KR20060130112A - Systems and methods of producing a crude product - Google Patents

Abstract

Contact of a crude feed with one or more catalysts produces a total product that includes a crude product. The crude feed has a residue content of at least 0.2 grams of residue per gram of crude feed. The crude product is a liquid mixture at 25 °C and 0.101 MPa. One or more properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed. In some embodiments, gas is produced during contact with one or more catalysts and the crude feed.

Description

Crude Oil Product Manufacturing System and Manufacturing Method {SYSTEMS AND METHODS OF PRODUCING A CRUDE PRODUCT}

FIELD OF THE INVENTION The present invention generally relates to systems and methods for processing crude oil feeds, for example to compositions prepared using such systems and methods. More specifically, the embodiments described herein comprise a crude oil feed having a residue content of at least 0.2 grams of residue per gram of crude oil feed (a) being a liquid mixture at 25 ° C., 0.101 MPa, and (b ) A system and method for converting a crude oil product having one or more properties as compared to the same properties of a crude oil feed.

Crude oils that have one or more unstable characteristics that prevent them from being economically returned or processed using conventional equipment are usually referred to as "low quality crude oil".

Low quality crude oil often contains relatively high levels of residue. Such crude oils tend to be difficult and expensive to transport and / or process using conventional equipment. Crude oil containing high levels of residue can be processed to convert crude oil to coke at high temperatures. Alternatively, crude oil containing a high level of residue is typically treated at high temperatures with moisture to produce crude oil and / or crude oil mixtures that are less viscous. During the treatment process, it may be difficult to remove moisture from crude oil and / or crude oil mixtures that are less viscous.

Low quality crude oil may comprise hydrogen deficient hydrocarbons. When treating hydrogen deficient hydrocarbons, especially when an unsaturated amount resulting from the cracking process is produced, usually a constant amount of hydrogen must be added. Hydrogenation during processing, usually involving the use of an active hydrogenation catalyst, is necessary to prevent the unsaturated portion from forming coke. Hydrogenation adds cost to production and / or cost to return to the treatment facility.

Coke may be formed and / or added to the catalyst surface at a high rate during low quality crude oil processing. It may be costly to regenerate the catalytic activity of catalysts contaminated by coke. High temperatures used during regeneration may also reduce the activity of the catalyst and / or degrade the catalyst.

Low quality crude oil may include an acidic component that contributes to the total acid value (“TAN”) of the crude feed. Low quality crude oil with a relatively high total acid value is a cause of corrosion of metal components during its conveyance and / or processing. Removing acidic components from poor crude oil involves chemically neutralizing the acidic components with various bases. Alternatively, the corrosion resistant metal may be used in the conveying device and / or the processing device. The use of corrosion resistant metals leads to a significant increase in cost, which makes it undesirable to use corrosion resistant metals in existing installations. Another method for preventing corrosion also involves adding a corrosion inhibitor to the crude oil prior to the return and / or treatment of the crude oil. The use of corrosion inhibitors can adversely affect the quality of the devices and / or products produced from the crude oil used in the crude oil treatment.

Low quality crude oil has a relatively high content of metal contaminants such as, for example, nickel, vanadium, and / or iron. During processing of such crude oil, metal contaminants and / or compounds of metal contaminants may be deposited on the surface of the catalyst or in the void volume of the catalyst. This deposition can degrade the catalytic activity.

Low quality crude oil usually contains organic heteroatoms such as sulfur, oxygen and nitrogen. Organic heteroatoms adversely affect the catalyst in some cases. Alkali metal salts and / or alkaline earth metal salts have been used in the desulfurization treatment of residues. This process involves inefficient desulfurization, production of sludge that does not decompose oil, inefficient demetallization, the formation of inseparable salt-oil mixtures, large amounts of hydrogen gas and / or relatively high hydrogen pressures. Tends to cause the use of

Some processes for improving the quality of crude oil include the addition of diluents to the crude oil of lower quality to lower the weight of components that produce undesirable properties. However, the addition of diluents usually raises the cost of processing the low quality crude oil due to the cost of entering the diluent and / or the increased cost of handling low quality crude oil. The addition of diluents to poor crude oil may, in some cases, reduce the stability of the crude oil.

U.S. Patent 3,136,714 to Gibson, U.S. Patent 3,558,747 to Gleim, U.S. Patent 3,847,797 to Pasternak, U.S. Grant to King Patent 3,948,759, US Patent No. 3,957,620 to Fukui, US Patent Nos. 3,960,706 and 3,960,708 to McCallum, US Patent No. 4,119,528 to Jr. Badd, Jr. No. 4,127,470, U.S. Patent 4,224,140 to Fujimori, U.S. Patent 4,437,980 to Heredy, U.S. Patent 4,591,426 to Krasuk, Mazurek US Pat. Nos. 4,665,261 to Kretschmar, US Pat. Nos. 5,064,523 and 5,166,118 to Gatsis, and US Pat. No. 5,288,681 to Sudhakar. US Patent No. 6,547,9 57; And US Patent Application Publication No. 20030000867 to Reynolds, US Patent Application Publication No. 20030149317 to Rendina, and the like describe various processes and systems for use in processing crude oil. However, the processes, systems and catalysts described in these patent documents have limited applicability because of the many technical problems described above.

In short, low quality crude oil typically has undesirable properties (eg, a relatively high residue, a tendency to corrode equipment, and / or a tendency to consume a relatively large amount of hydrogen during its processing). Other undesirable properties include undesirable components (eg, relatively high TAN, organic heteroatoms and / or metal contaminants). These properties tend to cause problems in conventional conveying and / or processing facilities, such as increased corrosion, shortened catalyst life, process occlusion and / or increased use of hydrogen during processing. Therefore, there is a significant economic and technical need for improved systems, methods and / or catalysts to convert low quality crude oil into crude oil products with more desirable properties.

The invention described herein generally relates to a system, a method for bringing a crude oil feed into contact with one or more catalysts for producing a crude product and, depending on the embodiment, the entire product comprising a non-condensable gas. In addition, the invention described herein generally relates to a constituent having a novel combination therein. Such components can be obtained using the systems and methods described herein.

The present invention provides a process for preparing a crude oil product comprising contacting a hydrogen source with a crude feed with at least one catalyst, wherein the at least one catalyst comprises a catalyst containing K ₃ Fe ₁₀ S ₁₄ .

The present invention also provides a process for preparing a crude product, wherein the crude product is a liquid mixture at 25 ° C., 0.101 MPa, at least one of the catalysts comprises at least one sulfide transition metal and the crude feed is in accordance with ASTM specification D5307. Contacting said crude feed with a hydrogen source having at least one catalyst to produce a total product comprising said crude product, with a content of at least 0.2 grams of residue per gram of crude oil feed as defined by; Crude products have 0.05 grams of maximum coke per gram of crude oil product, 0.001 grams of minimum naphtha per gram of crude oil product, and naphtha includes controlling such contact conditions to have a minimum 70 octane number. .

The present invention also provides a crude oil product preparation method wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, at least one of the catalysts comprises at least one sulfide transition metal, and the crude oil feed is in accordance with ASTM specification D5307. Contacting said crude feed with a hydrogen source having at least one catalyst to produce a total product comprising said crude product, with a content of at least 0.2 grams of residue per gram of crude oil feed as defined by; Kerosene has a freezing point at up to 30 ° C., as defined by ASTM specification D2386, with crude product having 0.05 grams of maximum coke per gram of crude product, and per gram of kerosene as defined by ASTM specification D5186. Methods such as controlling the contact conditions to include kerosine having at least 0.2 grams of aromatics.

The present invention also provides a process for preparing a crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, at least one of the catalysts comprises at least one sulfide transition metal and the crude feed is a gram of crude oil feed Contacting said crude feed with a hydrogen source having at least one catalyst to produce a total product comprising said crude product, with a content of at least 0.2 grams of sugar residues; Controlling the contact conditions such that crude oil products have up to 0.05 grams of coke per gram of crude oil product having a weight ratio of hydrogen atoms to carbon atoms (H / C) of up to 1.75, as defined by ASTM specification D6730. It includes the method of.

The present invention also provides a process for preparing a crude product, wherein the crude product is a liquid mixture at 25 ° C., 0.101 MPa, at least one of the catalysts comprises at least one sulfide transition metal and the crude feed is in accordance with ASTM specification D5307. Total containing the crude product, with a content of at least 0.2 grams of residue per gram of crude oil feed and with a weight ratio (H / C) of carbon atoms to hydrogen atoms in the crude feed at least 1.5; Contacting the crude oil feed with a hydrogen source having one or more catalysts to produce a product; The crude oil product has an H / C ratio of 80 to 120% of the H / C ratio of the crude oil feed, has a maximum of 30% of the residue content of the crude feed as defined by ASTM specification D5307, and has a minimum per gram of crude product Controlling contact conditions such that the naphtha having a octane number of 70 has a minimum of 0.001 grams.

The present invention also provides a process for preparing a crude product, wherein the crude product is a liquid mixture at 25 ° C., 0.101 MPa, at least one of the catalysts comprises at least one sulfide transition metal and the crude feed is in accordance with ASTM specification D5307. Contacting said crude feed with a hydrogen source having at least one catalyst to produce a total product comprising said crude product, with a content of at least 0.2 grams of residue per gram of crude oil feed as defined by; The crude product has at least 0.001 grams of naphtha having at least 70 octane number per gram of crude product; Has a freezing point of up to 30 ° C. as defined by ASTM specification D2386 and a minimum of 0.001 gram of kerosine having at least 0.2 grams of aromaticity per gram of kerosene as defined by ASTM specification D5186; Contact conditions such that a maximum of 0.05 grams of residue as defined by ASTM specification D5307 and a minimum of 0.001 gram of VGO having at least 0.3 grams of aromatics per gram of vacuum gas oil (VGO) as defined by IP standard 368/90 It includes a method such as to control.

The present invention also provides a process for preparing crude oil products wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, and the sulfided transition metal catalyst comprises at least 0.4 grams of one or more sulfided transition metals per gram of the total sulfided transition metal catalyst. The crude oil feed comprises a sulfided transition metal catalyst to produce the entire product comprising the crude oil product, with a content of at least 0.2 grams of residue per gram of crude oil feed as defined by ASTM specification D5307. Contacting the crude oil feed with a hydrogen source having at least one catalyst; And controlling contact conditions such that the crude product has a maximum of 0.05 grams of coke per gram of crude product, and has up to 30% of the residue content of the crude feed as defined by ASTM specification D5307.

The present invention also provides a process for preparing crude oil products wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa and the sulfided transition metal catalyst has a minimum of 0.4 grams of sulfide transition metal per gram of total sulfided transition metal catalyst. The crude oil feed has at least 0.001 grams of nitrogen per gram of crude oil feed and at least 0.2 grams of residue per gram of crude oil feed, so that at least one catalyst may be used to produce the entire product comprising the crude oil product. Contacting the crude oil feed with an existing hydrogen source; The crude oil product has a nitrogen content of up to 90% of the nitrogen content of the crude oil feed as defined by ASTM specification D5762 and a residue content of up to 30% of the residue content of the crude feed as defined by ASTM specification D5307. And a method of controlling the contact condition.

The present invention also provides a process for preparing crude oil products wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa and the sulfided transition metal catalyst has a minimum of 0.4 grams of sulfide transition metal per gram of total sulfided transition metal catalyst. To produce the entire product comprising the crude product, with the crude feed having a minimum 0.0001 gram of Ni / V / Fe content per gram of crude oil and a minimum content of 0.2 grams per gram of crude feed. Contacting the crude oil feed with a hydrogen source having at least one catalyst; The crude oil product has a maximum of 0.05 grams of coke per gram of crude oil product, and has a Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude feed, as defined by ASTM specification D5863. Methods such as controlling the contact conditions to have a residue content of up to 30% of the residue content of the crude oil feed, as determined by.

The present invention also provides a process for preparing crude oil products wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa and the sulfided transition metal catalyst has at least 0.4 grams of sulfide transition metal per gram of total sulfided transition metal catalyst. The crude oil feed has at least 0.001 grams of sulfur content per gram of crude oil feed and has a residual content of at least 0.2 grams per gram crude oil feed, so that at least one catalyst may be used to produce the entire product comprising the crude oil product. Contacting the crude oil feed with an existing hydrogen source; To ensure that the crude oil product has a sulfur content of up to 70% of the sulfur content of the crude feed as defined by ASTM specification D4294 and a maximum of 30% of the residue content of the crude feed as defined by ASTM specification D5307. Controlling the contact conditions.

The present invention also provides a method of making a sulfided transition metal catalyst construction, the method comprising mixing an oxide transition metal and a metal salt to form an oxidation transition metal / metal salt mixture; Reacting the oxidation transition metal / metal salt mixture with hydrogen to form an intermediate, reacting the formed intermediate with sulfur with one or more hydrocarbons to produce a sulfide transition metal catalyst, and the like.

The present invention also provides a process for preparing crude oil products, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, the sulfide transition metal catalyst comprises a sulfide transition metal, and the crude feed is defined by ASTM specification D5307. Contacting said crude feed with a hydrogen source having at least one catalyst to produce a total product comprising said crude product, with at least 0.2 grams of residue per gram of crude oil feed as it loses; The sulfided transition metal catalyst mixes an oxide transition metal and a metal salt to form an oxidation transition metal / metal salt mixture; Reacting the oxidation transition metal / metal salt mixture to hydrogen to form an intermediate; Obtained intermediates are reacted with sulfur together with one or more hydrocarbons to produce a sulfided transition metal catalyst, including contacting conditions such that the crude product has up to 30% of the residue content of the crude feed. do.

The present invention also provides a process for preparing crude oil products, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, and the crude oil feed has a minimum content of residue per gram of crude oil feed as defined by ASTM specification D5307. Contacting the crude oil feed with a hydrogen source having at least one catalyst to produce an overall product comprising the crude oil product with 0.2 grams; At least a portion of the total product is made of steam; Condense at least a portion of the steam at 25 ° C., 0.101 MPa; At least 0.001 grams of naphtha with a minimum of 70 octane number per gram of crude oil product, at least 0.001 grams of VGO with at least 0.3 grams of aromatics per gram of VGO, as defined by IP Specification 368/90, as per ASTM specification D5307 Forming crude oil products having a maximum of 0.05 grams of residue as it loses.

The present invention also provides a process for preparing crude oil products, wherein the sulfide transition metal catalyst comprises a sulfide transition metal, wherein the crude feed has a content of residues per gram of crude oil feed of at least 0.2, as defined by ASTM specification D5307. Grams, the crude product is a liquid mixture at 25 ° C., 0.101 MPa, and the crude product is at least 0.001 naphtha having at least 0.001 grams of monocyclic ring aromatics per gram of naphtha, as defined by ASTM specification D6730 per gram of crude product. Grams having a maximum of 0.05 grams of residue and at least 0.001 grams of distillate, as defined by ASTM specification D5307, a hydrogen source with an inorganic salt catalyst and the crude oil feed to produce the entire product comprising the crude product It includes a method of contacting.

The present invention also provides a process for producing crude product, wherein the crude feed has at least 0.2 grams of residue per gram of crude feed as defined by ASTM specification D5307, and the crude product is liquid at 25 ° C., 0.101 MPa. Mixture, the crude oil product having at least 0.001 grams of diesel having at least 0.3 grams of aromatics per gram of diesel as defined by IP Specification 368/90 per gram of crude oil product, and VGO as defined by IP Specification 368/90. At least 0.3 grams of aromatics per gram of have a minimum of 0.001 grams of VGO and with an inorganic salt catalyst to produce the entire product comprising the crude oil product, with a maximum of 0.05 grams of residue, as defined by ASTM specification D5307. Methods such as contacting a hydrogen source with the crude oil feed.

The present invention also provides a process for preparing crude oil products, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa and the crude oil feed has a residue of at least 0.2 per gram of crude oil feed as defined by ASTM specification D5307. Grams, the crude feed has a residue content of at least 0.2 grams residue per gram of crude oil feed, as defined by ASTM specification D5307, and the crude feed has a monocyclic ring aromatics per gram of crude oil feed. Contacting said crude oil feed with a hydrogen source with an inorganic salt catalyst to produce a total product comprising said crude oil product with a content of up to 0.1 grams; Up to 0.2 grams of hydrocarbons that do not condense at 25 ° C., 0.101 MPa during the contacting process are formed per gram of crude oil feed, as determined by mass resin, and the crude product has a monocyclic ring aromatic content as defined by ASTM standard D6730. Controlled conditions such as controlling the contact conditions to have a monocyclic ring aromatic at least 5% larger than the monocyclic ring aromatics in the crude feed.

The present invention also provides a process for preparing crude oil products, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa and the crude oil feed has a residue of at least 0.2 per gram of crude oil feed as defined by ASTM specification D5307. Grams, the crude oil feed has a olefin content in grams of olefins per gram of crude oil feed, and the crude oil feed is contacted with a hydrogen source with an inorganic salt catalyst to produce the entire product comprising the crude oil product. ; Crude oil products include methods such as controlling the contact conditions such that the olefin content has at least 5% greater olefin content than the olefin content of the crude feed, as defined by ASTM specification D6730.

The present invention also provides a process for preparing crude product, wherein the crude product is a liquid mixture at 25 ° C., 0.101 MPa, the crude feed having at least 0.2 grams of residue per gram of crude feed, The crude oil and the hydrogen source with the inorganic salt catalyst to produce the entire product comprising the crude oil product, while the inorganic salt catalyst prevents changes in radiant gas in the temperature range between 50 ° C and 500 ° C, as defined by TAP). Contacting the feed; Crude oil products may be controlled by contacting conditions such that the residue content defined by ASTM specification D5307 has a residue content expressed in grams of residue per gram of crude oil product up to 30% of the residue content of the crude oil feed. It includes.

The present invention also provides a process for preparing crude oil products, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, the inorganic salt catalyst comprises at least two inorganic salt metals, and the inorganic salt catalyst provides a temporary analysis of the manufactured product. Prevent changes in radiant gas in the temperature range defined by (TAP), the crude oil feed having at least 0.2 grams of residue per gram of crude oil feed, wherein the radiant gas change temperature range is (a) the two inorganic salt metals Contacting the crude oil feed with a hydrogen source having an inorganic salt catalyst to produce a total product comprising the crude oil product at a temperature between at least one of the DSC temperature and (b) the DSC temperature of the inorganic salt catalyst; Controlling contact conditions such that the crude product has a residue content expressed in gram residues per gram crude oil product of up to 30% of the residue content of the crude feed as defined by ASTM specification D5307.

The present invention also provides a process for preparing crude oil products, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, and the spinning gas in a temperature range between 50 ° C. and 500 ° C. as the inorganic salt catalyst is defined by TAP. Oil with an inorganic salt catalyst to produce the entire product comprising the crude oil product, with crude oil feed having at least 0.2 grams of residue per gram of crude oil feed as defined by ASTM specification D5307. Contacting the source with the crude oil feed; Preparing crude oil products such that the volume of crude oil product produced is at least 5% greater than the volume of crude oil feed at 25 ° C., 0.101 MPa.

The present invention also provides a process for preparing crude oil products, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, and the inorganic salt catalyst is selected from the spinning gas in a temperature range between 50 ° C. and 500 ° C. as defined by TAP. Contacting the crude oil feed with a hydrogen source with an inorganic salt catalyst to produce a total product comprising the crude oil product, with crude oil feed having at least 0.2 grams of residue per gram of crude oil feed; ; Controlling contact conditions such that up to 0.2 grams of hydrocarbons that cannot condense at 25 ° C., 0.101 MPa during the contacting process are formed per gram of crude oil feed as defined by the mass balance.

The present invention also provides a process for preparing crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa and the inorganic salt catalyst is 200 at a rate of 10 ° C. per minute as determined by differential scanning calorimetry (DSC). Hydrogen with an inorganic salt catalyst to produce the entire product comprising the crude product, having a thermal transition in the temperature range between < RTI ID = 0.0 > Contacting the source with the crude oil feed; Controlling the contact conditions such that the crude product is defined by ASTM specification D5307 and has a maximum of 30% of the residue content of the crude feed, expressed in grams of residue per gram of crude product.

The present invention also provides a process for preparing crude oil products, wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, and the inorganic salt catalyst has at least an inorganic salt of the inorganic salt catalyst in the temperature range between 300 ° C. and 500 ° C. The crude oil and the hydrogen source with an inorganic salt catalyst to produce the entire product comprising the crude product, having an ion conductivity of one ion conduction, with the crude feed having at least 0.2 grams of residue per gram of crude oil feed Contacting the feed; Controlling the contact conditions such that the crude product is defined by ASTM specification D5307 and has a maximum of 30% of the residue content of the crude feed, expressed in grams of residue per gram of crude product.

The present invention also provides a process for preparing crude oil products wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, and the inorganic salt catalyst is an alkali metal having an alkali metal having an atomic number of at least 11 and an atomic number of at least 11. Wherein the minimum atomic ratio of alkali metal having an atomic number of at least 11 relative to is at least 0.1 to 10 and at least one of the alkali metal salts includes alkali metal salts which are alkali carbonate metals, and the crude oil feed has a minimum residue per gram of crude oil feed. Contacting the crude oil feed with a hydrogen source with an inorganic salt catalyst to produce a total product comprising the crude oil product with 0.2 grams; Controlling the contact conditions such that the crude product has a maximum of 30% of the residue content of the crude feed as defined by ASTM specification D5307.

The present invention also provides a process for preparing crude oil products, wherein the inorganic salt catalyst is characterized by the minimum of an alkali metal having an atomic number of at least 11 for an alkali metal having an atomic number of at least 11 and an alkali number having at least 11 atomic numbers. At least one of the alkali metal salts having an atomic ratio of 0.1 to 10 and at least one of the alkali metal salts comprises alkali metal salts, said crude oil product having a crude feed having at least 0.2 grams of residue per gram of crude oil feed Contacting said crude oil feed with a hydrogen source with an inorganic salt catalyst to produce a whole product; At least a portion of the total product is steamed and at least a portion of the steam produced at 0.101 MPa is condensed to form a crude product having a maximum of 30% of the residue content of the crude feed. .

The present invention also provides a process for preparing crude oil products, wherein the method has a minimum atomic ratio of an alkali metal having an atomic number of at least 11 to an alkali metal having an atomic number of at least 11 and an atomic number of at least 11 relative to an alkali metal having an atomic number of at least 11. 10 and the inorganic salt catalyst comprises an alkali metal salt wherein at least one of the alkali metal salts is an alkali hydrogenated metal, wherein the crude product comprises the crude product, with the crude feed having at least 0.2 grams of residue per gram of crude oil feed. Contacting the crude oil feed with a hydrogen source with an inorganic salt catalyst to produce a product; Preparing at least a portion of the total product as a steam, condensing at least a portion of the steam produced at 25 ° C., 0.101 MPa to form a crude product having a maximum of 30% of the residue content of the crude feed. .

The present invention also provides a process for preparing crude oil products wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, the alkali metal has an atomic number of at least 11 and one of the alkali metal salts is an alkali carbonate metal and an inorganic salt. The catalyst comprises one or more alkali metal salts, one or more alkaline earth metal salts, or mixtures thereof, wherein the crude product has at least 0.2 grams of residue per gram of crude oil feed to produce the entire product comprising the crude oil product. Contacting the crude oil feed with a hydrogen source having a hazardous salt catalyst; Controlling the contact conditions such that the crude product has a maximum of 30% of the residue content of the crude feed as defined by ASTM specification D5307.

The present invention also provides a process for preparing crude oil products wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, the inorganic salt catalyst having at least 11 atomic numbers while the alkali metal has at least one alkali hydroxide metal Hydrogen with an inorganic salt catalyst to produce the entire product comprising the crude product, wherein the crude feed has at least 0.2 grams of residue per gram of crude oil feed; Contacting the source with the crude oil feed; Controlling the contact conditions such that the crude product has a maximum of 30% of the residue content of the crude feed as defined by ASTM specification D5307.

The present invention also provides a process for preparing crude oil products wherein the crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, the alkali salts have an atomic number of at least 11 and the inorganic salt catalyst comprises at least one alkali hydride metal, A hydrogen source with an inorganic salt catalyst to produce the entire product comprising the crude product, wherein the crude feed has at least 0.2 grams of residue per gram of crude oil feed; Contacting said crude oil feed with; Controlling contact conditions such that the crude product has a maximum of 30% of the residue content (expressed in grams of residue per gram of crude product) as defined by ASTM specification D5307.

