JP2007514822A - System and method for producing crude product - Google Patents

Abstract

A crude product containing 0.2 g or more of residue per gram of crude feed is contacted with one or more catalysts to produce a total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa. One or more properties of the crude product can vary by more than 10% compared to the respective properties of the crude feed. In some embodiments, gas is produced during the contacting.
[Selection] Figure 1

Description

The present invention relates generally to systems and methods for processing crude feed and compositions made using such systems and methods, for example. More particularly, the embodiment described herein is a crude feedstock having a residue content of 0.2 g or more per gram of crude feedstock, (a) a liquid mixture at 25 ° C. and 0.101 MPa, and (b) It relates to a system and method for converting to a crude product having one or more properties that are improved relative to the same properties of the crude feed.

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

  Unfavorable crude oils often contain relatively high levels of residue. Such high levels of residue tend to make it difficult and expensive to transport and / or process using conventional equipment. High residue crude oil may be converted to coke by high temperature treatment. Alternatively, high residue crude oil is typically treated with water at elevated temperatures to produce a low viscosity crude oil and / or crude oil mixture. During processing, it may be difficult to remove water from viscous crude oils and / or crude oil mixtures in a conventional manner.

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

  Unfavorable crude oil produces and / or deposits coke on the catalyst surface at a high rate during the processing of relatively large amounts of metal contaminants such as nickel, vanadium, and adverse crude oil. It can be expensive to regenerate the catalytic activity of a catalyst contaminated with coke. High temperatures used during regeneration may reduce the activity of the catalyst and / or degrade the catalyst.

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

  Unfavorable crude oils can contain relatively large amounts of metal contaminants, such as nickel, vanadium, and / or iron. During the processing of such crude oil, metal contaminants and / or compounds may be deposited on the surface or voids of the catalyst. Such deposition can reduce the activity of the catalyst.

  Unfavorable crude oils often contain organically bound heteroatoms (eg, sulfur, oxygen and nitrogen). Organically bonded heteroatoms can adversely affect the catalyst in some cases. Alkali metal salts and / or alkaline earth metal salts are used in the residue desulfurization process. These methods have low desulfurization efficiency, produce insoluble sludge, have poor demetallation efficiency, form a substantially inseparable salt-oil mixture, and use large amounts of hydrogen and / or relatively high hydrogen pressure. Tend.

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

USP 3,136,714 of Gibson et al., 3,558,747 of Gleim et al., 3,847,797 of Pasternak et al., 3,948,759 of King et al., 3,957,620 of Fukui et al. McCollum et al. 3,960,706, McCollum et al. 3,960,708, Baird Jr. Et al., 4, 119, 528, Baird Jr. 4,127,470, Fujimori et al. 4,224,140, Hereday et al. 4,437,980, Krasuk et al. 4,591,426, Mazurek et al. 4,665,261, Kretschmar No. 5,064,523, Kretschmar et al. 5,166,118, Gatsis et al. 5,288,681, Sudhakarl et al. 6,547,957, Reynolds et al. 20030300086 and Rendina et al. 20030149317 describe various methods and systems used for crude oil processing. However, the methods, systems, and catalysts described in these patents are limited in use due to the many technical problems discussed above.

In short, adverse crude oils generally have undesirable properties (eg, relatively high residue, tendency to corrode equipment, and / or tendency to consume relatively large amounts of hydrogen during processing). Other undesirable properties include relatively high amounts of undesirable components (eg, relatively high or high amounts of TAN, organically bound heteroatoms, and / or metal contaminants). These characteristics are prone to problems such as increased corrosion, reduced catalyst life, process blockage, and / or increased hydrogen usage during processing in conventional transportation and / or processing equipment.
USP 3,136,714 USP 3,558,747 USP 3,948,759 USP 3,957,620 USP 3,960,706 USP 3,960,708 USP 4,119,528 USP 4,127,470 USP 4,224,140 USP 4,437,980 USP 4,591,426 USP 4,665,261 USP 5,064,523 USP 5,166,118 USP 5,288,681 USP 6,547,957 US Patent Application Publication No. 20030000867 US Patent Application Publication No. 200301493317 USP 4,626,412 USP 5,039,489 USP 5,264,183 “Inorganic Sulfur Chemistry”, G.M. Edited by Nickless; Elesvier Publishing Company, Amsterdam-London-New York; 1968 Copyright; Chapter 19

Accordingly, there is a very economical and technical need for improved systems, methods, and / or catalysts for converting disadvantageous crudes into crude products with more desirable properties.

SUMMARY OF THE INVENTION The invention described herein generally involves contacting a crude feed with one or more catalysts to produce a crude product and, in some embodiments, a total product comprising non-condensable gases. The invention relates to a system, method and catalyst for manufacturing. The invention described herein also relates to novel compositions that generally consist of novel combinations of various components. Such compositions are obtained using the systems and methods described herein.

The present invention provides a method for producing a crude product by contacting a crude feed with a hydrogen source in the presence of one or more catalysts wherein one or more of the catalysts comprises K ₃ Fe ₁₀ S ₁₄ .

Further, the present invention provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, and at least one of the catalysts contains one or more transition metal sulfides. Producing a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa in contact with a hydrogen source in the presence of a catalyst, and the coke content of the crude product is a crude product There is also a method for producing a crude product including a step of controlling contact conditions so that naphtha having an octane number of 70 or more in 1 g of crude oil is 0.001 g or more per 1 g of crude product. provide.

  Further, the present invention provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, and at least one of the catalysts contains one or more transition metal sulfides. In contact with a hydrogen source in the presence of a catalyst at 25 ° C. to produce a total product comprising a crude product that is a liquid mixture at 0.101 MPa, and the crude product is a freezing point (ASTM Method D2386). ) Containing kerosene at a temperature of −30 ° C. or less (however, containing 0.2 g or more of aromatics per 1 g of kerosene (measured by ASTM method D5186)) and the coke content of the crude product is crude oil There is also provided a method for producing a crude product including a step of controlling contact conditions so that the amount is 0.05 g or less per gram of product.

Further, the present invention provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, and at least one of the catalysts contains one or more transition metal sulfides. Producing a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa in contact with a hydrogen source in the presence of a catalyst, and coke content of the crude product (ASTM Method D6730 The contact conditions are controlled so that the weight ratio of hydrogen source to carbon atoms (H / C) in the crude product is 0.05 g or less per gram of crude product with 1.75 or less. A method for producing a crude product comprising the steps is also provided.

Further, the present invention has a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude oil feedstock, and the weight ratio of hydrogen source element to carbon atom (H / C) in the crude feedstock is 1. .5 or more crude feeds in liquid mixture at 25 ° C. and 0.101 MPa in contact with a hydrogen source in the presence of one or more catalysts, wherein at least one of the catalysts comprises one or more transition metal sulfides. A process for producing an entire product including a crude product, and an H / C atomic ratio in the crude product is 80 to 120% of an H / C atomic ratio of the crude feed, and the crude product residue is contained The amount of naphtha (measured by ASTM method D5307) with an amount (measured by ASTM method D5307) of 30% or less of the residual content of the crude oil feedstock and an octane number of 70 or more in the crude product is 0.000 per gram of crude product. 001g or more So that the method for producing a crude product comprising the step of controlling the contacting conditions are also provided.

Further, the present invention has a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude oil feedstock, and the weight ratio of hydrogen source element to carbon atom (H / C) in the crude feedstock is 1. .5 or more crude feeds in liquid mixture at 25 ° C. and 0.101 MPa in contact with a hydrogen source in the presence of one or more catalysts, wherein at least one of the catalysts comprises one or more transition metal sulfides. The step of producing the entire product including the crude product, and the crude product has 0.001 g or more of naphtha having an octane number of 70 or more per 1 g of crude product, and the freezing point (measured by ASTM method D2386) is − Kerosene at a temperature of 30 ° C. or less (provided that 0.2 g or more of aromatics per 1 g of kerosene (measured by ASTM method D5186)) is 0.001 g or more, vacuum gas oil (VGO) [provided that V Contact conditions so as to contain 0.001 g or more of aromatics (measured by IP method 368/90) and 0.05 g or less of residues (measured by ASTM method D5307) per 1 g of O There is also provided a method for producing a crude product comprising a step of controlling the process.

The present invention also provides a crude feedstock having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude feedstock, and at least one catalyst contains one or more transition metal sulfides. Contacting a hydrogen source in the presence of a catalyst to produce a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, wherein the transition metal sulfide catalyst comprises a total transition The process containing at least 0.4 g of one or more transition metal sulfides per gram of metal sulfide catalyst, and the coke content of the crude product is 0.05 or less per gram of crude product, and the crude product There is also provided a method for producing a crude product comprising a step of controlling the contact conditions so that the residual content of is less than 30% of the residual content of the crude raw material.

Also, the present invention provides a crude oil having a nitrogen content (measured by ASTM method D5762) of 0.001 g or more per gram of crude material and a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material. Contacting the feedstock with a hydrogen source in the presence of one or more catalysts containing a transition metal sulfide catalyst having a total of 0.4 g or more of one or more transition metal sulfides per gram of transition metal sulfide catalyst; Producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and the nitrogen content of the crude product is 90% or less of the nitrogen content of the crude feed, and the crude product There is also provided a method for producing a crude product comprising a step of controlling contact conditions such that the residual content of the crude oil is 30% or less of the residual content of the crude raw material.

In addition, the present invention has a total Ni / V / Fe content (measured by ASTM method D5863) of 0.0001 g or more per gram of crude feed and a residue content (measured by ASTM method D5307) of 0.001 gram of crude feed. 2 g or more of crude feedstock in the presence of one or more catalysts containing a transition metal sulfide catalyst having a total of 0.4 g or more of one or more transition metal sulfides per gram of transition metal sulfide catalyst A total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and the total Ni / V / Fe content of the crude product is the total Ni / V of the crude feed / Production of crude oil product including a step of controlling contact conditions so that the Fe content is 90% or less and the crude product residue content is 30% or less of the crude material residue content. Direction It is also provided.

The present invention also provides a crude oil having a sulfur content (measured by ASTM method D4294) of 0.001 g or more per gram of crude material and a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material. Contacting the feed with a hydrogen source in the presence of one or more catalysts containing a transition metal sulfide catalyst having a total of 0.4 g or more of one or more transition metal sulfides per gram of transition metal sulfide catalyst; Producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and the sulfur content of the crude product is 70% or less of the sulfur content of the crude feed, and the crude product There is also provided a method for producing a crude product comprising a step of controlling contact conditions such that the residual content of the crude oil is 30% or less of the residual content of the crude raw material.

The present invention also includes a step of mixing a transition metal oxide and a metal salt to form a transition metal oxide / metal salt mixture, and reacting the transition metal oxide / metal salt mixture with hydrogen to form an intermediate. And a process for producing a transition metal sulfide catalyst composition comprising the steps of reacting sulfur with sulfur in the presence of one or more hydrocarbons to produce a transition metal sulfide catalyst.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, and the presence of one or more catalysts including a transition metal sulfide-containing transition metal sulfide catalyst. A process for producing a total product including a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and a residual content of the crude product is a crude raw material residue A method for producing a crude product comprising a step of controlling contact conditions so that the amount is 30% or less, wherein the transition metal sulfide catalyst comprises a transition metal oxide and a metal salt mixed to form a transition. Forming a metal oxide / metal salt mixture, reacting the transition metal oxide / metal salt mixture with hydrogen to form an intermediate, and then reacting the intermediate with sulfur in the presence of one or more hydrocarbons To produce a transition metal sulfide catalyst. Also it provides method for producing a raw oil product obtained by.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, brought into contact with a hydrogen supply source in the presence of one or more catalysts at 25 ° C. , Producing a whole product including a crude product which is a liquid mixture at 0.101 MPa, producing at least a part of the whole product as steam, condensing at least a part of the steam at 25 ° C. and 0.101 MPa And 0.001 g or more of naphtha having an octane number of 70 or more and 1 VGO (provided that 0.3 g or more of aromatics (measured by IP method 368/90) per 1 g of VGO) per 1 g of crude oil product. Also provided is a method for producing a crude product comprising the step of forming a crude product containing 0.001 g or more and 0.05 g or less of residue.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, in contact with a hydrogen supply source in the presence of an inorganic salt catalyst, A method for producing a crude product comprising the step of producing an entire product comprising a crude product that is a liquid mixture at 101 MPa, wherein each crude product is naphtha per gram of crude product [however, Also provided is a production method comprising 0.001 g or more of cyclic aromatic (containing 0.001 g or more (measured by ASTM method D6730)), 0.001 g or more of distillate, and 0.05 g or less of residue.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, in contact with a hydrogen supply source in the presence of an inorganic salt catalyst, A method for producing a crude product comprising the step of producing an overall product comprising a crude product that is a liquid mixture at 101 MPa, wherein the crude product is diesel oil per gram of crude product [provided that 1 g of diesel oil Contains 0.001 g or more of aromatic per unit (measured by IP method 368/90)], VGO [however, contains 0.3 g or more of aromatic per 1 g of VGO (measured by IP method 368/90) The production method further comprises 0.001 g or more and 0.05 g or less of the residue.

Further, the present invention has a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude oil feedstock and a monocyclic aromatic content (measured by ASTM method D6703) of 0.1 g per gram of crude feedstock. Contacting a crude feed which is the following with a hydrogen source in the presence of an inorganic salt catalyst to produce a total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and during contact: Hydrocarbons that do not condense at 25 ° C. and 0.101 MPa are formed in an amount of 0.2 g or less per gram of crude raw material (measured by mass balance), and the monocyclic aromatic content of the crude product is monocyclic aroma There is also provided a method for producing a crude product comprising a step of controlling contact conditions so that the content of the group is 5% or more higher than the group content.

In addition, the present invention contains a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude oil raw material, and contains olefins expressed in g of olefin per gram of crude oil raw material (measured by ASTM method D6730). ) Contacting the crude feed with a hydrogen source in the presence of an inorganic salt catalyst to produce a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and an olefin of the crude product There is also provided a method for producing a crude product including a step of controlling the contact conditions so that the content is 5% or more higher than the olefin content of the crude material.

In addition, the present invention provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of the crude material, and an emission gas inflection point of the emitted gas [measured by product time analysis (TAP). In the presence of an inorganic salt catalyst in the temperature range of 50 to 500 ° C. to produce a total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa in contact with a hydrogen source; And the contact conditions so that the residual content of the crude product (measured by ASTM method D5307) is expressed in terms of residual g per gram of crude product and is 30% or less of the residual content of the crude raw material. A method for producing a crude product comprising a controlling step is also provided.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, containing two or more inorganic metal salts, and (a) at least one inorganic Hydrogen in the presence of an inorganic salt catalyst showing the range of the inflection point of the released gas (measured by time analysis of the product (TAP)) between the DSC temperature of the metal salt and (b) the DCC temperature of the inorganic salt catalyst. Contacting the source to produce a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and the residue content of the crude product is g In other words, the present invention also provides a method for producing a crude product including a step of controlling the contact conditions so that the residual content of the crude crude material is 30% or less.

In addition, the present invention provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material. In the presence of an inorganic salt catalyst in the temperature range of 50 to 500 ° C. to produce a total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa in contact with a hydrogen source; And a method for producing a crude product including a step of producing the crude product such that the volume of the resulting crude product (measured at 25 ° C. and 0.101 MPa) is 5% or more larger than the volume of the crude feed. .

In addition, the present invention provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of the crude material, and an emission gas inflection point of the emitted gas [measured by product time analysis (TAP). In the presence of an inorganic salt catalyst in the temperature range of 50 to 500 ° C. to produce a total product including a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa in contact with a hydrogen source; And a method for producing a crude product product comprising a step of controlling contact conditions so that hydrocarbons that do not condense at 25 ° C. and 0.101 MPa during contact are formed in an amount of 0.2 g or less (measured by mass balance) per 1 g crude oil feedstock. Also provide.

In addition, the present invention provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, and has a thermal transition point (measured by differential scanning calorimetry (DSC)) per minute. Producing all products, including crude product, which is a liquid mixture at 25 ° C. and 0.101 MPa in the presence of an inorganic salt catalyst in the temperature range of 200-500 ° C. at a rate of 10 ° C. And the step of controlling the contact conditions so that the residual content of the crude product is expressed in terms of residual g per gram of crude product and is 30% or less of the residual content of the crude raw material. A method for producing a crude product containing is also provided.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, at least one kind of inorganic salt catalyst at a temperature in the range of 300 to 500 ° C. Producing a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa in contact with a hydrogen source in the presence of an inorganic salt catalyst exhibiting at least ionic conductivity of the inorganic salt; and crude oil Of the crude product including a step of controlling the contact conditions so that the residual content of the product is expressed as the residual g per gram of the crude product and is 30% or less of the residual content of the crude raw material. A manufacturing method is also provided.

