. The carrier has a pore volume distribution over the pore diameter range. In some embodiments, the carrier comprises a void having a pore diameter of at least 350 mm, at least 400 mm, at least 500 mm, or at least 1000 mm or about 350 mm to about 5000 mm, about 400 mm to about 1000 mm, or about 500 mm to about 900 mm, A total pore volume of carrier up to 15%, up to 10%, up to 5%, up to 3%, up to 1% or up to 0.5% is provided.

In some embodiments, the carrier comprises gamma alumina, theta alumina, delta alumina, alpha alumina, or combinations thereof. The amount of gamma alumina, delta alumina, alpha alumina, or a combination thereof is about 0.0001 grams to about 0.99 grams, about 0.001 grams to about 0.5 grams, about 0.01 grams per gram of catalyst carrier, as measured by x-ray diffraction. To about 0.1 gram, or up to 0.1 gram. In some embodiments, the carrier comprises 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 this carrier. In some embodiments, the carrier comprises 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 the carrier. In some embodiments, the carrier, alone or in combination with other forms of alumina, is from about 0.1 grams to about 0.99 grams, about 0.5 grams to about 0.9, per gram of carrier, as measured by x-ray diffraction. Gram, or theta alumina content in the range of about 0.6 grams to about 0.8 grams. In some embodiments, the carrier can have at least 0.1 grams, at least 0.3 grams, at least 0.5 grams, or at least 0.8 grams of theta alumina as measured by x-ray diffraction.

In some embodiments, the carrier comprises up to 0.2 grams, up to 0.1 grams, up to 0.08 grams, up to 0.06 grams, up to 0.05 grams, up to 0.04 grams, up to 0.03 grams, up to 0.02 grams, or up to 0.01 grams of silica per gram of carrier. do. In some embodiments, the carrier has between about 0.001 grams and about 0.2 grams, or between about 0.01 grams and about 0.1 grams of silica per gram of carrier. In some embodiments, the carrier comprises a combination of silica and alumina.

Carrier catalysts can be prepared using conventionally known catalyst preparation techniques. US Patent No. 6,218,333 to Gabriele et al., US Patent No. 6,290,841 to Gabriele et al., And US Patent Nos. 5,744,025 to Boon et al. And Bhan. Examples of catalyst preparation are described in US Patent Application No. 2003/0111391, all of which is incorporated herein by reference.

In some embodiments, the metal may be combined with the carrier to form a catalyst. In some embodiments, the carrier is heat treated at a temperature in the range of about 400 ° C. to about 1200 ° C., about 450 ° C. to about 1000 ° C., or about 600 ° C. to about 900 ° C. prior to compounding the metal. In some embodiments, impregnation aids may be used in the preparation of the catalyst. Examples of impregnation aids include hydrogen peroxide, organic acids, amines, ethylene diaminetetraacetic acid (EDTA), ammonia, or mixtures thereof. Examples of amines include, but are not limited to, alkanolamines, ammonia, alkyl amines, aromatic amines, and substituted ammonium compounds. Organic acids include, but are not limited to, citric acid, tartaric acid, oxalic acid, malonic acid, malic acid, or mixtures thereof.

In some embodiments, the carrier can 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. By controlling the pH of the metal solution, it is possible to promote metal dispersion into the carrier. Dispersed or substantially dispersed metal catalysts prepared using such pH controlled conditions can have a long catalyst life compared to the life of conventional catalysts when used to treat crude oil feed at the same contact conditions.

The metal solution may comprise a Group 6 metal (s). In some embodiments, the metal solution comprises a combination of Group 6 metal (s) and Group 7-10 metal (s). In some embodiments, the metal solution comprises a combination of Group 15 metal (s) and Group 6 metal (s) or a combination of Group 15 metal (s) and Group 6 metal (s) and Group 7-10 metal (s). Include.

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

In some embodiments, the metal solution is prepared by blending one or more Group 6-10 metal solutions with different pH values. Group 6-10 metal solutions with a pH in the range of about 4 to about 7 or about 5 to about 6 may be combined with different Group 6-10 metal solutions having a pH in the range of about 0.1 to about 4 or about 1 to about 3. Can be. In some embodiments, the Group 6-10 metal solution comprises an impregnation aid, mineral acid, organic acid, Group 15 element (s), or a combination thereof.

In certain embodiments, the Group 5-10 metal (s) may be added or incorporated into subsequent carriers ("overlaying") to form a catalyst. Overlaying a metal on a carrier having a substantially uniform metal concentration often gives the catalyst desirable catalyst properties. After each metal overlay, the heat treatment of the carrier tends to improve the catalytic activity of the catalyst. A process for preparing the catalyst using the overlay method is described in US Patent Application 2003/0111391 to Bhan.

In some embodiments, the carrier / Group 7-10 metal (s) mixture is prepared by combining the carrier with one or more Group 7-10 metal (s). In one embodiment, the final mixture comprises from about 0.01 grams to about 0.1 grams of Group 7-10 metal (s) per gram of the carrier / Group 7-10 metal (s) mixture. The carrier / group 7-10 metal (s) mixture is heat treated at a temperature of about 50 ° C. to about 100 ° C. or about 60 ° C. to about 90 ° C. for several hours and then about 400 ° C. to about 700 ° C. for about 2 hours. Heat treatment at a temperature of 450 ° C. to about 650 ° C., or about 500 ° C. to about 600 ° C. The final metal containing carrier is characterized in that the final catalyst contains at least 0.3 grams, at least 0.1 grams, or at least 0.08 grams of Group 6 metal (s) and from about 0.01 grams to about 0.2 grams or from about 0.05 grams to about 0.1 grams per gram of catalyst. It may be combined with Group 6 metal (s) and optionally with additional amounts of Group 7-10 metal (s) to have a total content of Group 7-10 metal (s) in the range. The final catalyst is heat treated at a temperature ranging from about 50 ° C. to about 100 ° C. or from about 60 ° C. to about 90 ° C. for several hours and then at a temperature ranging from about 350 ° C. to about 500 ° C. or 400 ° C. to 450 ° C. for about 2 hours. It may be heat treated. In some embodiments, the Group 15 element (s) may be combined with a carrier / Group 7-10 metal (s) mixture and / or Group 6 metal (s).

Typically, the Group 5-10 metal (s) and carrier can be mixed with a suitable mixing device to form the Group 5-10 metal (s) / carrier mixture. Examples of suitable mixing devices include tumblers, stationary shells or troughs, muller mixers (eg, batch type or continuous type), impact mixers, and other mixers commonly known or Devices suitable for providing a Group 5-10 metal (s) / carrier mixture. In some embodiments, the materials are mixed until the Group 5-10 metal (s) are substantially homogeneously dispersed in the carrier.