The present invention also provides a process for producing hydrogen gas, wherein the hydrocarbon has a carbon number in the range of 1 to 6, the crude oil feed has a residue content of at least 0.2 grams of residue per gram of crude oil feed, The salt catalyst is contacted with the crude oil feed with at least one hydrocarbon together with the inorganic salt catalyst and water while preventing the spinning gas from being deformed in the temperature range between 50 ° C. and 500 ° C. as defined by TAP; And a method of producing hydrogen gas.

The present invention also provides a process for preparing crude oil products wherein the first crude oil feed has a residue content of at least 0.2 grams of residue per gram of crude oil feed as defined using ASTM specification D5307, Contacting the first crude oil feed with the inorganic salt catalyst in the vapor to generate a gas stream comprising hydrogen while preventing the salt catalyst from deforming the radiant gas in the temperature range between 50 ° C. and 500 ° C. as defined by TAP. To; Contacting the second crude oil feed with the second catalyst in at least a portion of the generated gas stream to produce a whole product comprising the crude oil product that is a liquid mixture at 25 ° C., 0.101 MPa; And controlling one or more properties of the crude oil product to change by at least 10% relative to one or more relative one or more properties of the second crude oil feed.

The present invention also provides a method of generating a gas stream, wherein the crude oil in steam has a residue content of at least 0.2 grams of residue per gram of crude oil feed as defined by ASTM specification D5307. Contacting the feed with an inorganic salt catalyst; Methods such as generating a gas stream comprising hydrogen, carbon monoxide and carbon dioxide (the molar ratio of carbon dioxide to carbon monoxide is at least 0.3).

The present invention also provides a process for preparing crude oil products, which process comprises adjusting inorganic salt catalysts; The crude product is a liquid mixture at 25 ° C., 0.101 MPa and the inorganic salt catalyst adjusted to produce the entire product comprising the crude product, with the crude feed having a residue content of at least 0.2 grams of residue per gram of crude oil feed. Contacting the crude oil feed to a hydrogen source at; Controlling the contact conditions such that the crude product is defined by ASTM specification D5307 and has a maximum of 30% of the residue content of the crude oil feed (expressed in grams of residue per gram of crude product).

The present invention also provides a crude oil component, which component has a boiling point distribution between 30 ° C. and 538 ° C. (1,000 ° F.) at 0.101 MPa and iso for n-paraffins up to 1.4 as defined by ASTM specification D6730. Hydrocarbons comprising iso-paraffins and n-paraffins with a weight ratio of paraffins.

The present invention also provides crude oil components, which comprise at least 0.001 grams of hydrocarbons having a boiling point distribution of up to 204 ° C. (400 ° F.) at 0.101 MPa per gram of components, 204 ° C. and 300 ° C. at 0.101 MPa Minimum 0.001 grams of hydrocarbons with boiling point distribution in between, minimum 0.001 grams of hydrocarbons with boiling point distribution between 300 ° C and 400 ° C at 0.101 MPa, boiling point distributions between 400 ° C and 538 ° C (1000 ° F) at 0.101 MPa Hydrocarbons having a boiling point distribution of at least 0.001 grams and having a boiling point distribution of up to 204 ° C. include iso-paraffins and n-paraffins having a weight ratio of iso-paraffins to n-paraffins up to 1.4 as defined by ASTM specification D6730. do.

The present invention also provides a crude oil component, which component has a minimum 70 octane number per gram of the component and has a minimum of 0.001 gram of naphtha having a maximum of 0.15 grams of olefins per gram of naphtha, as defined by ASTM specification D6730, At least 0.001 gram of kerosene having a freezing point of up to -30 ° C as defined by ASTM standard D2386 and having at least 0.2 grams of aromatics per gram of kerosene as defined by ASTM standard D5186, up to 0.05 grams of residue as defined by ASTM standard D5307. Has

The present invention also provides a crude oil component, the component having a maximum of 0.3 grams of hydrocarbon having a carbon number of 1 to 3 (C ₁ to C ₃ ) per gram of non-condensable hydrocarbon gas per gram of the component and 25 At most 0.15 grams of non-condensable hydrocarbon gas that cannot condense at 0.101 MPa; At least 0.001 grams of naphtha having a minimum 70 octane number; At least 0.001 gram of kerosine having a freezing point of up to 30 ° C. as defined by ASTM specification D2386 and having at least 0.2 grams of aromatics per gram of kerosene as defined by ASTM specification D5186; Have a maximum of 0.05 grams of residue as defined by ASTM specification D5307.

The present invention also provides a crude oil component, the component comprising a maximum of 0.05 grams of residue as defined by ASTM specification D5307 per gram of component; At least 0.001 gram of hydrocarbon with a boiling point distribution of up to 204 ° C. (400 ° F.) at 0.101 MPa; At least 0.001 gram of hydrocarbon with a boiling point distribution between 204 ° C. and 300 ° C. at 0.101 MPa; At least 0.001 gram of hydrocarbon with boiling point distribution between 300 ° C. and 400 ° C. at 0.101 MPa; Hydrocarbons with a boiling point distribution between 400 ° C and 538 ° C (1000 ° F) at 0.101 MPa and having a boiling point distribution between 20 ° C and 204 ° C are internal double bonds as specified by ASTM standard D6730. Olefins having terminal double bonds with an at least 0.4 molar ratio of olefins having terminal double bonds to olefins having internal double bonds.

The present invention also provides a crude oil component, the component comprising a maximum of 0.05 grams of residue as defined by ASTM specification D5307 per gram of component; Having a minimum of 0.001 grams of hydrocarbon mixture with a boiling point distribution between 20 ° C. and 538 ° C. (1,000 ° F) as defined by ASTM specification D5307, wherein the hydrocarbon mixture is determined by paraffin as per ASTM specification D6730 per gram of hydrocarbon mixture. At least 0.001 grams; At least 0.001 grams of olefins per gram of olefins as defined by ASTM specification D6730 and at least 0.001 grams of olefins as defined by ASTM specification D6730; At least 0.001 grams of naphtha; At least 0.001 grams of kerosine having at least 0.2 grams of aromatics per gram of kerosene as defined by ASTM specification D5186; At least 0.001 gram of diesel having at least 0.3 grams of aromatics per gram of diesel as defined by IP Specification 368/90; It has a minimum of 0.001 grams of vacuum gas oil (VGO) with a minimum of 0.3 grams of aromatics per gram of VGO as defined by IP standard 368/90.

The present invention also provides a crude oil component, the component comprising a maximum of 0.05 grams of residue as defined by ASTM specification D5307 per gram of component; At least 0.001 gram of hydrocarbon with a boiling point distribution of up to 204 ° C. (400 ° F.) at 0.101 MPa; At least 0.001 gram of hydrocarbon with a boiling point distribution between 204 ° C. and 300 ° C. at 0.101 MPa; At least 0.001 gram of hydrocarbon with boiling point distribution between 300 ° C. and 400 ° C. at 0.101 MPa; A hydrocarbon having a boiling point distribution of up to 204 ° C. having a boiling point distribution of up to 204 ° C. having a boiling point distribution of up to 204 ° C. having a boiling point distribution between 400 ° C. and 538 ° C. (1000 ° F.) at 0.101 MPa as specified by ASTM specification D2887. At least 0.001 gram of olefin per gram of hydrocarbon with olefin as defined in ASTM specification D6730; Have a minimum of 0.001 grams of paraffin containing iso-paraffins and n-paraffins with a weight ratio of iso-paraffins to n-paraffins up to 1.4 as defined by ASTM specification D6730.

The present invention also provides a crude oil component, the component comprising a maximum of 0.05 grams of residue as defined in ASTM specification D5307 per gram of component; At least 0.001 gram of hydrocarbon with a boiling point distribution of up to 204 ° C. (400 ° F.) at 0.101 MPa; At least 0.001 gram of hydrocarbon with a boiling point distribution between 204 ° C. and 300 ° C. at 0.101 MPa; At least 0.001 gram of hydrocarbon with boiling point distribution between 300 ° C. and 400 ° C. at 0.101 MPa; A hydrocarbon having a boiling point distribution between -10 ° C. and 204 ° C. has a minimum of 0.001 grams of hydrocarbon with a boiling point distribution between 400 ° C. and 538 ° C. (1,000 ° F.) at 0.101 MPa as specified by ASTM specification D2887. Compound (C ₄ ) having a C ₄ compound has a minimum of 0.001 grams of butadiene per gram of C ₄ compound.

The present invention also provides a crude oil component comprising at most 0.05 grams of residue per gram of the component; At least 0.001 gram of hydrocarbon with a boiling point distribution of up to 204 ° C. (400 ° F.) at 0.101 MPa; At least 0.001 gram of hydrocarbon with a boiling point distribution between 204 ° C. and 300 ° C. at 0.101 MPa; At least 0.001 gram of hydrocarbon with boiling point distribution between 300 ° C. and 400 ° C. at 0.101 MPa; At least 0.001 gram of hydrocarbon with a boiling point distribution between 400 ° C. and 538 ° C. at 0.101 MPa; At least one catalyst greater than 0 grams and less than 0.01 grams has at least one alkali metal.

In some embodiments, the present invention also provides a crude oil feed in combination with one or more manufacturing methods or components according to the present invention, wherein the crude feed is (a) not treated to be purified, distilled and / or refined to distill. Without; (b) comprises a component having at least 4 carbon atoms and having at least 0.5 grams of said component per gram of crude oil feed; (c) hydrocarbons, portions of the hydrocarbons having a boiling point distribution of less than 100 ° C. at 0.101 MPa, a boiling point distribution between 100 ° C. and 200 ° C. at 0.101 MPa, and a boiling point distribution between 200 ° C. and 300 ° C. at 0.101 MPa. A boiling point distribution between 300 ° C. and 400 ° C. at 0.101 MPa, a boiling point distribution between 400 ° C. and 700 ° C. at 0.101 MPa, and (d) a boiling point distribution of 0.101 MPa up to 100 ° C. per gram of crude oil feed. 0.001 grams hydrocarbons minimum, 0.001 grams hydrocarbons with boiling point distribution between 100 ° C. and 200 ° C. at 0.101 MPa Minimum 0.001 grams hydrocarbons with boiling point distribution between 200 ° C. and 300 ° C. at 0.101 MPa, 300 ° C. and 400 at 0.101 MPa At least 0.001 grams of hydrocarbons having a boiling point distribution between ° C. and at least 0.001 grams of hydrocarbons having a boiling point distribution between 400 ° C. and 700 ° C. at 0.101 MPa; (e) has a TAN; (f) 0.2 to 0.99 grams, 0.3 to 0.8 grams, 0.4 to 0.7 grams of residue per gram of crude oil feed; (g) nickel, vanadium, iron or mixtures thereof; (h) nitrogen, including sulfur and / or (i) hydrocarbons.

In some embodiments, the present invention also provides a hydrogen source in combination with one or more manufacturing methods or components according to the present invention, wherein the hydrogen source is (a) a gas; (b) comprises hydrogen molecules; (c) comprises light hydrocarbons; (d) methane, ethane, propane, or mixtures thereof; (e) contains water and / or; (f) mixtures thereof.

In some embodiments, the present invention also provides a combination of one or more manufacturing methods or components according to the present invention: (a) heating an inorganic salt catalyst to a temperature of at least 300 ° C .; (b) a method of controlling the inorganic salt catalyst at conditions comprising heating the inorganic salt catalyst to a temperature of at least 300 ° C. and cooling to a temperature of at most 500 ° C.

In some embodiments, the present invention also provides a method comprising contacting a crude oil feed with at least one catalyst and controlling the contact conditions by combining at least one manufacturing method or component according to the present invention; (a) allowing hydrocarbons that do not condense at 25 ° C., 0.101 MPa during the contacting process to produce up to 0.2 grams, 0.15 grams, 0.1 grams, or 0.05 grams per gram of crude oil feed as determined by mass resin; (b) the contact temperature is in the range of 250 ° C. to 750 ° C. or between 260 ° C. and 550 ° C .; (c) the pressure is 0.1-20 MPa; (d) the proportion of hydrogen gas source to the crude oil feed is such that the normal volume of hydrogen source per unit volume (1 m 3) of the crude oil feed ranges from 1 to 16100 or 5 to 320 (m 3); (e) prevent coke formation; (f) prevent the formation of coke in the overall product or in the crude oil feed during the contacting process; (g) the crude product also has a maximum of 0.05 grams, 0.03 grams, 0.01 grams or 0.003 grams of coke per gram of crude oil product; (h) at least a portion of the inorganic salt catalyst is semi-liquid or liquid at such contacting conditions; (i) the crude product has a maximum of 90% of the TAN of the crude feed; (j) the crude product has a Ni / V / Fe content of at most 90%, at most 50%, or at most 10% of the Ni / V / Fe content of the crude feed; (k) the crude oil product has a sulfur content of up to 90%, up to 60% or up to 30% of the sulfur content of the crude feed; (l) the crude product has a nitrogen content of at most 90%, 70%, 50% or 10% of the nitrogen content of the crude feed; (m) the crude product has a residue content of up to 30%, 10% or 5% of the residue content of the crude feed; (n) allowing ammonia to be prepared with the crude product; (o) the crude oil product comprises methanol and the methanol regenerates methanol from the crude oil product; Further combining the regenerated methanol with additional crude oil feed to form a crude oil feed / methanol mixture; Heating the additional crude feed / methanol mixture such that the TAN of the additional crude feed is reduced to 1 or less; (p) allow one or more properties of the crude oil product to vary by up to 90% relative to one or more properties of the crude oil feed; (q) the amount of catalyst in the contacting zone is such that the total catalyst per 100 grams of crude oil feed is in the range of 1-60 grams; (r) The hydrogen source is added to the crude oil feed during or prior to the contacting process.

In some embodiments, the present invention also provides for contact conditions in combination with one or more manufacturing methods or components according to the present invention, wherein the contact conditions do not actually dissolve in the crude oil feed at temperatures below 500 ° C. Mixing the inorganic salt catalyst with the crude oil feed; (b) shaking the inorganic salt catalyst in the crude oil feed and / or; (c) contacting the inorganic salt catalyst with the crude oil feed together with moisture and / or steam to produce a whole product comprising crude oil product which is a liquid mixture in STP.

In some embodiments, the present invention also provides a method of contacting a crude oil feed with an inorganic salt catalyst in combination with one or more manufacturing methods or components according to the invention, further comprising (a) contacting during or prior to the contacting process. Providing steam to the zone; (b) forming an emulsion of the crude feed with moisture prior to contacting the crude feed with an inorganic salt catalyst and a hydrogen source; (c) spraying the crude oil feed into the contacting zone and / or; (d) contacting steam with an inorganic salt catalyst to at least partially remove coke from the surface of the inorganic salt catalyst, and the like.

In some embodiments, the present invention also provides a method comprising contacting a crude oil feed with an inorganic salt catalyst to produce a total product by combining one or more manufacturing methods or components according to the present invention, the method further comprising: Further condensing at least a portion of the steam at 25 ° C., 0.101 MPa to form a crude product, wherein the contacting conditions comprise (a) the crude product comprising a component having a selected boiling point distribution; And / or (b) the crude product comprises a component having a selected API specific gravity.

In some embodiments, the present invention also provides a method comprising combining one or more manufacturing methods or components according to the present invention to contact a crude feed with at least one catalyst and at least one catalyst is non-acidic.

In some embodiments, the present invention also provides a combination of one or more preparation methods or components according to the present invention to provide a K ₃ Fe ₁₀ S ₁₄ catalyst or a sulfide transition metal catalyst, which comprises (a) a K ₃ Fe ₁₀ S ₁₄ catalyst Or at least 0.4 grams, 0.6 grams, 0.8 grams of sulfide transition metal per gram of sulfide transition metal catalyst; (b) the atomic ratio of transition metal to sulfur in the K ₃ Fe ₁₀ S ₁₄ catalyst or sulfide transition metal catalyst is in the range of 0.2 to 20; (c) one or more alkali metals, one or more compounds of one or more alkali metals, or mixtures thereof; (d) one or more alkaline earth metals, one or more compounds of one or more alkaline earth metals, or mixtures thereof; (e) at least one alkali metal, at least one alkali, with an atomic ratio of transition metal to sulfur of 0.5 to 2.5 and an atomic ratio of alkali metal to transition metal of 0 to 1 in a K ₃ Fe ₁₀ S ₁₄ catalyst or a sulfided transition metal catalyst; At least one compound of the metal or mixtures thereof; (f) at least one alkaline earth metal, at least one alkali, with an atomic ratio of transition metal to sulfur of 0.5 to 2.5 and an atomic ratio of alkaline earth metal to transition metal of 0 to 1 in a K ₃ Fe ₁₀ S ₁₄ catalyst or a sulfided transition metal catalyst; One or more compounds of the earth metal or mixtures thereof; (g) comprises zinc; (h) KFe ₂ S ₃ ; (i) comprises KFeS ₂ ; And / or (j) be nonacidic.

In some embodiments, the present invention combines one or more manufacturing methods or components according to the present invention, such that a K ₃ Fe ₁₀ S ₁₄ catalyst is formed at the normal position.

In some embodiments, the present invention provides one or more sulfide transition metals, in combination with one or more manufacturing methods or components according to the present invention, wherein (a) one or more transitions from Groups 6 to 10 of the periodic table. Metals, compounds of transition metals, or mixtures thereof; (b) comprises at least one iron sulfide; (c) comprises FeS; (d) FeS ₂ ; (e) represented by the formula Fe _(1-b) S, b comprising a mixture of iron sulfide in the range of 0 to 0.17; (f) K ₃ Fe ₁₀ S ₁₄ after the contacting process with the crude oil feed; (g) one of the transition metals of the one or more sulfided transition metals is iron; And / or (h) a support and the sulfide transition metal catalyst will have a maximum of 0.25 grams of total support per 100 grams of catalyst.

In some embodiments, the present invention provides a method of forming a sulfided transition metal catalyst in combination with one or more manufacturing methods or components according to the present invention, wherein the method is oxidized to form an oxidation transition metal / metal salt mixture. Mixing transition metals and metal salts; Reacting hydrogen with an oxidation transition metal / metal salt mixture to form an intermediate; Reacting said intermediate with sulfur in at least one hydrocarbon to produce a sulfided transition metal catalyst, wherein (a) said metal salt comprises an alkali carbonate metal; (b) dispersing the intermediate in one or more liquid hydrocarbons during the reaction with sulfur; (c) at least one hydrocarbon has a boiling point of at least 100 ° C .; (d) at least one hydrocarbon is VGO, xylene or mixtures thereof; (e) mixing the oxidation transition metal with the metal salt mixes the oxidation transition metal with the metal salt in deionized water to form a wet paste; Drying the wet paste at a temperature in the range of 150-250 ° C .; Calcination of the dried paste at a temperature in the range of 300-600 ° C .; (f) reacting the intermediate with sulfur comprises heating the intermediate at a temperature in the range of 240 to 350 ° C. in at least one of the hydrocarbons; And / or (g) contacting the catalyst component to a crude oil feed comprising a sulfur and hydrogen source.

In some embodiments, the present invention combines one or more preparation methods or components according to the present invention and also provides an inorganic salt catalyst wherein the inorganic salt catalyst comprises (a) at least one alkali carbonate metal, at least one alkaline carbonate earth metal, or Mixtures thereof; (b) one or more alkali hydroxy metals, one or more alkali hydroxy earth metals or mixtures thereof; (c) one or more alkali hydride metals, one or more alkali hydride earth metals or mixtures thereof; (d) one or more sulfides of one or more alkali metals, one or more sulfides of one or more alkaline earth metals, or mixtures thereof; (e) one or more amides of one or more alkali metals, one or more amides of one or more alkaline earth metals, or mixtures thereof; (f) one or more metals of groups 6 to 10 of the periodic table, compounds of these metals or mixtures thereof; (g) at least one inorganic salt metal that generates hydrogen during catalyst use; (h) sodium, potassium, rubidium, cesium or mixtures thereof; (i) calcium and / or magnesium; (j) Sodium salts, potassium salts and potassium salts comprising potassium carbonate, hydroxide potassium, hydride potassium or mixtures thereof and sodium carbonate, sodium hydroxide, sodium hydride or mixtures thereof mixture; (k) mixtures thereof.

In some embodiments, the present invention provides an inorganic salt catalyst comprising an alkali metal, in combination with one or more manufacturing methods or components according to the present invention, wherein the alkali metal is (a) to an alkali metal having an atomic number of 11 or greater. The atomic ratio of alkali metal having an atomic number of at least 11 to that is in the range of 0.1 to 4; (b) at least two alkali metals are sodium and potassium and the atomic ratio of sodium to potassium is in the range of 0.1 to 4; (c) at least three alkali metals are sodium, potassium and rubidium, the atomic ratio of sodium to potassium, the atomic ratio of sodium to rubidium, and the atomic ratio of potassium to rubidium in the range of 0.1 to 5; (d) at least three alkali metals are sodium, potassium and cesium, the atomic ratio of sodium to potassium, the atomic ratio of sodium to cesium, and the atomic ratio of potassium to cesium in the range of 0.1 to 5; (e) At least three alkali metals are potassium, cesium and rubidium, the atomic ratio of potassium to cesium, the atomic ratio of potassium to rubidium, and the atomic ratio of cesium to rubidium in the range of 0.1-5.

In some embodiments, the present invention provides an inorganic salt catalyst comprising a support metal, in combination with one or more manufacturing methods or components according to the present invention, wherein (a) the support metal comprises zirconium oxide, calcium oxide, magnesium oxide Titanium oxide, hydrotalcite, aluminum, germanium, iron oxide, nickel oxide, zinc oxide, cadmium oxide, antimony oxide or mixtures thereof; And / or (b) the support metal comprises at least one metal in groups 6 to 10 of the periodic table and at least one compound of at least one metal, at least one alkali carbonate metal, at least one alkali hydroxide metal, at least one alkali hydride metal, One or more alkali carbonate earth metals, one or more alkali hydroxide earth metals, one or more alkali hydride earth metals and / or mixtures thereof are combined.

In one embodiment, the present invention provides a process comprising contacting a crude oil feed with an inorganic salt catalyst, in combination with one or more manufacturing methods or components according to the present invention, wherein the inorganic salt catalyst comprises (a) an inorganic The catalytic activity of the salt catalyst does not change substantially with sulfur and / or (b) the inorganic salt catalyst is added continuously to the crude oil feed.

In one embodiment, the present invention provides an inorganic salt catalyst in combination with one or more preparation methods or components according to the present invention, wherein the inorganic salt catalyst comprises (a) water vapor and / or carbon dioxide in the TAP temperature range. Emitted gas deformation; (b) thermal transition in a temperature range between 200-500 ° C., 250-450 ° C., or 300-400 ° C., as determined by differential projection calorimeter measurement at a heating rate of 10 ° C. per minute; (c) DSC temperature in a temperature range between 200 and 500 ° C., or between 250 and 450 ° C .; (d) an x-ray diffraction shape at a minimum 100 ° C. temperature that is wider than the x-ray diffraction shape of the inorganic salt catalyst of 100 ° C. or less; (e) Prevent ionic conductivity after conditioning at 300 ° C. which is less than the ionic conductivity of the inorganic salt catalyst before conditioning.

In some embodiments, the present invention provides an inorganic salt catalyst in combination with one or more manufacturing methods or components according to the present invention, wherein the inorganic salt catalyst prevents deformation of the radiant gas at a temperature range defined by TAP, The contact conditions also include a contact temperature of (a) at least T1 of 30 ° C., 20 ° C. or 10 ° C. below the TAP temperature of the inorganic salt catalyst, (b) at or above the TAP temperature, and / or (c) at least the inorganic salt catalyst. Is adjusted to be the TAP temperature.

In some embodiments, the present invention provides an inorganic salt catalyst in combination with one or more manufacturing methods or components according to the present invention, wherein the inorganic salt catalyst is (a) a TAP that is the minimum temperature at which spinning gas deformation can be prevented. At least at a temperature cannot be dissolved in the crude oil feed; at least at the TAP temperature is liquid or semi-liquid; (b) a mixture of a liquid and solid phase in the temperature range from 50 ° C. to 500 ° C .; And / or (c) at least one of the two inorganic salts will have a DSC temperature of at least 500 ° C.