The present invention also provides a crude feedstock having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude feedstock in contact with a hydrogen supply source in the presence of an inorganic salt catalyst. The inorganic salt catalyst includes a plurality of alkali metals having an atomic number of 11 or more, at least one of the alkali metals is an alkali metal carbonate, and one alkali having an atomic number of 11 or more. At least one atomic ratio of one alkali metal having a metal to atomic number greater than 11 is in the range of 0.1 to 10, producing at least a portion of all products as steam, at least one of the steam A crude product comprising a step of condensing a portion at 25 ° C. and 0.101 MPa and a step of forming a crude product having a residue content of 30% or less of the residue content of the crude feed The method is also provided.

The present invention also provides a crude feedstock having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude feedstock in contact with a hydrogen supply source in the presence of an inorganic salt catalyst. The inorganic salt catalyst includes a plurality of alkali metals having an atomic number of 11 or more, at least one of the alkali metals is an alkali metal hydroxide, and one of the inorganic salt catalysts having an atomic number of 11 or more. The step wherein the atomic ratio of at least one alkali metal to an alkali metal having an atomic number greater than 11 is in the range of 0.1 to 10, the step of producing at least a portion of the total product as steam, A crude product comprising: condensing a portion at 25 ° C. and 0.101 MPa; and forming a crude product having a residue content of 30% or less of the crude feed residue content. Also production method to provide.

The present invention also provides a crude feedstock having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude feedstock in contact with a hydrogen supply source in the presence of an inorganic salt catalyst. The inorganic salt catalyst includes a plurality of alkali metals having an atomic number of 11 or more, at least one of the alkali metals is an alkali metal hydride, and one alkali having an atomic number of 11 or more. At least one atomic ratio of one alkali metal having a metal to atomic number greater than 11 is in the range of 0.1 to 10, producing at least a portion of all products as steam, at least one of the steam A crude product comprising a step of condensing a portion at 25 ° C. and 0.101 MPa, and forming a crude product having a residue content of 30% or less of the residue content of the crude feed Also production method to provide.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, in contact with a hydrogen supply source in the presence of an inorganic salt catalyst, A process for producing a total product including a crude product that is a liquid mixture at 101 MPa, wherein the inorganic salt catalyst comprises one or more alkali metal salts having an alkali metal atomic number of 11 or more, one or more The alkaline earth metal salt, or a mixture thereof, wherein one of the alkali metal salts is an alkali metal carbonate, and the crude product residue content is 30% of the crude feed residue content. Also provided is a method for producing a crude product comprising a step of controlling the contact conditions so as to be not more than%.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, in contact with a hydrogen supply source in the presence of an inorganic salt catalyst, A process for producing a total product including a crude product that is a liquid mixture at 101 MPa, wherein the inorganic salt catalyst comprises one or more alkali metal hydroxides having an alkali metal atomic number of 11 or more; Control the contact conditions so that the residual content of the crude product is 30% or less of the process containing the alkaline earth metal salt of a species or more, or a mixture thereof, and the residual content of the crude product A method for producing a crude product comprising the steps is also provided.

The present invention also provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material, in contact with a hydrogen supply source in the presence of an inorganic salt catalyst, A process for producing a total product including a crude product that is a liquid mixture at 101 MPa, wherein the inorganic salt catalyst comprises one or more alkali metal hydrides having an alkali metal atomic number of 11 or more, The step of containing the above alkaline earth metal salt or a mixture thereof, and the step of controlling the contact conditions so that the residual content of the crude product is 30% or less of the residual content of the crude raw material. A method for producing a crude product comprising

In addition, the present invention provides a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material. Is also provided in the presence of an inorganic salt catalyst in the temperature range of 50 to 500 ° C., and a method for producing hydrogen gas comprising a step of contacting with a hydrocarbon having 1 to 6 carbon atoms and a step of generating hydrogen gas. .

The present invention also provides a first crude oil raw material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of the first crude oil raw material in the presence of water vapor. A step of generating a hydrogen-containing gas stream by contacting with an inorganic salt catalyst whose time analysis (TAP) of the product is in the temperature range of 50 to 500 ° C., in the presence of at least part of the generated gas stream Contacting a second crude feed with a second catalyst to produce a total product comprising a crude product that is a liquid mixture at 25 ° C. and 0.101 MPa, and wherein one or more characteristics of the crude product are second A method for producing a crude product is also provided that includes the step of controlling the contact conditions such that it changes by more than 10% relative to one or more respective properties of the crude feed.

The present invention also includes a step of contacting a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of the crude material with an inorganic salt catalyst in the presence of water vapor, hydrogen, carbon monoxide And a method for generating a gas stream comprising the step of generating a gas stream containing carbon dioxide and having a molar ratio of carbon monoxide to carbon dioxide of 0.3 or more.

In the process of conditioning the inorganic salt catalyst, in the presence of the conditioned inorganic salt catalyst, a crude material having a residue content (measured by ASTM method D5307) of 0.2 g or more per gram of crude material is brought into contact with the inorganic salt catalyst. The process of producing a total product comprising a crude product which is a liquid mixture at 25 ° C. and 0.101 MPa, and the residual content of the crude product is expressed in grams of residue per gram of crude product. Also provided is a method for producing a crude product comprising a step of controlling the contact conditions so that the residual content of the crude crude material is 30% or less.

In addition, the present invention has a boiling range distribution of 30 to 538 (1000-F) at 0.101 MPa, and isoparaffin and n-paraffin with a weight ratio of isoparaffin to n-paraffin of 1.4 or less (measured by ASTM method D6730). Also provided is a crude oil composition comprising hydrocarbons.

  In addition, the present invention has 0.001 g or more of hydrocarbons having a boiling range distribution of 204 ° C. (400 ° F.) or less at 0.101 MPa and 1 boiling point distribution of 204 to 300 at 0.101 MPa per 1 g of the composition. Hydrocarbon having a boiling range distribution of 0.001 g or more, hydrocarbon having a boiling range of 300 to 400 at 0.101 MPa, and hydrocarbon having a boiling range distribution of 400 to 538 (1000-F) at 0.101 MPa Is a crude oil composition in which a hydrocarbon having a boiling point distribution of 204 or less contains isoparaffin and n-paraffin in a weight ratio of isoparaffin to n-paraffin of 1.4 or less (measured by ASTM method D6730). Things are also provided.

In addition, the present invention contains naphtha having an octane number of 70 or more per 1 g of composition (provided that 0.15 g or less of olefin per 1 g of naphtha (measured by ASTM method D6730)) is 0.001 g or more and freezing point (ASTM method D2386). ) Kerosene at a temperature of −30 ° C. or less (provided that 0.2 g or more of aromatics per 1 g of kerosene (measured by ASTM method D5186)) is 0.001 g or more and the residue is 0.05 g or less A crude oil composition is also provided (measured by ASTM method D5307).

Further, the present invention relates to a non-condensable hydrocarbon gas at a temperature of 25 ° C. and 0.101 MPa per 1 g of the composition [however, a hydrocarbon having 1 to 3 carbon atoms (C _{1 to} C ₃ ) is converted into a non-condensable hydrocarbon gas. 0.35 g or less per gram] 0.15 g or less, naphtha having an octane number of 70 or more is 0.001 g or more, and kerosene having a freezing point (measured by ASTM method D2386) of -30 or less (however, per 1 g of kerosene Also provided is a crude oil composition containing 0.001 g or more of aromatics (measured by ASTM method D5186) and 0.05 g or less of residues (measured by ASTM method D5307).

Further, the present invention relates to 0.05 g or less of residue (measured by ASTM method D5307) and 0.001 g of hydrocarbon having a boiling range distribution of 204 ° C. (400 ° F.) or less at 0.101 MPa per 1 g of the composition. As described above, 0.001 g or more of hydrocarbon having a boiling range distribution of 204 to 300 at 0.101 MPa, 0.001 g or more of hydrocarbon having a boiling range distribution of 300 to 400 at 0.101 MPa, and 400 at 0.101 MPa. The hydrocarbon having a boiling range distribution of ˜538 (1000-F) is 0.001 g or more, and the hydrocarbon having a boiling range distribution of 20 to 204 is a terminal double bond olefin and an internal double bond olefin, 0.4 or more molar ratio of double bond olefin to internal double bond olefin (ASTM method D6 Also provided crude composition to be measured) contained in 30.

The present invention also relates to hydrocarbons having a residue of 0.05 g or less (measured by ASTM method D5307) and a boiling range distribution (measured by ASTM method D5307) of 20 to 538 ° C. (1000 ° F.) per 1 g of the composition. In addition, each hydrocarbon mixture contains 0.001 g or more of paraffin (measured by ASTM method D6730) and olefin (provided that the terminal olefin is 0.001 g / g of olefin). 0.001 g or more (having 001 g or more (measured by ASTM method D6730)), 0.001 g or more of naphtha, and kerosene (however, containing 0.2 g or more of aromatics (measured by ASTM method D5186) per 1 g of kerosene) 0.001 g or more, diesel oil (however, 0.3 g or less aromatic per gram of diesel oil (Measured by IP method 368/90)] and 0.001 g or more, and vacuum gas oil (VGO) [however, 0.3 g or more of aromatics (measured by IP method 368/90) per 1 g of VGO] The crude oil composition containing 0.001 g or more is also provided.

Further, the present invention relates to 0.05 g or less of residue (measured by ASTM method D5307) and 0.001 g of hydrocarbon having a boiling point range distribution of 204 ° C. (400 ° F.) or less at 0.101 MPa per 1 g of the composition. As described above, 0.001 g or more of hydrocarbon having a boiling range distribution of 204 to 300 at 0.101 MPa, 0.001 g or more of hydrocarbon having a boiling range distribution of 300 to 400 at 0.101 MPa, and 400 at 0.101 MPa. ˜538 (1000-F) hydrocarbons having a boiling range distribution of 0.001 g or more (measured by ASTM method D2887), and hydrocarbons having a boiling range distribution of 204 or less each contain olefins per gram of hydrocarbon. 0.001 g or more (measured by ASTM method D6730) and paraffin [however Isoparaffin and n- paraffins, also provides oil compositions comprising 1.4 or less (measured by ASTM method D6730) containing] over 0.001g in a weight ratio of isoparaffin-to-n- paraffins.

Further, the present invention relates to 0.05 g or less of residue (measured by ASTM method D5307) and 0.001 g of hydrocarbon having a boiling point range distribution of 204 ° C. (400 ° F.) or less at 0.101 MPa per 1 g of the composition. As described above, 0.001 g or more of hydrocarbon having a boiling range distribution of 204 to 300 at 0.101 MPa, 0.001 g or more of hydrocarbon having a boiling range distribution of 300 to 400 at 0.101 MPa, and 400 at 0.101 MPa. A hydrocarbon having a boiling point range distribution of ˜538 (1000-F) is 0.001 g or more (measured by ASTM method D2887), and a hydrocarbon having a boiling point range distribution of −10 to 204 has 4 carbon atoms (C ₄ ) of compound (however, containing butadiene containing _{C 4} compound 1g per 0.001g above] The oil composition is also provided.

Further, the present invention relates to 0.05 g or less of residue (measured by ASTM method D5307) and 0.001 g of hydrocarbon having a boiling point range distribution of 204 ° C. (400 ° F.) or less at 0.101 MPa per 1 g of the composition. As described above, 0.001 g or more of hydrocarbon having a boiling range distribution of 204 to 300 at 0.101 MPa, 0.001 g or more of hydrocarbon having a boiling range distribution of 300 to 400 at 0.101 MPa, 400 to 400 at 0.101 MPa. 0.001 g or more of hydrocarbons having a boiling point range distribution of 538 (1000-F) (measured by ASTM method D2887) and one or more catalysts having at least one alkali metal in excess of 0 g to 0.01 g A crude oil composition containing less than is also provided.

In some embodiments, the present invention is combined with one or more of the methods or compositions of the present invention to (a) not be refined, not distilled, and / or not fractionally distilled. Crude oil raw material, (b) containing at least 0.5 g of a component having 4 or more carbon atoms per gram of crude oil raw material, (c) containing hydrocarbons, some of which have a boiling range distribution at 0.101 MPa of 100 ° C. The boiling range distribution at 0.101 MPa is the range of 100-200 ° C., the boiling range distribution at 0.101 MPa is the range of 200-300 ° C., the boiling range distribution at 0.101 MPa is 300 A range of ˜400 ° C. and a boiling range distribution at 0.101 MPa of 400 to 700 ° C. (d) charcoal having a boiling range distribution at 0.101 MPa of less than 100 ° C. 0.001 g or more of hydrogen, hydrocarbon with a boiling range distribution at 1001 to 200 ° C. at 0.101 MPa, 0.001 g or more of hydrocarbon with a boiling point range distribution at 0.101 MPa of 200 to 300 ° C. 0.001 g or more, hydrocarbons with a boiling range distribution at 300-400 ° C. at 0.101 MPa are 0.001 g or more, and hydrocarbons with a boiling range distribution at 0.101 MPa are 400-700 ° C. 0.001 g or more, (e) having TAN, (f) having 0.2-0.99 g, 0.3-0.8 g, or 0.4-0.7 g residue per gram of crude feedstock, ( g) containing nickel, vanadium, iron or mixtures thereof, (h) containing sulfur, and / or (i) containing nitrogen-containing hydrocarbons;

In some embodiments, the invention combines (a) gaseous, (b) molecular hydrogen, (c) light hydrocarbons, in combination with one or more of the methods or compositions of the invention. Also provided are hydrogen sources comprising (d) comprising methane, ethane, propane or mixtures thereof, (e) comprising water and / or comprising mixtures thereof.

In some embodiments, the present invention comprises (a) heating the inorganic salt catalyst to a temperature of 300 ° C. or higher, and / or (b) inorganic, in combination with one or more of the methods or compositions of the present invention. There is also provided a method comprising conditioning the inorganic salt catalyst comprising heating the salt catalyst to a temperature of 300 ° C or higher and then cooling it to a temperature of 500 ° C or lower.

In some embodiments, the present invention, in combination with one or more of the methods or compositions of the present invention, comprises contacting the crude feed with one or more catalysts, and contact conditions as follows: A method is also provided that includes the step of controlling. (A) During contact, hydrocarbons that are not condensable at 25 ° C. and 0.101 MPa are 0.2 g or less, 0.15 g or less, 0.1 g or less, or 0.15 g or less (measured by mass balance). (B) the contact temperature is in the range of 250-750 ° C, or 260-550 ° C, (c) the pressure is 0.1-20 MPa, (d) the gaseous hydrogen source versus the crude feed. ratio is in the range of crude feed 1 m ³ of hydrogen per source 1-16100 standard ^{m 3,} or 5 to 320 standard ^{m 3,} (e) prevent the formation of coke, (f) in contact, the total product, or crude oil Prevent coke formation in the raw material, (g) the amount of coke in the crude product is also 0.05 g or less, 0.03 g or less, 0.01 g or less, or 0.003 g or less per gram of crude product, (h ) At least one of the inorganic salt catalysts Part is semi-liquid or liquid at such contact conditions, (i) the crude product TAN is not more than 90% of the crude feed TAN, (j) the crude product total Ni / V / Fe The content is 90% or less, 50% or less, or 10% or less of the total Ni / V / Fe content of the crude feedstock. (K) The sulfur content of the crude product is the sulfur content of the crude feedstock. 90% or less, 60% or less, or 30% or less, (l) The nitrogen content of the crude product is 90% or less, 70% or less, 50% or less, or 10% or less of the nitrogen content of the crude oil raw material (M) the residue content of the crude product is 30% or less, 10% or less, or 5% or less of the residue content of the crude feedstock; (n) together with the crude product, ammonia is (O) the crude product produced contains methanol, the process further comprising crude crude Recovering methanol from the product, combining the recovered methanol with additional crude feed to form an additional crude feed / methanol mixture, and additional crude feed / Heating the methanol mixture, wherein (p) one or more properties of the crude product vary by 90% or less compared to each of the one or more properties of the crude feed, (q) in the contact zone The amount of total catalyst is in the range of 1-60 g per 100 g of crude feed and / or (r) a hydrogen source is added to the crude feed before or during contact.

In some embodiments, the present invention comprises, in combination with the method or composition of the present invention, (a) contacting an inorganic salt catalyst substantially insoluble in the crude feed with the crude feed at a temperature below 500 ° C. (B) Stirring the inorganic salt catalyst in the crude feed and / or contacting the crude feed with the inorganic salt catalyst in the presence of water and / or steam to include a crude product that is a liquid mixture in the STP. Contact conditions are also provided that include a process to produce the entire product.