In some embodiments, the catalyst is heat treated at a temperature in the range of about 150 to about 750 ° C, about 200 to about 740 ° C, or about 400 to about 730 ° C after combining the carrier with the metal.

In some embodiments, the catalyst may be heat treated at a temperature in the range of about 400 ° C. to about 1000 ° C. in the presence of hot air and / or oxygen enriched air to remove volatiles, thereby reducing the amount of Group 5-10 metal (s) At least a portion may be converted to the corresponding metal oxide.

However, in another embodiment, the catalyst is run at about 35 ° C. for about 1 to about 3 hours in air to remove most of the volatile components without substantial conversion of the Group 5-10 metal (s) to the metal oxide (s). Heat treatment can be performed at a temperature in the range of about 500 ° C. Catalysts prepared in this way are commonly referred to as "uncalcined" catalysts. When the catalyst is prepared in this way in combination with the sulfiding method, the active metals can be substantially dispersed in the carrier. The preparation of such catalysts is described in US Pat. No. 6,218,333 and US Pat. No. 6,290,841 to Gabriellobe et al.

In some embodiments, the theta alumina carrier can be combined with the Group 5-10 metal (s) to form a mixture of Theta alumina carrier / 5 Group 10 metal (s). The theta alumina carrier / group 5 to 10 metal (s) mixture may be heat treated at a temperature of at least 400 ° C. to form a catalyst having a pore size distribution having an average pore diameter of at least 230 mm 3. Typically, this heat treatment is carried out at temperatures up to 1200 ° C.

In some embodiments, the bulk metal catalyst used to modify the characteristics of the crude oil feed includes one or more Group 6-10 metal (s). The bulk metal catalyst may have a total content of Group 6-10 metal (s) of at least 0.3 grams, at least 0.5 grams, at least 0.6 grams, at least 0.8 grams, or at least 0.9 grams per gram of catalyst. The total content of the Group 6-10 metal (s) may range 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 about 0.8 grams per gram of catalyst.

In some embodiments, the catalyst comprises Group 15 element (s) in addition to Group 6-10 metal (s). The bulk metal catalyst may have a total Group 15 element content 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 comprise a binder in some embodiments. The binder may comprise silica, alumina oxide, zinc oxide, oxides of Group 6-10 metal (s), carbon, zeolites or combinations thereof. In some embodiments, the catalyst comprises up to 0.2 grams, up to 0.1 grams, up to 0.05 grams, up to 0.01 grams, or up to 0.005 grams of binder per gram of catalyst.

Bulk metal catalysts are described in US Pat. No. 4,937,218 to Aqudelo et al., US Pat. No. 6,162,350 to Soled et al., And US Pat. No. 6,783,663 to Riley et al. US Patent Application 2004/0182749 to Domokos et al. And US Patent Application 2004/0235653 to Domokos et al., And “Hydrosulfurization of Methyl-Substituted Dibensothiophenes: Fundamental Study of Routes by Landau et al. to Deep Desulfurization "(Chemical Journal, 1996, 159 edition, pages 236-252), which are incorporated herein by reference.

In some embodiments, the at least one Group 6-10 metal slurry of water or other protic liquid is in contact with the slurry of water, alkaline compounds and binder at a temperature ranging from about 25 ° C. to about 95 ° C. Form a binder slurry. The Group 6-10 metal slurry can comprise 0.01 grams-0.8 grams, 0.02 grams-0.5 grams, or 0.05 grams-0.3 grams of Group 6-10 metal (s) per gram of slurry. In some embodiments, the alkaline compound is ammonia. The amount of alkaline compound is at least 0.5 moles, at least 0.7 moles, at least 0.8 moles, at least 0.9 moles or at most 2 moles per mole of Group 6-10 metal (s), based on the oxide form of the Group 6-10 metal (s). . In some embodiments, the binder may comprise silica, alumina, silica / alumina, titanium oxide, zirconium oxide, or a combination thereof.

The Group 6-10 metal / binder slurry may be maintained in the atmosphere and / or at slurry temperature for a predetermined period of time (eg, at least 10 minutes, at least 30 minutes, or at least 240 minutes) and then cooled if necessary. The bulk metal catalyst can be separated from the slurry using conventional separation techniques (eg, filtration, spray drying, flash drying, evaporation or vacuum distillation). The bulk metal catalyst may be heat treated in the range of about 25 ° C to about 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 heat treated at a temperature in the range of about 100 ° C to about 600 ° C, about 120 ° C to about 400 ° C, or at most 300 ° C. In some embodiments, the bulk metal catalyst may be blended with powdered, shaped and / or other materials.

Bulk metal catalysts can be characterized using powder x-ray diffraction. In some embodiments, the bulk metal catalyst may not exhibit significant reflectivity that can be imparted to Group 6-10 metal components. The fact that x-ray diffraction does not detect significant reflectivity is that the bulk metal catalyst is substantially amorphous or amorphous.

In some embodiments, the carrier (commercially available carrier or carrier prepared as described herein) may be combined with a supported catalyst and / or bulk metal catalyst. In some embodiments, the supported catalyst may comprise Group 15 metal (s). For example, the supported catalyst and / or bulk metal catalyst may be converted to a powder having an average particle size of about 1 to about 50 microns, about 2 to about 45 microns, or about 5 to about 40 microns. This powder is combined with a carrier to form an embedded metal catalyst. In some embodiments, the powder is combined with a carrier and then extruded using standard techniques to have an average pore diameter in the range of about 80 mm to about 200 mm or about 90 mm to about 180 mm, or about 120 mm to about 130 mm Catalysts with pore size distributions can be formed. In some embodiments, combining the catalyst with the carrier allows at least a portion of the metal to be present below the surface of the final metal supported catalyst such that fewer metals are present on the surface than in the case of a catalyst without metal. do. In some embodiments, having less metal on the surface of the catalyst allows at least a portion of the metal to migrate to the surface of the catalyst during use, thereby extending the life and / or catalyst activity of the catalyst. The metal may migrate to the catalyst surface through corrosion of the catalyst surface during contact of the catalyst with the crude oil feed.