In some embodiments, the present invention provides an inorganic salt catalyst in combination with one or more manufacturing methods or components according to the present invention, when the inorganic salt catalyst is tested in the form of particles that can pass through a 1000 micron filter, When heated to a temperature of at least 300 ° C., the magnetostriction below gravity and / or at a pressure of at least 0.007 MPa results in the inorganic salt catalyst being converted from the first form to the second form and the second form being at 20 ° C. of the inorganic salt catalyst. The cooling of the furnace prevents the return to the first form.

In some embodiments, the present invention provides an inorganic salt catalyst in combination with one or more manufacturing methods or components according to the present invention, wherein the inorganic salt catalyst is calculated as the weight of (a) lithium per gram of the inorganic salt catalyst. Compounds of lithium or up to 0.01 grams of lithium; (b) a maximum of 0.001 grams of halogen compound, calculated as the weight of halogen; And / or (c) up to 0.001 grams of oxidized free compound.

In some embodiments, the present invention combines one or more manufacturing methods or components according to the present invention to provide a total product, wherein the total product will have a minimum of 0.8 grams of crude oil feed per gram of total product.

In some embodiments, the present invention combines one or more manufacturing methods or components according to the present invention to provide a crude product, wherein the crude product comprises (a) 0.000001 to 0.1 grams, 0.00001 to grams of residue per gram of crude product. From 0.05 gram, 0.0001-0.03 gram up to 0.003 gram, 0.02 gram, 0.01 gram, 0.05 gram, 0.001 gram; (b) from 0 grams to 0.05 grams, 0.00001 to 0.03 grams or 0.0001 to 0.01 grams of coke per gram of crude oil product; (c) has an olefin content of at least 10% greater than the olefin content of the crude oil feed; (d) less than 0.1 gram but less than 0 gram of total inorganic salt catalyst per gram of crude oil product as defined by the mass resin; (e) from 0.00001 to 0.99 grams, 0.04 to 0.9 grams, 0.6 to 0.8 grams of at least 0.1 grams of VGO per gram of crude oil product; (f) VGO having at least 0.3 grams of aromatics per gram VGO; (g) from 0.1 to 0.5 grams of distillate or having 0.001 grams; (h) has an atomic H / C ratio of up to 1.4; (i) has an atomic H / C of 90-110% of the H / C of the crude oil feed; (j) has a monocyclic ring aromatic content of at least 10% greater than the monocyclic ring aromatic content of the crude oil feed; (k) has a monocyclic cyclic aromatic comprising a compound of xylene, ethylbenzene or ethylbenzene; (l) from 0.05 to 0.15 grams of toluene per gram of crude oil product, from 0.3 to 0.9 grams of meta-xylene, from 0.5 to 0.15 grams of ortho-xylene, from 0.2 to 0.6 grams of para-xylene Have a maximum of 0.1 grams; (m) has a minimum of 0.0001 grams from 0.01-0.5 grams of diesel; (n) diesel having at least 0.3 grams of aromatics per gram of diesel; (o) having a minimum of 0.001 grams from 0.001 to 0.5 grams of kerosene from 0 to 0.7 grams, and (p) a freezing point of at most -30 ° C, -40 ° C, or -50 ° C and / or a minimum of 0.2 aromatics per gram of kerosine Grams or 0.5 grams of kerosene; (q) have a minimum of 0.001 grams or 0.5 grams of naphtha; (r) a weight ratio of iso-paraffins up to 0.01 grams, up to 0.05 grams or up to 0.002 grams of benzene per gram of naphtha, with a octane number of at least 70, 80 or 90 and / or normal paraffins at naphtha up to 1.4 Have iso-paraffins and normal paraffins; And / or (s) have a volume of at least 10% greater than the volume of the crude oil feed.

In some embodiments, the present invention provides a method comprising combining one or more manufacturing methods or components according to the present invention to contact a catalyst with a crude oil feed to form a whole product comprising the crude product. The process comprises (a) combining the crude product with the same or different crude oil to form a mixture suitable for returning; (b) combining the crude oil product with the same or different crude oil as the crude oil feed to form a mixture suitable for processing equipment; (c) fractionating the crude product; (d) subdividing the crude oil product into one or more distillation classifications and preparing a return fuel from at least one of the distillation classifications; And / or (e) when the catalyst is a sulfided transition metal catalyst, treating the sulfided transition metal catalyst to regenerate metal from the sulfided transition metal catalyst, and the like.

In some embodiments, the present invention combines one or more manufacturing methods or components according to the present invention to provide a crude oil product, wherein the crude oil product comprises (a) at least 0.3 grams of aromatics per gram of VGO per gram of crude product At least 0.001 grams of VGO with; (b) at least 0.001 grams of diesel having at least 0.3 grams of aromatics per gram of diesel; (c) a minimum of 0.001 of naphtha having up to 0.5 grams of benzene per gram of naphtha and having at least 70 octane number and / or having iso-paraffins and n-paraffins having a weight ratio of iso-paraffins to n-paraffins up to 1.4. gram; (d) a minimum of 0.001 grams of the mixture of components having a maximum boiling point distribution of 204 ° C. (400 ° F.) with a maximum of 0.15 grams of olefins per gram of the mixture; (e) a component having a weight ratio of carbon atoms to hydrogen atoms of at most 1.75 or 1.8; (f) a minimum of 0.001 grams of kerosine having a freezing point of at most −30 ° C. and / or having at least 0.5 grams of aromatics per gram of kerosene; (g) 0.09 to 0.13 grams of hydrogen atoms per gram of component; (h) non-condensable hydrocarbon gas and naphtha having a maximum of 0.15 grams of olefin when bound per gram of naphtha with the combined non-condensable hydrocarbon gas; (i) non-condensable hydrocarbon gases and naphtha comprising iso-paraffins and n-paraffins up to 1.4 when the weight ratio of iso-paraffins to n-paraffins in the combined naphtha and non-condensable hydrocarbon gases is combined; (j) olefins and paraffins having 2 (C ₂ ) and 3 (C ₃ ) carbon atoms having a weight ratio of bound C ₂ and C ₃ olefins to bonded C ₂ and C ₃ paraffins up to 0.3; Olefins having 2 (C ₂ ) carbon atoms and paraffins having a weight ratio of C ₂ olefins to C ₂ paraffins up to 0.2; And / or hydrocarbons having a weight ratio of C ₃ olefins to C ₃ paraffins of at most 0.3, and having carbon numbers of 3 (C ₃ ) and olefins having 3 (C ₃ ) and carbon numbers up to 3; (k) has a butadiene content of at least 0.005 grams; (l) has an API specific gravity in the range from 15 to 30 at 15.5 ° C .; (m) has a maximum of 0.00001 grams of total Ni / V / Fe per gram of component; (n) paraffin content of hydrocarbons having a boiling point distribution of up to 204 ° C. in the range from 0.7 to 0.98 grams; (o) hydrocarbons having a boiling point distribution of up to 204 ° C. having hydrocarbons having a boiling point distribution of up to 204 ° C. per gram of olefin in the range of 0.001 to 0.5 grams of olefins; (p) hydrocarbons having a boiling point distribution of up to 204 ° C. comprising olefins having at least 0.001 grams of terminal olefins per gram of olefins; (q) hydrocarbons having a boiling point distribution of up to 204 ° C. comprising olefins having a mole ratio of terminal olefins to internal olefins of at least 0.4; And / or (r) from 0.001 to 0.5 grams of olefin per gram of hydrocarbon having a boiling point distribution between 20 ° C. and 204 ° C.

In some embodiments, the present invention combines one or more manufacturing methods or components according to the present invention to provide a crude oil product, wherein the crude oil product has at least one catalyst comprising one or more alkali metals; (a) at least one of said alkali metals is potassium, rubidium or cesium or mixtures thereof; And / or (b) at least one of said catalysts comprises a transition metal, a sulfided transition metal and / or bartonite.

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

In other embodiments, crude oil products may be obtained by the manufacturing methods and systems described herein.

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

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

1 is a schematic diagram showing one embodiment of a contacting system for contacting a crude oil feed to a hydrogen source having one or more catalysts to produce the overall product.

2 is a schematic diagram showing another embodiment of a contacting system for contacting a crude oil feed to a hydrogen source having one or more catalysts to produce the overall product.

3 is a schematic view showing one embodiment of a separation zone in combination with a contact system.

4 is a schematic diagram showing one embodiment of a mixing zone in combination with a contact system.

5 is a schematic diagram showing one embodiment of a separation zone, a contact system, and a mixing zone.

6 is a schematic diagram illustrating one embodiment of a multiple contact system.

7 is a schematic diagram illustrating one embodiment of an ion conductivity measurement system.

8 is a table showing the properties of crude oil products and the crude oil feed obtained from one embodiment of contacting a sulfide transition metal catalyst with a crude oil feed.

9 is a table showing the components of the non-condensable hydrocarbons obtained from one embodiment of contacting a sulfide transition metal catalyst with a crude oil feed and the components of the crude oil feed.

FIG. 10 is a plot of the properties and components of a crude oil product obtained from one embodiment of contacting a sulfide transition metal catalyst with a crude oil feed.

FIG. 11 is a graph showing the ion flow of the spinning gas of the inorganic salt catalyst as a function of log10 versus temperature as defined by TAP.

12 is a graph showing the logarithmic resistance of an inorganic salt catalyst and an inorganic salt to the resistance of potassium carbonate to temperature.

FIG. 13 is a graph showing the log function resistance of Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ catalyst to the resistance of potassium carbonate to temperature.

FIG. 14 is a graph showing the weight ratio of coke, liquid hydrocarbon and gas to various hydrogen sources prepared from one embodiment of contacting a crude oil feed to an inorganic salt catalyst.

FIG. 15 is a graph showing the weight ratio to carbon number of crude oil products prepared from one embodiment of contacting a crude oil feed to an inorganic salt catalyst.

FIG. 16 is a table of components prepared from one embodiment of contacting a crude oil feed with an inorganic salt catalyst, metal salt or silicon carbide.

The present invention is suitable for various modifications and alternative variations, and specific embodiments are shown in the drawings and will be described in detail below. The drawings are not to scale. The drawings and detailed description do not limit the invention to the specific forms, and include all modifications, equivalents, and alternatives within the scope of the invention.

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

"Alkali metal" refers to one or more metals of Group 1 of the Periodic Table, one or more compounds of one or more metals of Group 1 of the Periodic Table, or mixtures thereof.

"Alkaline earth metal" refers to one or more metals of Group 2 of the Periodic Table, one or more compounds of one or more metals of Group 2 of the Periodic Table, or mixtures thereof.

"AMU" refers to atomic weight units.

"ASTM" refers to the American Society for Testing and Materials.

"C ₅ Asphalt "refers to asphalt that does not dissolve in pentane. C ₅ Asphalt content is determined by ASTM specification D2007.

The atomic hydrogen percentage and atomic carbon percentage of crude oil feed, crude product, naphtha, kerosine, diesel and VGO are determined by ASTM specification D5291.

"API gravity" refers to the API gravity at 15.5 ° C. API specific gravity is determined by ASTM standard D6822.

"Bitumen" refers to a form of crude oil produced and / or distilled from hydrocarbon formation.

The boiling point distribution for the crude oil feed and / or the total product is determined by ASTM specification D5307, unless otherwise noted. For example, the content of hydrocarbon components (eg, aromatic elements in paraffins, iso-paraffins, olefins, naphthalene and naphtha) is determined by ASTM specification D6730. The aromatic content in diesel and VGO is determined by IP standard 368/90. The aromatic content of kerosine is determined by ASTM specification D5186.

"Botsted-Rouri acid" refers to a molecular material capable of providing protons from other molecular materials.

"Briested-Lowry base" refers to a molecular material that can be provided with protons in other molecular materials. Wherein Bronsted Examples of Lowry bases include hydroxide (OH ^-), water (H ₂ O), carboxylate (RCO ₂ ^-), halide (Br ^-, Cl ^-, F ^{- -,} I) include sulphate (HSO ₄ ^{- -)} and sulfate (SO ₄ ^2).

"Carbon number" refers to the total number of carbon atoms in a molecule.

"Coke" refers to a solid containing a carbonaceous solid that does not vaporize under process conditions. The content of coke is determined by the mass balance. The weight of coke is the total weight of the solid minus the total weight of the catalyst entered.

"Content" refers to the weight of a component in a substrate (eg, crude feed, total product, or crude product) in terms of weight percentage, ie, parts by weight, relative to the total weight of the substrate. "Wtppm" is the weight ratio in parts per million.

"Diesel" refers to a hydrocarbon having a boiling point distribution of 260 ° C to 343 ° C (500 to 650 ° F) at 0.101 MPa. Diesel content is defined by ASTM specification D2887.

"Distillate" refers to a hydrocarbon having a boiling point distribution at 204 ° C. to 343 ° C. (400 to 650 ° F.) at 0.101 MPa. Distillate content is defined by ASTM specification D2887. The distillate may include kerosene and diesel.

"DSC" refers to a differential scanning calorimeter measurement method.

"Freezing point" and "freezing point" refer to the temperature at which the formation of crystal grains occurs in a liquid. Freezing point is defined by ASTM standard D2386.

"GC / MS" refers to gas chromatography with gravimetric mass spectrometry.

"Strong base" refers to the anion described in Pearson's "Journal of American Chemical Society, 1963, 85, p. 3533".

"H / C" refers to the weight ratio of hydrogen atoms to carbon atoms. H / C is determined by the value measured by the weight ratio of hydrogen and carbon by weight according to ASTM specification D5291.

"Heteroatoms" refer to oxygen, nitrogen and / or sulfur contained in the molecular structure of hydrocarbons. The heteroatom content is determined by ASTM specification E385 for oxygen, D5762 for total nitrogen, and D4294 for sulfur.

A "hydrogen source" refers to hydrogen and / or a compound in a catalytic reaction with a crude oil feed to provide hydrogen to one or more compounds in the crude oil feed. Hydrogen sources include, but are not limited to, hydrocarbons (eg, C ₁ -C ₆ hydrocarbons such as methane, ethane, propane, butane, pentane, naphtha), water, or mixtures thereof. Mass balance can be analyzed to estimate the net amount of hydrogen supplied to the compound (s) in the crude oil feed.

"Inorganic salts" refer to compounds consisting of metal cations and anions.

"IP" refers to the Petroleum Institute, the energy association of London, England.

"iso-paraffin" refers to a hydrocarbon saturated with branched chains.

"Kerosine" refers to a hydrocarbon having a boiling point distribution of 204 ° C to 260 ° C (400 to 500 ° F) at 0.101 MPa. Kerosene content is defined by ASTM specification D2887.

"Lewis acid" refers to a compound or material capable of receiving one or more electrons from another compound.

"Lewis base" refers to compounds and / or materials capable of providing one or more electrons to other compounds.

"Light hydrocarbon" refers to a hydrocarbon having a carbon number between 1 and 6.

"Liquid mixture" means a composition comprising one or more compounds that are liquid at standard temperature and pressure (25 ° C., 0.101 MPa, hereinafter referred to as “STP”) or a liquid state in STP together with one or more compounds that are solid in STP Refers to a composition comprising a combination of one or more compounds.

The "micro residual carbon" ("MCR") content refers to the amount of residual carbon remaining after evaporation and pyrolysis of the substrate. MCR content is defined by ASTM specification D4530.

“Naphtha” refers to a hydrocarbon component having a boiling point range of 38 ° C. to 204 ° C. (100 ° F. to 400 ° F.) at 0.101 MPa. Naphtha content is defined by ASTM specification D2887.

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

"Ni / V / Fe content" refers to Ni / V / Fe content in the substrate. This Ni / V / Fe content is determined according to ASTM specification D5863.

"Nm ³ / m ³ " means normal cubic meters of gas per cubic meter of crude oil feed.

"Non-acidic" refers to Lewis base and / or Bronsted-Lowry base properties.

"Non-condensable gas" refers to a component and / or mixture of components that is a gas at standard temperature and pressure (25 ° C., 0.101 MPa, hereinafter “STP”).

"n-paraffin" refers to a normal (straight-chain) saturated hydrocarbon.

"Octane number" refers to a calculated numerical representation of the motor fuel properties of explosion proof compared to standard reference fuel. The calculated octane number of naphtha is defined in ASTM specification D6730.

"Olefin" refers to a compound having a non-aromatic carbon-carbon double bond. Forms of olefins include, but are not limited to, cis, trans, terminal, internal, branched and linear.

"Periodic Table" means the Periodic Table as set forth in November 2003 by the International Union of Pure and Applied Chemistry (IUPAC).

"Polyaromatic compound" refers to a compound comprising two or more aromatic systems. Examples of multiaromatic compounds include, but are not limited to, indene, naphthalene, anthracene, phenanthrene, benzothiophene, and dibenzothiophenene. .

“Residue” refers to a component having a boiling point region distribution of at least 538 ° C. (1000 ° F.) at 0.101 MPa, as defined in ASTM Standard D5307.

"Semi-liquid" refers to a phase of a substance that has the properties of a liquid phase and a solid phase of the substance. Examples of semi-liquid inorganic salt catalysts include slurries and / or phases that have conditions such as, for example, taffy, dough, or toothpaste.

"SCFB" means standard cubic feet of gas per barrel of crude oil feed.

"Superbase" refers to a material capable of deprotonating hydrocarbons such as paraffin and olefins under reaction conditions.

"TAN" refers to the total acid value expressed in milligrams of potassium hydroxide ("mg") per gram ("g") of the sample. "TAN" is defined by ASTM specification D664.

"TAP" refers to a transient-analytical-product.

"TMS" refers to a sulfide transition metal.

"VGO" refers to a component having a boiling point distribution of 343 ° C to 538 ° C (650 to 1000 ° F) at 0.101 MPa. VGO content is defined by ASTM specification D2887.

In the context of the present application, if the value obtained for the properties of the tested component is within the limits of the test method, the test method may be recalibrated to a test for that property. Standard reduction test methods that are considered equivalent to the standard test method may also be used.

Crude oil may be produced and / or distilled from the formation containing hydrocarbons and then stabilized. Crude oil is usually solid, semi-solid and / or liquid. Crude oil includes crude oil. Stabilization treatments include, but are not limited to, removal of non-condensable gases, water, salts or combinations thereof from crude oil to produce stabilized crude oil. Such stabilization is usually carried out at or near the site of production and / or distillation.

Typically, the stabilized crude oil is not distilled and / or partially distilled at the treatment plant to produce a number of components having a predetermined boiling point distribution (eg, naphtha, distillate, VGO and / or lubricants, etc.). Distillation methods include, but are not limited to, atmospheric distillation methods and / or vacuum distillation methods. Undistilled and / or undigested stabilized crude oil may comprise components having at least 4 carbon numbers in an amount of at least 0.5 grams of the components per gram of crude oil. Examples of stabilized crude oils include whole crude oil, atmospheric distilled crude oil, desalted crude oil, desalted atmospheric distilled crude oil, or combinations thereof. “Atmospheric distillation” refers to crude oil that has been treated to remove at least some of the components having a boiling point of at least 35 ° C. and below 0.101 MPa. Typically, atmospheric distillate crude oil will have such components per gram of the atmospheric distillate crude oil in an amount of at most 0.1 grams, at most 0.05 grams, or at most 0.02 grams.

Some stabilized crude oils have the property of allowing crude oil stabilized by conveying carriers (eg, pipelines, trucks or ships) to be returned to conventional processing facilities. Other crude oils have one or more unstable properties that disadvantage them. Low quality crude oil cannot be accepted as a carrier and / or processing facility, so the economic value of low quality crude oil is lowered. The economic value is so low that reservoirs containing poor quality crude oil are expensive to manufacture, return, and / or process.

Properties of low quality crude oil include, but are not limited to: a) a TAN of at least 0.5; b) a viscosity of at least 0.2 Pa.s; c) API gravity of up to 19; d) the total Ni / V / Fe content of at least 0.001 grams or at least 0.00005 grams of Ni / V / Fe per gram of crude oil; e) total heteroatom content of at least 0.005 grams of heteroatoms per gram of crude oil; f) residue content of at least 0.01 grams of residue per gram of crude oil; g) asphalt content of at least 0.04 grams of asphalt per gram of crude oil; h) MCR content of at least 0.02 grams of MCR per gram of crude oil; Or i) combinations thereof. In some embodiments, poor quality crude oil may comprise at least 0.2 grams, 0.3 grams, 0.5 grams, or 0.9 grams of residue per gram of poor quality crude oil. In some embodiments, poor quality crude oil has between 0.2 and 0.99 grams, 0.3 and 0.9 grams, or 0.4 and 0.7 grams of residue, per gram of poor quality crude oil. In some embodiments, the poor crude oil has a sulfur content of at least 0.001 grams, at least 0.005 grams, 0.01 grams, or 0.02 grams per gram of poor quality crude oil.

Low quality crude oil contains a mixture of hydrocarbons with a boiling point distribution. Low quality crude oils include at least 0.001 grams, 0.005 grams, 0.01 grams of hydrocarbons with a boiling point distribution between 200 ° C. and 300 ° C. at 0.101 MPa per gram of poor crude oil; At least 0.001 gram, 0.005 gram, 0.01 gram of hydrocarbon with a boiling point distribution of 300 ° C.-400 ° C. at 0.101 MPa; And at least 0.001 grams, 0.005 grams, 0.01 grams of hydrocarbons or combinations thereof with a boiling point distribution between 400 ° C. and 700 ° C. at 0.101 MPa.

In some embodiments, the low quality crude oil may also comprise a minimum of 0.001 grams, 0.005 grams, 0.01 grams with a boiling point distribution of up to 200 ° C. at 0.101 MPa in addition to components with higher boiling points per gram of low quality crude oil. have. Typically, low quality crude oil has a content of up to 0.2 grams, or up to 0.1 grams of hydrocarbons per gram of low quality crude oil.

In some embodiments, poor quality crude oil may comprise up to 0.9 grams or 0.99 grams of hydrocarbons having a boiling point distribution of at least 300 ° C. per gram of poor crude oil. In some embodiments, poor quality crude oil may also include at least 0.001 grams of hydrocarbons having a boiling point distribution of at least 650 ° C., per gram of poor quality crude oil. In some embodiments, poor quality crude oil may comprise up to 0.9 grams or 0.99 grams of hydrocarbons having a boiling point distribution of 300 ° C. to 1000 ° C. per gram of poor quality crude oil.

Examples of poor quality crude oil that can be processed using the process described herein may include, but are not limited to, crude oil extracted from the following countries and regions of the country: Alberta Canada, Venezuela Orinco, South California, USA North and Alaska, Camp Camp Gulf of Mexico, Argentine Mountain George Basin, Brazil Santos and Gampos Basin, Bohai Gulf of China, China Karamay, Iraq Zagros, Kazakhstan Caspian, Nigeria Offshore, North Sea of England, Northwest Madagascar, Oman And Schnebeck, The Netherlands.

Treatment of low quality crude oil may improve the properties of the low quality crude oil such that the crude oil is suitable for conveyance and / or processing. Crude oil and / or poor crude oil that is to be treated may be referred to as a "crude oil feed." The crude oil feed may be distilled at the top as described herein. Using the method described herein, the crude product resulting from the treatment of the crude oil feed is suitable for conveyance and / or purification. The characteristics of the crude oil product are closer to the corresponding properties of West Texas heavy oil than the crude oil feed, or closer to the corresponding properties of Brent crude oil than the crude oil feed, resulting in an increased economic value relative to the economic value of the crude oil feed. Such crude oil products can be purified with less pretreatment or without pretreatment, thereby increasing the purification efficiency. Pretreatment may include desulfurization, demetallization, and / or atmospheric distillation to remove impurities from crude oil products.

Methods of contacting a crude oil feed in accordance with the present invention are described herein. In addition, embodiments are described for producing products having various concentrations of naphtha, kerosine, diesel and / or VGO, which are not generally prepared in conventional forms of the manufacturing process.

The crude oil feed may be contacted with a hydrogen source with one or more catalysts in a contacting zone and / or a combination of two or more contacting zones.

In some embodiments, the hydrogen source is generated on site. Generation of a hydrogen source on site may include reacting at least a portion of the crude oil feed with an inorganic salt catalyst at a temperature in the range of 200-500 ° C. or 300-400 ° C. to form hydrogen and / or light hydrocarbons. The generation of hydrogen in situ may involve the reaction of at least a portion of the inorganic salt catalyst comprising, for example, alkali metal formate.

The total product generally comprises a gas, vapor, liquid or mixtures thereof prepared during the contacting process. The total product includes crude oil product, which is a liquid mixture in STP, and in some embodiments hydrocarbons that cannot condense in STP. In some embodiments, the total product and / or crude product may comprise a solid (such as an inorganic solid and / or coke). In some embodiments, the solid may be accompanied by a liquid and / or vapor produced during the contacting process.