In some embodiments, the invention combines the process or composition of the invention with contacting the crude feed with an inorganic salt catalyst, and (a) supplying steam to the contact zone before or during contact. (B) forming an emulsion of the crude feed and water before contacting the crude feed with the inorganic salt catalyst and hydrogen source, (c) spraying the crude feed into the contact zone, and / or Or (d) providing a method comprising contacting steam with an inorganic salt catalyst to remove at least a portion of coke from the surface of the inorganic salt catalyst.

In some embodiments, the present invention combines with one or more of the methods or compositions of the present invention to contact a crude feed with an inorganic salt catalyst to produce a total product that is at least partially produced as steam. And a step of condensing at least a portion of the steam at 25 ° C. and 0.101 MPa to form a crude product, and contact conditions comprising: (a) a boiling range distribution in which the crude product is selected. And / or (b) a method of controlling the crude product to contain components of a selected API gravity.

In some embodiments, the present invention also provides a method comprising contacting a crude feed with one or more non-acidic inorganic salt catalysts in combination with one or more of the methods or compositions of the present invention.

In some embodiments, the present invention combines (a) at least one transition metal sulfide with a K ₃ Fe ₁₀ S ₁₄ catalyst or transition metal sulfide in combination with one or more of the methods or compositions of the present invention. The atomic ratio of transition metal to sulfur in (b) K ₃ Fe ₁₀ S ₁₄ catalyst or transition metal sulfide catalyst is 0.4 g or more, 0.6 g or more, or 0.8 g or more per gram of catalyst. (C) further comprising one or more alkali metals, one or more compounds of one or more alkali metals, or a mixture thereof, and (e) further one or more alkali metals. Containing one or more compounds of one or more alkali metals, or mixtures thereof, and the atomic ratio of transition metal to sulfur in the K ₃ Fe ₁₀ S ₁₄ catalyst or transition metal sulfide catalyst is 0.5 In the range of ~ 2.5 and the atomic ratio of alkali metal to transition metal is more than 0 and 1 It ranges below, (f) further comprise one or more alkaline earth metals, one or more compounds of one or more alkaline earth metals, or with containing a mixture thereof, K ₃ Fe ₁₀ S ₁₄ The atomic ratio of transition metal to sulfur in the catalyst or transition metal sulfide catalyst is in the range of 0.5 to 2.5 and the atomic ratio of alkaline earth metal to transition metal is greater than 0 and less than or equal to 1 (G) further containing zinc, (h) further containing Kfe ₂ S ₃ , (i) further containing KfeS ₂ , and / or (j) non-acidic, K ₃ Fe ₁₀ S ₁₄ Catalysts or transition metal sulfide catalysts are also provided.

In some embodiments, the present invention also provides for forming K ₃ Fe ₁₀ S ₁₄ in situ in combination with one or more of the methods or compositions of the present invention.
In some embodiments, the present invention is combined with one or more of the methods or compositions of the present invention to: (a) one or more transition metals in columns 6-10 of the periodic table, columns 6-10 of the periodic table. Including one or more compounds of one or more transition metals, or a mixture thereof, (b) including one or more iron sulfides, (c) including FeS, (d) including Fe ₂ S, (E) includes the formula Fe _(1-b) S (where b is in the range of greater than 0 and less than or equal to 0.17), and further includes (f) K ₃ Fe ₁₀ S ₁₄ after contact with the crude oil feedstock. (G) at least one of the transition metals of the one or more transition metal sulfides is iron, and / or (h) is deposited on the support and the transition metal sulfide catalyst provides the entire support. Also provided are one or more transition metal sulfides containing 0.25 g or less per 100 g of catalyst.

In some embodiments, the present invention also provides a method of forming a transition metal sulfide catalyst composition in combination with one or more of the methods or compositions of the present invention. In this method, a transition metal oxide and a metal salt are mixed to form a transition metal oxide / metal salt mixture, and the transition metal oxide / metal salt mixture is reacted with hydrogen to form an intermediate. And a step of reacting the intermediate with sulfur in the presence of one or more hydrocarbons to produce a transition metal sulfide catalyst, wherein (a) the metal salt comprises an alkali metal carbonate , (B) further comprising a step of dispersing the intermediate in one or more liquid hydrocarbons while reacting the intermediate with sulfur, (c) one or more of the hydrocarbons has a boiling point of 100 ° C. or higher. (D) One or more kinds of hydrocarbons are VGO, xylene or a mixture thereof. (E) The step of mixing the transition metal oxide and the metal salt is performed in the presence of deionized water. To form a wet paste, the wet paste Including a step of drying at a temperature in the range of 50 to 250 ° C. and a step of firing the dried paste at a temperature in the range of 300 to 600 ° C. (f) one or more reaction steps of the intermediate and sulfur Heating the intermediate to a temperature in the range of 240-350 ° C. in the presence of hydrocarbons, and / or (g) contacting the catalyst composition with a crude feed containing sulfur and hydrogen sources. In addition.

  In some embodiments, the present invention also provides an inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. The catalyst comprises (a) one or more alkali metal carbonates, one or more alkaline earth metal carbonates, or a mixture thereof, (b) one or more alkali metal hydroxides, one or more alkalis. (C) one or more alkali metal hydrides, one or more alkaline earth metal hydrides, or a mixture thereof; (d) one or more alkali metal hydrides, or mixtures thereof; One or more sulfides, 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 alkaline earths One or more amides of a similar metal, or a mixture thereof, (f) one or more metals in columns 6-10 of the periodic table, one or more compounds of one or more metals in columns 6-10 of the periodic table Or a mixture thereof, (g) one or more inorganic metal salts At least one of the inorganic metal salts generates a hydride during use of the catalyst, (h) sodium, potassium, rubidium, cesium, or mixtures thereof, (i) calcium and / or magnesium, (j) sodium A mixture of a salt and a potassium salt, wherein the potassium salt is potassium carbonate, potassium hydroxide, potassium hydride, or a mixture thereof, and a sodium salt is sodium carbonate, sodium hydroxide, sodium hydride, or a mixture thereof And / or (k) mixtures thereof.

  In some embodiments, the present invention also provides an alkali metal-containing inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. In this catalyst, (a) the atomic ratio of an alkali metal having an atomic number of 11 or more to an alkali metal having an atomic number of more than 11 is in the range of 0.1 to 4, (b) at least two of the alkali metals are sodium And potassium, wherein the atomic ratio of sodium to potassium ranges from 0.1 to 4, (c) at least three of the alkali metals are sodium, potassium and rubidium, sodium to potassium, sodium to rubidium, and potassium to rubidium (D) At least three of the alkali metals are sodium, potassium and cesium, and each atomic ratio of sodium to potassium, sodium to cesium, and potassium to cesium is 0. (E) at least three of the alkali metals are potassium, cesium and rubidium, Um versus cesium, potassium to rubidium, and each atom ratio of cesium pair rubidium is in the range of 0.1 to 5.

In some embodiments, the present invention also provides a support material-containing inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. Here, (a) the support material is zirconium oxide, calcium oxide, magnesium oxide, titanium oxide, hydrotalcite, alumina, germania, iron oxide, nickel oxide, zinc oxide, cadmium oxide, antimony oxide, or a mixture thereof And / or (b) in the support material, one or more metals of columns 6-10 of the periodic table, one or more compounds of one or more metals of columns 6-10 of the periodic table, One or more alkali metal carbonates, one or more alkali metal hydroxides, one or more alkali metal hydrides, one or more alkaline earth metal carbonates, one or more alkaline earth metal hydroxides One or more alkaline earth metal hydrides and / or mixtures thereof are incorporated.

In some embodiments, the present invention also provides a method comprising contacting a crude feed with an inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. Here, (a) the catalytic activity of the inorganic salt catalyst does not substantially change in the presence of sulfur, and / or (b) the inorganic salt catalyst is continuously added to the crude feed.

  In some embodiments, the present invention also provides an inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. In this catalyst, (a) the inflection point of the generated gas is in the TAP temperature range, and the generated gas contains water vapor and / or carbon dioxide. (B) Thermal transition point [measured by differential scanning calorimetry (DSC) ] In a temperature range of 200-500 ° C, 250-450 ° C or 400-500 ° C at a heating rate of 10 ° C per minute, (c) DSC temperature in the range of 200-500 ° C or 250-450 ° C (D) the X-ray diffraction pattern at a temperature of 100 ° C. or higher is wider than the X-ray diffraction pattern of the inorganic salt catalyst at less than 100 ° C. and / or (e) at 300 ° C. after conditioning. The ionic conductivity is smaller than the ionic conductivity of the inorganic salt catalyst before the state adjustment.

In some embodiments, the present invention also provides an inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. In this catalyst, the generated inflection point indicates the temperature range measured by TAP, and the contact condition is also (a) T ₁ (where T ₁ is 30 ° C. or 20 ° C. higher than the TAP temperature of the inorganic salt catalyst). (B) TAP temperature or higher than the TAP temperature, and / or (c) at least the TAP temperature of the inorganic salt catalyst.

In some embodiments, the present invention also provides an inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. This catalyst is (a) semi-liquid or liquid at least at the TAP temperature of the inorganic salt catalyst (the lowest temperature indicating the gas inflection point generated by the inorganic salt catalyst), and at least at the TAP temperature, it is substantially insoluble in crude oil feedstock. (B) is a mixture of a liquid phase and a solid phase at a temperature in the range of 50-500 ° C, and / or (c) the DSC temperature of at least one of the two inorganic salts is above 500 ° C.

In some embodiments, the present invention also provides an inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. This catalyst is tested in the form of particles that can pass through a 1000 μ filter, and when heated to a temperature of 300 ° C. or higher, it self-deforms under gravity and / or pressure of 0.007 MPa or higher, resulting in an inorganic salt catalyst. When the inorganic salt catalyst is cooled to 20 ° C., it cannot return from the second form to the first form.

In some embodiments, the present invention also provides an inorganic salt catalyst in combination with one or more of the methods or compositions of the present invention. This catalyst is 0.01 g or less, calculated as lithium weight, (a) lithium or a lithium compound, and 0.001 g or less, calculated as halogen weight, per 1 g of inorganic salt catalyst. And / or 0.001 g or less of a glassy oxide compound.

In some embodiments, the present invention also provides a total product containing 0.8 g or more of crude product per gram of total product, in combination with one or more of the methods or compositions of the present invention.

In some embodiments, the present invention also provides all the following products in combination with one or more of the methods or compositions of the present invention. This total product consists of (a) residues of 0.003 g or less, 0.02 g or less, 0.01 g or less, 0.05 g or less, 0.001 g or less, 0.000001 to 0.1 g per gram of crude product. 0.00001 to 0.05 g, or 0.0001 to 0.03 g, (b) 0 g or more and 0.05 g or less, 0.00001 to 0.03 g, or 0.0001 per 1 g of crude product. -0.01 g contained, (c) The olefin content is 10% or more higher than the olefin content of the crude feed, (d) more than 0 g less than 0.01 g per gram of crude product of the total inorganic salt catalyst ( (E) VGO is contained in an amount of 0.1 g or more, 0.00001 to 0.99 g, 0.04 to 0.9 g, and 0.6 to 0.8 g per gram of crude product. (F) VGO The VGO contains aromatics in an amount of 0.3 g or more per gram of VGO, (g) contains 0.001 g or 0.1 to 0.5 g of distillate, and (h) has an H / C atomic ratio of 1. 4 or less, (i) the H / C atomic ratio is 90 to 110% with respect to the H / C atomic ratio of the crude product, (j) the monocyclic aromatics content of the crude product is 10% or more higher than the cyclic aromatic content, (k) containing a monocyclic aromatic containing xylene, ethylbenzene, or a compound of ethylbenzene, (l) 0.05 to 0.5 toluene per gram of crude product, respectively. 0.15 g, m-xylene 0.3-0.9 g, o-xylene 0.5-0.15 g, p-xylene 0.2-0.6 g, (m) diesel oil (N) Diese containing 0001g or more, or 0.01-0.5g The diesel oil contains not less than 0.3 g of aromatics per gram of diesel oil, and (o) not less than 0.001 g of kerosene, or more than 0 g and not more than 0.7 g, or 0.001 to 0.00 g. 5 g contained, (p) containing kerosene, the kerosene contains aromatics in an amount of 0.2 g or more or 0.5 g or more per 1 g of kerosene, and / or a freezing point of −30 or less, −40 or less, or − The temperature is 50 or less, (q) contains 0.001 g or more, or 0.5 g or more of naphtha, (r) contains naphtha, and the naphtha contains 0.01 g or less of benzene per naphtha, 0.05 g Or less, 0.002 g or less, octane number of 70 or more, 80 or more, or 90 or more, and / or isoparaffin and n-paraffin in naphtha Containing 1.4 in a weight ratio of n- paraffins, and / or (s) volume of 10% or more than the volume of crude feed large.

In some embodiments, the invention also includes a method comprising combining a crude feed with a catalyst in combination with one or more of the inventive methods or compositions to form a residual product comprising the crude product. provide. The method further includes (a) blending the crude product with a crude oil that is the same or different from the crude feed to form a blend suitable for transport; (b) the crude product is the same or different from the crude feed. Blending with crude oil to form a blend suitable for processing equipment, (c) fractionating the crude product, (d) fractionating the crude product into one or more distillate fractions and then distilling A step of producing a transportation fuel from at least one of the product fractions, and / or (e) a step of treating the transition metal sulfide catalyst and recovering a metal from the catalyst if the catalyst is a transition metal sulfide catalyst ,including.

In some embodiments, the present invention also provides the following crude product in combination with one or more of the methods or compositions of the present invention. The crude products each contain (a) 0.001 g or more of VGO per gram of crude product, and the VGO contains aromatics and 0.3 g or more per gram of VGO. In addition to containing 001 g or more, the diesel oil contains aromatics in an amount of 0.3 g or more per gram of diesel oil, (c) contains 0.001 g or more of naphtha, and the naphtha contains benzene in an amount of 0.5 g or less per naphtha. Naphtha has an octane number of 70 or more, and / or naphtha contains isoparaffin and n-paraffin in a weight ratio of isoparaffin to n-paraffin of 1.4 or less, (d) a boiling range distribution is 204 ° C. ( A total of 0.001 g or more of a mixture of a plurality of components having a temperature of 400 ° F. or less, and (E) the weight ratio of hydrogen atoms to carbon atoms in the composition is 1.75 or less or 1.8 or less, (f) contains 0.001 g or more of kerosene, Kerosene contains 0.5 g or more of aromatics per gram of kerosene, and / or the freezing point of kerosene is at a temperature of -30 ° C. or less, (g) 0.09 hydrogen atom (atomic hydrogen) per gram of composition (H) containing non-condensable hydrocarbon gas and naphtha, and containing 0.15 g or less of olefin in 1 g of the non-condensable hydrocarbon gas and naphtha. (I) Containing non-condensable hydrocarbon gas and naphtha, and isoparaffin and n-paraffin in the combination of the non-condensable hydrocarbon gas and naphtha containing 1.4 in a weight ratio of n- paraffins, olefins and (j) as well as containing the number 3 or less hydrocarbon carbon, the hydrocarbon each having a carbon number of 2 _{(C 2)} and 3 _{(C 3)} Containing no more than 0.3 paraffins in a weight ratio of a combination of C ₂ and C ₃ olefins to a combination of C ₂ and C ₃ paraffins, each containing 2 (C ₂ ) olefins and paraffins in C ₂ contained in a weight ratio of olefin to _{C 2} paraffins 0.2, and / or each carbon atoms 3 olefins and paraffins _{(C 3)} containing 0.3 or less in a weight ratio of _{C 3} olefin to _{C 3} paraffins, (K) butadiene content is 0.005 g or more, (l) API specific gravity is in the range of 15-30 with 15.5, (m) total Ni / V / Fe is 0.00001 g or less per gram of composition Contain (N) The paraffin content of hydrocarbons having a boiling range distribution of 204 or less is in the range of 0.7 to 0.98 g. (O) The hydrocarbon has a boiling range distribution of 204 or less per gram of olefin. The hydrocarbon with a boiling range distribution of 204 or less contains 0.001 to 0.5 g of olefin, (p) the hydrocarbon with a boiling range distribution of 204 or less containing olefin, and the olefin is a terminal olefin The olefin contains a hydrocarbon having a boiling point range distribution of 204 or less, and the molar ratio of the terminal olefin to the internal olefin of the olefin is 0.4 or more. And / or (r) 0.001-0.5 g of olefin per 1 g of hydrocarbon having a boiling range distribution of 20-204.