In some embodiments, the catalyst can be characterized by the pore structure. Various pore structure parameters include, but are not limited to, pore diameter, pore volume, surface area, or a combination thereof. The catalyst can have a total amount of pore size distribution versus pore diameter. The median pore diameter of the pore size distribution can range from about 30 mm to about 1000 mm, about 50 mm to about 500 mm or about 60 mm to about 300 mm. In some embodiments, the catalyst comprising at least 0.5 grams of gamma alumina per gram of catalyst comprises from about 50 kPa to about 500 kPa, about 60 kPa to about 200 kPa, about 90 kPa to about 180 kPa, about 100 kPa to about 140 kPa, or about 120 kPa to about It has a pore size distribution with a median pore diameter in the range of 130 mm 3. In another embodiment, a catalyst comprising at least 0.1 gram of theta alumina per gram of catalyst has a pore size distribution having a median pore diameter in the range of about 180 kPa to about 500 kPa, about 200 kPa to about 300 kPa, or about 230 kPa to about 250 kPa. Have This intermediate pore diameter is typically up to 1000 mm 3.

In some embodiments, the median pore diameter of the pore size distribution is at least 110 mm, at least 120 mm, at least 130 mm, at least 140 mm, at least 150 mm, at least 200 mm, or at least 250 mm. This median pore diameter is typically up to 300 mm 3. The median pore diameter of the pore size distribution may range from about 115 mm to about 290 mm, about 120 mm to about 190 mm, about 130 mm to about 180 mm, or about 140 mm to about 160 mm.

In some embodiments, in a catalyst having a pore size distribution, at least 60% of the total number of pores has a pore diameter within about 45 mm, about 35 mm, about 30 mm, about 25 mm, or about 20 mm of the median pore diameter of the pore distribution. Has a size distribution. In embodiments in which the pore size distribution has a median pore diameter of at least 180 mm, at least 200 mm, or at least 230 mm, at least 60% of the total pore size of the pore size distribution is within about 50 mm, about 70 mm, or about 90 mm of the median pore diameter. Has a pore diameter. In some embodiments, the catalyst has a pore size distribution having a median pore diameter in the range of about 180 kPa to about 500 kPa, about 200 kPa to about 400 kPa, or about 230 kPa to about 300 kPa, and the minimum number of pore totals of this pore size distribution. 60% have a pore diameter within about 50 mm, about 70 mm, or about 90 mm of the median pore diameter.

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

Catalysts having a pore size distribution having a median pore diameter in the range of about 60 Hz to about 500 Hz may, in some embodiments, be at least 100 m ² / g, at least 120 m ² / g, at least 170 m ² / g, at least 220 m ^It may have a surface area of ² / g or at least 270 m ² / g. Such surface area may range from about 100 to about 300 m ² / g, about 120 to about 270 m ² / g, about 130 to about 250 m ² / g, or about 170 to about 220 m ² / g. In some embodiments, the surface area of the shaped bulk metal catalyst is in the range of at least 30 m ² / g, at least 60 m ² / g, or from about 10 to about 350 m ² / g.

In some embodiments, the bulk metal catalyst, supported catalyst, and / or catalyst precursor are prepared by techniques known in the art (eg, ACTICAT ^™ Process, CRI International, Inc.) to sulfide to form metal sulfides (before use). In some embodiments, the catalyst (s) and / or catalyst precursor may be dried and then sulfided. Alternatively, the catalyst or catalyst precursor may be contacted with a crude oil feed comprising a sulfur containing compound to sulfide the catalyst (s) and / or catalyst precursor in situ. In situ sulfidation may utilize gaseous hydrogen sulfide in the presence of hydrogen or liquid sulfiding agents such as organosulfur compounds (including alkylsulfides, polysulfides, thiols, and sulfoxides). Off-site sulfidation processes are described in US Pat. No. 5,468,372 and US Pat. No. 5,688,736 to Seamans et al., Which are incorporated herein by reference.

In some embodiments, the first type of catalyst (“first catalyst”) comprises Group 5-10 metal (s) in combination with the theta alumina carrier. The first catalyst has a pore size distribution having a median pore diameter of at least 180 kPa, at least 220 kPa, at least 230 kPa, at least 250 kPa, at least 300 kPa, or at most 500 kPa. The carrier may comprise at least 0.1 grams, at least 0.5 grams, or at least 0.9 grams or at most 0.999 grams of theta alumina per gram of carrier. In some embodiments, the carrier has an alpha alumina content of 0.1 gram or less per gram of catalyst. The catalyst, in some embodiments, includes up to 0.1 grams of Group 6 metal (s) per gram of catalyst and at least 0.0001 grams of Group 6 metal (s) per gram of catalyst. In some embodiments, the Group 6 metal (s) are molybdenum and / or tungsten. In some embodiments, the first catalyst may comprise Group 5 metal (s). The first catalyst can remove alkali metal and alkaline earth metal in the organic acid metal salt. The first catalyst can typically remove at least a portion of the alkali metal and / or alkaline earth metal of the organic acid metal salt, thereby reducing the viscosity and / or surface tension of the crude oil feed. This makes it easier to contact the final crude feed with the catalyst located after the first catalyst.

In some embodiments, the second type of catalyst (“second catalyst”) comprises a Group 6-10 metal (s) in combination with a carrier. The second catalyst has a median pore diameter of at least 110 mm 3. The second catalyst has pores with a pore diameter of at least 350 mm 3, which occupies up to 10% of the pore volume of the second catalyst. The second catalyst, in some embodiments, comprises a total content of Group 6 metal (s) in the range of about 0.0001 grams to about 0.3 grams per gram of the second catalyst, Group 7-10 metals in the range of about 0.0001 grams to about 0.1 grams ( (S), and a total content of Group 15 element (s) in the range of about 0.00001 grams to about 0.1 grams. In some embodiments, the second catalyst carrier has at least 0.9 grams of gamma alumina per gram of carrier. The second catalyst is capable of removing at least some of the components that cause thermal degradation and removing at least some of the organic nitrogen-containing compounds, typically from the crude oil feed, as measured by MCR from the crude oil feed. At least a portion of the C ₅ asphaltenes may be removed. The second catalyst, in some embodiments, removes at least a portion of the residue, removes at least a portion of Ni / Fe / V, removes at least some of the components causing high viscosity, and / or lowers the API specific gravity. Remove at least some of the triggering ingredients.

In some embodiments, the third type of catalyst (“third catalyst”) may have a median pore diameter of about 250 mm 3. The third catalyst has pores with a pore diameter of at least 350 mm 3, which occupies up to 10% of the pore volume of the third catalyst. The third catalyst may remove at least some of the components that cause thermal degradation, remove at least some of the heteroatom containing compounds, and / or the crude oil feed, typically as measured by MCR, from the crude oil feed. At least a portion of the C ₅ asphaltenes can be removed. The third catalyst, in some embodiments, removes components that cause high viscosity and / or low API specific gravity.