The contacting region may comprise a reactor, a part of the reactor, a plurality of parts of the reactor or a plurality of reactors. Examples of reactors used to contact the hydrogen source and crude oil feed with catalysts include stacked bed reactors, fixed bed reactors, continuous stirred tank reactors ("CSTR"), spray reactors, plug-flow reactors and liquid / liquid It includes a contactor. Examples of CSTRs include fluidized bed reactors and ebullating bed reactors.

Contact conditions typically include temperature, pressure, crude oil feed stream, total product flow, residue time, hydrogen feed stream, or combinations thereof. Contact conditions can be adjusted to produce crude oil products with specific properties.

The contact temperature may range from 200 to 800 ° C, 300 to 700 ° C or 400 to 600 ° C. In embodiments in which the hydrogen source is supplied as a gas (eg hydrogen gas, methane or ethane), the ratio of gas to crude oil feed is generally 1 to 16,100 Nm 3 / m 3, 2 to 8000 Nm 3 / m 3, 3 to 4000 Nm 3 / m 3, or 5 to 300 Nm 3 / m 3. Typically the contact process occurs in a pressure range between 0.1 and 20 MPa, 1 and 16 MPa, 2 and 10 MPa, or 4 and 8 MPa. In some embodiments where steam is added, the ratio of steam to crude oil feed is in the range of 0.01 to 3 kilograms of steam, 0.03 to 2.5 kilograms, 0.1 to 1 kilogram, per kilogram of crude oil feed. The flow rate of the crude oil feed may be sufficient to maintain the volume of crude oil feed in the contacting zone of at least 10%, 50%, or 90% of the total volume of the contacting zone. Typically, the volume of crude oil feed in the contacting zone is 40%, 60% or 80% of the total volume of the contacting zone. In some embodiments, the contact can be done with additional gases, such as argon, nitrogen, methane, ethane, propane, butane, propene, butyne, or combinations thereof.

1 is a schematic diagram of an embodiment of a contacting system 100 used to produce the entire product as steam. Crude feed enters the contact region 102 through the conduit 104 in the crude feed 101. The amount of catalyst used in the contacting zone can range from 1 to 100 grams, 2 to 80 grams, 3 to 70 grams, or 4 to 60 grams, per 100 grams of crude oil feed in the contacting zone. In some embodiments, diluents may be added to lower the viscosity of the crude oil feed. In some embodiments, the crude oil feed enters the bottom of the contact region 102 through the passage 104. In some embodiments, the crude feed may be heated to a temperature of at least 100 ° C. or at least 300 ° C. during and / or prior to introduction of the crude feed into contacting region 102. Typically, the crude oil feed may be heated to a temperature in the range of 100 to 500 ° C or 200 to 400 ° C.

In some embodiments, the catalyst is combined with the crude oil feed and sent to the contacting zone 102. The crude oil feed / catalyst mixture may be heated to a temperature of at least 100 ° C. or 300 ° C. prior to introduction into the contacting zone 102. Typically, the crude oil feed may be heated to a temperature in the range of 200-500 ° C or 300-400 ° C. In some embodiments, the crude oil feed / catalyst mixture is in the form of a slurry. In some embodiments, the TAN of the crude oil feed may be reduced prior to the introduction of the crude oil feed into the contacting zone. For example, when the crude feed / catalyst mixture is heated to a range of 100-400 ° C. or 200-300 ° C., an alkali salt of the acid component of the crude feed may be formed. The formation of this alkali salt may remove some acid components from the crude feed in order to reduce the TAN of the crude feed.

In some embodiments, crude oil feed may be continuously added to the contacting region 102. Mixing in the contacting zone 102 can be efficient to prevent separation of the catalyst from the crude oil feed / catalyst mixture. In some embodiments at least a portion of the catalyst may be removed from the contacting region 102, and in some embodiments such catalysts may be regenerated and reused. In some embodiments, new catalyst may be added to the contacting zone 102 during the reaction process.

In some embodiments, the crude oil feed with inorganic salt catalyst and / or the mixture of crude oil feed is introduced into the contacting zone as an emulsion. The emulsion can be prepared by combining the crude oil feed / surfactant mixture with the inorganic salt catalyst / water mixture. In some embodiments, the stabilizer is added to the emulsion. The emulsion may remain stable for at least 2 days, 4 days, or 7 days. Typically, the emulsion may remain stable for 30 days, 10 days, 5 days, or 3 days. Surfactants include organic polycarboxylic acids (Tennex 2010; Midwestbacco Special Group; Charleston, South Carolina, USA), C ₂₁ dicarboxyl patic acid (Diacid 1550; Midwestbacco Special Group), petroleum sulfonic acid Salts (Hostar SAS 30; Clariant Corporation, Charlotte, NC, USA), Tertary NP-40 surfactants (Union Carbide; Dunbury, Connecticut, USA) or mixtures thereof. Stabilizers include, but are not limited to, diethyleneamine (Aldrich Chemical, Milwaukee, Wisconsin, USA) and / or monoethanolamine (J. T. Baker, Phillipsburg, New Jersey, USA).

Recirculation passage 106 may be associated with passage 108 and passage 104. In some embodiments, the recycle passage 106 can enter and / or exit the direct contact region 102. Recirculation passage 106 may include flow control valve 110. Flow control valve 110 allows at least a portion of the material to be recycled from passage 108 to passage 104 and / or contact region 102. In some embodiments, the condensation unit is located in the passage 108 to condense or recycle at least a portion of the material to the contact region 102. In some embodiments, the recycle passage 106 can be a gas regeneration line. Flow control valves 110 and 110 ′ can be used to control flow to and from the contacting zone such that a volume of liquid is maintained in the contacting zone 102. In some embodiments, the actual selected volume range of the liquid can be maintained in the contact region 102. The volume supplied in the contact region 102 can be adjusted using standard instruments. As the crude oil feed enters the contacting zone 102, the gas inlet 112 allows for the addition of a hydrogen source and / or additional gas to the crude oil feed. In some embodiments, steam inlet 114 may be used to add steam to contact region 102. In some embodiments, the flow of water is introduced into the contact region 102 through the steam inlet portion 114.

In some embodiments, at least a portion of the total product is prepared as vapor from the contacting region 102. In some embodiments, the entire product is prepared as a vapor containing a small amount of liquid and solid from the top of the vapor and / or contact region 102. Vapor is returned to the separation zone 116 via the passage 108. The ratio of the crude oil feed in the contacting zone 102 and / or the hydrogen source to the pressure in the contacting zone can be varied to control the vapor and / or liquid phase produced from the top of the contacting zone 102. In some embodiments, the steam produced from the top of the contacting zone 102 comprises at least 0.5 grams, 0.8 grams, 0.9 grams or 0.97 grams of crude oil product per gram of crude oil feed. In some embodiments, the vapor produced from the top of the contacting zone 102 comprises 0.8-0.99 grams, or 0.9-0.98 grams of crude oil product per gram of crude oil feed.

The catalyst and / or solids used may remain as by-products of the contacting process in the contacting zone 102. The solid and / or catalyst used may comprise residual crude oil feed and / or coke.

In separation unit 116, the steam is cooled and separated to form crude product and gas using standard separation techniques. The crude product exits separation unit 116 and enters crude product receiver 119 via passage 118. Crude oil products may be suitable for conveying and / or processing. Crude product receiver 119 may comprise one or more pipelines, one or more storage units, or one or more return vessels, or a combination thereof. In some embodiments, the separated gas (eg, hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide or methane) is returned to another manufacturing unit (eg, a raw cell or sulfur regeneration plant) and / or the passage 120 Through the contact area 102. In some embodiments, the solids and / or liquids entrained in the crude oil product may be removed using standard physical separation methods (eg, filtration, centrifugation, or membrane separation).

2 shows a contacting system 122 for treating a crude feed with one or more catalysts to produce a whole product, which may be a liquid or a liquid mixed with a gas or solid. Crude feed may enter the contacting region 102 through the passage 104. In some embodiments, the crude oil feed is received from the crude oil feed supply. The passageway 104 may include a gas inlet 112. In some embodiments, the gas inlet 112 can enter the direct contact region 102. In some embodiments, steam inlet 114 may be used to add steam to contact region 102. The crude oil feed can be contacted with the catalyst in the contacting zone 102 to produce the entire product. In some embodiments, the passages 106 allow at least a portion of the total product to be recycled to the contacting regions 102. The mixture comprising the entire product and / or solid and / or unreacted crude oil feed exits the contacting zone 102 and enters the separation zone 124 through the passage 108. In some embodiments, the condensation unit may be positioned such that at least a portion of the mixture in the passage is condensed and recycled to the contacting region 102 for another process (eg, within passage 106). In some embodiments, the recycle passage 106 can be a gas recycle line. In some embodiments, passageway 108 may include a filter for removing particles from the overall product.

At least a portion of the crude product in separation zone 124 may be separated from the entire product and / or catalyst. In embodiments where the total product comprises a solid, the solid may be separated from the total product using standard solid separation techniques (eg, centrifugation, filtration, decantation, membrane separation). Solids include, for example, a combination of catalyst, catalyst used and / or coke. In some embodiments, the portion of the gas is separated from the total product. In some embodiments, at least a portion of the entire product and / or solid is recycled to passage 104 and / or in some embodiments, to passage area 102 through passage 126. For example, the recycled portion can be combined with the crude oil feed and enter the contacting zone 102 for other processing. The crude product exits separation zone 124 through passageway 128. In some embodiments, the crude product may be returned to the crude product receiver.

In some embodiments, the total product and / or crude product may comprise at least a portion of the catalyst. The gas entrained in the whole product and / or crude oil product can be separated using standard gas / liquid separation techniques (eg sparging, membrane separation and pressure reduction). In some embodiments, the separated gas is returned to other processing equipment (eg, for use in fuel cells, sulfur regeneration plants, other manufacturing equipment, or a combination thereof) and / or recycled to the contacting zone.

In some embodiments, separation of at least a portion of the crude feed is performed before the crude feed enters the contacting zone. 3 is a schematic diagram of an embodiment of a separation region in combination with a contact system. Contact system 130 may be contact system 100 and / or contact system 122 (shown in FIGS. 1 and 2). Crude feed enters the separation zone 132 through the passage 104. In separation zone 132, at least a portion of the crude oil feed is separated using standard separation techniques to produce separated crude oil feed and hydrocarbons. In some embodiments, the separated crude oil feed comprises a mixture of components having a boiling point distribution of at least 100 ° C., 120 ° C. or in other embodiments at least 200 ° C. Typically, the separated crude oil feed comprises a mixture of components having a boiling point distribution between 100-1000 ° C., 120-900 ° C. or 200-800 ° C. Hydrocarbons separated from the crude oil feed exit the separation zone 132 and pass through the passage 134 to another manufacturing apparatus, processing facility, storage facility, or combination thereof.

At least a portion of the separated crude feed is further prepared to exit the separation zone 132 and enter the contact system 130 through the passage 136 to form the crude product and exit the contact system 130 through the passage 138. .

In some embodiments, the crude product produced from the crude feed by the manufacturing method described herein is mixed with crude oil that is the same as or different from the crude feed. For example, crude oil products can be mixed with crude oil of different viscosities resulting in a mixed product having a viscosity value between the viscosity of the crude oil product and the viscosity of the crude oil. As a result, the mixed product may be suitable for conveyance and / or treatment.

4 is a schematic diagram of a combination embodiment of the mixed region 140 and the contact region 130. In some embodiments, at least a portion of the crude oil product exits the contact system 130 through the passage 138 and enters the mixing region 140. In mixing zone 140, at least a portion of the crude oil product is one or more process streams (eg, one or more crude oil feeds, or hydrocarbon streams produced from separation of naphtha), crude oil, crude oil feed to produce a mixed product. Combined with water, or mixtures thereof. The process stream, crude feed, crude oil, or mixtures thereof enters the mixing zone 140 directly or through the passage 142 upstream of the mixing zone. The mixing system can be located inside or near the mixing region 140. The mixed product can meet certain product specifications. Specific product specifications include, but are not limited to, API specific gravity limit ranges, TANs, viscosities, or combinations thereof. The mixed product exits the mixing zone 140 and flows into the passage 144 to be conveyed and / or made.

In some embodiments, methanol is generated during the contacting process with the catalyst. For example, hydrogen and carbon monoxide can react to form methanol. The regenerated methanol may contain dissolved salts such as potassium hydroxide. The recycled methanol can be combined with additional crude feed to form a crude feed / methanol mixture. The combination of methanol and crude oil feed can lower the viscosity of the crude oil feed. Heating the crude feed / methanol mixture up to 500 ° C. can reduce the TAN of the crude feed below 1.

5 is a schematic diagram of one embodiment of a separation zone in combination with a contact system in combination with a mixing zone. Crude feed enters the separation zone 132 through the passage 104. The crude feed is separated as previously described to form a separate crude feed. The separated crude feed enters the contact system 130 through the passage 136. The crude product exits contact system 130 and enters mixing zone 140 through passage 138. In the mixing zone 140, crude oil introduced through other process flows and / or passages 142 is combined with the crude oil product to form a mixed product. The mixed product leaves the mixing zone 140 and flows into the passage 144.

6 is a schematic diagram of a multiple contact system 146. Contact system 100 (shown in FIG. 1) may be located before contact system 148. In alternative embodiments, the position of the contact system can be interchanged. Contact system 100 includes an inorganic salt catalyst. Contact system 148 may include one or more catalysts. The catalyst in the contact system 148 can be an additional inorganic salt catalyst, a sulfided transition metal catalyst, an industrial catalyst or a mixture thereof. The crude oil feed enters the contacting system 100 through the passage 104 and is contacted with a hydrogen source with an inorganic salt catalyst to produce the entire product. The total product includes hydrogen and in some embodiments crude oil products. The whole product exits contact system 100 and flows into passageway 108. Hydrogen resulting from the contact of the crude oil feed with the inorganic salt catalyst may be used as the hydrogen source in the contacting system 148. At least a portion of the generated hydrogen is conveyed through the passage 150 from the contact system 100 to the contact system 148.

In alternative embodiments, the hydrogen so generated is separated and / or processed and returned to the contact system 148 via the passage 150. In some embodiments, the contact system 148 can be part of the contact system 100 such that the generated hydrogen can flow directly from the contact system 100 to the contact system 148. In some embodiments, the vapor stream produced from the contact system 100 is mixed directly with the crude oil feed entering the contact system 148.

The second crude oil feed enters the contact system 148 through the passage 152. In contacting system 148, the contacting of the crude oil feed with at least a portion of the generated hydrogen and catalyst produces a product. In some embodiments, the product is the entire product. The product exits contact system 148 and flows into passage 154.

In some embodiments, a system comprising a contact system, a contact zone, a separation zone, and / or a mixing zone, as shown in FIGS. 1-6, may be located at or near the point of manufacture that produces a crude oil feed. After the process through the catalyst system, the crude oil feed may be considered to be suitable for the use of the conveying and / or refining process.

In some embodiments, the crude oil product and / or mixed product is returned to a purification and / or treatment facility. Crude oil products and / or mixed products may be processed to produce industrial products such as return fuels, heated fuels, lubricants or chemicals. The process may include distilling and / or subdividing crude oil products and / or mixed products to produce one or more fractions of distillation. In some embodiments, the fraction of crude product, mixed product and / or one or more distillations may be hydrated.

In some embodiments, the total product comprises up to 0.05 grams, 0.03 grams, or 0.01 grams of coke per gram of total product. In some embodiments, the entire product is substantially free of coke (ie, no coke is detected). In some embodiments, the crude product may comprise up to 0.05 grams, 0.03 grams, 0.01 grams, 0.005 grams, or 0.003 grams of coke per gram of crude oil product. In some embodiments, the crude product has no coke content or is detected in the range of from 0 to 0.05 per gram of crude product, in the range of 0.00001 to 0.03 grams, 0.0001 to 0.01 grams, or 0.001 to 0.005 grams.

In some embodiments, the crude product has an MCR content that is at most 90%, 80%, 50%, 30%, or 10% of the MCR content of the crude feed. In some embodiments, the crude oil product has an insignificant MCR content. In some embodiments, the crude product has a maximum of 0.05 grams, 0.03 grams, 0.01 grams, or 0.001 grams of MCR per gram of crude oil product. Typically, the crude product has from 0 grams to 0.04 grams, 0.000001 to 0.03 grams, or 0.00001 to 0.01 grams of MCR per gram of crude oil product.

In some embodiments, the total product comprises a non-condensable gas. Typically non-condensable gases include, but are not limited to, carbon dioxide, ammonia, hydrogen sulfide, hydrogen, carbon monoxide, methane, other hydrocarbons that cannot condense in STP, or mixtures thereof.

In some embodiments, hydrogen gas, carbon dioxide, carbon monoxide, or a combination thereof may be formed in situ by contacting steam and light hydrocarbons with an inorganic salt catalyst. Typically, the molar ratio of carbon monoxide to carbon dioxide under thermodynamic conditions is 0.07. In some embodiments, the molar ratio of carbon monoxide generated to carbon dioxide generated is at least 0.3, 0.5, or 0.7. In some embodiments, the molar ratio of carbon monoxide generated to carbon dioxide generated is in the range of 0.3-1.0, 0.4-0.9, or 0.5-0.8. The ability to selectively generate carbon monoxide on carbon dioxide in the field can benefit other processes located near or upstream of the process. For example, the generated carbon monoxide can be used to reduce chemicals in the hydrocarbon formation process or in other processes such as syngas processes.

In some embodiments, the entire product as prepared herein may comprise a mixture of compounds having a boiling point distribution between −10 ° C. and 538 ° C. The mixture may comprise a hydrocarbon having a carbon number in the range of 1-4. The mixture may comprise from 0.001 to 0.8 grams, from 0.003 to 0.1 grams, or from 0.005 to 0.01 grams of C ₄ hydrocarbons per gram of mixture. The C ₄ hydrocarbons may comprise 0.001 to 0.8 grams, 0.003 to 0.1 grams, or 0.005 to 0.01 grams of butadiene per gram of C ₄ hydrocarbons. In some embodiments, the iso-paraffins are prepared in a weight ratio of at most 1.5, 1.4, 1.0, 0.8, 0.3, or 0.1 relative to n-paraffins. In some embodiments, the iso-paraffins are prepared in a weight ratio in the range of 0.00001 to 1.5, 0.0001 to 1.0, or 0.001 to 0.1 relative to n-paraffins. Paraffin may include iso-paraffins and / or n-paraffins.

In some embodiments, the whole product and / or crude product may comprise olefins and / or paraffins in proportions or amounts not generally found in crude oils prepared and / or distilled from tissue. Olefins include mixtures of olefins with terminal double bonds ("alpha olefins") and olefins with internal double bonds. In some embodiments, the olefin content of the crude oil product is greater than the olefin content of the crude oil feed by a factor of 2, 10, 50, 100, or at least 200. In some embodiments, the olefin content of the crude oil product is greater than the olefin content of the crude feed by a factor of up to 1,000, 500, 300, or 250.

In some embodiments, the hydrocarbon having a boiling point distribution between 20 and 400 ° C. is 0.00001 to 0.1 grams, 0.0001 and 0.05 grams, or 0.01 to 0.04 grams per gram of hydrocarbon having a boiling point distribution between 20 and 400 ° C. Has an olefin content.

In some embodiments, at least 0.001 grams, 0.005 grams, or 0.01 grams of alpha olefins per gram of crude oil product may be prepared. In some embodiments, the crude product has between 0.0001 and 0.5 grams, between 0.001 and 0.2 grams, or between 0.01 and 0.1 grams of alpha olefins per gram of crude oil product. In some embodiments, a hydrocarbon having a boiling point distribution between 20 and 400 ° C. is alpha in a range of 0.0001 to 0.08 grams, 0.001 to 0.05 grams, or 0.01 to 0.04 grams per gram of hydrocarbon having a boiling point distribution between 20 and 400 ° C. Has an olefin content.

In some embodiments, the hydrocarbon having a boiling point distribution of 20-204 ° C. has a weight ratio of alpha olefins to internal double bond olefins of at least 0.7, 0.8, 0.9, 1.0, 1.4 or 1.5. In some embodiments, the hydrocarbon having a boiling point distribution of 20-204 ° C. has a weight ratio of alpha olefins to internal double bond olefins in the range of 0.7-10, 0.8-5, 0.9-3, or 1-2. The weight ratio of the alpha olefins to the internal double bond olefins of crude oil and industrial products is typically at most 0.5. The ability to produce increased amounts of alpha olefins relative to olefins with internal double bonds can easily convert crude oil products to industrial products.

In some embodiments, contacting the hydrogen source with the inorganic salt catalyst and the crude oil feed can produce a hydrocarbon having a boiling point distribution between 20 and 204 ° C. comprising linear olefins. Linear olefins have cis and trans double bonds. The weight ratio of linear olefins with trans double bonds to linear olefins with cis double bonds is at most 0.4, 1.0 or 1.4. In some embodiments, the weight ratio of linear olefins with trans double bonds to linear olefins with cis double bonds is in the range of 0.001 to 1.4, 0.01 to 1.0, or 0.1 to 0.4.

In some embodiments, a hydrocarbon having a boiling point distribution between 20 and 204 ° C. has an n-paraffin content of at least 0.1 grams, 0.15 grams, 0.20 grams, or 0.30 grams per gram of hydrocarbon having a boiling point distribution between 20 and 400 ° C. Have The n-paraffin content of such hydrocarbons per gram of hydrocarbon may range from 0.001 to 0.9 grams, 0.1 to 0.8 grams, or 0.2 to 0.5 grams. In some embodiments, such hydrocarbons have a weight ratio of iso-paraffins to n-paraffins up to 1.5, 1.4, 1.0, 0.8, or 0.3. The n-paraffin content of the crude oil product from the n-paraffin content in such hydrocarbons can be measured in the range of 0.001 to 0.9 grams, 0.01 to 0.8 grams, or 0.1 to 0.5 grams per gram of crude oil product.

In some embodiments, the crude product has a Ni / V / Fe content of at most 90%, 50%, 10%, 5%, or 3% of the Ni / V / Fe content of the crude feed. In some embodiments, the crude product comprises a maximum of 0.0001 grams, 1 × 10 ⁻⁵ grams, 1 × 10 ⁻⁶ grams of Ni / V / Fe per gram of crude oil product. In some embodiments, the crude product is from 1 × 10 ⁻⁷ grams to 5 × 10 ⁻⁵ grams, 3 × 10 ⁻⁷ grams to 2 × 10 ⁻⁵ grams, or 1 × 10 ⁻⁶ grams, per gram of crude oil product Ni / V / Fe content in the range of 1 × 10 ⁻⁵ grams.

In some embodiments, the crude product has a TAN of at most 90%, 50%, or 10% of the TAN of the crude feed. In some embodiments, the crude oil product has a TAN of at most 1, 0.5, 0.1, or 0.05. In some embodiments, the TAN of the crude oil product may range from 0.001 to 0.5, 0.01 to 0.2, 0.05 to 0.1.

In some embodiments, the API gravity of the crude oil product is at least 10%, 50%, or 90% higher than the API gravity of the crude oil feed. In some embodiments, the API specific gravity of the crude oil product is between 13-50, 15-30, or 16-20.

In some embodiments, the crude oil product has a heteroatom content of up to 70%, 50%, or 30% of the total heteroatomic content of the crude feed. In some embodiments, the crude oil product has a heteroatom content of at least 10%, 40%, or 60% of the total heteroatom content of the crude oil feed.

The crude product has a sulfur content of up to 90%, 70%, or 60% of the sulfur content of the crude feed. The sulfur content of the crude oil product can be up to 0.02 grams, 0.008 grams, 0.005 grams, 0.004 grams, 0.003 grams, or 0.001 grams per gram of crude oil product. In some embodiments, the crude product has a sulfur content in the range of 0.0001 to 0.02 grams or 0.005 to 0.01 grams per gram of crude oil product.

In some embodiments, the crude product may have a nitrogen content of up to 90%, or 80% of the nitrogen content of the crude feed. The nitrogen content of the crude oil product may be at most 0.004 grams, 0.003 grams, or 0.001 grams per gram of crude oil product. In some embodiments, the crude product may have a nitrogen content in the range of 0.0001 to 0.005 grams, or 0.001 to 0.003 grams per gram of crude oil product.