In some embodiments, the present invention also provides the following crude product in combination with one or more of the methods or compositions of the present invention. The crude product contains at least one catalyst containing one or more alkali metals, wherein (a) at least one of the alkali metals is potassium, rubidium, cesium or mixtures thereof; and At least one of (b) the catalyst further contains a transition metal, a transition metal sulfide and / or bartonite.
In further embodiments, features of certain embodiments according to the present invention may be combined with features of other embodiments of the present invention. For example, features of one embodiment may be combined with features of any of the other embodiments.
In further embodiments, the crude product is obtained from any of the methods and systems described herein.
In further embodiments, other embodiments may be added to the specific embodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS Advantages of the present invention will become apparent to those of ordinary skill in the art by reference to the following detailed description and the accompanying drawings.
FIG. 1 is a schematic diagram of one embodiment of a contact system for contacting a crude feed with a hydrogen source in the presence of one or more catalysts to produce a total product.
FIG. 2 is a schematic diagram of another embodiment of a contact system for contacting a crude feed with a hydrogen source in the presence of one or more catalysts to produce a total product.
FIG. 3 is a schematic diagram of one embodiment of a separation band in combination with a contact system.
FIG. 4 is a schematic diagram of one embodiment of a blending band in combination with a contact system.
FIG. 5 is a schematic diagram of one embodiment of a separation zone, a contact zone, and a blending zone.

FIG. 6 is a schematic diagram of one embodiment of a multiple contact system.
FIG. 7 is a schematic diagram of one embodiment of an ionic conductivity measurement system.

FIG. 8 is a table showing the properties of the crude feed and the properties of the crude product obtained in one embodiment of contacting the crude feed with a transition metal sulfide catalyst.
FIG. 9 is a table showing the composition of the crude feed and the composition of the non-condensable hydrocarbons obtained in the embodiment where the crude feed is contacted with the transition metal sulfide catalyst.

FIG. 10 is a table showing the properties and composition of the crude product obtained in the embodiment in which the crude feed is contacted with the transition metal sulfide catalyst.
FIG. 11 is a graph (measured by TAP) in which the ionic current of the released gas of the inorganic salt catalyst is plotted with the natural logarithm of temperature.

  FIG. 12 is a graph plotting the logarithm of temperature by comparing the resistance of the inorganic salt catalyst and the inorganic salt with the resistance of potassium carbonate.

FIG. 13 is a graph in which the resistance of the Na ₂ Co ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ catalyst is compared with the resistance of potassium carbonate and logarithmically plotted with respect to temperature.

FIG. 14 is a graph showing the weight ratio (%) of coke, liquid hydrocarbon, and gas produced in an embodiment in which a crude oil raw material is brought into contact with an inorganic salt catalyst to various hydrogen supply sources.

FIG. 15 is a graph showing the weight ratio (%) to the carbon number of the crude product produced in the embodiment in which the crude feed is brought into contact with the inorganic salt catalyst.

FIG. 16 is a table showing components produced in an embodiment in which a crude oil feed is contacted with an inorganic salt catalyst, a metal salt or silicon carbide.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are illustrated in the drawings. These drawings cannot have a constant reduction ratio. The drawings and detailed description thereof are not intended to limit the invention to the particular forms disclosed, but on the contrary, the invention is intended to be within the spirit and scope of the invention as defined by the appended claims. It should be understood that all variations, equivalents and alternatives are included.

DETAILED DESCRIPTION OF THE INVENTION Specific embodiments of the present invention will now be described in detail. The terms used here are defined as follows.
“Alkali metal” refers to one or more metals in the first column of the periodic table, one or more compounds of one or more metals in the first column of the periodic table, or mixtures thereof.

“AMU” refers to atomic mass unit.
“ASTM” refers to American Standard Testing and Materials.
Say the asphaltenes insoluble in pentane and "C ₅ asphaltenes". C ₅ asphaltenes content is as determined by ASTM Method D2007.
The ratio of hydrogen atoms (%) and carbon atoms (%) of crude feedstock, crude product, naphtha, kerosene, diesel oil, and VGO are determined by ASTM method D5291. API specific gravity at 60 ° F. API specific gravity is measured by ASTM method D6822.

“Bitumen” refers to a type of crude oil produced by hydrocarbon formation and / or retorted.
Unless otherwise indicated, the boiling range distribution of crude feed and / or all products is measured by ASTM method D5307. The aromatic content in hydrocarbon components such as paraffin, isoparaffin, olefin, naphthene, and naphthene is measured by ASTM method D6730. The aromatic content in diesel oil and VGO is measured by IP method 368/90. The aromatic content in kerosene is measured by ASTM method D5186.

“Bronsted-Lowry base” refers to a molecular entity that can accept protons from other molecular entities. Bronsted - The decree of Lowry bases, hydroxide (OH ^-), water (H ₂ O), carboxylate (RCO ₂ ^-), halide ^{(Br -, Cl -, F} -, I -), bisulfate (HSO ₄ ⁻ ) and sulfate (HSO ₄ ²⁻ ).
“Carbon number” refers to the total number of carbon atoms in the molecule.
“Coke” refers to a solid comprising a carbonaceous solid that does not evaporate under processing conditions. The coke content is obtained from the mass balance. The coke weight is the total weight of the solid minus the weight of the input catalyst.

“Content” refers to the weight of a component in a substrate (eg, crude feed, total product, or crude product) expressed as a weight fraction or weight percentage (%) relative to the total weight of the substrate. “Weight ppm” refers to parts by weight per million parts by weight.
“Diesel oil” refers to a hydrocarbon having a boiling range distribution of 260-343 ° C. (500-650 ° F.) at 0.101 MPa. The diesel oil content is measured by ASTM method D2887.
“DSC” refers to differential scanning calorimetry.

“Freezing point” refers to the temperature at which crystalline particles form in a liquid.
“GC / MS” refers to gas chromatography combined with mass spectroscopy.
“Hard base” refers to Journal of American Chemical Society, 1963, 85, p. An anion as described by Pearson in 3533.
“H / C” refers to the weight ratio of hydrogen source to carbon atoms. H / C is calculated | required from the measured value of the weight ratio (%) of hydrogen and the weight ratio (%) of carbon measured by ASTM method D5291.

“Heteroatom” refers to oxygen, nitrogen and / or sulfur contained in the molecular structure of a hydrocarbon. The heteroatom content is measured by ASTM method E385 for oxygen, D5762 for nitrogen, and D4294 for sulfur.
“Hydrogen source” refers to a compound that reacts in the presence of hydrogen and / or crude feed and catalyst to give hydrogen to one or more compounds in the crude feed. As the hydrogen source, but are not limited to, hydrocarbons (e.g. methane, ethane, propane, butane, pentane, C ₁ -C ₆ hydrocarbons such as naphtha), water, or mixtures thereof. To evaluate the total amount of hydrogen given to one or more compounds in crude oil feedstocks, a mass balance is made.

“Inorganic salt” refers to a compound composed of a metal cation and an anion.
“IP” refers to the Institute of Petroleum in the UK and now the Energy Institute of London.
“Isoparaffin” refers to a branched chain saturated hydrocarbon.
“Kerosin” refers to a hydrocarbon with a boiling range distribution of 204-260 ° C. (400-500 ° F.) at 0.101 MPa. Kerosene content is measured by ASTM method D2887.

“Lewis acid” refers to a compound or material that has the ability to accept one or more electrons from another compound.
“Lewis base” refers to a compound or material that has the ability to donate one or more electrons to another compound.
“Light hydrocarbon” refers to a hydrocarbon having 1 to 6 carbon atoms.

“Liquid mixture” refers to a composition comprising one or more compounds that are liquid at standard temperature and pressure (25 ° C., 0.101 MPa; hereinafter referred to as “STP”), or one or more liquids in STP. And a composition comprising one or more compounds that are solid in STP.
“Microcarbon residue” (“MCR”) refers to the amount of carbon residue remaining after evaporation and pyrolysis of the substrate. The MCR content is measured by ASTM method D4530.

“Naphtha” refers to a hydrocarbon component having a boiling range distribution of 38 ° C.-204 (100-400-F) at 0.101 MPa. Naphtha content is measured by ASTM method D2887.
“Ni / V / Fe” refers to nickel, vanadium, iron, or a combination thereof.
“Ni / V / Fe content” refers to the content of nickel, vanadium, iron, or a combination thereof in the substrate. The Ni / V / Fe content is measured by ASTM method D5863.

“Nm ³ / m ³ ” refers to the standard m ³ of gas per m ^{3 of} crude feed.
“Non-acidic” refers to the properties of Lewis bases and / or Bronsted-Lowry bases.
“Non-condensable gas” refers to a component and / or a mixture of components that are gases at standard temperature and pressure (25 ° C., 0.101 MPa) (hereinafter referred to as STP).

“N-paraffin” refers to normal (straight chain) saturated hydrocarbons.
“Octane number” refers to a numerical representation of the anti-knock properties of automobile fuels compared to standard reference fuels. The calculated octane number of naphtha is measured by ASTM method D6730.
“Olefin” refers to a compound having a non-aromatic carbon-carbon double bond. The type of olefin includes, but is not limited to, soot, trans, terminal, internal, branched, and linear.

The “periodic table” refers to a periodic table defined in November 2003 by the International Union of Pure and Applied Chemistry (IUPAC).
“Polyaromatic compound” refers to a compound having two or more aromatic rings. Examples of polyaromatic compounds include, but are not limited to, indene, naphthalene, anthracene, phenanthrene, benzothiophene, and dibenzothiophene.
“Residue” refers to a component having a boiling range distribution exceeding 538 ° C. (1000 ° F.) at 0.101 MPa as measured by ASTM method D5307.

“Semi-liquid” refers to a phase of a substance having 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 having, for example, toffy, dough or toothpaste consistency.
“SCFB” refers to standard cubic feet of gas per barrel of crude feed.
“Superbase” refers to a material that can deprotonate hydrocarbons such as paraffins and olefins under reaction conditions.
“TAN” refers to the total acid number expressed as mg KOH / g sample. TAN is measured by ASTM method D664.

“TAP” refers to the temporal analysis of the product.
“TMS” refers to transition metal sulfides.
“VGO” refers to a hydrocarbon having a boiling range distribution of 343 to 538 ° C. (650 to 1000 ° F.) at 0.101 MPa. The VGO content is measured by ASTM method D2887.
In the context of this application, if the value obtained by testing for the properties of the composition is outside the limits of the test method, the test method may be modified and / or recalibrated to test such properties. It should be understood as good. It should also be understood that other standardized test methods may be used that are considered equivalent to the reference test method.

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

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

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

Unfavorable characteristics of crude oil include, but are not limited to: (a) TAN of 0.5 or more, b) Viscosity of 0.2 Pa · s or more, c) API specific gravity of 19 or less, d) Total Ni / V / Fe content of 0.00005 g or more or 0.0001 g or more per gram of crude oil, e) Total heteroatom content of 0.005 g or more per gram of crude oil, (f) Residue content of 0.01 g or more per gram of crude oil G) asphaltene content of 0.04 g or more per gram of crude oil, h) MCR content of 0.02 g or more per gram of crude oil, or i) a combination thereof. In some embodiments, the disadvantaged crude may contain 0.2 g or more, 0.3 g or more, 0.5 g or more, or 0.9 g or more of residue per gram of the crude oil. In certain embodiments, a disadvantaged crude may contain 0.2-0.99 g, 0.3-0.9 g, 0.4-0.7 residue per gram of the crude. In certain embodiments, the disadvantaged crude oil may contain 0.001 g or more, 0.005 g or more, 0.01 g or more, or 0.02 g or more of sulfur per gram of the crude oil.

Unfavorable crude oil may contain a mixture of hydrocarbons in a certain boiling range.
Unfavorable crude oil is 0.001 g or more, 0.005 g or more or 0.01 g or more of hydrocarbons having a boiling point range distribution of 0.101 MPa per gram of crude oil; 0.001 g or more, 0.005 g or more or 0.01 g or more of 400 hydrocarbons; and 0.001 g or more, 0.005 g or more or 0.01 g or more of 400 to 700 hydrocarbons at a boiling range distribution of 0.101 MPa Or a combination thereof.

In some embodiments, the crude oil that is disadvantageous is 0.001 g or more, 0.005 g or more, or 0.005 g or more of hydrocarbons having a boiling point range distribution of 0.101 MPa and 200 ° C. or less per 1 g of the crude oil, in addition to the high-boiling components. You may contain 01g or more. Generally, disadvantaged crudes have no more than 0.2 g, or no more than 0.1 g of such hydrocarbons per gram of crude oil.

In a particular embodiment, the disadvantaged crude oil may contain 0.9 g or less, or 0.99 g or less of hydrocarbons having a boiling range distribution of 300 ° C. or more per gram of the crude oil. In a particular embodiment, the unfavorable crude oil may contain 0.001 g or more of hydrocarbons having a boiling range distribution of 650 ° C. or more per gram of the crude oil. In a particular embodiment, the unfavorable crude oil may contain 0.9 g or less, or 0.99 g or less of hydrocarbons having a boiling range distribution of 300 to 1000 ° C. per gram of the crude oil.

Examples of unfavorable crudes that may be processed in the manner described herein include, but are not limited to, the following countries and regions: Alberta, Canada, Orinoco, Venezuela, Southern California, United States, the slope Alaska, Campeche Bay, Mexico, San Jorge Basin in the United States, Sanos and Campos Basin in Brazil, Bohai Bay in China, Zagros in Iraq, Caspian in Kazakhstan, offshore Nigeria, North Sea in Britain, Northwest Madagascar, and the Netherlands Schonebek.

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

The crude feed contact method according to the present invention will now be described. Furthermore, embodiments are described for producing products containing various concentrations of naphtha, kerosene, diesel oil and / or VGO that are not generally produced by conventional methods.
The crude feed may be contacted with a hydrogen source in the presence of one or more catalysts in one contact zone or a combination of two or more contact zones.

In some embodiments, the hydrogen source is generated on site. For on-site generation of a hydrogen source, the reaction of at least a portion of the crude feedstock with the inorganic salt catalyst at a temperature in the range of 200-500 ° C or 300-400 ° C to form hydrogen and / or light hydrocarbons. May be included. The on-site generation of hydrogen may include a reaction between at least a portion of the crude feed and an inorganic salt catalyst such as an alkali metal formate salt.

The total product generally contains gases, vapors, liquids or mixtures thereof produced during contact. The total product contains a crude product that is a liquid mixture in STP and, in some embodiments, hydrocarbons that are not condensable in STP. In some embodiments, the total product and / or crude product may contain solids (eg, inorganic solids and / or coke). In certain embodiments, these solids may be entrained in the liquid and / or vapor generated during contact.

The contact zone usually comprises a reactor, a part of the reactor, a multi-part of the reactor, or a multi-reactor. Examples of reactors that can be used to contact a crude feed with a hydrogen source in the presence of a catalyst include stacked bed reactors, fixed bed reactors, continuous stirred tank reactors (CSTR), spray reactors, plugged flow reactors. A reactor, and a liquid / liquid contactor are mentioned. Examples of CSTRs are fluidized bed reactors and ebullated bed reactors.
Contact conditions typically include temperature, pressure, crude feed stream, total product stream, residence time, hydrogen source stream, or combinations thereof. The contact conditions may be controlled to produce a crude product with specific characteristics.

The contact temperature may be in the range of 200-800 ° C, 300-700 ° C, or 400-600 ° C. In embodiments where the hydrogen source is supplied as a gas (eg, hydrogen gas, methane or ethane), the ratio of gas to crude feed is typically 1-16,100 Nm ³ / m ³ , 2-8000 Nm ³ / m ³ , 3 ~4000Nm ³ / ^{m 3,} or from 5~300Nm ³ / ^{m 3.} The contact is usually performed at a pressure in the range of 0.1 to 20 MPa, 1 to 16 MPa, 2 to 10 MPa, and 4 to 8 MPa. In embodiments where steam is added, the steam to crude feed ratio is in the range of 0.01 to 3 kg, 0.03 to 2.5 kg, or 0.1 to 1 kg steam per kg crude feed. The flow rate of the crude feed may be sufficient to maintain the amount of crude feed in the contact zone at 10% or more, 50% or more, or 90% or more with respect to the total volume of the contact zone. Usually, the volume of crude feed in the contact zone is 40%, 60% or 80% of the total volume of the contact zone. In some embodiments, the contacting may be performed in the presence of another gas, such as argon, nitrogen, methane, ethane, propane, butane, propene, butene, or combinations thereof.