In some embodiments, the second catalyst (s) and the third catalyst (s) comprise pores and selected intermediates having selected pore diameters that occupy up to 10%, up to 5%, up to 3%, or up to 1% of the pore volume. Has a pore diameter. This catalyst contributes to the reduction of the C ₅ asphaltene content in the crude feed and / or to the reduction of at least some of the components that cause thermal degradation of the crude feed as measured by MCR. By reducing these compounds using a catalyst having a selected median pore diameter and a selected pore volume, the number of catalysts can be minimized. Typically, crude oil feeds are first treated with conventional catalysts with relatively low catalytic activity to remove C ₅ asphaltenes and / or components that cause thermal degradation. Conventional catalysts of this type typically remove C ₅ asphaltenes and / or other components by introducing a relatively large amount of C ₅ asphaltenes and / or other components into the pores of the catalyst to fill these pores. Once the voids are filled, C ₅ asphaltenes and / or other components can be physically removed from the crude oil feed. When the voids are filled and / or clogged, conventional catalyst life is reduced. The catalyst with the selected median pore diameter and the selected pore volume, in some cases, limits the C ₅ asphaltenes and / or other components entering the catalyst pores, thereby eliminating C ₅ asphaltenes and / or other components that cause thermal degradation. Remove By doing so, the lifetime of the catalyst may not be reduced by contacting the catalyst with C ₅ asphaltene and / or other components.

In some embodiments, the second catalyst (s) and / or third catalyst (s) may remove at least some of the alkali metals and alkaline earth metals of the organic acid metal salt. In some embodiments, the second catalyst (s) and / or third catalyst (s) are alkali metals and / or alkaline earths of organic acid metal salts that result in the formation of compounds that increase the viscosity and / or surface tension of the crude oil feed. At least some of the metal may be removed. In some embodiments, the second catalyst (s) and / or third catalyst (s) may remove at least some of the components that cause the relatively high viscosity of the crude oil feed.

In some embodiments, the fourth type of catalyst (“fourth catalyst”) can be obtained by combining a carrier with a Group 6 metal (s) to produce a catalyst precursor. Typically, the catalyst precursor is heated to at least 100 ° C. for about 2 hours. In some embodiments, the fourth catalyst (s) comprises a Group 15 element in the range of about 0.001 grams to about 0.03 grams, about 0.005 grams to about 0.02 grams, or 0.008 grams to about 0.01 grams per gram of the fourth catalyst (s). S) content. The fourth catalyst (s) may exhibit significant activity and stability when used to treat crude oil feeds as described herein. In some embodiments, the catalyst precursor is heated at a temperature of 500 ° C. or less in the presence of one or more sulfur compounds. The fourth catalyst (s) can typically remove some of the nitrogenous compounds from the crude oil feed. By removing the nitrogen containing compounds, the corrosiveness of the crude product is reduced compared to that of the crude oil feed. The fourth catalyst (s) may remove at least some of the components causing the TAN of the crude oil feed, may remove some of the metal of the organic acid metal salt, may remove at least some of the Ni / V / Fe, and And / or at least some of the components causing the high viscosity of the crude oil feed may be removed.

The fourth catalyst (s) may, in some embodiments, reduce at least a portion of the MCR content of the crude feed while maintaining the stability of the crude feed / total product. In some embodiments, the fourth catalyst (s) is from about 0.0001 grams to about 0.1 grams, from about 0.005 grams to about 0.05 grams or from about 0.001 grams to about 0.01 grams of Group 6 metal (s) per gram of the fourth catalyst (s). ), And from about 0.0001 grams to about 0.05 grams, from about 0.005 grams to about 0.03 grams, or from about 0.001 grams to about 0.01 grams of Group 10 metal (s). The fourth catalyst (s) may have a temperature in the range of about 300 ° C. to about 500 ° C. or about 350 ° C. to about 450 ° C. and about 0.1 MPa to about 20 MPa, about 1 MPa to about 10 MPa, or about 2 MPa to about 8 MPa. At pressures in the range, it is possible to improve the removal of at least some of the components that cause the MCR of the crude oil feed.

In some embodiments, the fifth type of catalyst (“fifth catalyst”) may be a bulk metal catalyst. The fifth catalyst (s) comprise at least 0.3 grams of Group 6-10 metal (s) per gram of the fifth catalyst (s). In some embodiments, the fifth catalyst (s) also includes a binder. The fifth catalyst (s), in some embodiments, comprises a combination of Group 6 metal (s) with Group 9 metal (s) and / or Group 10 metal (s). The fifth catalyst (s) may remove at least some of the components that cause thermal degradation, as typically measured by MCR. The fifth catalyst (s) may, in some embodiments, comprise at least a portion of the C ₅ asphaltenes, at least a portion of the heteroatom containing organic compound, at least a portion of the Ni / V / Fe total content, at least a portion of the component causing high viscosity And / or remove at least some of the components that cause low API specific gravity.

The first catalyst (s), second catalyst (s), third catalyst (s), fourth catalyst (s), and fifth catalyst (s) are at least 3 months, at least 6 months when in contact with the crude oil feed. Or at least 370 ° C., at least 380 ° C., at least 390 ° C., at least 400 ° C., or at least 420 ° C. and at least 8 Nm ³ / m ³ , at least 10 Nm ³ / m ³ , or at least 14 Nm ^{3 for at} least one year. It may be stable at a pressure of / m ³ .

In some embodiments, the crude oil feed may be contacted with additional catalyst after contacting the first catalyst. Additional catalysts may include one or more of the following catalysts, ie a second catalyst, a third catalyst, a fourth catalyst, a fifth catalyst, a commercially available catalyst described herein, or a combination thereof.

Other embodiments of the first catalyst (s), second catalyst (s), third catalyst (s), fourth catalyst (s) and fifth catalyst (s) may also be prepared and / or used differently as described herein. Can be.

Selecting the catalyst (s) of the present application and controlling the operating conditions, the crude oil product with MCR content, nitrogen content, metal content of the organic acid metal salt and / or selected properties TAN and / or selected properties for the crude oil feed Can be prepared. The final crude oil product may have improved properties than the crude oil feed, and therefore may be more suitable for conveying and / or refining.

Arranging two or more catalysts in a predetermined order may control the order of improving properties for the crude oil feed. For example, the metal of the organic acid metal salt of the crude feed may be reduced before reducing at least some of the components that cause the MCR and / or heteroatoms of the crude feed.