In some embodiments, the crude oil product has 0.05 to 0.2 grams, or 0.09 to 0.15 grams of hydrogen per gram of crude oil product. The H / C of the crude oil product can be up to 1.8, 1.7, 1.6, 1.5, or 1.4. In some embodiments, the H / C of the crude oil product is 80-120%, or 90-110% of the H / C of the crude oil feed. In another embodiment, the H / C of the crude oil product is 100-120% of the H / C of the crude oil feed. Crude oil product H / C, which is less than 20% of the crude oil feed H / C, results in minimal hydrogen acquisition and / or consumption in the process.

Crude oil products include ingredients with a boiling range. In some embodiments, the crude oil product comprises at least 0.001 grams, or 0.001 to 0.5 grams of hydrocarbons having a boiling point distribution of at most 200 ° C. or 204 ° C. at 0.101 MPa; At least 0.001 gram, or 0.001 to 0.5 gram of hydrocarbon with a boiling point distribution between 200 ° C. and 300 ° C. at 0.101 MPa; A minimum of 0.001 gram, or 0.001 to 0.5 gram of hydrocarbon with a boiling point distribution between 0.101 MPa and 300 ° C. or 400 ° C .; And a minimum of 0.001 gram, or 0.001 to 0.5 gram of hydrocarbon with a boiling point distribution between 0.101 MPa and 400 ° C. or 538 ° C.

In some embodiments, the crude oil product has a naphtha content of 0.00001 to 0.2 grams, 0.0001 to 0.1 grams, or 0.001 to 0.05 grams per gram of crude oil product. In some embodiments, the crude oil product has between 0.001 and 0.2 grams or between 0.01 and 0.05 grams of naphtha. In some embodiments, naphtha has a maximum of 0.15 grams, 0.1 grams, or 0.05 grams of olefins per gram of naphtha. In some embodiments, the crude oil product has between 0.00001 and 0.15 grams, 0.0001 and 0.1 grams, or 0.001 and 0.05 grams of olefins per gram of crude oil product. In some embodiments, naphtha has a benzene content of at most 0.01 grams, 0.005 grams, and 0.002 grams per gram of naphtha. In some embodiments, naphtha cannot be detected or is from 1 × 10 ⁻⁷ grams to 1 × 10 ⁻² grams, from 1 × 10 ⁻⁶ grams to 1 × 10 ⁻⁵ grams, from 5 × 10 ⁻⁶ grams to 1 It has a benzene content in the range up to x 10 ^-4 grams. Ingredients containing benzene can be harmful to handle, so crude products with relatively low benzene content do not require special control.

In some embodiments, naphtha may comprise an aromatic compound. Aromatic compounds may include monocyclic ring compounds and / or polycyclic ring compounds. Monocyclic ring compounds include benzene, toluene, ortho-xylene, meta-xylene, para-xylene, ethyl benzene, 1-ethyl-3-methyl benzene; 1-ethyl-2-methyl benzene; 1,2,3-trimethyl benzene; 1,3,5-trimethyl benzene; 1-methyl-3-propyl benzene; 1-methyl-2-propyl benzene; 2-ethyl-1,4-dimethyl benzene; 2-ethyl-2,4-dimethyl benzene; 1,2,3,4-tetra-methyl benzene; Ethyl, pentylmethyl benzene; 1,3 diethyl-2,4,5,6-tetramethyl benzene; Tri-isopropyl-ortho-xylene; Benzene, toloene, ortho-xylene, meta-xylene, para-xylene, or mixtures thereof of the same nature, but may not be limited thereto. Monocyclic aromatics may be used in a variety of industrial products and / or solids as individual components. As described herein, crude oil products typically have an increased content of monocyclic aromatics.

In some embodiments, the crude product has a toluene content of 0.001 to 0.2 grams, 0.05 to 0.15 grams, or 0.01 to 0.1 grams per gram of crude oil product. The crude oil product has a meta-xylene content of 0.001 to 0.1 grams, 0.005 to 0.09 grams, or 0.05 to 0.08 grams per gram of crude oil product. The crude oil product has an ortho-xylene content of 0.001 to 0.2 grams, 0.005 to 0.1 grams, or 0.01 to 0.05 grams per gram of crude oil product. Crude oil products have a para-xylene content of 0.001 to 0.09 grams, 0.005 to 0.08 grams, or 0.001 to 0.06 grams per gram of crude oil product.

Increasing the aromatic content of naphtha tends to increase the octane number of naphtha. Crude oil is evaluated based on the measurement of the gasoline potential of crude oil. Gasoline potentials include, but are not limited to, measured octane numbers for the naphtha portion of crude oil. Crude oil typically has a measured octane number in the range of 35-60. The octane number of gasoline tends to reduce the need for additives to increase the octane number of gasoline. In some embodiments, the crude oil product comprises naphtha having a octane number of at least 60, 70, 80, 90. Typically, the octane number of naphtha is in the range of 60-99, 70-98, or 80-95.

In some embodiments, the crude product is at least 5%, 10 in hydrocarbons having a boiling point distribution between 204 ° C. and 500 ° C. relative to the total aromatic content (total “naphtha and kerosine”) in the total naphtha and kerosine of the crude feed. %, 50%, or 99% higher total aromatic content. Typically, the total aromatics content of the total naphtha and kerosene in the crude feed is 8%, 20%, 75%, or 100% greater than the total aromatics content in the total naphtha and kerosine in the crude feed.

In some embodiments, the kerosine and naphtha may have a total multiaromatic compound content in the range of 0.00001 to 0.5 grams, 0.0001 to 0.2 grams, or 0.001 to 0.1 grams per gram of total kerosine and naphtha.

The crude oil product has a distillate content in the range of 0.0001 to 0.9 grams, 0.001 to 0.5 grams, 0.005 to 0.3 grams, or 0.01 to 0.2 grams per gram of crude oil product. In some embodiments, the weight ratio of kerosene to diesel in the distillate is in the range of from 1: 4 to 4: 1, from 1: 3 to 3: 1 or from 2: 5 to 5: 2.

In some embodiments, the crude product has a minimum of 0.001 grams of kerosine, from 0 to 0.7 grams, from 0.001 grams to 0.5 grams, or from 0.01 grams to 0.1 grams per gram of crude product. In some embodiments, the crude oil product has between 0.001 and 0.5 grams or between 0.01 and 0.3 grams of kerosene. In some embodiments, the kerosine has an aromatic content of at least 0.2 grams, 0.3 grams, or 0.4 grams per gram of kerosine. In some embodiments, the kerosine has an aromatic content of 0.1-0.5 grams, or 0.2-0.4 grams per gram of kerosine.

In some embodiments, the freezing point of kerosine may be -30 ° C, -40 ° C, or -50 ° C or less. Increasing the aromatic content of the kerosene portion of the crude product tends to increase the density of the kerosene portion of the crude product and reduce the freezing point. Crude oil products having kerosine moieties with high density and low freezing point can be refined to produce sail turbine fuels with desirable properties of high density and low freezing point.

In some embodiments, the crude oil product has a diesel content in the range of 0.001 to 0.8 grams or 0.01 to 0.4 grams per gram of crude oil product. In some embodiments, the diesel has an aromatic content of at least 0.1 grams, 0.3 grams, or 0.5 grams per gram of diesel. In some embodiments, the diesel has an aromatic content in the range of 0.1-1 gram, 0.3-0.8 gram, or 0.2-0.5 gram per gram of diesel.

In some embodiments, the crude oil product has a VGO content in the range of 0.0001-0.99 grams, 0.001-0.8 grams, or 0.1-0.3 grams per gram of crude oil product. In some embodiments, the VGO content in the crude oil product is in the range of 0.4-0.9 grams or 0.6-0.8 grams per gram of crude oil product. In some embodiments, the VGO has an aromatic content in the range of 0.1-0.99 grams, 0.3-0.8 grams, or 0.5-0.6 grams per gram of VGO.

In some embodiments, the crude product has a residue content of up to 70%, 50%, 30%, 10%, or 1% of the crude oil feed. In some embodiments, the crude product has a residue content of at most 0.1 grams, 0.05 grams, 0.03 grams, 0.02 grams, 0.01 grams, 0.005 grams, or 0.001 grams per gram of crude oil product. In some embodiments, the crude product has a residue content in the range of 0.000001 to 0.1 grams, 0.00001 to 0.05 grams, 0.001 to 0.03 grams, or 0.005 to 0.04 grams per gram of crude oil product.

In some embodiments, the crude oil product may comprise at least a portion of the catalyst. In some embodiments, the crude oil product comprises at least 0 grams, but no more than 0.01 grams, ie, 0.000001 to 0.001 grams or 0.00001 to 0.0001 grams of catalyst per gram of crude oil product. The catalyst may help to stabilize the crude oil product during conveyance and / or treatment at the process facility. The catalyst can prevent corrosion, friction and / or increase water separation of the crude oil product. Crude oil products comprising at least a portion of the catalyst can be processed to produce lubricants and / or other industrial products.

The catalyst used for the treatment of the crude oil feed in the hydrogen source to produce the whole product may be a single catalyst or a plurality of catalysts. The catalyst of the application can be a catalyst precursor that is converted to a catalyst in the contacting zone when hydrogen and / or crude feed comprising sulfur is contacted with the catalyst precursor.

The catalyst used to contact the crude oil feed to the hydrogen source to produce the overall product can help reduce the molecular weight of the crude feed. Without wishing to be bound by theory, the catalyst in combination with the hydrogen source reduces the molecular weight of the component in the crude oil feed through the action of the catalyst's base (Lewis base or Bronsted-Lowry base) and / or superbase components. You can. Examples of catalysts that may have Lewis base and / or Bronsted-Lowry base properties include the catalysts described herein.

In some embodiments, the catalyst is a TMS catalyst. TMS catalysts include compounds containing sulfide transition metals. For the purpose of this application, the weight of sulfide transition metal in the TMS catalyst is determined by adding the total weight of transition metals to the total weight of sulfur in the catalyst. The atomic ratio of transition metal to sulfur is typically in the range of 0.2-20, 0.5-10, or 1-5. Examples of sulfide transition metals can be found in "Inorganic Sulfur Chemistry; G. Nickless; Elsevier Publishing Company; Amsterdam-London-New York; 1968 Publication; Chapter 19".

In some embodiments, the TMS catalyst may comprise at least 0.4 grams, 0.5 grams, 0.8 grams, or 0.99 grams total of one or more sulfided transition metals per gram of catalyst. In some embodiments, the TMS catalyst has a total content of one or more sulfided transition metals in the range of 0.4-0.999 grams, 0.5-0.9 grams, or 0.6-0.8 grams per gram of catalyst.

TMS catalysts comprise one or more sulfide transition metals. Examples of the transition metal sulfide is hwangcheol nickel (Fe ₄ Ni _{4 .5 .5 8} S), scan Mai tight _{(smythite) (Fe 6 .75 Ni} 2 .25 S 11), bra Voigt (bravoite) (Fe _{0. 7 Ni 0 .2 Co 0 .1 S} 2), every key White _{(mackinawite) (Fe 0 .75 Ni} 0 .25 S 0 .9), hwangcheol nickel is _{(AgFe 6 Ni 2 S 8)} , iso-nitro Cuba _{(isocubanite) (CuFe 2 S 3} ), iso nose knife light _{(isocalcopyrite) (Cu 8 Fe 9} S 16), sphalerite _{(Zn 0 .95 Fe 0 .05 S} ), a kite (mooihoekite) to Mui call (Cu ₉ Fe ₉ S ₁₆ ), chatkalite (Cu ₆ FeSn ₂ S ₈ ), sternbergite (AgFe ₂ S ₃ ), chalcopyrite (CuFeS ₂ ), trolly ore (FeS), pyrite (FeS ₂ ), pyrite (Fe _(1-x) S (x = 0 to 0.17)), hezlewoodite (Ni ₃ S ₂ ) or vaesite (NiS ₂ ).

In some embodiments, the TMS catalyst comprises a combination of an alkali metal, alkaline earth metal, zinc, zinc compound or mixture thereof with one or more sulfide transition metals. In some embodiments, the TMS catalyst is represented by the general formula A _c [M _a S _b ] _d (A is an alkali metal, alkaline earth metal or zinc; M is a transition metal of groups 6 to 10 of the periodic table; S is sulfur). The atomic ratio of a to b is in the range of 0.5 to 2.5, or 1 to 2. The atomic ratio of c to a is in the range of 0.0001 to 1, or 0.1 to 0.8, or 0.3 to 0.5. In some embodiments, the transition metal is iron.

In some embodiments, the TMS catalyst is generally known alkali metal and / or alkaline earth metal / sulfide transition metal (eg, bartonite (K ₃ Fe ₁₀ S ₁₄ ), rasbuumite (KFe) ₂ S _3), Fisher becomes light _{(djerfisherite) (K 6 NaFe 19} Cu 4 NiS 26 Cl), close-Barr Saturday Night _{(chlorobartonite) (K 6 .1 Fe} 24 Cu 0 .2 S 26 .1 Cl 0 .7) And / or coyoteite (NaFe ₃ S ₅ (H ₂ O) ₂ )). In some embodiments, the TMS catalyst comprises bartonite prepared in situ. Bartonite prepared in situ may be referred to as synthetic bartonite. Natural and / or synthetic bartonite can be used as the TMS catalyst in the methods described herein.

In some embodiments, the TMS catalyst may comprise up to 25 grams, 15 grams, or 1 gram of support material per 100 grams of TMS catalyst. Typically, the TMS catalyst has 0 to 25 grams, 0.00001 to 20 grams, and 0.0001 to 10 grams of support material per 100 grams of TMS catalyst. Examples of support materials that can be used with the TMS catalyst include refractory oxides, porous carbon materials, zeolites, or mixtures thereof. In some embodiments, the TMS catalyst is not actually limited by the support material.

TMS catalysts comprising alkali metals, alkaline earth metals, zinc, zinc compounds, or mixtures thereof include one or more sulfide transition metals, such as those determined using x-ray diffraction, alkali metal-sulfide transition metals of two metals, higher Valent sulfide transition metals, oxidation transition metals, or mixtures thereof. Alkali metal constituents, alkaline earth metal constituents, zinc constituents, and / or sulfide transition metal constituents of the TMS catalyst are in some embodiments an amorphous constituent that cannot be detected by x-ray rotation techniques. May exist.

In some embodiments, the mixture of crystalline particles of the TMS catalyst and / or crystalline particles of the TMS catalyst may have a particle size of at most 10 ⁸ mm ³ , 10 ³ mm ³ , 100 mm ³ , or 40 mm ³ . In normal circumstances, the crystal grain size of the TMS catalyst will generally be at least 10 mm 3.

TMS catalysts comprising alkali metals, alkaline earth metals, zinc, zinc compounds, or mixtures thereof include a sufficient amount of deionized water, a preferred amount of transition metal oxide and a preferred amount of Group 1 to 2 metal carbonate, 1 to 2 It can be prepared by mixing a hydroxide of a group metal, an acetate of a group 1-2 metal, zinc carbonate, zinc acetate, zinc hydroxide, or a mixture thereof to form a wet paste. The wet paste may be dried at a temperature of 100-300 ° C. or 150-250 ° C. to form an oxidation transition metal / mixture salt. The oxidation transition metal / mixture salt may be calcined at a temperature in the range of 300-1000 ° C., 500-800 ° C., or 600-700 ° C. to form the oxidation transition metal / mixture salt metal. Oxidation transition metal / mixture metal salts may be reacted with hydrogen to form reduced intermediate solids. The addition of hydrogen may be done at a flow rate sufficient to provide excess of hydrogen to the oxidation transition metal / mixed metal salt. Hydrogen may be added to the oxidation transition metal / mixture metal salt for 10-50 hours or 20-40 hours to produce reduced intermediate solids comprising transition metal elements. The addition of hydrogen can be carried out at a temperature of 35 to 500 ° C., 50 to 400 ° C., or 100 to 300 ° C., at a total pressure of 10 to 15 MPa, 11 to 14 MPa, or 12 to 13 MPa. Reduction time, reaction temperature, selection of reducing gas, pressure of reducing gas, and / or flow rates used to prepare the intermediate solids often vary with respect to the absolute mass of the oxidation transition metal selected. The reduced intermediate solids will in some embodiments flow into the 40-mesh sieve with minimal force.

The reduced intermediate solids can be added incrementally to a heated (eg, 100 ° C.) diluent / elemental sulfur, and / or a mixture of one or more sulfur compounds, a ratio to control the release of heat and the production of the gas. The diluent may include a suitable diluent that provides a means for dispersing heat of sulfide. The diluent may comprise a solvent having a boiling point distribution of at least 100 ° C, 150 ° C, 200 ° C, or 300 ° C. Diluents typically have a boiling point distribution between 100-500 ° C., 150-400 ° C., or 200-300 ° C. In some embodiments, the diluent is VGO and / or xylene. Sulfur compounds include, but are not limited to, hydrogen sulfide and / or thiols. The amount of sulfur and / or sulfur compounds is from 1 to 100 mol%, from 2 to 80 mol%, from 5 to 50 mol%, based on the moles of the Group 1 metal or zinc in the salts or zinc salts of Group 1 to 2 metals, It may be in the range of 10 to 30 mol%. After adding the reduced intermediate solids to the diluent / sulfur mixture element, the resulting mixture can be heated to a final temperature of 200 to 500 ° C, 250 to 450 ° C, or 300 to 400 ° C and at least 1 hour, 2 hours at the final temperature. Or 10 hours. Typically, the final temperature is maintained for 15 hours, 10 hours, 5 hours, or 1.5 hours. After heating to the increased sulfidation temperature, the diluent / catalyst mixture is cooled to a temperature in the range of 0-100 ° C., 30-90 ° C., or 50-80 ° C. to facilitate recovery of the catalyst from the mixture. The sulfided catalyst is separated from the diluent using standard techniques in an oxygen free atmosphere and washed with at least a portion of a low boiling solvent (eg pentane, heptane, or hexane) to produce a TMS catalyst. TMS catalyst can be milled using standard techniques.

In some embodiments, the catalyst is an inorganic salt catalyst. Anions of the inorganic salt catalyst may include inorganic compounds, organic compounds, or mixtures thereof. Inorganic salt catalysts include carbonate alkali metals, hydroxide alkali metals, hydride alkali metals, amide alkali metals, alkali metal sulfides, alkali metal acetates, alkali metal hydroxides, alkali metal formate, pyruvate alkali metals, carbonates Alkaline earth metals, hydroxy alkaline earth metals, hydride alkaline earth metals, amide alkaline earth metals, alkaline earth metal sulfides, acetate alkaline earth metals, hydrate alkaline earth metals, formate alkaline earth metals, pyruvate alkaline earth metals, or mixtures thereof.

Inorganic salt catalysts include NaOH / RbOH / CsOH; KOH / RbOH / CsOH; NaOH / KOH / RbOH; NaOH / KOH / CsOH; K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; Na ₂ O / K ₂ O / K ₂ CO ₃ ; NaHCO ₃ / KHNO ₃ / Rb ₂ CO ₃ ; LiHCO ₃ / KHCO ₃ / Rb ₂ CO ₃ ; KOH / RbOH / CsOH mixed with a mixture of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; K ₂ CO ₃ / CaCO ₃ ; K ₂ CO ₃ / MgCO ₃ ; Cs ₂ CO ₃ / CaCO ₃ ; Cs ₂ CO ₃ / CaO; Na ₂ CO ₃ / Ca (OH) ₂ ; KH / CsCO ₃ ; KOCHO / CaO; CsOCHO / CaCO ₃ ; CsOCHO / Ca (OCHO) ₂ ; NaNH ₂ / K ₂ CO ₃ / Rb ₂ O; K ₂ CO ₃ / CaCO ₃ / Rb ₂ CO ₃ ; K ₂ CO ₃ / CaCO ₃ / Cs ₂ CO ₃ ; K ₂ CO ₃ / MgCO ₃ / Rb ₂ CO ₃ ; K ₂ CO ₃ / MgCO ₃ / Cs ₂ CO ₃ ; Or Ca (OH) ₂ mixed with a mixture of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ .

In some embodiments, the inorganic salt catalyst contains at most 0.00001 grams, 0.001 grams, or 0.01 grams of lithium, calculated as the weight of lithium per gram of inorganic salt catalyst. In some embodiments, the inorganic salt catalyst has at least 0 grams but no more than 0.01 grams, ie, 0.0000001 to 0.001 grams, or 0.00001 to 0.0001 grams of lithium, calculated as the weight of lithium per gram of the inorganic salt catalyst.

In some embodiments, the inorganic salt catalyst comprises one or more alkali metal salts including alkali metals having an atomic number of at least 11. In some embodiments, the atomic ratio of the alkali metal having an atomic number of at least 11 to the alkali metal having an atomic number of at least 11 is 0.1 to 10, 0.2 to 6, or 0.3 to 4 when the inorganic salt catalyst has two or more alkali metals. Is in the range of. For example, the inorganic salt catalyst may include sodium, potassium, and rubidium, with the ratio of sodium to potassium in the range of 0.1-6; The ratio of sodium to rubidium is in the range of 0.1 to 6; The ratio of potassium to rubidium is in the range of 0.1-6. In another example, the inorganic salt catalyst includes sodium and potassium salts having an atomic ratio of sodium to potassium in the range of 0.1-4.

In some embodiments, the inorganic salt catalyst also includes metals and metal compounds of Groups 8-10 of the Periodic Table, metals and metal compounds of Group 6 of the Periodic Table, or mixtures thereof. Metals of Groups 8 to 10 include, but are not limited to, iron, ruthenium, cobalt, or nickel. Metals of Group 6 include, but are not limited to, chromium, molybdenum, or tungsten. In some embodiments, the inorganic salt catalyst comprises 0.1-0.5 grams, or 0.2-0.4 grams of raney nickel per gram of inorganic salt catalyst.

In some embodiments, the inorganic salt catalyst also includes metal oxides of groups 1-2 and / or 13 of the periodic table. Metals of Group 13 include but are not limited to boron or aluminum. Examples of metal oxides include lithium oxide (Li ₂ O), potassium oxide (K ₂ O), calcium oxide (CaO), or aluminum oxide (Al ₂ O ₃ ).

In some embodiments, the inorganic salt catalyst is actually a Lewis acid (eg, BCl ₃ , AlCl ₃ and SO ₃ ), Bronsted-Lowry acid (eg, H ₃ O ⁺ , H ₂ SO ₄ , HCl and HNO ₃ ), glass-forming constituents (eg borate and silicate) and halides. Inorganic salt catalysts per gram of inorganic salt catalyst: a) halides; b) a component that forms glass at a temperature of at least 350 ° C. and at most 1000 ° C .; c) Lewis acid; d) Bronsted-Louri acid; e) 0 to 0.1 grams, 0.000001 to 0.01 grams, or 0.00001 to 0.005 grams of mixtures thereof.

Inorganic salt catalysts can be prepared using standard techniques. For example, a preferred amount of each component of the catalyst can be combined using standard mixing techniques (eg milling and / or milling). In other embodiments, the inorganic component is dissolved in a solvent (eg, water or a suitable organic solvent) to form an inorganic component / solvent mixture. Solvents can be removed using standard separation techniques to prepare inorganic salt catalysts.

In some embodiments, the inorganic salts of the inorganic salt catalyst may be combined in the support to form supported inorganic salt catalysts. Examples of supports include, but are not limited to, zirconium oxide, calcium oxide, magnesium oxide, titanium oxide, hydrotalcite, alumina, germanium, iron oxide, nickel oxide, zinc oxide, cadmium oxide, antimony oxide, and mixtures thereof. Do not. In some embodiments, the inorganic salts, metals of groups 6-10 and / or metal compounds may be saturated at the support. Alternatively, the inorganic salts can be energized and thermally melted or softened on and / or in the support metal or supported metal oxide to form a supported inorganic salt catalyst.

Typically the structure of the inorganic salt catalyst is uneven, permeable and / or mobile at a defined temperature or temperature range when loss of order occurs in the catalyst structure. Inorganic salt catalysts can be disordered without substantial change in constituents (eg, without decomposition of salts). Without being bound by theory, inorganic salt catalysts become disordered (moved) when the distance between ions in the lattice of the inorganic salt catalyst increases. As the distance of ions increases, crude oil feed and / or hydrogen source may seep through the inorganic salt catalyst instead of along the surface of the inorganic salt catalyst. Penetration of the crude oil feed and / or hydrogen source through the inorganic salts is often increased in the contact area between the inorganic salt catalyst and the crude oil feed and / or the hydrogen source. Increases in the contacting zone and / or reaction zone of the inorganic salt catalyst often increase the yield of the crude oil product and limit the production of residues and / or coke and / or of the characteristics in the crude oil product for the same characteristics of the crude oil feed. Facilitate change The disorder (eg, heterogeneity, permeability, and / or mobility) of the inorganic salt catalyst is determined using the DSC method, ion conductivity measurement method, TAP method, visual observation method, x-ray diffraction method, or a combination thereof.