FIG. 1 is a schematic diagram of one embodiment of a contact system 100 used to produce the entire product as steam. Crude oil feed leaves the crude feed feed section 101 and enters the contact zone 102 via conduit 104. The amount of catalyst used in the contact zone may be in the range of 1-100 g, 2-80 g, 3-70 g, or 4-60 g per 100 g of crude feed in the contact zone. In certain embodiments, a diluent may be added to the crude feed to reduce the viscosity of the crude feed. In some embodiments, the crude feed enters the bottom of contact zone 102 via conduit 104. In certain embodiments, the crude feed may be heated to a temperature of 100 or more or 300 or more before and / or during introduction into the contact zone 102. Usually, the crude feed may be heated to a temperature in the range of 100-500 or 200-400.

In some embodiments, the catalyst may be transferred to the contact zone 102 in combination with the crude feed. This crude feed / catalyst mixture may be heated to a temperature of 100 ° C. or higher or 300 ° C. or higher before being introduced into the contact zone 102. Typically, the crude feed may be heated to a temperature in the range of 200-500 ° C or 300-400 ° C. In some embodiments, the crude feed / catalyst mixture is a slurry. In certain embodiments, the crude feed TAN may be reduced prior to placing the crude feed into the contact zone. For example, when a crude material is heated to a temperature in the range of 100 to 400 ° C. or 200 to 300 ° C., an alkali metal as an acidic component may be formed in the crude material. When the alkali metal is formed, some acidic components are removed from the crude oil feed, and the TAN of the crude feed can be reduced.

In some embodiments, the crude feed is continuously added to the contact zone 102. The mixing in contact zone 102 may be sufficient to prevent the catalyst from separating from the crude feed / catalyst mixture. In certain embodiments, at least a portion of the catalyst may be removed from the contact zone 102, and in some embodiments such catalyst is regenerated and reused. In certain embodiments, fresh catalyst may be added to the contact zone 102 during the reaction process.

In some embodiments, the crude feed and / or the crude feed and inorganic salt catalyst mixture is introduced into the contact zone as an emulsion. Emulsions can be made by blending an inorganic salt catalyst / water mixture with a crude feed / surfactant mixture. In some embodiments, a stabilizer is added to the emulsion. The emulsion may remain stable for more than 2 days, more than 4 days, or more than 7 days. Usually, the emulsion may remain stable for 30 days, 10 days, 5 days, or 3 days. As the surfactant, but are not limited to, organic polycarboxylic acids (Tenax 2010; Mead Westvaco Specialty Product Group; Charleston, South California, USA), C 21 dicarboxy fatty acid (DIACID 1550; Mead Westvaco Specialty Product Group ), Petroleum sulfonate (Hostapur SAS 30; Clarient Corporation, Charriote, North Carolina, USA), Tergital NP-40 surfactant (Union Carbide; Danbury, Connecticut, US, A.) or mixtures thereof. Stabilizers include, but are not limited to, diethyleneamine (Aldrich Chemical Co .; Milwaukeee, Wisconsin, USA) and / or monoethanolamine (JT Baker; Phillipsburg. New Jersey, USA).

Recirculation conduit 106 may be coupled to conduit 108 and conduit 104. In one embodiment, the recirculation conduit 106 may enter and / or exit the contact zone 102 directly. The recirculation conduit 106 may include a flow control valve 110. The flow control valve 110 can recirculate at least a portion of the material from the conduit 108 to the conduit 104 and / or the contact zone 102. In some embodiments, a condensing unit may be disposed within conduit 102 to condense at least a portion of the material and recirculate it to contact zone 102. In certain embodiments, the recirculation conduit 106 may be a gas recirculation line. Flow control valves 110, 110 ′ may be used to control the flow into and out of the contact zone 102 so that a certain amount of liquid is maintained in the contact zone 102. In some embodiments, a substantially selected range of liquids can be maintained in the contact zone 102. The volume of the raw material in the contact zone 102 may be monitored using standard instruments. The gas inlet 112 may be used to add a hydrogen source and / or additional gas to the crude feed as the crude feed enters the contact zone 102. In some embodiments, the steam inlet 114 may be used to add steam to the crude feed. In certain embodiments, an aqueous stream is introduced into the contact zone 102 from the water vapor inlet 114.

In some embodiments, at least a portion of the total product is produced as steam from the contact zone 102. In certain embodiments, the entire product is produced from the top of the contact zone 102 as vapor and / or vapor containing small amounts of liquids and solids. Steam is conveyed to separation zone 116 via conduit 108. The hydrogen source to crude feed ratio in the contact zone 102 and / or the pressure in the contact zone may be varied to control the vapor and / or liquid phase produced at the top of the contact zone 102. In some embodiments, the steam produced at the top of the contact zone 102 contains 0.5 g or more, 0.8 g or more, 0.9 g or more, or 0.97 g or more of crude product per gram of crude feed. In certain embodiments, the steam produced at the top of contact zone 102 contains 0.8 to 0.99 g, or 0.9 to 0.98 g, of crude product per gram of crude feed.
Spent catalyst and / or solids may remain in the contact zone 102 as a by-product of the contacting process. The solid and / or spent catalyst can include residual crude feed and / or coke.

In the separation unit 116, the steam is cooled and separated by standard separation methods to form crude product and gas. The crude product exits separation unit 116 and enters crude product receiver 119 via conduit 118. The resulting crude product may be suitable for transportation and / or processing. The crude product receiver 119 comprises one or more pipelines, one or more storage units, one or more transport containers, or a combination thereof. In some embodiments, the separated gas (eg, hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, or methane) is conveyed to another processing unit (eg, for a fuel cell or sulfur recovery plant) and / or Recirculated to contact zone 102 via conduit 120. In certain embodiments, solids and / or liquids entrained in the crude product may be removed using standard physical separation methods (eg, filtration, centrifugation, or membrane separation).

FIG. 2 shows a contact system 122 for treating a crude feed with one or more catalysts to produce a total product that may be a liquid or a liquid mixed with a gas or solid. Crude oil feed may enter contact zone 102 via conduit 104. In some embodiments, the crude feed is received from a crude feed supply. The conduit 104 may include a gas inlet 112. In some embodiments, the steam inlet 114 may enter steam directly into the contact zone 102. In certain embodiments, the water vapor inlet 114 may be used to add water vapor to the contact zone 102. The crude feed may be contacted with the catalyst in the contact zone 102 to produce the entire product. In some embodiments, conduit 106 recirculates at least a portion of the total product to contact zone 102. The total product and / or the mixture comprising solid and / or unreacted crude feed exits contact zone 102 and enters separation zone 124 via conduit 108. In some embodiments, a condensation unit may be placed (eg, in conduit 106) to condense at least a portion of the mixture in the conduit and recirculate to contact zone 102 for further processing. In certain embodiments, the recirculation conduit 106 may be a gas recirculation line. In some embodiments, conduit 108 may include a filter to remove particles from the entire product.

  In the separation zone 124, at least a portion of the crude product may be separated from the total product and / or catalyst. In embodiments where the total product comprises solids, the solids may be separated from the total product using standard solid separation techniques (eg, centrifugation, purification, decantation, membrane separation). The solid includes, for example, a combination of catalyst, spent catalyst, and / or coke. In some embodiments, a portion of the gas is separated from the total product. In some embodiments, at least a portion of the total product and / or solids may be recycled to contact zone 102 via conduit 104 and / or in some embodiments via conduit 126. The recycle portion may be placed in the contact zone 102 for further processing, for example in combination with a crude feed. The crude product may exit separation zone 124 via conduit 128. In certain embodiments, the crude product may be conveyed to a crude product receiver.

  In some embodiments, the total product and / or crude product may contain at least a portion of the catalyst. The gas entrained in the total product and / or crude product may be separated using standard gas / liquid separation techniques such as sparging, membrane separation and vacuum. In some embodiments, the separated gas is conveyed to other units (eg, for fuel cells, sulfur recovery plants, other processing units, or combinations thereof) and / or recycled to the contact zone.

  In some embodiments, separation of at least a portion of the crude feed occurs before the crude feed enters the contact zone. FIG. 3 is a schematic diagram of one embodiment of a separation band 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 oil feed enters separation zone 132 via conduit 104. In separation zone 132, at least a portion of the crude feed is separated using standard separation techniques to produce separated crude feed and hydrocarbons. The separated crude feed contains, in some embodiments, components having a boiling range distribution of 100 ° C. or higher, 120 ° C. or higher, or in some embodiments, mixtures of components having a boiling range distribution of 200 ° C. or higher. Usually, the separated crude oil feed contains a mixture of components having a boiling range distribution of 100-1000 ° C, 120-900 ° C, or 200-800 ° C. Hydrocarbons separated from the crude feed leave the separation zone 132 via conduit 134 and are transported to other processing units, processing facilities, storage facilities, or combinations thereof.

At least a portion of the separated crude feed exits the separation zone 132 and enters the contact system 130 via conduit 136 and is further processed to produce a crude product. The crude product exits contact zone 130 via conduit 138.
In some embodiments, a crude product produced from a crude feed in any of the ways described herein is blended with a crude that is the same as or different from the crude feed. For example, the crude product can be blended with crude oils having different viscosities to obtain a blended product having a viscosity between that of the crude product and that of the crude product. The resulting blended product may be suitable for transportation and / or processing.

  FIG. 4 is a schematic view of an embodiment in which the blending zone 140 and the contact zone 130 are combined. In certain embodiments, at least a portion of the crude product exits contact zone 138 via conduit 138 and enters blending zone 140. In blending zone 140, at least a portion of the crude product is one or more process streams (eg, one or more crude feeds, or a hydrocarbon stream produced from the separation of naphtha), crude oil, crude feed or combinations thereof. To produce a blended product. Process streams, crude oil, crude feed or combinations thereof are introduced directly into the blending zone 140 or upstream of the blending zone via conduit 142. The mixing system may be located in or near the blending zone 140. The blend product may meet certain product specifications. Specific product specifications include, but are not limited to, API specific gravity, TNA, viscosity or range or limit of their combined properties.

  In some embodiments, methanol is generated during the catalytic process that uses the catalyst. For example, when hydrogen and carbon monoxide are reacted, methanol may be generated. The recovered methanol can contain dissolved salts, such as potassium hydroxide. The recovered methanol may be combined with additional crude feed to form a crude feed / methanol mixture. When methanol is combined with a crude feed, the viscosity of the crude product tends to decrease. When the crude feed / methanol mixture is heated below 500 ° C., the TAN of the crude feed may drop below 1.

  FIG. 5 is a schematic view of an embodiment in which a separation band is combined with a combination of a blending band and a contact system. Crude feed enters separation zone 132 from conduit 104. The crude feed is separated as described above to form a separated crude feed. The separated crude feed enters contact zone 130 through conduit 136. The crude product exits contact zone 130 and enters conduit 140 through conduit 138. In the blend zone 140, other process streams and / or crude oil introduced via conduit 142 combine with the crude product to form a blended product. The blended product exits blend zone 140 via conduit 144.

  FIG. 6 is a schematic diagram of the multiple contact system 146. Contact zone 100 (shown in FIG. 1) may be placed in front of contact system 148. In an alternative embodiment, the position of the contact system can be reversed. Contact system 100 contains an inorganic salt catalyst. Contact system 148 may contain one or more catalysts. The catalyst in contact system 148 may be an additional inorganic salt catalyst, a transition metal sulfide catalyst, a commercially available catalyst, or a mixture thereof. The crude feed enters the contact zone 100 via conduit 104 and contacts the hydrogen source in the presence of the inorganic salt catalyst to produce the entire product. The total product contains hydrogen and, in some embodiments, a crude product. The entire product may exit contact system 100 via conduit 108. Hydrogen generated from the contact between the inorganic salt and the crude feed may be used as a hydrogen source for the contact system 148. At least a portion of the generated hydrogen gas is transferred from the contact system 100 to the contact system 148 via the conduit 150.

  In an alternative embodiment, the hydrogen thus generated may be separated and / or processed and then transferred to the contact system 148 via conduit 150. In certain embodiments, contact system 148 may be part of contact system 100 such that the generated hydrogen flows directly from contact system 100 to contact system 148. In some embodiments, the vapor stream produced by the contact system 100 is mixed directly with the crude feed that enters the contact system 148.

The second crude feed enters contact system 148 via conduit 152. In the contact system 148, a product is produced by contacting the crude feed with at least a portion of the generated hydrogen and the catalyst. In some embodiments, the product is the total product. This product exits contact system 148 via conduit 154.
In certain embodiments, as shown in FIGS. 1-6, a system having a contact system, a contact zone, a separation zone, and / or a blending zone is located in or near an area of production that produces disadvantaged crude feedstock. You can do it. After treatment in the contact system, the crude feed is considered suitable for transportation and / or refinery processing.

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

  In some embodiments, the total product contains 0.05 g or less, 0.03 g or less, or 0.01 g or less of coke per gram of total product. In certain embodiments, the entire product is substantially free of coke (ie, no coke is detectable). In some embodiments, the crude product contains 0.05 g or less, 0.03 g or less, 0.01 g or less, 0.005 g or less, or 0.003 g or less of coke per gram of crude product. In certain embodiments, the coke content of the total product is greater than 0 g / g crude product, 0.05 g or less, 0.00001-0.03 g, 0.0001-0.01 g, or 0.001-0. It cannot be detected whether it is in the range of 005g.

  In certain embodiments, the crude product has an MCR content of 90% or less, 80% or less, 50% or less, 30% or less, or 10% or less of the MCR content of the crude feed. In some embodiments, the MCR content of the crude product is negligible. In some embodiments, the MCR is 0.05 g or less, 0.03 g or less, 0.01 g or less, or 0.001 g or less per gram of crude product. Usually, the crude product contains 0 to 0.04 g, 0.000001 to 0.03 g, or 0.00001 to 0.01 g of MCR per gram of crude product.

  In some embodiments, the entire product contains a non-condensable gas. Non-condensable gases include, but are not limited to, typically carbon dioxide, ammonia, hydrogen sulfide, hydrogen, carbon monoxide, methane, other non-condensable hydrocarbons in STP, or mixtures thereof. It is done.

  In certain embodiments, hydrogen gas, carbon monoxide, carbon dioxide, or combinations thereof can be formed in situ by contact of water vapor and light hydrocarbons with an inorganic salt catalyst. Usually, under thermodynamic conditions, the molar ratio of carbon monoxide to carbon dioxide is 0.07. In some embodiments, the molar ratio of generated carbon monoxide to generated carbon dioxide is 0.3 or more, 0.5 or more, or 0.7 or more. In some embodiments, the molar ratio of generated carbon monoxide to generated carbon dioxide ranges from 0.3 to 1.0, 0.4 to 0.9, or 0.5 to 0.8. The ability to generate carbon monoxide preferentially over carbon dioxide in the field may be beneficial to other processes located in areas close to the process or upstream of the process. For example, the generated carbon monoxide may be used as a reducing agent in the treatment of hydrocarbon formations or other processes, such as the synthesis gas process.

In some embodiments, the total product produced herein may contain a mixture of compounds having a boiling range distribution of -10 to 538 ° C. The mixture may contain 0.001 to 0.8 g, 0.003 to 0.1 g, or 0.005 to 0.01 g of C ₄ hydrocarbon per gram of mixture. The C ₄ hydrocarbon may contain 0.001 to 0.8 g, 0.003 to 0.1 g, and 0.005 to 0.01 g of butadiene per 1 g of C ₄ hydrocarbon. In some embodiments, isoparaffin is produced at a weight ratio to n-paraffin of 1.5 or less, 1.4 or less, 1.0 or less, 0.8 or less, 0.3 or less, or 0.1 or less. In certain embodiments, isoparaffin is produced in a weight ratio to n-paraffin of 0.00001-1.5, 0.0001-1.0, or 0.001-0.1. The paraffin may contain isoparaffin and / or n-paraffin.

  In some embodiments, the total product and / or crude product may contain olefins and / or paraffins in proportions or amounts commonly found in crude oil produced and / or distilled from the formation. Olefins contain a mixture of olefins having terminal double bonds (“α-olefins”) and olefins having internal double bonds. In certain embodiments, the olefin content in the crude product is greater by a factor of 2, 10, 50, 100, or at least 200, of the olefin content of the crude oil. In some embodiments, the olefin content of the crude product is greater by a factor of 1,000 or less, 500 or less, 300 or less, or 250 or less of the olefin content of the crude feed.

In certain embodiments, the olefin content of a hydrocarbon with a boiling range distribution of 20-400 ° C. is 0.00001-0.1 g, 0.0001-0.05 g, or 0.01-0. The range is 04 g.