Arrangement and / or selection of the catalyst may, in some embodiments, improve catalyst life and / or stability of the crude oil feed / total product mixture. If the catalyst life and / or stability of the crude oil feed / total product mixture is improved during the treatment process, the contact system may be operated for at least 3 months, at least 6 months, or at least 1 year without replacement of the catalyst in the contacting zone. The lifetime of the catalyst can be measured by measuring the change in temperature of the contacting zone over a period of time (eg, 1 month, 2 months, 3 months, 6 months and / or 1 year), and other contact conditions can be It is kept relatively constant so that the specification is maintained. The need for a temperature increase of about 15 ° C., about 13 ° C., or about 10 ° C. above the initial temperature required for the treatment may indicate that the effectiveness of the catalyst is reduced.

If the selected catalysts are combined, while maintaining the stability of the crude oil feed / total product mixture during the treatment process (e.g., maintaining the crude oil feed P-value above 1.5), before the other properties of the crude oil feed change, At least a portion of the MCR content from the crude feed, at least a portion of Ni / V / Fe, C ₅ At least some of the asphaltenes, at least some of the metals in the organic acid metal salt, at least some of the components contributing to the TAN, at least some of the residues, or combinations thereof can be reduced. Alternatively, by contacting the crude oil feed with the selected catalyst, C ₅ It is possible to incrementally reduce the asphaltenes, TAN and / or API specific gravity. The ability to incrementally and / or selectively alter the properties of the crude oil feed allows the stability of the crude oil feed / total product mixture to be maintained during the processing.

In some embodiments, the first catalyst removes at least a portion of the metal in the organic acid metal salt from the crude oil feed. For example, reducing at least a portion of the metals in the organic acid metal salts of the crude feed / total product mixture as compared to the crude feed can prevent the occlusion of other catalysts disposed downstream, allowing the contact system to operate without replenishment of the catalyst. Extend your time. Removing at least a portion of the metal of the organic acid metal salt from the crude oil feed may, in some embodiments, extend the life of one or more catalysts disposed after the first catalyst.

The second catalyst (s), third catalyst (s) and / or fourth catalyst (s) may be disposed downstream of the first catalyst. Further contact of the crude oil feed / total product mixture with the second catalyst (s), third catalyst (s) and / or fourth catalyst (s) results in MCR content, Ni / V / Fe content, sulfur content, oxygen The content, viscosity and / or metal content in the organic acid metal salt can be further reduced.

In some embodiments, the fifth catalyst (s) can be disposed downstream of the commercial catalyst. Commercial catalysts can be used to remove at least a portion of Ni / V / Fe in the crude oil feed. Further contact of the crude oil feed / total product mixture with the fifth catalyst (s) can reduce the MCR content, sulfur content, nitrogen content and / or oxygen content.

In some embodiments, combining catalyst selection and / or sequence of catalysts with controlled contact conditions (eg, temperature and / or crude oil feed flow rate) reduces hydrogen uptake by the crude oil feed and Maintains the stability of the heavy crude feed / total product mixture and also helps to change one or more characteristics of the crude product for each of the characteristics of the crude feed. The stability of the crude feed / total product mixture can be affected by various phase separations from the crude feed / total product mixture. For example, insoluble of the crude feed and / or crude product in the crude feed / total product mixture, aggregation of asphaltenes from the crude feed / total product mixture, precipitation of components from the crude feed / total product mixture, Or due to the combination thereof, phase separation may occur.

At any time during the contacting period, the concentration of the crude feed and / or total product in the crude feed / total product mixture may vary. As the concentration of the total product in the crude feed / total product mixture changes due to the formation of the crude product, the solubility of the components of the crude feed / total product in the crude feed / total product mixture and / or solubility of the components of the total product changes. For example, the crude oil feed may contain components that can be dissolved in the crude oil feed early in the processing process. As the nature of the crude feed (eg TAN, MCR, C ₅ asphaltene, P-value, or combinations thereof) changes, the components become less soluble in the crude feed / total product mixture. . In some cases, the crude oil feed and the total product cannot form two phases and / or dissolve each other. In addition, variations in solubility cause the crude feed / total product mixture to form two or more phases. Formation of two phases through the aggregation of asphaltenes results in fluctuations in the concentrations of the crude oil feed and the total product, and / or precipitation of components shortens the life of one or more catalysts. In addition, the efficiency of the treatment process may be reduced. For example, repeated treatment of the crude oil feed / total product mixture may be necessary to produce the crude oil product with the desired properties.

During the process, the P-value of the crude oil feed / total product mixture can be monitored and the stability of the process, crude oil feed, and / or crude oil feed / total product mixture can be assessed. Typically, a P-value of up to 1.5 indicates that aggregation of asphaltenes from crude oil feed generally occurs. If the P-value is initially at least 1.5, this P-value increases during contact or is relatively stable, after which the P-value indicates that the crude feed is relatively stable during contact. By controlling the contact conditions, by selecting the catalyst, it is possible to control the stability of the crude oil feed / total product mixture, which is assessed by the P-value, either by selective order of the catalyst or by a combination thereof. Control of such contact conditions may include LHSV, temperature, pressure, hydrogen uptake, crude oil feed flow, or a combination thereof.

The catalysts described herein can promote a reduction in viscosity and MCR content at elevated temperatures and elevated pressures, and also maintain stability of the crude oil feed / total product mixture and / or maintain catalyst life.

In some embodiments, the contact conditions are controlled such that the temperatures at one or more contact areas are different. Operating at different temperatures allows for selective modification of the properties of the crude feed while maintaining the stability of the crude feed / total product mixture. The crude oil feed enters the first contacting zone at the start of the treatment process. The first contact temperature is the temperature in the first contact region. The other contact temperature (eg, second temperature, third temperature, fourth temperature, etc.) is the temperature at the contact region disposed behind the first contact region. The first contact temperature may range from about 100 ° C. to about 420 ° C., and the second contact temperature may vary from about 20 ° C. to about 100 ° C., from about 30 ° C. to about 90 ° C., or about 40 different from the first contact temperature. ℃ to about 60 ℃ range. In some embodiments, the second contact temperature is higher than the first contact temperature. Due to the different contact temperatures, in some cases, the TAN of the crude oil feed is to a greater extent than the decrease in the content of TAN and / or C ₅ asphaltenes when the first and second contact temperatures are the same or have a temperature difference within 10 ° C of each other. And / or C ₅ TAN and / or C ₅ of crude oil products relative to asphaltene content It is possible to reduce the asphaltene content.

Example

The following describes embodiments of a system having a carrier preparation, a catalyst preparation, and a selected arrangement of catalysts and controlled contact conditions, but is not limited to these examples.