The use of TAPs to determine the properties of catalysts is described in US Pat. No. 4,626,412 filed by Avner et al .; US Patent No. 5,039,489 to Glebe et al .; And US Pat. No. 5,264,183, filed by Avner et al. The TAP system can be obtained from Mitsura Technology (Foley, Missouri, USA). TAP analysis is performed at 25 to 850 ° C., 50 to 500 ° C., or 60 to 400 ° C., 10 to 50 ° C., or 20 to 40 ° C. heat ratios, and from 1 × 10 ^{− 13} to 1 × 10 ⁻ It can be carried out in a vacuum in the range of ⁸ torr. The temperature is constant and / or increases as a function of time. When the temperature of the inorganic salt catalyst increases, gas evolution from the inorganic salt catalyst is measured. Examples of gases emitted from inorganic salt catalysts include carbon monoxide, carbon dioxide, hydrogen, water, or mixtures thereof. The temperature at which a change (rapid increase) in gas evolution from the inorganic salt catalyst is detected is considered the temperature at which the inorganic salt catalyst is disordered.

In some embodiments, the change in gas released from the inorganic salt catalyst can be sensed over a defined temperature range using TAP. The temperature or temperature range is referred to as the "TAP temperature". The initial temperature in the temperature range determined using the TAP is referred to as the "minimum TAP temperature".

The emission gas change exhibited by the inorganic salt catalyst suitable for contact with the crude oil feed is in the TAP temperature range of 100-600 ° C, 200-500 ° C, or 300-400 ° C. Typically, the TAP temperature is in the range of 300 to 500 ° C. In some embodiments, other components of suitable inorganic salt catalysts also exhibit gas changes at different TAP temperatures.

The amount of ion strain associated with the effluent gas can indicate particle ranking in the crystal structure. In highly ordered crystal structures, ionic particles are generally tightly bound and release of ions, molecules, gases, or a combination thereof from the structure requires more energy (ie, heat). In an ordered crystal structure, the ions do not bind to each other as strongly as the ions in the highly ordered crystal structure. Because of the low ionic bonds, generally less energy is required to release ions, molecules and / or gases from the disordered crystal structure and therefore the amount of ions and / or gases released from the disordered crystal structure is typically at a selected temperature. It is typically greater than the amount of ions and / or gases released from the highly ordered crystal structure.

In some embodiments, the heat of decomposition of the inorganic salt catalyst may be observed in the range of 50 ° C. to 500 ° C. at a heating rate or cooling rate of 10 ° C., as determined using differential scanning calorimetry. In the DSC method, the sample is heated to the first temperature, cooled to room temperature and heated again. The transition observed during the first heating is generally expressed in entrained water and / or solvent and not in the heat of decomposition. For example, heat or hydrated examples that are readily observed upon drying of moisture can generally occur below 250 ° C., typically between 100 and 150 ° C. The transition is observed during the cooling cycle and the second heating corresponds to the heat of decomposition of the sample.

"Thermal transition" refers to a process that occurs when ordered molecules and / or atoms in the structure are disordered when the temperature increases in the DSC analysis. "Cooling transition" refers to a process that occurs when molecules and / or atoms are more uniform in structure when the temperature decreases in DSC analysis. In some embodiments, the heating / cooling transition of the inorganic salt catalyst occurs at a temperature range sensed using DSC. The temperature or temperature range at which thermal transition of the inorganic salt catalyst occurs during the second heating cycle is referred to as "DSC temperature". The lowest DSC temperature during the second heating cycle is referred to as the "minimum DSC temperature". The inorganic salt catalyst can prevent heat transition in the range between 200 to 500 ° C, 250 to 450 ° C, or 300 to 400 ° C.

In inorganic salts containing inorganic salt particles, which are relatively homogeneous mixtures, the shape of the peaks combined with the heat absorbed during the second heating cycle can be relatively narrow. In inorganic salt catalysts containing inorganic salt particles in a relatively heterogeneous mixture, the shape of the peaks that combine with the heat absorbed during the second heating cycle can be relatively wide. The absence of peaks in the DSC spectrum indicates that the salt does not absorb or release in the scan temperature range. Lack of heat transfer generally indicates that the structure of the sample does not change upon heating.

When the homogeneity of the particles of the inorganic salt mixture increases, the ability of the mixture to remain solid and / or semi-liquid during heating decreases. Homogeneity of the inorganic mixture is related to the ionic radius of the cations in the mixture. In cations with smaller ionic radii, the cation's ability to share electron density with the corresponding anion increases and the acidity of the corresponding anion increases. In a series of similarly charged ions, if the anion is a strong base, the smaller the ion radius, the higher the attraction between the ions between the cation and the anion. The attraction between higher ions leads to higher heat transition temperatures for salts and / or mixtures of more homogeneous particles in the salts (rapid peaks and increasing regions under the DSC curve). Mixtures containing cations with small ionic radii tend to be more acidic than cations with larger ionic radii, so that the acidity of the inorganic salt mixture increases with decreasing ionic radii. For example, contacting a hydrogen source with a crude oil feed with an inorganic mixture comprising a lithium cation may be achieved by contacting the gas and / or coke for the contact of the hydrogen source with the crude oil feed in an inorganic salt catalyst comprising a cation having a larger ionic radius than lithium. There is a tendency to produce an increasing amount of. The ability to prevent the generation of gases and / or coke increases the overall liquid product yield of the process.

In some embodiments, the inorganic salt catalyst may comprise two or more inorganic salts. The minimum DSC temperature can be determined for each of the inorganic salts. The minimum DSC temperature of the inorganic salt catalyst may be below the minimum DSC temperature of at least one of the inorganic metal salts in the inorganic salt catalyst. For example, the inorganic salt catalyst may include potassium carbonate and cesium carbonate. Potassium carbonate and cesium carbonate exhibit DSC temperatures greater than 500 ° C. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalysts exhibit DSC temperatures ranging from 290 to 300 ° C.

In some embodiments, the TAP temperature may be between at least one DSC temperature of the inorganic salt and the DSC temperature of the inorganic salt catalyst. For example, the TAP temperature of the inorganic salt catalyst may be in the range of 350-500 ° C. The DSC temperature of the same inorganic salt catalyst may be in the range of 200-300 ° C., and the DSC temperature of each salt may be at least 500 ° C. or at most 1000 ° C.

Inorganic salt catalysts having a TAP and / or DSC temperature between 150-500 ° C., 200-450 ° C., or 300-400 ° C. and in many embodiments that do not decompose at such temperatures have high molecular weight and / or high viscosity components ( For example, crude oil feed) can be used to facilitate the conversion to a liquid product.

In some embodiments, the inorganic salt catalyst may exhibit increased conductivity for each inorganic salt during heating of the inorganic salt catalyst at a temperature in the range of 200-600 ° C., 300-500 ° C., or 350-450 ° C. The increased conductivity of the inorganic salt catalyst is generally that of particles of the movable inorganic salt catalyst. The ion conductivity of some inorganic salt catalysts varies at temperatures lower than the temperature at which the ionic conductivity of a single component of the inorganic salt catalyst changes.

The ion conductivity of the inorganic salt can be determined by applying Ohm's law (V = IR, V is voltage, I is current, R is resistance). In order to measure the ionic conductivity, the inorganic salt catalysts were separated from each other, but can be placed in two vessels (eg copper wire or platinum wire) and quartz vessel immersed in the inorganic salt catalyst.

7 is a schematic of a system that can be used to measure ion conductivity. The quartz vessel 156 containing the sample 158 can be placed in a heating device and gradually heated to a desired temperature. Voltage from the power supply 160 is applied to the wire 162 while heating. Current through wires 162 and 164 is measured at meter 166. Meter 166 may be, but is not limited to, a multimeter or a Wheatstone bridge. When the sample 158 becomes less homogeneous (more mobile) without decomposition, the resistivity of the sample should decrease and the observed current at the meter 166 should increase.

In some embodiments, at the desired temperature, the inorganic salt catalyst may have other ion conductivity after heating, cooling, and reheating. The difference in ion conductivity may indicate that the crystal structure of the inorganic salt catalyst changes from its original form (first form) to another form (second form) during heating. After heating, the ionic conductivity can be similar or identical if the type of inorganic salt catalyst does not change during heating.

In some embodiments, the inorganic salt catalyst has a particle size in the range of 10 to 1000 microns, 20 to 500 microns, or 50 to 100 microns, as determined by passing the inorganic salt catalyst through a mesh or sieve.

The inorganic salt catalyst may become soft when heated to temperatures above 50 ° C. and below 500 ° C. When the inorganic salt catalyst becomes soft, the liquid and catalyst particles can coexist in the matrix of the inorganic salt catalyst. In some embodiments, when the catalyst particles are heated to a temperature of at least 300 ° C., or at most 800 ° C., the inorganic salt catalyst converts from the first type to the second type under a pressure of at least 0.007 MPa, at most 0.101 MPa, or under gravity. To be self-deformed. When the inorganic salt catalyst is cooled to 20 ° C., the second type of inorganic salt catalyst cannot return to the first type of inorganic salt catalyst. The temperature at which the inorganic salt catalyst is converted from the first type to the second type is referred to as the "strain" temperature. The deformation temperature can be a temperature range or a single temperature. In some embodiments, the particles of the inorganic salt catalyst self-strain to a strain temperature below the strain temperature of each inorganic salt catalyst under gravity or pressure when heated. In some embodiments, the inorganic salt catalyst comprises two or more inorganic salts with different modification temperatures. In some embodiments, the modification temperature of the inorganic salt catalyst is different from the modification temperature of each inorganic metal salt.

In some embodiments, the inorganic salt catalyst is liquid and / or semi-liquid at or above TAP and / or DSC temperatures. In some embodiments, the inorganic salt catalyst is liquid or semi-liquid at the minimum TAP and / or DSC temperature. At or above the minimum TAP and / or DSC temperatures, the liquid or semi-liquid inorganic salt catalyst mixed with the crude oil feed may in some embodiments form a separation paste from the crude oil feed. In some embodiments, the liquid or semi-liquid inorganic salt catalyst has a low solubility in the crude oil feed (eg, 0 grams to 0.5 grams, 0.0000001 to 0.2 grams, or 0.0001 to 0 grams of inorganic salt catalyst per gram of crude oil feed). 0.1 gram), insoluble in crude oil feed at minimum TAP temperature (eg, 0 grams to 0.05 grams, 0.000001 grams to 0.01 grams, or 0.00001 to 0.001 grams of inorganic salt catalyst per gram of crude oil feed).

In some embodiments, powder x-ray diffraction is used to determine to separate atoms in the inorganic salt catalyst. The shape of the D ₀₀₁ peak in the x-ray spectrum can be monitored and the relative order of the inorganic salt particles can be measured. Peaks in x-ray diffraction represent other compounds of the inorganic salt catalyst. In powder x-ray diffraction, the D ₀₀₁ peak is monitored and the space between atoms is measured. In inorganic salt catalysts containing highly ordered inorganic salt atoms, the shape of D ₀₀₁ is relatively narrow. In inorganic salt catalysts (eg, K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalysts) containing optionally ordered inorganic salt atoms, the shape of the D ₀₀₁ peak is relatively broad or free of D ₀₀₁ peaks. Can be. To determine if the disorder of the inorganic salt atoms changes during heating, the x-ray diffraction spectrum of the inorganic salt catalyst can be done before heating and compared with the x-ray diffraction spectrum done after heating. The D ₀₀₁ peak (corresponding to inorganic salt atoms) in the x-ray diffraction spectrum done at a temperature above 50 ° C. may be absent or wider than the D ₀₀₁ peak in the x-ray diffraction spectrum done at a temperature below 50 ° C. In addition, the x-ray diffraction shape of each inorganic salt may exhibit a relatively narrow D ₀₀₁ peak at the same temperature.

Contact conditions may be varied for a given crude feed in addition to the overall product constituent (and thus crude product) limiting and / or preventing the formation of by-products. Total product components include, but are not limited to, paraffins, olefins, aromatics, or mixtures thereof. This compound makes up the components of crude oil products and non-condensable hydrocarbon gases.

By controlling the contact conditions in combination with the catalysts described herein, it is possible to produce the entire product lower than the predicted coke content. The comparison of the MCR content of the various crude oils can be ordered based on the tendency for the crude oil to form coke. For example, crude oil with an MCR content of 0.1 grams of MCR per gram of crude oil may produce more coke than crude oil with an MCR content of 0.001 grams of MCR per gram crude. Low quality crude oil typically has an MCR content of at least 0.05 grams of MCR per gram of poor quality crude oil.

In some embodiments, the residue content and / or coke content accumulated in the catalyst during the reaction period may be up to 0.1 grams, 0.05 grams, or 0.03 grams and / or coke of the residues per gram of catalyst. In some embodiments, the weight of residue and / or coke accumulated in the catalyst may be in the range of 0.0001 to 0.1 grams, 0.001 to 0.05 grams, or 0.01 to 0.03 grams. In some embodiments, the catalyst used may be substantially free of residue and / or coke. In some embodiments, the contact conditions are controlled such that up to 0.015 grams, 0.01 grams, 0.005 grams, or 0.003 grams of coke is formed per gram of crude oil product. The contact of the crude oil feed with the catalyst in controlled contacting conditions is reduced relative to the amount of coke and / or coke produced by heating the crude feed with or without a catalyst purified using the same contacting conditions and / or Or to produce a residue.

In some embodiments, the contact conditions are adjusted to convert at least 0.5 grams, 0.7 grams, 0.8 grams, or 0.9 grams of crude oil feed per gram of crude oil feed to crude oil product. Typically, 0.5 to 0.99 grams, 0.6 to 0.9 grams, or 0.7 to 0.8 grams of crude product per gram of crude oil feed is prepared during the contact. The conversion of the crude product with the minimum yield of residues and / or coke to the crude product results in the crude product being converted to industrial products with a minimum amount of pretreatment upon purification. In some embodiments, up to 0.2 grams, 0.1 grams, 0.05 grams, 0.03 grams, or 0.01 grams of crude oil feed per gram of crude oil feed is converted to non-condensable hydrocarbons. In some embodiments, 0 to 0.2 grams, 0.0001 to 0.1 grams, 0.001 to 0.05 grams, or 0.01 to 0.03 grams of non-condensable hydrocarbons are prepared per gram of crude oil feed.

Controlling the contact zone temperature, the flow rate of the crude oil feed, the flow rate of the overall product, the ratio and / or amount of the catalyst feed, or combinations thereof can be performed to maintain the desired reaction temperature. In some embodiments, temperature control at the contacting zone may be performed by varying the flow of hydrogen gas source and / or inert gas through the contacting zone to dilute the amount of hydrogen from the contacting zone and / or to remove excess heat. have.

In some embodiments, the temperature in the contact region can be adjusted to be at a preferred temperature "T ₁ ", above "T ₁ ", or below "T ₁ ". In some embodiments, the contact temperature is adjusted such that the contact zone temperature is below the minimum TAP temperature and / or the minimum DSC temperature. In some embodiments, T ₁ May be 30 ° C. or less, 20 ° C. or less, or 10 ° C. or less at the minimum TAP temperature and / or the minimum DSC temperature. For example, in one embodiment, the contact temperature can be adjusted to 370 ° C., 380 ° C., or 390 ° C. during the reaction period when the minimum TAP temperature and / or the minimum DSC temperature is 400 ° C.

In other embodiments, the contact temperature is adjusted such that the temperature is at or above the catalyst TAP temperature and / or the catalyst DSC temperature. For example, the contact temperature is adjusted to be 450 ° C., 500 ° C., or 550 ° C. during the reaction period such that the minimum TAP temperature and / or minimum DSC temperature is 450 ° C. Adjusting the contact temperature based on the catalyst TAP temperature and / or the catalyst DSC temperature can improve crude oil product properties. For example, such control can reduce coke formation, non-condensable gas formation, or a combination thereof.

In some embodiments, the inorganic salt catalyst may be adjusted prior to the addition of the crude oil feed. In some embodiments, the adjustment may occur in the crude oil feed. Adjusting the inorganic salt catalyst comprises heating the inorganic salt catalyst to a first temperature of at least 100 ° C, 300 ° C, 400 ° C, or 500 ° C and cooling to a second temperature of at most 250 ° C, 200 ° C, or 100 ° C. Include. In some embodiments, the inorganic salt catalyst is heated to a temperature in the range of 150-700 ° C., 200-600 ° C., or 300-500 ° C. and in the range of 25-240 ° C., 30-200 ° C., or 50-90 ° C. Cooled to the second temperature. The control temperature can be determined by establishing an ion conductivity measurement at another temperature. In some embodiments, the controlled temperature can be determined by heating and cooling the inorganic salt catalyst several times in the DSC, ie, the DSC temperature obtained from the heating / cooling transition. Control of the inorganic salt catalyst allows the contact of the crude oil feed to be carried out at reaction temperatures lower than the temperatures at which conventional hydrotreating catalysts are used.

In some embodiments, the content of naphtha, diluent, VGO, or mixtures thereof in the total product can be varied by varying the overall product removal rate from the contacting zone. For example, the rate of reduction of total product removal tends to increase the contact time of the crude oil feed with the catalyst. Alternatively, increasing pressure relative to the initial pressure can increase the contact time, increase the generation of crude oil product, and increase hydrogen bonding from gas to crude product at the mass flow rate of a given crude oil or hydrogen source. Can be. Increasing the contact time of the crude oil feed with the catalyst can increase the amount of diesel, kerosine, or naphtha, and the amount of VGO relative to the amount of diesel, kerosine, naphtha and VGO produced in a shorter contact time. Can be reduced. Increasing the contact time of the entire product in the contacting zone can also change the average carbon number of the crude product. Increased contact time can lead to higher weight ratios of lower carbon numbers (thus higher API specific gravity).

In some embodiments, the contact conditions can change over time. For example, the contact pressure and / or contact temperature can be increased to increase the amount of hydrogen that the crude feed receives to produce the crude product. While improving other properties of the crude oil feed, the ability to vary the hydrogen uptake of the crude oil feed can increase the form of crude product that can be prepared from a single crude feed. The ability to produce multiple crude oil products from a single crude oil feed can allow different conveying and / or processing specifications to be satisfied.

The uptake of hydrogen can be estimated by comparing the H / C of the crude feed with the H / C of the crude product. The increase in H / C of the crude oil product relative to the H / C of the crude oil feed indicates the binding of hydrogen from the hydrogen source to the crude oil product. The relatively low increase in H / C of the crude oil product (20% compared to the crude feed) indicates a relatively low consumption of hydrogen gas during the process. Significant improvements in crude product properties are needed for crude oil feeds obtained with minimal consumption of hydrogen.

The ratio of hydrogen source to crude oil feed can be varied to alter the properties of the crude oil product. For example, increasing the ratio of hydrogen source to crude oil feed can result in crude oil products with increased VGO content per gram of crude oil product.

In some embodiments, the contact of the crude salt feed with the inorganic salt catalyst in light hydrocarbons and / or steam is more liquid hydrocarbon and less coke in the crude oil product than the contact of the inorganic salt catalyst with the crude feed in hydrogen and steam. Generates. In embodiments involving the contact of the crude salt feed with methane of the inorganic salt catalyst, at least a portion of the components of the crude oil product may include carbon atoms and hydrogen (from methane) bonded to the molecular structure of the components.

In some embodiments, the volume of crude product produced from the crude oil feed in contact with the hydrogen source in the inorganic salt catalyst is at least 5%, 10%, or 15%, or 100 greater than the volume of crude product produced from the thermal process in STP. % Bigger The total volume of crude oil product produced by contacting the inorganic salt catalyst with the crude oil feed may be 110 vol% of the volume of the crude oil feed in the STP. The increase in volume is due to the decrease in density. The lower density may be at least partly due to the hydrogen evolution of the crude oil feed.

In some embodiments, a crude oil feed having at least 0.02 grams, 0.05 grams, 0.1 grams of sulfur and / or at least 0.001 grams of Ni / V / Fe per gram of crude oil feed is a hydrogen source in the inorganic salt catalyst without reducing the activity of the catalyst. Contact with

In some embodiments, the inorganic salt catalyst can be at least partially regenerated by removing one or more constituents that contaminate the catalyst. Contaminants include, but are not limited to, metals, sulfur, nitrogen, coke, or mixtures thereof. Sulfur contaminants can be removed from the used inorganic salts by contacting steam and carbon dioxide with the catalyst used to produce hydrogen sulfide. Nitrogen contaminants can be removed by contacting steam with the inorganic salt catalyst used to produce ammonia. Coke contaminants can be removed from the inorganic salt catalyst used by contacting the inorganic salt catalyst used with steam and / or methane to produce hydrogen and carbon oxides. In some embodiments, one or more gases are generated from the mixture of inorganic salt catalyst and residual crude oil feed used.

In some embodiments, inorganic salts used (eg, K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; KOH / Al ₂ O ₃ ; Cs ₂ CO ₃ / CaCO ₃ ; or NaOH / KOH / LiOH / ZrO ₂ ), unreacted crude oil feeds and / or mixtures of residues and / or coke to produce gas and / or liquids in steam, hydrogen, carbon dioxide and / or light hydrocarbons to produce a liquid state and / or gas Heat to a temperature range of 700 to 1000 ° C or 800 to 900 ° C until the minimum is The gas may comprise increasing amounts of hydrogen and / or carbon dioxide relative to the reactant gas. For example, the gas may comprise 0.1 to 99 moles or 0.2 to 8 moles of hydrogen and / or carbon dioxide per mole of reaction gas. The gas may contain relatively small amounts of light hydrocarbons and / or carbon monoxide. For example, it may contain up to 0.05 grams of light hydrocarbons per gram of gas and up to 0.01 grams of carbon monoxide per gram of gas. For example, the liquid phase may contain 0.5-0.99 grams, or 0.9 grams or more water per gram of liquid.

In some embodiments, the catalyst and / or solids used in the contacting zone can be treated to recover metals (eg vanadium and / or nickel) from the catalysts and / or solids used. The catalysts and / or solids used may be treated using generally known metal separation techniques (eg, heating, chemical treatment, and / or gasification).

Yes

Nonlimiting examples of catalyst preparation, testing of catalysts, and systems under controlled contact conditions will be described below.

Example 1.K- Fe  Preparation of Sulfide Catalyst

K-Fe sulfide catalysts are prepared by combining 1000 grams of iron oxide (Fe ₂ O ₃ ) and 580 grams of potassium carbide with 412 grams of deionized water to form a wet paste. The wet paste is dried at 200 ° C. to form an iron oxide / potassium carbide mixture. The iron oxide / potassium carbide mixture is calcined at 500 ° C. to form an iron oxide / potassium carbide mixture. The iron oxide / potassium carbide mixture is reacted with hydrogen to form the reduced intermediate solids contained in the iron oxide. The addition of hydrogen is carried out at 450 ° C., 11.5-12.2 MPa (1665-1765 psi) for 48 hours. The intermediate solids pass through the 40-mesh with minimal force.

The intermediate solids are added to the flow rate for controlling the release of heat and production gas at 100 ° C. with the VGO / m-xylene / sulfur element mixture. After addition of the intermediate solid, the resulting mixture is heated to 300 ° C. and held at 300 ° C. for 1 hour. The solvent / catalyst mixture is cooled down to 100 ° C. and the sulfidation catalyst is separated from the mixture. The sulfided catalyst is separated by filtration in a dry box under argon atmosphere and washed with m-xylene to produce 544.7 grams of sulfided K-Fe catalyst. The sulfided K-Fe catalyst is ground by passing the catalyst through a 40-mesh body.

The resulting sulfided K-Fe catalyst is analyzed using x-ray diffraction techniques. From the analysis of the x-ray diffraction spectrum, the catalyst is defined to include iron sulfide (FeS), sulfide K-Fe (KFeS ₂ ), pyrrhotite and iron oxide (eg magnetite, Fe ₃ O ₄ ). Peaks combined with disulfide iron (eg pyrite, FeS ₂ ) are not observed in the x-ray diffraction spectrum.