In some embodiments, alpha-olefins can be produced in 0.001 g or more, 0.005 g or more, or 0.01 g or more per gram of crude product. In certain embodiments, the crude product contains 0.0001-0.5 g, 0.001-0.2 g, or 0.01-0.1 g of α-olefin per gram of crude product. In certain embodiments, the α-olefin content of a hydrocarbon having a boiling range distribution of 20-400 ° C. is 0.0001-0.08 g, 0.001-0.05 g, or 0.01- The range is 0.04 g.

In some embodiments, hydrocarbons having a boiling range distribution of 20-204 ° C. have a weight ratio of α-olefin to internal double bond olefin of 0.7 or more, 0.8 or more, 0.9 or more, It is 0 or more, 1.4 or more, or 1.5 g or more. In some embodiments, the weight ratio of hydrocarbon α-olefin to internal double bond olefin having a boiling range distribution of 20-204 ° C. is 0.7-10, 0.8-5.0, 0.9- 3, or in the range of 1-2. The weight ratio of α-olefin to internal double bond olefin in crude oil and commercial products is usually 0.5 or less. The ability to produce more α-olefins relative to internal double bond olefins may facilitate the conversion of crude products to commercial products.

In some embodiments, contacting a crude feed with a hydrogen source in the presence of an inorganic salt catalyst can produce hydrocarbons having a boiling range distribution of 20-204 ° C. containing linear olefins. Linear olefins have cis and trans double bonds. The weight ratio of the linear olefin having a trans double bond to the linear olefin having a cis double bond is 0.4 or less, 1.0 or less, or 1.4 or less. In certain embodiments, the weight ratio of linear olefin having a trans double bond to linear olefin having a cis double bond is 0.001 to 1.4, 0.01 to 1.0, or 0.1. It is in the range of ~ 0.4.

In certain embodiments, hydrocarbons having a boiling range distribution of 20-204 ° C. have an n-paraffin content of 0.1 g or more, 0.15 g or more, 0.20 g or more, or 0.30 g or more per gram of the hydrocarbon. It is. The n-paraffin content of such hydrocarbons is in the range of 0.001 to 1.9 g, 0.1 to 0.8 g, or 0.2 to 0.5 g. In some embodiments, the weight ratio of isoparaffin to n-paraffin is 1.5 or less, 1.4 or less, 1.0 or less, 0.8 or less, or 0.3 or less. From the n-paraffin content in such hydrocarbons, the n-paraffin content of the crude product is 0.001 to 0.9 g, 0.01 to 0.8 g, or 0.1 per gram of crude product. It may be estimated to be in the range of ~ 0.5 g.

In some embodiments, the total Ni / V / Fe content of the crude product is 90% or less, 50% or less, 10% or less, 5% or less, relative to the Ni / V / Fe content of the crude feed, or 3% or less. In certain embodiments, the crude product contains no more than 0.0001 g Ni / V / Fe per g crude product, no more than 10 ^-5 g, or no more than 10 ^-6 g. In certain embodiments, the crude product has a total Ni / V / Fe content of 1 ra 10 ^{-7 to} 5 ra 10 ^-5 g, 3 ra 10 ^-7 to 2 ra 10 ^-5 g per gram of crude product, Or it is the range of 1 ra 10 ^<-6 > -1 la 10 ^{< -5>} g.

In some embodiments, the TAN of the crude product is 90% or less, 50% or less, or 10% or less relative to the TAN of the crude feed. In certain embodiments, the TAN of the crude product may be 1 or less, 0.5 or less, 0.1 or less, 0.05 or less. In some embodiments, the TAN of the crude product may range from 0.001 to 0.5, 0.01 to 0.2, or 0.05 to 0.1.
In certain embodiments, the crude product has an API specific gravity that is at least 10% higher, at least 50% higher, or at least 90% higher than the API specific gravity of the crude feed. In certain embodiments, the crude product has an API specific gravity of 13-50, 15-30, or 16-20.

In some embodiments, the total heteroatom content of the crude product is 70% or less, 50% or less, or 30% or less relative to the total heteroatom content of the crude feed. In certain embodiments, the total heteroatom content of the crude product is 10% or greater, 40% or greater, or 60% or greater relative to the total heteroatom content of the crude feed.
The sulfur content of the crude product is 90% or less, 70% or less, or 60% or less with respect to the sulfur content of the crude material. The sulfur content of the crude product may be 0.02 g or less, 0.008 g or less, 0.005 g or less, 0.004 g or less, 0.003 g or less, or 0.001 g or less per gram of crude product. In certain embodiments, the sulfur content of the crude product ranges from 0.0001 to 0.02 g, or 0.005 to 0.01 g, per gram of crude product.

In certain embodiments, the nitrogen content of the crude product may be 90% or less or 80% or less relative to the nitrogen content of the crude feed. The nitrogen content of the crude product may be 0.004 g or less, 0.003 g or less, or 0.001 g or less per gram of crude product. In some embodiments, the nitrogen content of the crude product ranges from 0.0001 to 0.005 g, or 0.001 to 0.003 g, per gram of crude product.

  In some embodiments, the crude product contains 0.05 to 0.2 g, or 0.09 to 0.15 g, of hydrogen per gram of crude product. The H / C of the crude product may be 1.8 or less, 1.7 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, or 1.4 or less. In some embodiments, the H / C of the crude product is 80-120%, or 90-110%, relative to the H / C of the crude feed. In another embodiment, the H / C of the crude product is 100-120% relative to the H / C of the crude feed. Crude product H / C within 20% of crude feed H / C indicates minimal hydrogen uptake and / or consumption during the process.

  Crude oil products contain components in a certain boiling range. In some embodiments, the crude product is 0.001 g or more, or 0.001 to 0.5 g of hydrocarbons having a boiling range distribution of 0.101 MPa and 200 ° C. or lower or 204 ° C. or lower per gram of crude product, respectively. Boiling point range distribution of 0.101 Mpa and 200 to 300 hydrocarbons 0.001 g or more; or 0.001 to 0.5 g; boiling point distribution 0.101 MPa and 300 to 400 hydrocarbons of 0.001 g or more; Or 0.001 to 0.5 g; and 0.001 g or more, or 0.001 to 0.5 g of 400 to 538 hydrocarbons with a boiling range distribution of 0.101 MPa.

In some embodiments, the naphtha content of the crude product is 0.00001 to 0.2 g, 0.0001 to 0.1 g, or 0.001 to 0.05 g per gram of crude product. In certain embodiments, the crude product contains 0.001 to 0.2 g or 0.01 to 0.05 g naphtha. In some embodiments, the naphtha contains no more than 0.15 g, no more than 0.1 g, or no more than 0.05 g of olefin per gram of naphtha. Specific embodiments contain 0.00001 to 0.15 g, 0.0001 to 0.1 g, or 0.001 to 0.05 g of olefin per gram of crude product. In some embodiments, the benzene content of naphtha is 0.01 g or less, 0.005 g or less, or 0.002 g or less per naphtha. In certain embodiments, the benzene content of naphtha is undetectable or 1 la 10 ⁻⁷ to 1 la 10 ⁻² g, 1 la 10 ⁻⁶ to 1 la 10 ⁻⁵ g, 5 ra 10 ⁻⁶ to It is in the range of 1 la 10 ^-4 g. Benzene-containing compositions are considered handling hazards and, therefore, crude products with relatively low benzene content do not require special handling.

In certain embodiments, naphtha may contain aromatic compounds. The aromatic compound may contain a monocyclic compound and / or a polycyclic compound. Monocyclic compounds include, but are not limited to, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, 1-ethyl-3-methylbenzene; 1-ethyl-2-methylbenzene 1,2,3-trimethylbenzene; 1,3,5-trimethylbenzene; 1-methyl-3-propylbenzene; 1-methyl-2-propylbenzene; 1,2,3-trimethylbenzene; 2-trimethylbenzene; 2-ethyl-1,4-dimethylbenzene; 2-ethyl-2,4-dimethylbenzene; 1,2,3,4-tetramethylbenzene; ethyl, pentylmethylbenzene; -2,4,5,6-tetramethylbenzene; tri-isopropyl-o-xylene: benzene, toluene, o-xylene, m-xylene , P- xylene, or substituted congeners mixtures thereof (congener) can be mentioned. Monocyclic aromatics are used in various commercial products and / or are sold as individual components. The crude product produced as described herein usually contains a large amount of monocyclic aromatics.

In certain embodiments, the toluene content of the crude product is 0.001 to 0.2 g, 0.05 to 0.15 g, or 0.01 to 0.1 g per gram of crude product. The m-xylene content of the crude product is 0.001 to 0.1 g, 0.005 to 0.09 g, or 0.05 to 0.08 g per gram of crude product. The o-xylene content of the crude product is 0.001 to 0.2 g, 0.005 to 0.1 g, or 0.01 to 0.05 g per gram of crude product. The p-xylene content of the crude product is 0.001 to 0.09 g, 0.005 to 0.08 g, or 0.001 to 0.06 g per gram of crude product.

Increasing the aromatic content of naphtha tends to improve the octane number of naphtha. Crude oil can be evaluated based on an estimate of the gasoline potential of the crude oil. Gasoline potential includes, but is not limited to, the octane number calculated for the naphtha portion in crude oil. Crude oil usually has a calculated octane number in the range of 35-60. The octane number of gasoline tends to reduce the need for additives that improve the octane number. In certain embodiments, the crude product contains naphtha having an octane number of 60 or more, 70 or more, 80 or more, or 90 or more. Usually, the octane number of naphtha is in the range of 60-99, 70-98, or 80-95.

In some embodiments, the crude product has a total aromatic content of hydrocarbons with a boiling range distribution of 204-500 ° C. (total “naphtha and kerosene”) compared to the total naphtha and kerosene of the crude feed. Is 5% or more, 10% or more, 50% or more, or 99% or more. Typically, the total aromatic content of total naphtha and kerosene in the crude feed is 8%, 20%, 75%, or 100% higher than the total aromatic content of total naphtha and kerosene in the crude product.

In some embodiments, the total polyaromatic content of kerosene and naphtha is 0.00001-0.5 g, 0.0001-0.2 g, 0.001-0.1 g per gram of total kerosene and naphtha. Range.
The distillate content of the crude product is in the range of 0.0001-0.9 g, 0.001-0.5 g, 0.005-0.3 g or 0.01-0.2 g per gram of crude product. . In some embodiments, the weight ratio of kerosene to diesel oil in the distillate ranges from 1: 4 to 4: 1, 1: 3 to 3: 1, or 2: 5 to 5: 2.

In some embodiments, the crude product contains no less than 0.001 g of kerosene, or greater than 0 g and no greater than 0.7 g, 0.001-0.5 g, or 0.01-0.1 g per gram of crude product. . In certain embodiments, the crude product contains 0.001 to 0.5 g, or 0.01 to 0.3 g of kerosene. In some embodiments, the aromatic content of kerosene is 0.2 g or more, 0.3 g or more, or 0.4 g or more per gram of kerosene. In certain embodiments, the aromatic content of kerosene ranges from 0.1 to 0.5 g, or 0.2 to 0.4 g.

In certain embodiments, the freezing point of kerosene may be less than −30 ° C., less than −40 ° C., or less than −50 ° C. As the aromatic content of the kerosene moiety in the crude product increases, the density of the kerosene moiety increases and the freezing point tends to decrease. A crude product having a high density, low freezing point kerosene moiety may be refined to produce a desired high density, low freezing point aircraft turbine fuel.

In certain embodiments, the diesel product content of the crude product ranges from 0.001 to 0.8 g or 0.01 to 0.4 g per gram of crude product. In certain embodiments, the aromatic content of diesel oil is 0.1 g or more, 0.3 g or more, or 0.5 g or more per gram of diesel oil. In some embodiments, the aromatic content of the diesel oil ranges from 0.1 to 1 g, 0.3 to 0.8 g, or 0.2 to 0.5 g.

In some embodiments, the VGO content of the crude product ranges from 0.0001 to 0.99 g, 0.001 to 0.8 g, or 0.1 to 0.3 g per gram of crude product. In certain embodiments, the VGO content in the crude product ranges from 0.4 to 0.9 g, or 0.6 to 0.8 g, per gram of crude product. In certain embodiments, the aromatic content of VGO ranges from 0.1 to 0.99 g, 0.3 to 0.8 g, or 0.5 to 0.6 g per gram of VGO.

In some embodiments, the crude product residue content is 70% or less, 50% or less, 30% or less, 10% or less, or 1% or less of the crude feed. In certain embodiments, the crude product residue content is 0.1 g or less, 0.05 g or less, 0.03 g or less, 0.02 g or less, 0.01 g or less, 0.005 g or less per gram of crude product. Or 0.001 g or less. In some embodiments, the crude product residue content is 0.000001 to 0.1 g, 0.00001 to 0.05 g, 0.001 to 0.03 g, or 0.005 to 0.005 g of crude product. The range is 0.04 g.

In some embodiments, the crude product may contain at least a portion of the catalyst. In some embodiments, the crude product contains more than 0 g and less than 0.01 g, or 0.000001 to 0.001 g, or 0.00001 to 0.0001 g of catalyst per gram of crude product. The catalyst helps stabilize the crude product during transportation and / or processing. The catalyst can also prevent corrosion and friction and / or improve the water separation capacity of the crude product. The crude product containing at least a portion of the catalyst may be further processed to produce lubricants and / or other commercial products.

The catalyst used to process the crude product in the presence of a hydrogen source to produce the entire product may be a single catalyst or multiple catalysts. The catalyst for this application may be a catalyst precursor that first converts to a catalyst in the contact zone when the hydrogen and / or sulfur containing crude feed comes into contact with the catalyst precursor.

The catalyst used to contact the crude product with the hydrogen source to produce the entire product may help reduce the molecular weight of the crude feed. Without being bound by a particular theory, a catalyst combined with a hydrogen source can be produced in crude oil feeds by the action of a base (Lewis base or Bronsted-Lowry base) and / or superbase component in the catalyst. May reduce the molecular weight of the component. Examples of catalysts that may have Lewis base or Bronsted-Lowry base properties include the catalysts described herein.

In some embodiments, the catalyst is a TMS catalyst. The TMS catalyst has a transition metal sulfide-containing catalyst. For the purposes of this application, the weight of the transition metal sulfide in the TMS catalyst is determined by adding the total weight of the transition metal to the total weight of sulfur in the catalyst. The atomic ratio of transition metal to sulfur is usually in the range of 0.2-20, 0.5-10, or 1-5. Examples of transition metal sulfides are “Inorganic Sulfur Chemistry”, G.C. Edited by Nickless; Elesvier Publishing Company, Amsterdam-London-New York; 1968 Copyright; See Chapter 19.

In certain embodiments, the TMS catalyst contains 0.4 g or more, 0.5 g or more, 0.8 g or more, or 099 g or more of one or more transition metal sulfides per gram of catalyst. In certain embodiments, the total content of one or more transition metal sulfides in the TMS catalyst is 0.4-0.999 g, 0.5-0.9 g, or 0.6-0.8 g per gram of catalyst. It is a range.

The TMS catalyst contains one or more transition metal sulfides. Examples of transition metal sulfides, pentlandite _{(pentlandite) (Fe 4. 5} Ni 4. 5 S 8), Sumi site _{(Smithite) (Fe 6. 75} Ni 2. 25 S 11), Buraboaito (bravoite) _{(Fe 0. 7 Ni 0.} 2 Co 0. 1 S 2), Makkina Wight _{(mackinawite) (Fe 0. 75} Ni 0. 26 S 0. 9), earth Gent pentlandite (argentopentlandite) (AgFe ₆ Ni ₂ S _8), Isokyubanaito (CuFe ₂ S _3), iso chalcopyrite _{(isocalcopyrite) (Cu 8 Fe 9} S 16), the scan fail lights _{(sphalerite) (Zn 0. 95} Fe 0. 05 S), Muihokaito (mooihoekite) ( Cu ₉ Fe ₉ S _16), Chatokaraito _{(chatkarite) (Cu 6 FeSn 2} S 8), Stern bar Gaito (sternbergite) AgFe ₂ S _3), Virtual Kopai light (chalcopyrite) (CuFeS _2), FeS (troilite) (FeS), pyrite (pyrite) (FeS _2), Pirotaito _{(pyrrhotite) (Fe (1-} x) S (x = 0 -0.17)), heezlewoodite (Ni ₃ S ₂ ) or baesite (NiS ₂ ).

In some embodiments, the TMS catalyst contains one or more transition metal sulfides in combination with alkali metals, alkaline earth metals, zinc, zinc compounds or mixtures thereof. In some embodiments, the TMS catalyst has the general chemical formula A _c [M _a S _b ] _d (where A represents an alkali metal, alkaline earth metal or zinc, and M represents a transition metal in columns 6-10 of the periodic table). And S is sulfur, the atomic ratio of a to b is in the range of 0.5 to 2.5, or 1-2, and the atomic ratio of c to a is 0.0001 to 1, 0.1. It is represented by -0.8 or 0.3-0.5. In some embodiments, the transition metal is iron.