Example 1 Preparation of Catalyst Carrier

A carrier was prepared by grinding 576 grams of alumina (Criterion Catalysts and Technologies LP, Michigan, Mich.) With 585 grams of water and 8 grams of glacial nitric acid for 35 minutes. The resulting pulverized mixture was extruded through a 1.3 mm die plate, heat treated at about 90 ° C. to about 125 ° C., and further heat treated at about 918 ° C. to obtain 650 grams of carrier having a median pore diameter of 182 mm 3. This heat treated carrier was placed in a Lindberg furnace. The temperature of this furnace was raised to about 1000 degreeC-about 1100 degreeC over 1.5 hours, and it hold | maintained for 2 hours in this temperature range, and the carrier was manufactured. As measured by x-ray diffraction, this carrier contained 0.0003 grams of gamma alumina, 0.0008 grams of alpha alumina, 0.0208 grams of delta alumina, and 0.9781 grams of theta alumina per gram of carrier. This carrier had a surface area of 110 m ² / g and a total pore volume of 0.821 cm ³ / g. This carrier had a pore size distribution having a median pore diameter of 232 mm 3, and 66.7% of the total pore number of this pore size distribution had a pore diameter within 85 mm 3 of the median pore diameter.

Example 1 shows a process for the preparation of a carrier comprising at least 0.1 gram of theta alumina per gram of carrier.

Example  2. Theta  Preparation of Molybdenum Catalysts Containing Alumina

The molybdenum catalyst was prepared by the following method. The alumina carrier prepared by the method described in Example 1 was blended into the molybdenum impregnation solution. Molybdenum impregnation solution is 4.26 grams of (NH ₄ ) ₂ Mo ₂ O ₇ , 6.38 grams of MoO ₃ , 1.12 grams of 30% H ₂ O ₂ , 0.27 grams of monoethanolamine (MEA), and 6.51 grams of deionized water It was prepared by blending to form a slurry. The slurry was heated to 65 ° C. until the solids were dissolved and then cooled to room temperature. The pH of the solution was 5.36. With deionized water, the volume of the solution was adjusted to 82 mL.

Alumina carrier (100 grams) was blended into the molybdenum impregnated solution, aged for 2 hours with occasional stirring and then heat treated at 125 ° C. for several hours, followed by heat treatment at 480 ° C. for 2 hours. The resulting catalyst contained 0.04 grams of molybdenum per gram of catalyst and the remainder of the carrier. The molybdenum catalyst had a pore size distribution having a median pore diameter of 250 mm ³ , a pore volume of 0.77 cm ³ / g, and a surface area of 116 m ² / g. Further, in the pore size distribution of this molybdenum catalyst, 67.7% of the total number of pores had a pore diameter within 86 kPa of the middle pore diameter.

Example 2 shows the preparation of a Group 6 metal catalyst comprising a theta alumina carrier.

Example  3. Molybdenum / Vanadium Catalyst Containing Theta  Preparation of Alumina

A molybdenum / vanadium catalyst was prepared by the following method. An alumina carrier prepared by the method described in Example 1 was impregnated into a molybdenum / vanadium impregnation solution made as follows. A slurry was formed by combining 2.14 grams of (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 MEA, and 3.28 grams of DI water to form a slurry Was prepared. The slurry was heated to 65 ° C. until the solids dissolved and then cooled to room temperature.

A second solution was prepared by combining 3.57 grams of VOSO ₄ .xH ₂ O (x = 3-5) with 40 grams of DI water. The molybdenum / vanadium impregnated solution was prepared by combining the first solution and the second solution and adding sufficient deionized water to make the combined solution volume 82 mL. Alumina is impregnated in this molybdenum / vanadium impregnation solution and aged for two hours with occasional stirring. The resulting carrier / metal mixture was heat treated at 125 ° C. for several hours and then at 480 ° C. for 2 hours. The resulting catalyst contained 0.02 grams of vanadium and 0.02 grams of molybdenum per gram of catalyst and the remainder of the carrier. Included. This molybdenum / vanadium catalyst had a pore size distribution with a median pore diameter of 300 mm 3.

This example shows the preparation of a Group 6 metal / 5 group metal catalyst comprising a theta alumina carrier.

Example  4. Crude Oil Feed  Contact with two catalysts

The tubular reactor with a central batch of thermal wells was equipped with a thermocouple to measure temperature across the catalyst bed. The catalyst bed was formed by filling the space between the heat well and the inner wall of the reactor with catalyst and silicon carbide (20-grid, Stanford Materials, Aliso Viejo, Calif.). Such silicon carbide, in some cases, is believed to have low catalytic properties under the processing conditions described herein. All catalysts were mixed with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part catalyst before placing the mixture in the contacting zone of the reactor. The crude oil feed flow to the reactor was from the top of the reactor to the bottom of the reactor.

Silicon carbide was placed at the bottom of the reactor to serve as the bottom carrier. On top of the silicon carbide a bottom catalyst / silicon carbide mixture (81 cm 3) is arranged to form a bottom contact region, the bottom catalyst being a molybdenum / nickel / phosphorus carrier catalyst. This bottom catalyst was formed by combining the carrier with the molybdenum / nickel / phosphorus impregnation solution. The carrier was prepared by grinding 550 grams of alumina / silica mixture, 26 grams of calcined alumina particles, 585 grams of water, and 8 grams of 16M nitric acid for 35 minutes. The alumina / silica mixture was prepared by combining a minimum of 0.98 grams of alumina / silica mixture (Criterion Catalysts and Technologies LP) per gram of carrier with a maximum of 0.02 grams of silica (Criterion Catalysts and Technologies LP) per gram of alumina / silica mixture. The milled mixture was extruded through die plates of 1.94 mm and 3.28 mm diameters and then 93 ° C. (200 ° F.) to 121 until an ignition loss in the range of 27 wt% to 30 wt% was obtained, based on the weight of the initial extrudate. Heat treatment at temperatures in the range of < RTI ID = 0.0 > The relative weight lost by the extrudate is measured after the ignition loss has occurred by heating the extrudate to 540 ° C. for 15-50 minutes. The extrudate was further heat treated at 918 ° C. (1685 ° F.) for 1 hour. Molybdenum / nickel / phosphorus impregnation solution is prepared as follows. A first solution was prepared by combining 62.34 grams (NH ₄ ) ₂ Mo ₂ O ₇ , 17.49 grams MoO ₃ , 12.22 grams 30% H ₂ O ₂ , and 50.47 grams of DI water to form a slurry. MEA (3.0 grams) was added to the slurry in a proportion sufficient to control the exotherm of the dissolution. The slurry was heated to 65 ° 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 prepared 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 DI 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 second solutions were combined and sufficient deionized water was added to bring the volume of the combined solution up to 218.75 mL to prepare a 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 several hours with occasional stirring. The resulting carrier / metal mixture was heat treated at 125 ° C. for several hours and then at 482 ° C. (900 ° F.) for 2 hours to form a molybdenum / nickel / phosphorus carrier catalyst.