Example 2. K- Fe  Crude oil from sulfiding catalyst Supplies and  Contact of hydrogen source

A continuously stirred 600 mL reaction tank (made of 316 stainless steel) is fitted with a rushton turbine with a football inlet with a bottom inlet supply, a single steam outlet, a thermocouple located inside the reactor, and six blades of 1.25 inch diameter. It is installed.

A sulfided K-Fe catalyst (110.3 grams) prepared as described in Example 1 was injected into the reactor. Hydrogen gas, measured at 8,000 Nm3 / m3 (50,000 SCFB), is mixed in the reactor with bitumen (Lloydminister region, Canada). Bitumen is injected into the reactor through the bottom inlet feed to form a hydrogen / crude feed mixture. For the duration of the reaction of 185 hours, hydrogen gas and crude feed are continuously injected into the reactor and the product is removed through the steam outlet of the reactor. Crude feed is injected at a rate of 67.0 g / hr to maintain the crude feed liquid level at 60% of the reactor volume. A 50 milli-Curi ¹³⁷ cesium gamma ray source and a sodium iodide scintillation detector were used to measure the liquid level in the reactor.

The hydrogen gas / crude oil feed is contacted with the catalyst at an average internal reactor temperature of 430 ° C. Contacting the hydrogen / crude feed with the catalyst produces the entire product in the form of reactor effluent vapors. The reactor effluent vapor leaves the vessel through a single top outlet. The reactor head is electrically heated to 430 ° C. to prevent internal condensation of the reactor effluent vapor in the reactor head.

After exiting the reactor, the steam exiting the reactor is cooled and separated to produce a liquid stream and a gas stream in the high pressure gas / liquid separator and the low pressure gas / liquid separator. The gas stream is sent to a countercurrent caustic scrubber to remove acid gases and then quantified using standard chromatography techniques. The total product comprises 0.918 grams of crude oil product, 0.089 grams of non-condensable hydrocarbon gas, per gram of total product. In the reactor, 0.027 grams of solids are left per gram of crude oil feed. The properties and components of the crude oil products and the non-condensable hydrocarbon gases produced by this process are summarized in Table 1 in FIG. 8, Table 2 in FIG. 9 and Table 3 in FIG. 10.

This example illustrates a method of contacting a crude oil feed with hydrogen in a sulfided transition metal catalyst to produce the entire product with minimal coke mate production. The total product was a crude mixture with a liquid mixture in STP and having up to 0.1 grams of non-condensable hydrocarbon gas per gram of total product.

By comparing the MCR content (13.7 wt%) of the crude feed in Table 1 (2.7 wt%) formed during the process, a combination of controlled conditions and catalyst produces less coke than the one indicated by ASTM specification D4530. .

Non-condensable hydrocarbons are C ₂ , C ₃ And C ₄ hydrocarbons. From the sum of the weight percentages of C ₂ hydrocarbons (20.5 grams) summarized in Table 2, the ethylene content per gram of total C ₂ hydrocarbons can be calculated. The C ₂ hydrocarbons in the hydrocarbon gas contained 0.073 grams of ethylene per gram of total C ₂ hydrocarbons. From the sum of the weight ratios of C ₃ hydrocarbons (23.9 grams) in Table 2, the propene content per gram of total C ₃ hydrocarbons can be calculated. The C ₃ hydrocarbons in the non-condensable hydrocarbon gas contained 0.21 grams of propene per gram of total C ₃ hydrocarbons. C _{4 in} non-condensable hydrocarbon gases The hydrocarbon has iso-butane having a weight ratio of 0.2 to n-butane.

This example shows a minimum of 0.001 grams of hydrocarbons with a boiling point distribution of up to 204 ° C (400 ° F) at 0.101 MPa, at least 0.001 grams of hydrocarbons with a boiling point distribution between 204 ° C and 300 ° C at 0.101 MPa, and 300 ° C at 0.101 MPa. A method for producing crude oil products comprising a minimum 0.001 gram of hydrocarbon with a boiling point distribution between and 400 ° C. and a minimum 0.001 gram of a hydrocarbon with a boiling point distribution between 400 ° C. and 538 ° C. (1,000 ° F) at 0.101 MPa. do. Hydrocarbons having a boiling point distribution below 204 ° C. include n-paraffins and iso-paraffins with a maximum ratio of iso-paraffins to n-paraffins of 1.4.

Crude oil products included boiling point distributions combined with naphtha, kerosine, diesel and VGO. The crude oil product has at least 0.001 grams of naphtha and the naphtha portion of the crude product has at least 70 octane numbers. The naphtha portion of the crude product has a benzene content of up to 0.01 grams per gram of naphtha. The naphtha portion of the crude oil product has a maximum of 0.15 grams of olefins per gram of naphtha. The naphtha portion of the crude product has up to 0.1 grams of monocyclic ring aromatics per gram of naphtha.

Crude oil products have a minimum of 0.001 grams of kerosine. The kerosene portion of the crude product has a freezing point of -30 ° C or lower. The kerosene portion of the crude oil product comprises aromatics and the kerosine portion of the crude oil product has an aromatic content of at least 0.3 grams per gram of kerosene. The kerosene portion of the crude oil product has at least 0.2 grams of monocyclic ring aromatics per gram of kerosene.

Crude oil products have a minimum of 0.001 grams of diesel. The diesel portion of the crude oil product contains aromatics, and the diesel portion of the crude oil product has an aromatic content of at least 0.4 grams per gram of diesel.

Crude oil products have at least 0.001 grams of VGO. The VGO portion of the crude oil product contains aromatics and the VGO has an aromatic content of at least 0.5 grams per gram of VGO.

Example 3. Hydrocarbons In diluent  Sulfide K- Fe  Preparation of the catalyst

K-Fe sulfide catalysts are prepared by combining a wet paste with 1000 grams of iron oxide and 173 grams of potassium carbide with 423 grams of deionized water. The wet paste is treated to form intermediate solids as described in Example 1. The intermediate solids pass through the 40-mesh with minimal force.

In contrast to Example 2, the intermediate solids are mixed with elemental sulfur without hydrocarbon diluent. In a dry box using an argon atmosphere, the intermediate solids are combined with elemental sulfur powder and placed in a sealed carbon steel cylinder, heated to 400 ° C. and held at 400 ° C. for 1 hour. The sulfided catalyst is recovered from the carbon steel reactor as a solid. The potassium sulfide-iron catalyst is ground into powder using mortar and pestle to allow the catalyst powder to pass through the 40-mesh body.

Potassium sulfide catalysts are analyzed using x-ray diffraction techniques. In the analysis of the x-ray diffraction spectrum, the catalyst is defined to include pyrite (FeS ₂ ), iron sulfide (FeS) and magnetite (Fe _{1 - x} S). Mixed potassium iron sulfide and iron oxide species are not detected using x-ray diffraction techniques.

Example 4. Crude Oil On feed  For hydrogen gas Increased  Sulfide K- in proportions Fe  Hydrogen source and crude oil in catalyst Feed  contact

The apparatus, crude oil feed and reaction sequence are the same as in Example 2 except that the ratio of hydrogen gas to crude feed is 16,000 Nm 3 / m 3 (100,000 SCFB). A sulfided K-Fe catalyst (75.0 grams) prepared as described in Example 3 is injected into the reactor.

The properties of crude oil products prepared in this way are summarized in Table 1 of FIG. 8 and Table 3 of FIG. 10. The weight percentage of the VGO prepared in Example 4 is greater than the weight percentage of the VGO prepared in Example 2. The weight percentage of the diluent prepared in Example 4 is less than the weight percentage of the diluent prepared in Example 2. The API specific gravity of the crude oil product prepared in Example 4 is lower than the API specific gravity of the crude oil product prepared in Example 2. High API specific gravity indicates that hydrocarbons with higher carbon numbers are produced.

After contact with the crude oil feed, the TMS catalyst in the reactor is analyzed. In this analysis, after being in the crude oil feed and hydrogen, the sulfided transition metal catalyst comprises K ₃ Fe ₁₀ S ₁₄ .

Example 5. K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Of catalyst and each inorganic salt TAP  exam

In all TAP tests, 300 mg samples are heated at a rate of 50 ° C. per minute from room temperature (27 ° C.) to 500 ° C. Emitted water vapor and carbon dioxide gas are monitored using a mass spectrometer in the TAP system.

Aluminum-supported K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalysts have a current inflection greater than 0.2 volt for emitted carbon dioxide and 0.01 for carbon dioxide emitted from an inorganic salt catalyst at 360 ° C. Shows the current inflation of the volts. The minimum TAP temperature is 360 ° C. as defined by the log 10 function of ion flow over temperature. 11 is K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ versus temperature (“T”). It is a graphical representation of log 10 of the ion flow of gas exiting the catalyst (“log (I)”). Curves 168 and 170 are log 10 values of ion flow for water and CO ₂ withdrawn from the inorganic salt catalyst. Rapid inflection for CO ₂ and water discharged from the inorganic salt catalyst occurs at 360 ° C.

K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ In contrast to catalysts, potassium carbide and cesium carbide have current influx that is not detectable at 360 ° C. for both discharged water and carbon dioxide.

The actual increase in the emitted gas for the K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst may result in an inorganic salt catalyst consisting of two or more different inorganic salt catalysts more disordered than each pure carbonate.

Example 6. Inorganic Salt Catalysts and Their Inorganic Salts DSC  exam

In all DSC tests, 10 mg samples were heated to 520 ° C. at a rate of 10 ° C. per minute using DSC-7, a Differential Scanning Calorimer model manufactured by Perkin-Elmer (Norwalk, Connecticut, USA). It is cooled from 520 ° C. to 0.0 ° C. at a rate of 10 ° C. per minute and reheated from 0 ° C. to 600 ° C. at a rate of 10.0 ° C. per minute.

DSC analysis of the K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst during the second heating period of the sample showed that the mixture salt exhibited a wide thermal transition between 219 ° C. and 260 ° C. The midpoint of the temperature range is 250 ° C. The area under the heat transfer curve is calculated to be -1.75 J per gram. The onset of crystal disorder is determined to begin at a minimum DSC temperature of 219 ° C.

In contrast to this result, no constant thermal transition is observed for cesium carbide.

DSC analysis of the mixture of Li ₂ CO ₃ , Na ₂ CO ₃ , and K ₂ CO ₃ during the second heating cycle showed that the Li ₂ CO ₃ / Na ₂ CO ₃ / K ₂ CO ₃ mixture was abruptly between 390 ° C. and 400 ° C. Heat transition. The midpoint of the temperature range is 385 ° C. The area under the heat transfer curve is calculated to be -182 J per gram. The onset of mobility is determined to begin at the minimum DSC temperature of 390 ° C. Rapid thermal transitions indicate a substantially homogeneous mixture of salts.

Example 7. Inorganic Salt Catalyst or of Each Inorganic Salt K ₂ CO ₃  Ionic Conductivity Test

All tests are performed by placing the inorganic salt catalyst or 3.81 cm (1.5 inches) of each inorganic salt in a quartz vessel with platinum or copper wires separated from each other but immersed in the sample in a muffle furnace. The wire is connected to a 9.55 volt battery and a 220,000 ohm current limiting resistor. The muffle furnace is heated to 600 ° C so that the current is measured using a microammeter.

12 is a graphical representation of the logarithmic function of sample resistance relative to potassium carbonate resistance (“log (r K ₂ CO ₃ )”) over temperature (“T”). Curves 172, 174, 176, 178, 180 are K ₂ CO ₃ Resistance, CaO resistance, K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst resistance, Li ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst resistance and Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ is the logarithmic function of each catalyst resistance.

CaO (curve 174) shows a relatively large and stable resistance to K ₂ CO ₃ (curve 172) at temperatures between 380 and 500 ° C. Stable resistance represents an ordered structure and / or ions that tend not to fall from each other during heating. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst, Li ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst and Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO _{The 3} / Cs ₂ CO ₃ catalyst (shown in curves 176, 178 and 180) has a K ₂ CO ₃ at a temperature in the range 350 to 500 ° C. The resistivity decreases rapidly with respect to. The decrease in resistivity indicates that current flow is sensed while applying voltage to the wires embedded in the inorganic salt catalyst. The data from FIG. 12 shows that the mobility is better than that of pure inorganic salts at temperatures in the range of 350-600 ° C.

FIG. 13 shows Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ relative to K ₂ CO ₃ resistance (“log (r K ₂ CO ₃ )”) over temperature (“T”). It is a graphical representation of the logarithmic function of catalyst resistance. Curve 182 is Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ for the heating temperature for the CO ₃ Catalyst K ₂ CO ₃ resistors relative Na ₂ CO a (curve _{172) 3 / K 2 CO 3} / Rb ₂ CO ₃ / Cs ₂ CO ₃ is a function of the ratio of catalyst resistance. After heating, the Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst is cooled to room temperature and heated in the conducting device. Curve 184 shows Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst resistance relative to K ₂ CO ₃ resistance to temperature during heating of the inorganic salt catalyst after cooling from 600 ° C. to 25 ° C. Log function. The ion conductivity of the reheated Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst is based on the ion conductivity of the original Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst. Increases relative to

From the difference in the ion conductivity of the inorganic salt catalyst during the first heating and the second heating, the inorganic salt catalyst can form a form upon cooling (second form) that is different from the form before the heating (first form).

Example 8. Flow Characteristic Test of Inorganic Salt Catalyst

A 1-2 cm thick layer of powdered K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst is placed in a quartz dish. The dish is placed in a furnace and heated to 500 ° C. for 1 hour. To determine the flow characteristics of the catalyst, the dish is tilted manually in the oven after heating. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO _{3 The} catalyst does not flow. When pressurized with a spatula, the catalyst has a concentration of tapestry.

In contrast, each carbonate becomes a free flowing powder under the same conditions.

The Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst becomes liquid and readily flows into the dish under the same conditions (eg, similar to water).

Example 9-10: K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Hydrogen source and crude oil in catalyst and steam Feed  contact

The following apparatus and general procedure are used in Examples 9-27 except where the variable is described.

Reactor : A mechanical stirrer in a 250 ml Hastelloy C Parr Autoclave (Parr Model # 4576) at 35 MPa operating pressure (5000 psi) at 500 ° C., capable of maintaining the autoclave in ± 5 ° C. from ambient to 625 ° C. An 800 watt Gaumer band heater, gas inlet, steam inlet, outlet, and thermocouple for registering the internal temperature are installed at the Eurosum controller. Prior to heating, the top of the autoclave is insulated with a glass cloth.

Additional vessel : Flow of heated, viscous and / or pressurized crude oil feed in an additional vessel (250 ml, 316 stainless steel hawk vessel) with a controlled heating system, appropriate gas control valve, pressure relief device, thermocouple, pressure gauge It is equipped with a high temperature control valve (Swajilock Valve # SS-4UW) that can adjust the flow rate from 0 to 500g / min. After the crude oil feed is injected into the further vessel, the outside of the high temperature control valve is attached to the first inlet of the reactor. Prior to use, additional container lines are insulated.

Product Collection : Vapor from the reactor is introduced into a series of cooling traps (dip tubes connected to a series of 150 ml, 316 stainless steel hawk vessels) that exit the reactor and reduce the temperature. The liquid from the vapor is condensed in the cold trap to form a gas stream and a liquid condensation stream. The flow rate of the steam flowing out of the reactor and through the cold trap is adjusted using a back pressure regulator as necessary. The flow rate of the gas stream leaving the cold trap and the total gas volume are measured using a wet test meter (liter model #TG 05 wet test meter). After leaving the wet test meter, the gas flow is collected in a gas bag (Tetla gas collection bag) for analysis. The gas is analyzed using GC / MS (Hewlett-Packard Model 5890, currently Agilent Model 5890; manufactured by Agilent Technologies, Inc. (Zion Illinois, USA)). The liquid condensate stream is removed from the cold trap and weighed. Crude oil product and water are separated from the liquid condensate stream. Crude oil products are weighed and analyzed.

Order : longitudinal nigro (137.5 grams) is added to the additional container. Crude feed has an API share of 6.7. The crude feed has a sulfur content of 0.042 grams per gram of crude oil feed, a nitrogen content of 0.011 grams and a total Ni / V content of 0.009 grams. The crude oil feed is heated to 150 ° C. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst (31.39 grams) is injected into the reactor.

A K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst is prepared by combining 16.44 grams of K ₂ CO ₃ , 19.44 grams of Rb ₂ CO ₃ , and 24.49 grams of Cs ₂ CO ₃ . K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst has a minimum TAP temperature of 360 ° C. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst has a DSC temperature of 250 ° C. Each salt (K ₂ CO ₃ , Rb ₂ CO ₃ , Cs ₂ CO ₃ ) does not exhibit a DSC temperature in the range of 50-500 ° C. This TAP temperature is below the DSC temperature of each carbonate metal and above the DSC temperature of an inorganic salt catalyst.

The catalyst is heated rapidly to 450 ° C. in an atmospheric flow of methane of 250 cm 3 / min. After reaching the desired reaction temperature, methane is measured in the reactor with steam at a rate of 0.4 ml / min, at a rate of 250 cm 3 / min. Steam and methane are continuously measured for more than 2.6 hours while adding crude feed to the reactor. The crude feed is pressurized in the reactor using CH ₄ at 1.5 MPa (229 psi) for 16 minutes. After addition of the crude feed is made, the remaining crude feed (0.56 grams) is left in the additional vessel. A decrease in temperature to 370 ° C. is observed during addition of the crude oil feed.

The catalyst / crude feed mixture is heated to a reaction temperature of 450 ° C. and maintained at that temperature for 2 hours. After 2 hours, the reactor is cooled and weighed to determine the percentage of coke in which the resulting residue / catalyst mixture is not produced and / or consumed in the reaction.

From the difference in initial catalyst weight and coke / catalyst mixture weight, 0.046 grams of coke is left in the reactor per gram of crude oil feed. The total product contains 0.87 grams of crude oil product and gas with an API specific gravity of 13 on average. The gas comprises unreacted CH ₄ , hydrogen, C ₂ and C ₄ to C ₆ hydrocarbons and CO ₂ (0.08 grams of CO ₂ per gram of gas).

The crude product has 0.01 grams of sulfur per gram of crude oil product and 0.000005 grams of total Ni and V. Crude oil products are no longer analyzed.

In Example 10, the reaction procedure, conditions, crude oil feed and catalyst are the same as in Example 9. The crude product of Example 10 is determined to determine the boiling point distribution for the crude product. The crude product has 0.14 grams of naphtha, 0.19 grams of diluent, 0.45 grams of VGO and 0.001 grams of residue content and an undetectable amount of coke per gram of crude oil product.

Examples 9 and 10 contact a crude oil feed with a hydrogen source with up to 3 grams of catalyst per 100 grams of crude oil feed to produce the entire product comprising the crude product, which is a liquid mixture in STP. The crude product has a residue content of up to 30% of the residue content of the crude oil feed. Crude oil products have up to 90% of the sulfur and Ni / V contents of the crude feed.

Crude oil products contain a minimum of 0.001 grams of hydrocarbons with a boiling point distribution of up to 200 ° C. at 0.101 MPa, a minimum of 0.001 grams of hydrocarbons with a boiling point distribution between 200 and 300 ° C. at 0.101 MPa, and a maximum of 400 to 538 ° C. (1000 ° F.) at 0.101 MPa. It contains at least 0.001 grams of hydrocarbons with a boiling point distribution between).

Example 11-12. K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Contact of crude oil feed with hydrogen source in catalyst and steam

In Examples 11 and 12, the reaction sequence, conditions and K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst consisted of 130 grams of crude oil feed (vertical nigro) and K ₂ CO ₃ / Rb ₂ CO ₃ / Cs _{As in} Example 9, except that 60 grams of ₂ CO ₃ catalyst is used. In Example 11, methane is used as the hydrogen source. In Example 12, hydrogen gas is used as the hydrogen source. A graph of the amount of non-condensable gas, crude product and coke is shown in FIG. 14. Based on the weight of the crude oil feed, bars 186 and 188 represent wt% of the coke prepared, bars 190 and 192 represent wt% of the prepared liquid hydrocarbons, and bars 194 and 196 represent wt% of the produced gas. .

In Example 11, 93 wt% of crude oil product (rod 192), 3 wt% of gas (rod 196), and 4 wt% of coke (rod 188) are prepared based on the weight of Cerro Nigro.

In Example 12, 84 wt% of crude oil product (rod 190), 7 wt% of gas (rod 194), 9 wt% of coke (rod 186), and the like are prepared based on the weight of Cerro Nigro.

Examples 11 and 12 provide a comparison of the use of methane as a hydrogen source and the use of hydrogen gas as a hydrogen source. In general, methane is less expensive than hydrogen in production and / or return, and therefore a process using methane is preferred. As described, methane is at least as efficient as hydrogen gas as the hydrogen source when contacted with the crude oil feed in the inorganic salt catalyst to produce the entire product.

Example 13-14: Selected API  Preparation of Crude Oil Products with Specific Gravity

The apparatus, reaction procedure and inorganic salt catalyst are as in Example 9 except that the reaction pressure is changed.

In Example 13, the reaction pressure was 0.1 MPa (14.7 psi) during the contact period. Crude oil products with an API specific gravity of 25 at 15.5 ° C. are prepared. The total product has hydrocarbons with a distribution of carbon numbers from 5 to 32 (curve 198 in FIG. 15).

In Example 14, the reaction pressure was 3.4 MPa (514.7 psi) during the contact period. A crude oil product with an API specific gravity of 51.6 at 15.5 ° C. is prepared. The entire product has a hydrocarbon with a distribution of carbon numbers ranging from 5 to 15 (curve 200 in FIG. 15).

These examples illustrate a method of contacting a crude oil source with hydrogen at an inorganic salt catalyst at various pressures to produce a crude oil product having a selected API specific gravity. By varying the pressure, crude oil products with higher or lower API specific gravity are produced.

Examples 15-16: without external hydrogen source K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Crude Oil From Catalytic Or Silicon Carbide Feed  contact

In Examples 15 and 16, the apparatus, crude oil feed and reaction procedure are the same as Example 9 except that the crude oil feed and the catalyst (or silicon carbide) are injected directly into the reactor at the same time. Carbon dioxide (CO ₂ ) is used as the carrier gas. In Example 15, 138 grams of Cerro Nigro are combined with 60.4 grams of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst (the same catalyst as Example 9). In Example 16, 132 grams of longitudinal nigro are combined with 83.13 grams of silicon carbide (CA, Aliso Viezo, Stanford material, 40 mesh). Such silicon carbide will have low catalytic properties under the process described herein.

In each example, the mixture is heated to a reaction temperature of 500 ° C. for at least 2 hours. CO ₂ is measured in the reactor at a rate of 100 cm 3 / min. Steam from the reactor is collected in the cold trap and gas bag using a back pressure of 3.2 MPa (479.7 psi). The crude oil product solidifies from the cold trap and is analyzed.

In Example 15, 36.82 grams of a colorless hydrocarbon liquid (26.68 wt% based on the weight of the crude product) with a specific gravity of API of at least 50 are prepared from contacting the inorganic salt catalyst with the crude oil feed in a carbon dioxide atmosphere.

In Example 16, 15.78 grams (11.95 wt% based on the weight of crude oil feed) of a yellow hydrocarbon liquid with an API specific gravity of 12 are prepared from contacting the crude oil feed with silicon carbide in a carbon dioxide atmosphere.

Although the yield is low in Example 15, the occurrence at the site location of the hydrogen source for inorganic salt catalysts is greater than the onsite generation of hydrogen at noncatalytic conditions. The yield of crude oil product in Example 16 is half the yield of crude oil product in Example 15. Example 15 also occurs during the contact of the crude oil feed with hydrogen in the inorganic salts and no gaseous hydrogen source.

Example 17-20: under atmospheric pressure K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Crude oil in bathrobes with catalyst, calcium oxide and silicon carbide Supplies and  Contact of hydrogen source

The apparatus, reaction procedure, crude oil feed and inorganic salt catalyst are the same as in Example 9 except that vertical nigro is added directly to the reactor and hydrogen gas is used as the hydrogen source instead of being added via an additional vessel. The reaction pressure is 0.101 MPa (14.7 psi) during the contact period. Hydrogen gas flow is 250 cm 3 / min. The reaction temperatures, steam flow rates and ratios of the crude oil product, gas and coke are tabulated in Table 4 of FIG.

In Examples 17 and 18, K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalysts are used. In Example 17, the contact temperature is 375 ° C. In Example 18, the contact temperature is in the range of 500-600 ° C.