The TMS catalyst some embodiments, well-known alkali and / or alkaline earth metal / transition metal sulfides [e.g. Bad Night _{(bartnite) (K 3 Fe 10} . 5 S 14), Rasubyumaito (rasvumite) (K Fe _{2. 5} S _3), gels Fi Shah light _{(djerfisherite) (K 6 naFe 19} Cu 4 NiS 26 Cl), black Robert Knight _{(chlorobartnite) (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 in situ manufactured barnite. Knight may be referred to as synthetic barnite, and natural and / or synthetic barnite may be used as a TMS catalyst in the manner described herein.

  In some embodiments, the TMS catalyst may contain no more than 25 g, no more than 15 g, or no more than 1 g of support material per 100 g of TMS catalyst. Usually, the TMS catalyst contains 0-25 g, 0.00001-20 g, or 0.0001-10 g of support material per 100 g of TMS catalyst. Examples of support materials used in combination with TMS catalysts include refractory oxides, porous carbon materials, zeolites, or mixtures thereof. In some embodiments, the TMS catalyst is free or substantially free of support material.

  A TMS catalyst comprising an alkali metal, alkaline earth metal, zinc, zinc compound or mixtures thereof includes one or more transition metal sulfides, alkali metal-transition metal bimetal sulfides, high valent transition metal sulfides, transitions Metal oxides or mixtures thereof may be included (measured by X-ray diffraction). In some embodiments, the alkali metal component, alkaline earth metal component, zinc component, and / or transition metal sulfide portion of the TMS catalyst is present as an amorphous composition that cannot be detected by X-ray diffraction. Also good.

In some embodiments, the TMS catalyst crystalline particles and / or the mixture of TMS catalyst crystal particles has a particle size of 10 ^{8 ８} or less, 10 ³ Å or less, 100 Å or less, or 40 Å or less. In normal practice, the size of the crystalline particles of the TMS catalyst is generally 10 mm or more.

  A sufficient amount of deionized water, a desired amount of transition metal oxide, and a desired amount of first, to produce a TMS catalyst comprising an alkali metal, alkaline earth metal, zinc, zinc compound or mixture thereof. The column-2 metal carbonate, column 1-2 metal oxalate, column 1-2 metal acetate, zinc carbonate, zinc acetate, zinc oxalate, or mixtures thereof may be mixed to form a wet paste. The wet paste may be dried at a temperature of 100-300 ° C or 150-250 ° C to form a transition metal oxide / salt mixture. The transition metal oxide / salt mixture may be fired at a temperature in the range of 300-1000 ° C., 500-800 ° C., or 600-700 ° C. to form a transition metal oxide / metal salt mixture. The transition metal oxide / metal salt mixture may be reacted with hydrogen to form a reduced intermediate solid. The hydrogen addition may be performed at a flow rate sufficient to supply an excess amount of hydrogen to the transition metal oxide / metal salt mixture. Hydrogen may be added to the transition metal oxide / metal salt mixture over a period of 10 to 50 hours or 20 to 40 hours to produce a reduced intermediate solid comprising elemental transition metal. Hydrogenation may be performed at a temperature of 35 to 500 ° C., 50 to 400 ° C., or 100 to 300 ° C., and a pressure of 10 to 15 MPa, 11 to 14 MPa, or 12 to 13 MPa. The reduction time, reduction temperature, choice of reducing gas, reducing gas pressure, and / or reducing gas flow rate used to produce the intermediate solid can be varied with respect to the absolute mass of the selected transition metal oxide. Many should be understood. The reduced intermediate solid can pass through a 40 mesh screen with minimal force in some embodiments.

  The reducing intermediate solid may be incrementally added to the heat (eg, 100 ° C.) diluent / elemental sulfur and / or one or more sulfur compound mixtures at a rate that controls heat generation and gas generation. The diluent can be any suitable diluent that provides a means for dissipating the heat of sulfidation. Examples of the diluent include solvents having a boiling point range distribution of 100 ° C. or higher, 150 ° C. or higher, 200 ° C. or higher, or 300 ° C. or higher. Usually, the boiling point range distribution of the diluent is 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 compound is 1 to 100 mol%, 2 to 80 mol%, 5 to 5 mol, based on the mol of the column 1 or 2 metal or zinc in the column 1 or 2 metal salt or zinc salt. The range may be 50 mol% or 10 to 30 mol%. After the reducing intermediate solid is added to the diluent / elemental sulfur mixture, the resulting mixture is incrementally heated to a final temperature of 200-500 ° C, 250-450 ° C, or 300-400 ° C, and this final temperature 1 hour or more, 2 hours or more, or 10 hours or more. Typically, the final temperature is maintained for 15 hours, 10 hours, 5 hours or 1.5 hours. After heating to a high sulfurization reaction temperature, the catalyst may be cooled to a temperature in the range of 0-100 ° C, 30-90 ° C, -100 ° C, or 50-80 ° C to facilitate recovery of the catalyst from the mixture. The sulfurized catalyst is isolated from the diluent using standard techniques in an oxygen free atmosphere and then washed with at least a portion of a low boiling solvent (eg, pentane, heptane, or hexane) to produce a TMS catalyst. Good. The TMS catalyst may be pulverized using standard methods.

  In some embodiments, the catalyst is an inorganic salt catalyst. The anion of the inorganic salt catalyst includes an inorganic compound, an organic compound, or a mixture thereof. Examples of inorganic salt catalysts include alkali metal carbonates, alkali metal hydroxides, alkali metal hydrides, alkali metal amides, alkali metal sulfides, alkali metal acetates, alkali metal oxalates, alkali metal formates, and alkali metal pyruvic acids. Salt, alkaline earth metal carbonate, alkaline earth metal hydroxide, alkaline earth metal hydride, alkaline earth metal amide, alkaline earth metal sulfide, alkaline earth metal acetate, alkaline earth metal oxalate Alkaline earth metal formate, alkaline earth metal pyruvate, or mixtures thereof.

Examples of the inorganic salt catalyst include, but are not limited to, 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 / KHCO ₃ / Rb ₂ CO ₃ ; LiHCO ₃ / KHCO ₃ / Rb ₂ CO ₃ ; K ₂ CO ₃ / Rb ₂ CO ₃ / Cs KOH / RbOH / CsOH mixed with ₂ CO ₃ mixture; 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 K ₂ CO ₃ / Rb ₂ And a mixture of Ca (OH) ₂ ; mixed with CO ₃ / Cs ₂ CO ₃ .

  In some embodiments, the inorganic salt catalyst contains 0.00001 g or less, 0.001 g or less, or 0.01 g or less, calculated as lithium weight per gram of inorganic salt catalyst. In some embodiments, the inorganic salt catalyst contains 0 g to less than 0.01 g, 0.0000001 to 0.001 g, or 0.00001 to 0.0001 g, calculated as lithium weight per gram of inorganic salt catalyst. To do.

  In certain embodiments, the inorganic salt catalyst contains one or more alkali metals including an alkali metal having an atomic number of 11 or more. When the inorganic salt catalyst is two or more alkali metals, in some embodiments, the atomic ratio of an alkali metal having an atomic number of 11 or more to an alkali metal having an atomic number of more than 11 is 0.1 to 10, 0.2. It is the range of ~ 6 or 0.3-4. For example, the inorganic salt catalyst may contain sodium, potassium and rubidium salts in a sodium to potassium ratio of 0.1 to 6, a sodium to rubidium ratio of 0.1 to 6, and a potassium to rubidium ratio of 0.1 to 6. . In other examples, the inorganic salt catalyst contains sodium and potassium salts in a sodium to potassium ratio of 0.1-4.

  In some embodiments, the inorganic salt catalyst comprises a metal in columns 8-10 of the periodic table, a compound of metal in columns 8-10 of the periodic table, a metal in column 6 of the periodic table, and a metal compound in column 6 of the periodic table. Or mixtures thereof. Examples of metals in columns 8 to 10 of the periodic table include, but are not limited to, iron, rhenium, cobalt, or nickel. Examples of the metal in the sixth column of the periodic table include, but are not limited to, chromium, molybdenum, or tungsten. In some embodiments, the inorganic salt catalyst contains 0.1-0.5 g, or 0.2-0.4 g of Raney nickel per gram of inorganic salt catalyst.

In certain embodiments, the inorganic salt catalyst also contains metal oxides in columns 1 and 2 and / or 13 of the periodic table. The metal in column 13 includes, but is not limited to, fluorine or aluminum. Non-limiting 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 certain embodiments, the inorganic salt catalyst is a Lewis acid (eg, BCl ₃ , AlCl ₃ and SO ₃ ), Bronsted-Lorry acid (eg, H ₃ O ⁺ , H ₂ SO ₄ , HCl and HNO ₃ ), glass forming properties. It is free or substantially free of composition (eg borate and silicate) and halide. The inorganic salt is a) a halide, b) a composition that forms a glass at a temperature of 350 ° C. or higher, or 1000 ° C. or lower, c) a Lewis acid, d) a Bronsted-Lorry acid, or e) per 1 g of the inorganic salt catalyst. These mixtures may contain from 0 g to 0.1 g, 0.000001 to 0.01 g, or 0.00001 to 0.005 g.

  Inorganic salt catalysts may be prepared using standard techniques. For example, each component of the catalyst may be blended in the desired amount using standard mixing techniques (eg, kneading and / or grinding). In other embodiments, the inorganic composition is dissolved in a solvent (water or a suitable organic solvent) to form an inorganic composition / solvent mixture. Standard separation techniques can be used to remove the solvent and produce the inorganic salt catalyst.

  In some embodiments, the inorganic salt of the inorganic salt catalyst may be introduced into the support to form a supported inorganic salt catalyst. Examples of the support include, but are not limited to, zirconium oxide, calcium oxide, magnesium oxide, titanium oxide, magnesium oxide, titanium oxide, hydrotalcite, alumina, germania, iron oxide, nickel oxide, zinc oxide, Cadmium oxide, antimony oxide, and mixtures thereof. In some embodiments, the support may be impregnated with an inorganic salt, a column 6-10 metal and / or a column 6-10 metal compound. Alternatively, the inorganic salt may be melted or softened with heat and pushed into and / or on the metal support or metal oxide support to form a supported inorganic salt catalyst.

  The inorganic salt structure is usually heterogeneous, permeable, and / or susceptible to movement at a particular temperature or temperature range when a reduction in order occurs in the catalyst structure. Inorganic salt catalysts become disordered with little compositional change (eg, salt decomposition). Without being bound by theory, it is believed that when the distance between ions in the lattice of the inorganic salt catalyst increases, the inorganic salt catalyst becomes disordered (easy to move). As the distance between ions increases, the crude feed and / or hydrogen source may penetrate the inorganic salt instead of crossing the surface of the inorganic salt catalyst. As the crude feed and / or hydrogen source penetrates the inorganic salt, the contact area between the inorganic salt catalyst and / or the crude feed and / or hydrogen source often increases. Increasing the contact area and / or reaction area of the inorganic salt catalyst increases the yield of liquid organisms, suppresses the formation of residues and / or coke, and / or the crude product compared to the same properties of the crude feed. It is likely that the characteristics of are likely to change. The disorder (eg, heterogeneity, permeability, and / or mobility) of the inorganic salt catalyst can be determined by DSC method, ionic conductivity measurement method, TAP method, visual inspection, X-ray diffraction method or a combination thereof. May be used to measure. In some embodiments of the present invention, the catalyst is in such a disordered state and is contacted with the crude feed in the disordered state.

Methods for measuring catalyst properties using TAP are described in USP 4,626,412 by Ebner et al., USP 5,039,489 by Greaves et al., USP 5,264,183 by Ebner et al. The TAP system is obtained from Mitra Technologies (Foley, MO, USA). The TAP analysis is performed at a temperature range of 25-850 ° C., 50-500 ° C. or 60-400 ° C., a heating rate of 10-50 ° C. or 20-40 ° C., and a range of 1 × 10 ⁻¹³ to 1 × 10 ⁻⁸ . You may carry out by pressure reduction. The temperature may be kept constant and / or increased as a function of time. As the temperature of the inorganic salt catalyst increases, the gas release from the inorganic salt catalyst is measured. Examples of the gas released from the inorganic salt catalyst include carbon monoxide, carbon dioxide, hydrogen, water, or a mixture thereof. The temperature at which an inflection point (a sharp increase) is detected by gas generation from the inorganic salt catalyst is regarded as a temperature at which the inorganic salt catalyst becomes disordered.

  In some embodiments, the inflection point in the gas released from the inorganic salt catalyst may be detected over a temperature range measured using TAP. This temperature or temperature range is referred to as the “TAP temperature”. The initial temperature in the temperature range measured using TAP is referred to as the “TAP minimum temperature”.

  The outgassing inflection point shown for inorganic salt catalysts suitable for contact with crude feed is in the TAP temperature range of 100-600 ° C, 200-500 ° C or 300-400 ° C. Usually, the TAP temperature range is in the range of 300-500 ° C. In some embodiments, different compositions of suitable inorganic salt catalysts also exhibit gas inflection points, but different TAP temperatures.

  The magnitude of the ionization inflection point associated with the released gas may be an indicator of the order of the particles in the crystal structure. In a highly ordered crystal structure, the ionic particles are generally closely associated and require more energy (ie, more heating) to release ions, molecules, gases, or combinations thereof from the crystal structure. In a disordered crystal structure, ions are not as strongly associated with each other as ions in a highly ordered crystal structure. Such low ionic association generally requires less energy to release ions, molecules and / or gases from the disordered crystal structure, and thus the amount of ions and / or gases released from the disordered crystal structure is usually selected. Greater than the amount of ions and / or gases released from the highly ordered crystal structure at a given temperature.

  In some embodiments, the heat of dissociation of the inorganic salt catalyst may be observed in the range of 50-500 ° C. with a heating or cooling rate of 10 ° C. as measured with a differential scanning calorimeter. In the DSC method, the sample is heated to a first temperature, cooled to room temperature, and then heated second. In general, the transition observed during the first heating indicates entrained water and / or solvent and may not show heat of dissociation. For example, the easily observed heat of drying of a wet or hydrated sample can generally occur below 250 ° C, usually 100-150 ° C. The transition observed during the cooling cycle and second heating corresponds to the heat of dissociation of the sample.

  “Heating transition” refers to the process that occurs when the temperature decreases during DSC analysis and the ordered molecules and / or atoms in the structure become disordered. “Cooling transition” refers to the process that occurs when the temperature and temperature of a molecule and / or atoms in a structure become more homogeneous during DSC analysis. In some embodiments, the thermal / cooling transition of the inorganic salt catalyst occurs over the temperature range detected by DSC. The temperature or temperature range at which the inorganic salt catalyst heating transition occurs during the second heating cycle is referred to as the “DSC temperature”. The lowest DSC temperature in the temperature range during the second heating cycle is referred to as the “minimum DSC temperature”. The inorganic salt catalyst exhibits a heating transition in the range of 200-500 ° C, 250-450 ° C, or 300-400 ° C.

  For inorganic salts containing inorganic salt particles as a relatively homogeneous mixture, the shape of the peak associated with the heat absorbed during the second heating cycle may be relatively narrow. For inorganic salt catalysts that include inorganic salt particles in a relatively heterogeneous mixture, the shape of the peak associated with the heat absorbed during the second heating cycle may be relatively broad. Absence of a peak in the DSC spectrum indicates that the salt does not absorb or release heat in the scanning temperature range. The absence of a heating transition generally indicates that the sample structure does not change upon heating.

  As the particle homogeneity of the inorganic salt mixture increases, the ability of the mixture to remain solid and / or semi-solid during heating decreases. The homogeneity of the inorganic mixture can be related to the ionic radius of the cations in the mixture. For cations with a small ionic radius, the ability of the cation to share electron density with the corresponding anion and the acidity of the corresponding anion are increased. In a series of ions having a similar charge, if the anion is a hard base, the ion attractive force between the cation and the anion tends to be high due to a small ionic radius. Such high interionic attractive forces increase the heating transition temperature for the salt and / or the more homogeneous particle mixture in the salt (sharp peaks and area increase in the DSC curve). Mixtures containing cations with small ionic radii tend to be more acidic than cations with large ionic radii, thus increasing the acidity of the inorganic salt mixture as the cation radius decreases. For example, when a crude material and a hydrogen source are brought into contact in the presence of a lithium cation-containing inorganic mixture, the crude material and the hydrogen source are brought into contact in the presence of an inorganic salt catalyst containing a cation having a larger ion radius than lithium. The amount of gas and / or coke produced is likely to increase as compared with the case of the above. The ability to prevent gas and / or coke generation improves the yield of the total liquid product by the present process.