Top catalyst / silicon carbide mixture (9 cm ³ ) Was disposed on top of the lower contact area to form the upper contact area. This top catalyst is described in Example 3.

Silicon carbide was disposed on top of the upper contact region to fill a dead space and serve as a preheating region. The catalyst bed was mounted in a Lindberg furnace comprising a preheating zone, an upper contact zone, a lower contact zone, and four heating zones corresponding to the lower carrier.

The catalysts were sulfided by introducing a gaseous mixture of 5% by volume hydrogen sulfide and 95% by volume hydrogen gas in the contact zones at a rate of about 1.5 liters of gaseous mixture per total catalyst volume (mL) for the period described below (silicon carbide Not calculated as part of the volume of the catalyst). The pressure in the reactor is about 1.9 MPa (279.7 psi). The temperature of the contacting zone was raised to 204 ° C. (400 ° F.) over 1 hour at ambient and maintained at 204 ° C. for 2 hours. After maintaining at 204 ° C., the contact area was raised incrementally at a rate of 10 ° C. (about 50 ° F.) per hour to 316 ° C. (600 ° F.). The contact area was held at 316 ° C. for one hour, incrementally raised to 370 ° C. (700 ° F.) over one hour, and then at 370 ° C. for two hours. Thereafter, the contact region was cooled to room temperature.

After sulfiding, the contacting zone was heated to 204 ° C. over 2 hours, and a crude oil feed (BC-10, Brazil) having the characteristics listed in Table 1 was introduced into the top of the reactor. This crude feed was flowed through the preheat zone, the top contact zone, the bottom contact zone, and the bottom carrier of the reactor. The crude oil feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions are as follows. The ratio of hydrogen gas to crude oil feed to the reactor was 656 Nm ³ / m ³ (4000 SCFB), LHSV 0.5 h ⁻¹ , and pressure 13.8 MPa (2014.7 psi). The two contact zones were heated incrementally from 204 ° C. to 390 ° C. at a rate ranging from 0.1 ° C. to 10 ° C. per hour and then held at 390 ° C. for 311 hours. The temperature of the catalyst bed was raised incrementally to 400 ° C. and maintained at 400 ° C. for 352 hours.

Total product (ie crude product and gas) exited the catalyst bed. This total product was introduced into a gas-liquid separator. In this gas phase-liquid separator, the total product was separated into crude product and gas. Gas input to the system was measured with a mass flow controller. The gas exiting the system is cooled to a temperature sufficient to remove any liquid component with at least 5 carbon atoms from the gas. The separated gas was measured by a wet test meter. The crude product was analyzed periodically to determine the weight percentage of adults of this crude product. The characteristics of the crude product are summarized in Table 1.

As shown in Table 1, the crude product had 0.0024 grams of nitrogen content, 0.046 grams of MCR content, and 0.043 grams of C ₅ asphaltene content per gram of crude oil product. In addition, the crude product had a calcium content of 0.6 wtppm, a potassium content of 1.3 wtppm, and a sodium content of 0.6 wtppm.

In Example 4, it was described that the total product, including the crude product, was produced by contacting the crude feed with at least one catalyst at controlled contact conditions. At least one catalyst is a Group 5-10 metal catalyst comprising a theta alumina carrier. As measured by the P-value, the stability of the crude oil feed / total product mixture was maintained. Crude oil products have reduced MCR, alkali and alkaline earth metals, Ni / V / Fe content, sulfur content, nitrogen content, C ₅ asphaltenes, and oxygen content in organic acid metal salts as compared to crude oil feeds.

Example  5. Crude Oil Supplies and  Contact of two catalysts

The reactor apparatus (excluding the content of the contacting zone), the crude oil feed, the catalytic sulfiding method, the total product separation method, the contact conditions, the contact time and the analysis of the crude product are the same as described in Example 4. The crude oil feed flows from the top of the reactor to the bottom of the reactor.

In the lower contact region was placed a molybdenum / cobalt / phosphorus carrier catalyst / silicon carbide mixture (81 cm 3). Molybdenum / cobalt / phosphorus carrier catalysts were prepared by combining a carrier with a molybdenum / cobalt / phosphorus impregnation solution. The carrier was prepared by grinding 550 grams of alumina powder (Criterion Catalysts and Technologies LP), 26 grams of calcined alumina particles, 585 grams of water, and 8 grams of 16M nitric acid for 35 minutes. The ground mixture was extruded through die plates of 1.94 mm and 3.28 mm diameters, heat treated at temperatures of 93 ° C. (200 ° F.), 107 ° C. (225 ° F.), and then 27 wt%-based on the initial extrudate weight. The heat treatment was performed at 121 ° C. (250 ° F.) until an ignition loss in the range of 30 wt% was obtained. Ignition loss was carried out as described in Example 4. The extrudate was further heat treated at 918 ° C. (1685 ° F.) for 1 hour to form a carrier. Molybdenum / cobalt / phosphorus impregnation solution was 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 make a molybdenum / phosphorus solution. Co (OH) ₂ (29.83 grams) was added to this molybdenum / phosphorus solution, and the resulting molybdenum / cobalt / phosphorus solution was heated to 100 ° C. Citric acid monohydrate (21.5 grams) is added to the molybdenum / cobalt / phosphorus solution, heated to 100 ° C. and maintained at 100 ° C. for 1 hour. The resulting solution was reduced in volume to 252 mL to produce a molybdenum / cobalt / phosphorus impregnation solution. The impregnation solution has a pH of 3.22. This immersion solution is combined with an alumina carrier (300.0 grams) and aged for several hours with occasional stirring. The resulting carrier / metal mixture was heat treated at 120 ° C. for several hours, then heat treated at 426 ° C. (800 ° F.) for 2 hours, and further heat treated at 593 ° C. (1100 ° F.) for 2 hours, resulting in molybdenum / cobalt / The phosphorus carrier catalyst was prepared.

The molybdenum / vanadium catalyst prepared as described in Example 3 was mixed with silicon carbide. The molybdenum catalyst / silicon carbide mixture (9 cm 3) was placed in the upper contact region.

The properties of crude oil products are summarized in Table 2.

As shown in Table 2, the crude product had a nitrogen content of 0.0047 grams, an MCR content of 0.072 grams, and a C ₅ asphaltene content per gram of crude oil product. In addition, the crude oil product had a calcium content of 0.5 wtppm, a potassium content of 1.5 wtppm, and a sodium content of 0.6 wtppm.