As shown in Table 4 (FIG. 16), in Examples 17 and 18, as the temperature increases from 375 ° C. to 500 ° C., the production of gas increases from 0.02 grams of gas per gram of total product to 0.05 grams. However, coke production is reduced from 0.17 grams to 0.09 grams per gram of crude oil feed at higher temperatures. The sulfur content of the crude oil product is reduced from 0.01 grams to 0.008 grams of sulfur per gram of crude oil product at higher temperatures. Both crude products have an H / C of 1.8.

In Example 19, the crude oil product was subjected to CaCO under conditions similar to those described in Example 18.₃ Contact with The proportions of crude oil product, gas, coke production are tabulated in Table 4 of FIG. The gas production of Example 19 is relatively increased compared to the gas production of Example 18. Desulfurization of the crude oil feed is not as efficient as in Example 18. The crude product prepared in Example 19 has 0.01 grams of sulfur per gram of crude product, compared to a sulfur content of 0.008 per gram of crude product of the crude product prepared in Example 18.

Example 20 is an example compared with Example 18. In Example 20, 83.13 grams of silicon carbide are injected into the reactor instead of the inorganic salt catalyst. Gas production and coke production are significantly increased compared to gas production and coke production in Example 18. Under this noncatalytic condition, 0.22 grams of coke, 0.25 grams of non-condensable gas and 0.5 grams of crude oil product are produced per gram of crude oil product. The crude oil product prepared in Example 20 has 0.036 grams of sulfur per gram of crude oil product as compared to 0.01 grams of sulfur per gram of crude oil product prepared in Example 18.

This example provides improved results for the catalysts used in Examples 17 and 18 for non-catalytic conditions and conventional metal salts. At hydrogen flow rates of 500 ° C. and 250 cm 3 / min, the amount of coke and non-condensable gases is significantly less than the amount of coke and non-condensable gases produced under non-catalytic conditions.

In an example using an inorganic salt catalyst (Examples 17-18 in Table 4 of FIG. 16), at a weight ratio of the production gas relative to the production gas formed during a controlled experiment (eg, Example 20 in Table 4 of FIG. 16) A decrease is observed. From the amount of hydrocarbons in the gas produced, the thermal decomposition of the crude oil feed may be up to 20 wt%, 15 wt%, 10 wt%, 5 wt%, or none based on the total amount of crude oil feed in contact with the hydrogen source. Is measured.

Example 21 and 22: K ₂ CO ₃ Of RbCO ₃ Of Cs ₂ CO ₃  Crude hydrogen source and crude oil with catalyst or silicon carbide and water Feed  contact.

The apparatus of Examples 21 and 22 is the same as Example 9 except that hydrogen gas was used as the hydrogen source. In Example 21, 130.4 grams of longitudinal nigro combine with 30.88 grams of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst to form a crude oil feed mixture. In Example 22, 139.6 grams of longitudinal nigro combine with 80.14 grams of silicon carbide to form a crude oil feed mixture.

The crude oil feed mixture is filled directly into the reactor. Hydrogen gas is metered at 250 cm 3 / min in the reactor during the heating and holding cycle. The crude feed mixture is heated at 300 ° C. for at least 1.5 hours and maintained at 300 ° C. for 1 hour. The reaction temperature is increased at 400 ° C. for at least 1 hour and maintained at 400 ° C. for 1 hour. After the reaction temperature reaches 400 ° C., water enters the reactor at a rate of 0.4 g / min that is combined with hydrogen gas. Water and hydrogen are metered in during the heating and maintenance cycles in the reactor. After maintaining the reaction mixture at 400 ° C., the reaction temperature is increased to 500 ° C. and maintained at 500 ° C. for 2 hours. Steam generated from the reactor is collected in cold traps and gas bags. The liquid product from the cold trap is condensed and analyzed.

In Example 21, 86.17 grams (66.1 wt% of the crude oil based feed) of dark reddish brown hydrocarbon liquid (crude oil) and water (97.5 g) were subjected to K ₂ CO ₃ / Rb ₂ CO ₃ / Cs in a hydrogen atmosphere. _It is produced as steam from the contact of a ₂ CO ₃ catalyst with a crude oil feed.

In Example 22, water vapor and a small amount of gas are produced from the reactor. The reactor is observed and dark brown sticky hydrocarbon liquid is removed from the reactor. Dark brown sticky liquids of less than 50 wt% are produced from the contact of silicon carbide with the crude oil feed in a hydrogen atmosphere. The yield of crude product observed in Example 21 is increased by 25% relative to the yield of crude product produced in Example 22.

Example 21 illustrates an improvement in the properties of crude oil products produced using the methods described herein over crude oil products prepared using hot water. In particular, the crude oil product in Example 21 boils at a lower temperature than the crude product in Example 22, as demonstrated by the crude oil product produced in Example 22 cannot be produced as a vapor. The crude product produced in Example 21 has improved flow properties compared to the crude product produced in Example 22, as measured by visual inspection.

Examples 23-24: for producing crude oil products having an increased volume compared to crude oil product volumes produced under non-catalytic conditions K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Contact of crude oil with hydrogen source with catalyst.

The apparatus, crude oil feed, inorganic catalyst and reaction procedure are the same as in Example 9 except that the crude feed is directly charged to the reactor and hydrogen gas is used as the hydrogen feed. Crude feed (Vertical Nigro) has an API specific gravity of 6.7 and a density of 1.02 g / ml at 15.5 ° C.

In Example 23, 102 grams of crude oil feed (100 ml of crude oil feed) and 31 grams of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst are charged to the reactor. At 15.5 ° C. a crude oil feed (87.6 grams, 112 ml) with a specific gravity of 50 and a density of 0.7796 g / ml was produced.

In Example 24, 102 grams of crude oil feed (100 ml of crude oil feed) and 80 grams of silicon carbide are charged to the reactor. At 15.5 ° C. a crude oil feed (70 grams, 70 ml) with an API specific gravity of 12 and a density of 0.9861 g / ml is produced.

Under these conditions, the volume of crude oil product from Example 23 is approximately 10% greater than the volume of crude oil feed. The volume of crude product produced from Example 24 is significantly less than the volume of crude product produced in Example 23 (40% less). A significant increase in the volume of the product enhances the producer's ability to produce a larger volume of crude product per volume of input crude oil.

Example 25. K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Contact of crude oil feed with hydrogen source with catalyst, sulfur and coke.

The apparatus and reaction procedure are the same as in Example 9 except that the flow is metered at 300 cm 3 / min in the reactor. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst contains 27.2 grams of K ₂ CO ₃ , 32.2 grams of Rb ₂ CO ₃ And 40.6 grams of Cs ₂ CO ₃ .

The crude oil feed (130.35 grams) and K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst (31.6 grams) are charged to the reactor. Cerro Nigro crude oil contains: 0.04 grams total aromatic content, boiling point 0.000640 grams of nickel and combined vanadium, 0.042 grams of sulfur, and 0.56 grams of residue, per gram of crude oil feed. It includes. The API share of crude oil feed is 6.7.

Contacting methane with a K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst and the crude oil feed yields 0.95 grams and 0.041 grams of coke per gram of crude oil feed.

The total product comprises 0.91 grams of crude oil product, 0.028 grams of hydrocarbon gas per gram of total product. The total gas collected comprises 0.16 moles of hydrogen, 0.045 moles of carbon dioxide and 0.025 moles of C ₂ and C ₄ -C ₆ hydrocarbons per mole of gas, as measured by GC / MS. The balance of the gas is traces (0.004 moles) of methane, air, carbon monoxide and evaporated crude oil products.

Crude oil products are analyzed using a combination of gas chromatography and mass spectrometry. Crude oil products contain a mixture of hydrocarbons having a boiling point of 100-538 ° C. The whole liquid product mixture contains 0.006 grams of ethyl benzene (monocyclic ring compound having a boiling point of 136.2 ° C. at 0.101 MPa) per gram of the mixture. This product is not found in crude oil feeds.

The catalyst used ("first used catalyst") was removed from the reactor, weighed and analyzed. The first catalyst used had an increase in weight from 31.6 grams to a total mass of 37.38 grams (about 18% increase based on the mass of the original K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst). The first catalyst used contained 0.15 grams additional coke, 0.0035 grams sulfur, 0.0014 grams Ni / V, and 0.845 grams K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ per gram of catalyst used. .

An additional crude oil feed (152.71 grams) is contacted with the first used catalyst (36.63 grams) to produce the total product recovered after 150 grams of loss. The total product contains 0.92 grams of liquid crude product, 0.058 grams of additional coke, and 0.017 grams of gas per gram of total product. This gas contains 0.18 moles of hydrogen, 0.07 moles of carbon dioxide, and 0.035 moles of C ₂ -C ₆ hydrocarbons per mole of gas. The balance of the gas is traces (<1% mole) of methane, nitrogen, some air and evaporated crude oil products.

Crude oil products include mixtures of hydrocarbons with boiling points between 100 and 538 ° C. The portion of the mixture whose boiling point is below 149 ° C. is comprised of 0.018 mol% ethyl benzene, 0.04 mol% toluene, 0.03 mol% meta-xylene and 0.060 mol% para-xylene (149 at 0.101 MPa) per mole of total liquid hydrocarbon Monocyclic ring compounds having a boiling point of &lt; RTI ID = 0.0 &gt; This product cannot be found in the crude oil feed.

The catalyst used ("second used catalyst") is removed from the reactor, weighed and analyzed. The second catalyst used increased the total mass from 36.63 grams to 45.44 grams (about 43 wt% increase based on the weight of the original K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst). The second catalyst used contained 0.32 grams of coke, 0.01 grams of sulfur, 0.67 grams per gram of catalyst used.

An additional crude oil feed (104 grams) is contacted with the second used catalyst (44.84 grams) to collect 104 grams of total product, 0.114 grams of coke per gram of crude oil feed. The coke portion contributes to coke composition in the additional vessel due to overheating of the additional vessel because 104.1 grams of the 133 grams of crude oil feed returned are crude feeds.

The total product comprises 0.86 grams of crude oil product and 0.025 grams of hydrocarbon gas per gram of total product. The total gas contains 0.18 moles of hydrogen, 0.052 moles of carbon dioxide, and 0.03 moles of C ₂ -C ₆ hydrocarbons per mole of gas. The balance of the gas is traces of methane, air, carbon monoxide, hydrogen sulfide and evaporated oil.

Crude oil products include mixtures of hydrocarbons with boiling points between 100 and 538 ° C. The portion of the mixture whose boiling point is below 149 ° C. is fractions per gram of hydrocarbon mixture, 0.021 grams ethyl benzene, 0.027 grams toluene, 0.042 grams meta-xylene and 0.020 grams para-, as previously determined by GC / MS. Xylene.

The catalyst used (“the third catalyst used”) is removed from the reactor, weighed and analyzed. The third used catalyst had an increase in weight from 44.84 grams to 56.59 grams in total mass (about 79 wt% based on the weight of the original K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst). The urea analysis of the specific third used catalyst is carried out. The third catalyst used was 0.90 grams of carbon, 0.028 grams of hydrogen, 0.0025 grams of oxygen, 0.046 grams of sulfur, 0.017 grams of nitrogen, with the balance being the other transition metals such as chromium, titanium and zirconium per gram of additional material. 0.0018 grams of vanadium, 0.0007 grams of nickel, 0.0015 grams of iron and 0.00025 grams of chloride.

As described in this example, coke, sulfur, and / or metals on and / or in the inorganic salt catalyst may be reduced to the crude oil product produced by contacting the crude oil feed with a hydrogen source with an inorganic salt catalyst. Does not affect the overall yield of at least 80%). The content of monocyclic cyclic aromatics in this crude product is at least 100 times greater than the content of monocyclics in crude oil feeds with boiling points below 149 ° C.

For three runs, the average crude product yield (based on the weight of the crude feed) is 89.7 wt% with a standard deviation of 2.6%, and the average coke yield is 7.5 wt% (with the weight of the crude feed) Average mass yield of gaseous split hydrocarbons is 2.3 wt% (based on the weight of the crude oil feed) with a standard deviation of 0.46%. The relatively large standard deviation in both coke and liquid is due to the third experiment where the temperature control of the feed vessel failed and the crude feed was heated in the further vessel. Nevertheless, the amount of coke tested here is high, but there are obviously no significant adverse effects on the activity of the catalyst system.

The ratio of C ₂ olefins to total C ₂ is 0.19. The ratio of C ₃ olefins to total C ₃ is 0.4. The ratio of alpha olefins to internal olefins of C ₄ hydrocarbons is 0.61. The C ₄ cis / trans olefins ratio is 6.34. This ratio is substantially greater than 0.68, which is the ratio of the predicted thermodynamic C ₄ cis / trans olefins. The ratio of alpha olefins to internal olefins of C ₅ hydrocarbons is 0.92. This ratio is greater than 0.194, which is the ratio of alpha olefins to the predicted thermodynamic C ₅ internal olefins. The C ₅ cis / trans olefins ratio is 1.25. This ratio is substantially greater than 0.9, which is the ratio of the predicted thermodynamic C ₅ cis / trans olefins.

Example 26: K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Crude hydrogen source and relatively high sulfur content Feed  contact.

The apparatus and reaction procedure are the same as described in Example 9, except that the crude oil feed, methane and steam are continuously fed to the reactor. The degree of feed in the reactor is adjusted using a change in the weight of the reactor. Methane gas is continuously metered at 500 cm 3 / min in the reactor. The steam is continuously metered in at 6 g / min in the reactor.

Inorganic salts are 27.2 grams K ₂ CO ₃ , 32.2 grams Rb ₂ CO ₃ And 40.6 grams of Cs ₂ CO ₃ Ready K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ Catalyst (59.88 grams) is charged to the reactor.

The crude oil feed (bitumen, Lloydminster, Canada) with an API specific gravity of 9.4, a sulfur content of 0.02 grams per gram of crude oil feed, and a 0.40 gram residue is heated to 150 ° C. in an additional vessel. Hot bitumen is continuously fed at 10.5 g / min from the additional vessel to the reactor to continuously maintain a 50% crude feed liquid level of the reactor volume, but the ratio is insufficient to maintain this level.

The methane / vapor / crude feed is contacted with the catalyst at an average reactor internal temperature of 456 ° C. Contact of the methane / steam / crude oil feed with the catalyst produces the entire product (in this example in the form of reactor effluent steam).

A total of 1640 grams of crude oil feed is processed for more than six hours. From the difference between the initial catalyst weight and the residue / catalyst mixture weight, 0.085 grams of coke per gram of crude oil feed remains in the reactor. From the contact of the crude oil feed with methane with K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ yields 0.93 grams of total product per gram of crude oil feed. The total product contained 0.03 grams of gas, 0.97 grams of crude oil per gram of total product, excluding the amounts of water and methane used in the reaction.

The gas contains 0.014 grams of hydrogen, 0.018 grams of carbon monoxide, 0.08 grams of carbon dioxide, 0.13 grams of hydrogen sulfide, and 0.68 grams of non-condensed hydrocarbons per gram of gas. It can be estimated that the sulfur content of the crude feed is reduced by 18 wt% from the amount of hydrogen sulfide produced. As shown in this example, hydrogen, carbon monoxide, and carbon dioxide are produced. The molar ratio of carbon monoxide to carbon dioxide is 0.4.

C ₂ -C ₅ hydrocarbons are 0.30 grams of C ₂ per gram of hydrocarbon Compound, 0.32 grams C ₃ Compound, 0.26 grams C ₄ Compound and 0.10 grams of C ₅ compound. The mass ratio of iso-pentane to n-pentane in the non-condensed hydrocarbon is 0.3. The mass ratio of isobutane to n-butane in non-condensed hydrocarbons is 0.189. The C ₄ compound has 0.003 grams of butadiene content per gram of unit C ₄ compound. Inside C ₄ The weight ratio of alpha C ₄ olefins to olefins is 0.75. Internal C ₅ The weight ratio of alpha C ₅ olefins to olefins is 1.08.

The data in this Example 26 demonstrate that the continuous process of a relatively high sulfur crude oil feed with the same catalyst with coke does not reduce the activity of the inorganic salt catalyst and produces a crude oil product suitable for conveyance.

Example 27: K ₂ CO ₃ Of Rb ₂ CO ₃ Of Cs ₂ CO ₃  Hydrogen source and crude oil with catalyst and coke Feed  contact.

The apparatus and reaction procedure are performed using the conditions as described in Example 26. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ Catalyst (56.5 grams) is charged to the reactor. A total of 2550 grams of crude oil feed is processed for more than six hours. From the difference between the initial catalyst weight and the residue / catalyst mixture weight, based on the weight of the crude feed, 0.114 grams of coke per gram of crude feed is left in the reactor. A total of 0.89 grams of total product is produced per gram of crude oil feed. The total product comprises 0.04 grams of gas, 0.96 grams of crude oil product per gram of total product, excluding the amount of water and methane used in the reaction.

The gas includes 0.021 grams of hydrogen, 0.018 grams of carbon monoxide, 0.052 grams of carbon dioxide, 0.18 grams of hydrogen sulfide, and 0.65 grams of non-condensed hydrocarbons per gram of gas. It can be estimated that the sulfur content of the crude feed is reduced by 14 wt% from the amount of hydrogen sulfide produced. As shown in this example, hydrogen, carbon monoxide, and carbon dioxide are produced. The molar ratio of carbon monoxide to carbon dioxide is 0.6.

C ₂ -C ₆ hydrocarbons are 0.44 grams of C ₂ per gram of C ₂ -C ₆ hydrocarbons Compound, 0.31 gram C ₃ Compound, 0.19 grams C ₄ Compound and 0.068 grams of C ₅ compound. The weight ratio of iso-pentane to n-pentane in non-condensed hydrocarbons is 0.25. The weight ratio of isobutane to n-butane in non-condensed hydrocarbons is 0.15. The C ₄ compound has 0.003 grams of butadiene content per gram of C ₄ compound.

This example illustrates that the repetitive process of the same catalyst (56.5 grams) with coke and a relatively high sulfur crude feed (2550 grams crude oil feed) does not reduce the activity of the inorganic salt catalyst and is suitable for returning crude oil. To produce the product.

In addition, modifications or other embodiments in various aspects of the invention are possible to those skilled in the art in view of the present specification. Therefore, this specification is intended to enable those skilled in the art to understand the general method of carrying out the invention and should be construed as illustrative only. The form of the invention described and illustrated herein is to be understood as an example of embodiments. The elements and materials may be other than those described herein, the parts and processes may be reversed, the features of the invention may be used independently, and all will become apparent to those skilled in the art once the invention is described. As described in the following claims, variations in the elements of the invention are possible without departing from the scope of the invention.

Claims (23)

Contacting the hydrogen source with the crude oil feed in an inorganic salt catalyst to produce a whole product comprising the crude oil product, The crude oil product is a liquid mixture at 25 ° C., 0.101 MPa, the crude oil feed has a residue content of at least 0.2 grams of residue per gram of crude oil feed, the inorganic salt catalyst comprises at least two inorganic metal salts, As defined by the Temporal Analysis of Products (TAP), the emission of radiant gas in the temperature range between (a) the DSC temperature of at least one of the two inorganic metal salts and Displaying the deformation; And Controlling the contact conditions such that the crude product has a residue content, expressed in grams of residue per gram of crude oil product, of up to 30% of the residue content of the crude oil feed as defined by ASTM specification D5307. Process for preparing crude oil product. The method of claim 1, At least one of the two inorganic salts has a DSC temperature of at least 500 ° C. The method according to claim 1 or 2, The DSC temperature of the inorganic salt catalyst is a method for producing a crude oil product, characterized in that the temperature range between 250 ~ 450 ℃ or 300 ~ 400 ℃. The method according to any one of claims 1 to 3, Wherein said radiant gas comprises water vapor and / or carbon dioxide. Contacting the hydrogen source with the crude oil feed in an inorganic salt catalyst to produce a total product comprising the crude oil product, The crude product is a liquid mixture at 25 ° C., 0.101 MPa, the crude feed having a residue content having at least 0.2 grams of residue per gram of crude oil feed, and the inorganic salt catalyst at the temperature of 300 ° C. to 500 ° C. Said ion conductivity being at least one ion conductivity of said inorganic salt of said inorganic salt catalyst; And The crude product comprises controlling the contact conditions to have a residue content, expressed in grams of residue per gram of crude oil product, of up to 30% of the residue content of the crude oil feed, as defined in ASTM specification D5307. Method of preparation. Adjusting the inorganic salt catalyst; Contacting the hydrogen source with the crude oil feed in the controlled inorganic salt catalyst to produce a whole product comprising the crude oil product, Said crude product is a liquid mixture at 25 ° C., 0.101 MPa, said crude feed having a residue content of at least 0.2 grams of residue per gram of crude feed; And Controlling the contact conditions such that the crude product has a residue content, expressed in grams of residue per gram of crude oil product, of up to 30% of the residue content of the crude oil feed as defined by ASTM specification D5307. Process for preparing crude oil product. The method of claim 6, Wherein said inorganic salt catalyst exhibits an ionic conductivity after a controlling step that is different from the ionic conductivity of said inorganic salt catalyst before said adjusting step. The method according to claim 6 or 7, Wherein said inorganic salt catalyst exhibits an ionic conductivity after a conditioning step at 300 ° C. that is less than the ionic conductivity of the inorganic salt catalyst before the conditioning step. The method according to any one of claims 1 to 8, The inorganic salt catalyst may comprise one or more alkali carbonate metals, one or more alkali carbonate earth metals, one or more alkali hydroxide metals, one or more alkali hydroxide earth metals, one or more alkali hydride metals, one or more alkali hydride earth metals, one or more alkalis. A process for producing crude oil products comprising at least one sulfide of a metal, at least one sulfide of at least one alkaline earth metal, at least one amide of at least one alkali metal, at least one amide of at least one alkaline earth metal, or mixtures thereof. The method of claim 9, Wherein said at least one alkali metal is sodium, potassium, rubidium, cesium, or mixtures thereof and / or said at least one alkaline earth metal is calcium, magnesium, or mixtures thereof. The method according to any one of claims 1 to 10, Wherein said hydrogen source comprises hydrogen, light hydrocarbons, water, or mixtures thereof. The method according to any one of claims 1 to 11, The step of contacting the crude oil feed with the hydrogen source in the inorganic salt catalyst occurs in the contacting zone and further comprises providing steam to the contacting zone prior to or during the contacting step. . The method according to any one of claims 1 to 12, Wherein the minimum portion of the total product is prepared as a steam, further comprising condensing the minimum portion of the steam at 25 ° C., 0.101 MPa to produce the crude oil product. The method according to any one of claims 1 to 13, The contact conditions may also be up to 0.2 grams, up to 0.15 grams, up to 0.1 grams, or up to 0.05 grams per gram of crude oil feed as hydrocarbons that cannot condense at 25 ° C., 0.101 MPa are defined by mass balance. A process for producing a crude oil product, characterized in that it is controlled to form. The method according to any one of claims 1 to 14, Wherein said crude feed has a residue of 0.2 to 0.99 grams or 0.3 to 0.8 grams per gram of crude oil feed. The method according to any one of claims 1 to 15, The crude oil product has a coke per gram of crude oil product 0.00001 ~ 0.03 grams or 0.0001 ~ 0.01 grams, characterized in that the crude oil product production method. The method according to any one of claims 1 to 16, The crude oil feed also has TAN, total Ni / V / Fe content, total heteroatomic content, expressed in grams of heteroatoms or grams of Ni / V / Fe, per gram of crude oil feed, and the contact conditions include: Also control the product to have a TAN, total Ni / V / Fe content and / or total heteroatomic content of up to 90% of the TAN, the total Ni / V / Fe content and / or the total heteroatomic content of the crude oil feed. Process for producing a crude oil product, characterized in that. The method according to any one of claims 1 to 17, The crude oil product also comprises, per gram of crude oil product, from 0.00001 to 0.2 grams of naphtha, from 0.0001 to 0.9 grams of distillate, from 0.0001 to 0.99 grams of vacuum gas oil (VGO), or mixtures thereof. Method of preparation of the product. The method according to any one of claims 1 to 18. Combining the crude oil product with the same or different crude oil feed to form a mixture. Crude oil products or mixtures obtainable according to the process for the production of crude oil products according to claims 1 to 19. A process for producing a return fuel, a heated fuel, a lubricant, or a chemical comprising treating the crude oil product or mixture according to claim 20. The method of claim 21, Wherein said treating process comprises distilling said crude product or said mixture into one or more distillation fractions. The method of claim 21 or 22, Wherein said treating process comprises a hydrotreating step.

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