In Example 5, it was described that the total product, including the crude product, was produced by contacting the crude feed with at least one catalyst at controlled contact conditions. At least one catalyst is a Group 5-10 metal catalyst comprising a theta alumina carrier. Crude oil products have reduced MCR, alkali and alkaline earth metals, Ni / V / Fe content, sulfur content, nitrogen content, C ₅ asphaltenes, and oxygen content in organic acid metal salts as compared to crude oil feeds.

In view of the present specification, other modifications and variations of the various aspects of the present invention will be apparent to those skilled in the art. Accordingly, this specification is to be construed as illustrative only and is also for the purpose of informing the person skilled in the art of the conventional methods of carrying out the invention. The forms of the invention shown and described herein are to be taken as exemplary embodiments. With the aid of this specification of the present invention, the elements and materials may be substituted with the elements and materials shown and described herein, the elements and processes may be reversed, and certain features of the present invention may be independent It can be used to all will be apparent to those skilled in the art. Changes may be made in the elements described herein without departing from the spirit and scope of the invention as set forth in the claims below.

Claims (18)

As a process for preparing crude oil product, Contacting the crude feed with at least one catalyst to produce a total product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa and the crude feed is At least one alkali metal salt, at least one alkaline earth metal salt of at least one organic acid, or mixtures thereof, wherein the crude feed has a total content of alkali metals and alkaline earth metals in at least 0.00001 grams of organic acid metal salts per gram of crude oil feed , At least one catalyst is a Group 5-10 metal catalyst, the catalyst is a carrier comprising theta alumina and at least one metal in Groups 5-10 on the periodic table and / or at least one metal in Groups 5-10 on the periodic table The contacting step comprising at least a compound, and Contact condition temperature, pressure, crude oil feed flow or such that the crude oil product has a total content of alkali metals and alkaline earth metals in the organic acid metal salt of up to 90% of the content of alkali metals and alkaline earth metals in the organic acid metal salts of the crude feed A control step of controlling a combination thereof, wherein the content of alkali metal and alkaline earth metal in the organic acid metal salt comprises the control step measured by ASTM method D1318. The method of claim 1, wherein the total content of alkali and alkaline earth metals in the organic acid metal salt in the crude oil product is at most 80%, at most 50%, at most 30% of the content of alkali and alkaline earth metals in the organic acid metal salt in the crude feed. Or up to 10%. The crude oil feed according to claim 1 or 2, having an alkali metal and an alkaline earth metal in an organic acid metal salt of 0.00001 grams to 0.005 grams, 0.00005 grams to 0.05 grams or 0.0001 grams to 0.01 grams per gram of the crude oil feed. Characterized in that the process for producing a crude oil product. The crude oil product according to claim 1, wherein the crude oil product is from 1 × 10 ⁻⁷ grams to 5 × 10 ⁻⁵ grams, 5 × 10 ⁻⁷ grams to 1 × 10 ⁻⁵ grams, per gram of the crude oil product, Or 1 × 10 ⁻⁶ grams to 5 × 10 ⁻⁶ grams of the organic acid metal salt having an alkali metal and an alkaline earth metal. The crude oil feed of claim 1, wherein the crude oil feed also comprises at least one zinc salt of at least one organic acid and the crude oil product comprises at most 90%, up to 80%, of the organic acid zinc salt content of the crude oil feed, A process for the production of crude oil products, characterized by having a total content of organic acid zinc salts of up to 50%, up to 30%, or up to 10%. The metal catalyst of any one of claims 1 to 5, wherein the Group 5-10 metal catalyst further comprises one or more compounds of one or more elements in Group 15 on the periodic table and / or one or more elements in Group 15 on the periodic table. Method for producing a crude oil product, characterized in that. The crude oil product according to claim 1, wherein the carrier has at least 0.1 grams, at least 0.3 grams, at least 0.5 grams, at least 0.7 grams or at least 0.9 grams of theta alumina per gram of carrier. Way. 8. The Group 5-10 metal catalyst has a pore size distribution having a median pore diameter of at least 180 mm, at least 200 mm, at least 230 mm, at least 250 mm, or at least 300 mm. The distribution is measured by ASTM method D4282. The crude oil feed according to claim 1, wherein the crude oil feed also has a C ₅ asphaltene content and the crude oil product is at most 90%, at most 80%, at most 70 of the C ₅ asphaltene content in the crude feed. And a C ₅ asphaltene content of%, up to 50%, up to 30%, or up to 10%, wherein the C ₅ asphaltene content is determined by ASTM method D2007. 10. The crude oil product of claim 1, wherein the crude oil product is at most 90%, at most 80%, at most 70%, at least 50%, at most 30, of the viscosity of the crude oil feed (at 100 ° F.). %, Or a viscosity of at most 10% (at 37.8 ° C. (100 ° F.), wherein the viscosity is measured by ASTM method D445. The crude oil feed according to any one of the preceding claims, wherein the crude oil feed also has a sulfur content, the crude oil product comprising up to 90%, up to 80%, up to 70%, up to 50%, A process for the production of crude oil products having a sulfur content of at most 30%, or at most 10%, wherein the sulfur content is measured by ASTM method D4294. The crude oil feed according to claim 1, wherein the crude oil feed also has a residue content and the crude oil product has a maximum of 90%, maximum 80%, maximum 70%, maximum 50 of the residue content in the crude oil feed. A residue content of%, up to 30%, or up to 10%, the residue content being measured by ASTM method D5307. 13. The process according to any one of claims 1 to 12, wherein the contact is carried out in the presence of a hydrogen source and the flow of the hydrogen source is controlled during the contacting conditions to produce a crude oil product. The contact conditions as claimed in claim 1, wherein the contact conditions are temperatures in the range from 50 ° C. to 500 ° C., total pressure in the range from 0.1 MPa to 20 MPa, liquid space velocity per hour above 0.05 h ⁻¹ , and 0.1 Nm ^3. and a ratio of the gaseous hydrogen source to the crude oil feed in the range of from / m ³ to 100,000 Nm ³ / m ³ . The process of claim 1, wherein the crude oil feed / total product mixture has a P-value of at least 1.5 upon contact. 16. The crude oil feed of claim 1, wherein the crude oil feed further has a content of chromium and / or arsenic in the organic acid metal salt, and the crude oil product contains 90% of the chromium and / or arsenic content of the organic acid metal salt of the crude oil feed. A process for producing a crude oil product, characterized by having a content of chromium and / or arsenic in an organic acid metal salt of less than%. 17. The method of any one of claims 1 to 16, further comprising a blending step of combining the same or different crude oil with the crude product or mixture to form a mixture. 18. The method of any one of the preceding claims, further comprising a processing step of treating the crude product or mixture to produce a transfer fuel, heating fuel, lubricating oil and chemicals.

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