In certain embodiments, the inorganic salt catalyst may contain two or more inorganic salts. You may measure each minimum DSC temperature of these inorganic salts. The minimum DSC temperature of the inorganic salt catalyst may be less than the minimum DSC temperature of at least one inorganic salt in the inorganic salt catalyst. For example, the inorganic salt catalyst may contain potassium carbonate and cesium carbonate. Potassium carbonate and cesium carbonate exhibit DSC temperatures in excess of 500 ° C. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; The DSC temperature of the catalyst is in the range of 290 to 300 ° C.

  In some embodiments, the TAP temperature may be between the 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 to 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 individual inorganic salts may be 500 ° C or higher or 1000 ° C or lower.

  In many embodiments, the inorganic salt catalyst having a TAP temperature and / or DSC temperature of 150-500 ° C., 200-450 ° C. or 300-400 ° C. and not subject to decomposition at these temperatures is a high molecular weight and / or It can be used to catalyze the conversion of high viscosity compositions (eg, crude feed) to liquid products.

  In certain embodiments, the inorganic salt catalyst may have increased conductivity compared to the individual inorganic salt during heating at a temperature in the range of 200-600 ° C, 300-500 ° C, or 350-450 ° C. Such an increase in the conductivity of the inorganic salt catalyst is considered to be because particles in the inorganic salt catalyst generally move easily. The ionic conductivity of some inorganic salt catalysts changes at a lower temperature than the temperature at which the ionic conductivity of the single component of the catalyst changes.

  The ionic conductivity of the inorganic salt catalyst may be measured by applying Ohm's law, ie, V = IR (where V is voltage, I is current, and R is resistance). In order to measure the ionic conductivity, the inorganic salt catalyst is put into a quartz container with two wires (for example, copper wire or platinum wire) separated from each other, and these wires are immersed in the inorganic salt catalyst.

  FIG. 7 is a schematic diagram of a system that can be used to measure ionic conductivity. The quartz container 156 containing the sample 158 is placed in a heating device and heated to a desired temperature gradually. During heating, the voltage of the power supply 160 is applied to the wire 162. The current obtained through the wires 162, 164 is measured with a meter 166. The meter 166 may be, but is not limited to, a multimeter or Wheatstone bridge. If sample 158 is slightly homogenized (more mobile) without causing degradation, the conductivity of the sample decreases and the current observed at meter 166 increases.

  In some embodiments, after heating, cooling and then heating, the inorganic salt catalyst may have a different ionic conductivity at the desired temperature. The difference in ionic conductivity may indicate that the crystal structure of the inorganic salt catalyst has changed from the original shape (first form) to a different shape (second form). If the form of the inorganic salt catalyst does not change during heating, the ionic conductivity is expected to be similar or the same after heating.

  In certain embodiments, the particle size of the inorganic salt catalyst is in the range of 10-1000μ, 20-500μ, or 50-100μ as measured by passing the catalyst through a mesh or sieve.

  Inorganic salt catalysts may soften when heated to temperatures above 50 ° C. and below 500 ° C. As the inorganic salt catalyst softens, the liquid and catalyst particles may coexist in the matrix of the inorganic salt catalyst. In some embodiments, the catalyst particles may self-deform when heated to a temperature of 300 ° C. or higher or 800 ° C. or lower under a specific gravity or under a pressure of 0.007 MPa or higher or 0.101 MPa or lower. As a result, the inorganic salt catalyst rearranges from the first form to the second form. When the inorganic salt catalyst is cooled to 20 ° C., the second form of the inorganic salt catalyst cannot return to the first form of the inorganic salt catalyst. The temperature at which the inorganic salt rearranges from the first form to the second form is said to be the “deformation” temperature. The deformation temperature may be a temperature range or a single temperature. In certain embodiments, the inorganic salt catalyst particles self-deform upon heating to a deformation temperature below the deformation temperature of any of the individual inorganic salts. In some embodiments, the inorganic salt catalyst comprises two or more inorganic salts having different deformation temperatures. In some embodiments, the deformation temperature of the inorganic salt catalyst is different from the deformation temperature of the individual inorganic metal salt.

  In certain embodiments, the inorganic salt catalyst is liquid and / or semi-liquid above the TAP temperature and / or above the DSC temperature. In some embodiments, the inorganic salt catalyst is liquid and / or semi-liquid at the lowest TAP temperature and / or DSC temperature. In some embodiments, an inorganic salt catalyst that is liquid or semi-liquid above the minimum TAP temperature and / or above the DSC temperature forms a separate phase from the crude feed when mixed with the crude feed. In some embodiments, such liquid or semi-liquid inorganic salt catalysts have low solubility in crude feed (eg, from 0 to 0.5 g inorganic salt catalyst per gram of crude feed, 0.0000001 to 0.000). 2 g, or 0.0001 to 0.1 g) or not dissolved in the crude feed at the lowest TAP temperature (for example, 0 g to 0.05 g or less, 0.000001 to 0.01 g, or 0.000001 to 0.01 g of inorganic salt catalyst per g of crude feed). 00001-0.001 g).

In some embodiments, powder X-ray diffraction is used to measure interatomic spacing in inorganic salt catalysts. By monitoring the shape of the _D001 peak in the X-ray spectrum, the relative order of the inorganic salt particles can be estimated. The peak in X-ray diffraction represents a different compound in the inorganic salt catalyst. In powder X-ray diffraction, the _D001 peak can be monitored to estimate the interatomic spacing. In inorganic salt catalysts having highly ordered inorganic salt atoms, the shape of the _D001 peak is relatively narrow. In an inorganic salt catalyst (eg, K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; catalyst), the shape of the D ₀₀₁ peak may be relatively wide, or the D ₀₀₁ peak may not exist. In order to measure whether the disorder of inorganic salt atoms changes during heating, an X-ray diffraction spectrum of the inorganic salt catalyst is taken before heating and compared with the X-ray diffraction spectrum taken after heating. The _D001 peak (corresponding to an inorganic salt atom) in an X-ray diffraction spectrum taken at a temperature higher than 50 ° C is not present in the X-ray diffraction spectrum taken at a temperature lower than 50 ° C, or the X-ray diffraction spectrum It may be wider than the middle _D001 peak. Furthermore, the X-ray diffraction pattern of individual inorganic salts may show a relatively narrow _D001 peak at the same temperature.

  In addition to inhibiting and / or preventing the formation of by-products, the contact conditions may be controlled so that for a given crude feed, the total product composition (and hence the crude product) can be varied. The total product composition includes, but is not limited to, paraffins, olefins, aromatics or mixtures thereof. These compounds constitute a composition of crude product and non-condensable hydrocarbon gas.

  Controlled contact conditions in combination with the catalyst described herein can produce a total product that is less than the expected coke content. From the comparison of the MCR content of various crude oils, the crude oil can be rated based on the ease of coke formation. For example, crude oil with an MCR content of 0.1 g / g crude oil is expected to form more coke than crude oil with an MCR content of 0.001 g / g crude oil. Unfavorable crude oil is usually 0.05 g or more per gram of crude oil with disadvantaged MCR content.

  In some embodiments, the residue content and / or coke content deposited on the catalyst during the reaction period is 0.1 g or less, 0.05 g or less, or 0.03 g or less per gram of catalyst. In certain embodiments, the amount of residue and / or coke deposited on the catalyst ranges from 0.0001 to 0.1 g, 0.001 to 0.05 g, or 0.01 to 0.03 g per gram of catalyst. . In some embodiments, the spent catalyst is substantially free of residue and / or coke. In certain embodiments, the contact conditions are controlled so that coke is produced at 0.015 g or less, 0.01 g or less, 0.005 g or less, or 0.003 g or less per gram of crude product. When a crude feed is contacted with a catalyst under controlled contact conditions, the crude feed is compared to the amount of coke and / or residue produced by heating the crude feed in the presence of a refined catalyst or in the absence of a catalyst under the same contact conditions. As a result, the amount of coke and / or residue is reduced.

  In some embodiments, the contact conditions are such that the crude feed is converted to a crude product of 0.5 g or more, 0.5 g or more, 0.7 g or more, 0.8 g or more, or 0.9 g or more per gram of crude feed. You may control. The crude product produces 0.5-0.99 g, 0.6-0.9 g, or 0.7-0.8 g / g crude feed during contact. If the crude feed is converted to a crude product containing residue and / or coke, if present, in the lowest yield, the crude product is a commercial product that requires minimal pre-treatment at the refinery. Can be converted to In certain embodiments, the crude feed is converted to 0.2 g or less, 0.1 g or less, 0.05 g or less, 0.03 g or less, or 0.01 g or less per non-condensable hydrocarbon per gram of crude feed. In some embodiments, non-condensable hydrocarbons are produced from 0 to 0.2 g, 0.0001 to 0.1 g, 0.001 to 0.05 g, or 0.01 to 0.03 g per gram of crude feed.

  In order to maintain the desired reaction temperature, the contact zone temperature, crude feed flow rate, total product flow rate, catalyst feed rate and / or feed rate, or combinations thereof may be controlled. In some embodiments, the temperature control of the contact zone may be performed to dilute the gaseous hydrogen source stream and / or the amount of hydrogen passing through the contact zone and / or to remove excess heat from the contact zone. The flow of the inert gas passing through the belt may be changed.

In some embodiments, the temperature of the contact zone may be controlled to be higher or lower than the desired temperature “T ₁ ”. In certain embodiments, the contact temperature is controlled such that the temperature in the contact zone is below the minimum TAP temperature and / or below the minimum DSC temperature. In certain embodiments, T ₁ is 30 ° C., 20 ° C. or 10 ° C. below the lowest TAP temperature and / or the lowest DSC temperature. For example, in one embodiment, the contact temperature may be controlled to be 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 controlled to be above the catalyst TAP temperature and / or above the catalyst DSC temperature. For example, the contact temperature may be controlled to be 450 ° C., 500 ° C. or 550 ° C. during the reaction period when the minimum TAP temperature and / or the minimum DSC temperature is 450 ° C. Controlling the contact temperature with the catalytic TAP temperature reference and / or the catalytic DSC temperature reference can improve the properties of the resulting crude product. Such control may be, for example, reducing coke formation, reducing non-condensable gas formation, or a combination thereof.

  In certain embodiments, the inorganic salt catalyst may be conditioned prior to adding the crude feed. In some embodiments, conditioning may be performed in the presence of a crude feed. Conditioning of the inorganic salt catalyst is carried out by heating the catalyst to a first temperature of 100 ° C. or higher, 300 ° C. or higher, 400 ° C. or higher, or 500 ° C. or higher, then 250 ° C. or lower, 200 ° C. or lower, or 100 ° C. The step of cooling to the following second temperature may be included. In certain 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 then in the range of 25-240 ° C, 30-200 ° C, or 50-90 ° C. Cool to the second temperature. Conditioning temperature may be determined by measuring ionic conductivity at different temperatures. In some embodiments, the conditioning temperature can be determined from the DSC temperature determined from the heating / cooling transition obtained by heating and cooling the inorganic salt catalyst multiple times in the DSC. When the inorganic salt catalyst is conditioned, the crude feed can be contacted at a lower reaction temperature than conventional hydrotreating catalysts.

  In some embodiments, the content of naphtha, distillate, VGO or mixtures thereof in the total product may be varied by changing the removal rate of the total product from the contact zone. For example, if the removal rate of all products is reduced, the contact time between the crude oil feedstock and the catalyst tends to be increased. Alternatively, increasing the pressure relative to the initial pressure improves the yield of the crude product and increases the amount of hydrogen taken from the gas into the crude product at a given mass flow rate of the crude feed or hydrogen source. Alternatively, the combination of these effects can be changed. When the contact time between the crude oil raw material and the catalyst becomes longer, a larger amount of diesel oil, kerosene or naphtha and a smaller amount of VGO are produced compared to the amount of diesel oil, kerosene, naphtha and VGO produced by shorter contact time. To do. Moreover, when the contact time of all the products becomes long in the contact zone, the average carbon number of the crude product can be changed. Long contact times increase the weight percentage of low carbon numbers (thus increasing the API specific gravity).

  In some embodiments, the contact conditions may change over time. For example, the contact pressure and / or contact temperature may be increased to increase the amount of hydrogen absorbed by the crude feed to produce the crude product. The ability to change the hydrogen absorption of a crude feed while improving other properties of the crude feed increases the variety of crude products that can be produced from a single crude feed. The ability to produce a wide variety of crude products from a single crude feed enables compliance with various transportation and / or processing standards.

  The amount of hydrogen absorbed may be evaluated by comparing the H / C of the crude feed with the H / C of the crude product and then performing a hydrogen balance between the feed and the total product. When compared to the H / C of the crude feed, an increase in the H / C of the crude product indicates that hydrogen has been incorporated into the crude product from a hydrogen source. A relatively small increase in crude product H / C (20% compared to crude feed) indicates a relatively low consumption of hydrogen gas in the process. It is desirable that the properties of the crude product obtained with the minimum amount of hydrogen consumption be significantly improved compared to the properties of the crude feed.

  The ratio of hydrogen source to crude feed may also be changed due to changes in the properties of the crude product. For example, increasing the hydrogen source to crude feed ratio results in a crude product with an increased VGO content per gram of crude product.

  In a particular embodiment, contacting the crude feed with the inorganic salt catalyst in the presence of light hydrocarbons and / or steam compared to contacting the crude feed with the inorganic salt catalyst in the presence of hydrogen and steam. As a result, liquid hydrocarbons in the crude oil product increase while coke decreases. In embodiments that include contacting the crude feed with methane in the presence of an inorganic salt catalyst, at least some of the components of the crude product are composed of carbon and hydrogen atoms (from methane) in the molecular structure of these components. May have taken in.

  In certain embodiments, the volume of the crude product produced from the crude feed that has been contacted with the hydrogen source in the presence of the inorganic salt catalyst is 5% relative to the volume of the crude product produced by the thermal process at STP. More than 10%, more than 15%, or more than 100%. The total volume of the crude product produced by contacting the crude feed with the inorganic salt catalyst may be 110% or more by volume of the crude feed at STP. The increase in volume is thought to be due to a decrease in density. The low density is generally likely at least partially due to the hydrogenation of the crude feed.

  In a particular embodiment, the crude feed containing 0.02 g or more, 0.05 g or more, or 0.1 g or more and / or 0.001 g or more of Ni / V / Fe, respectively, per 1 g of crude feed. Contact with hydrogen in the presence of a salt catalyst without reducing the catalytic activity.

  In some embodiments, the inorganic salt catalyst can be at least partially regenerated by removing one or more components that contaminate the catalyst. Contaminants include, but are not limited to metals, sulfides, nitrogen, coke or mixtures thereof. Sulfide contaminants can be removed from the spent inorganic salt catalyst by contacting water vapor and carbon dioxide with the spent inorganic salt catalyst to produce hydrogen sulfide. Nitrogen contaminants can be removed by contacting the spent inorganic salt catalyst with steam to produce ammonia. Coke contaminants can be removed from the spent inorganic salt catalyst by contacting the spent inorganic salt catalyst with steam and / or methane to produce hydrogen and carbon monoxide. In some embodiments, one or more gases are generated from a mixture of spent inorganic salt catalyst and residual crude feed.

In certain embodiments, an inorganic salt catalyst (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 feedstock and / or residue and / or coke is 700 until gas and / or liquid production is minimized in the presence of water vapor, hydrogen, carbon dioxide, and / or light hydrocarbons. Heat to a temperature in the range of ~ 1000 ° C or 800-900 ° C to produce a liquid phase and / or gas. The gas may contain increased amounts of hydrogen and / or carbon dioxide compared to the reactive gas. For example, the gas may contain 0.1 to 99 moles or 0.2 to 8 moles of hydrogen and / or carbon dioxide per mole of reactive gas. The gas may contain a relatively small amount of light hydrocarbons and / or carbon monoxide. For example, light hydrocarbons are less than 0.05 g / g gas and carbon monoxide is less than 0.01 g / g gas. The liquid phase contains, for example, more than 0.5 g and 0.99 g or less, or more than 0.9 g and 0.9 g or less per gram of liquid.

  In some embodiments, spent catalyst and / or solids in the contact zone may be treated to recover metals (eg, vanadium and / or nickel) from them. Spent catalyst and / or solids may be treated by well-known metal separation techniques such as heating, chemical treatment, and / or gasification.

  The following is a non-limiting example of a system having catalyst production, catalyst testing, and controlled contact conditions.

Example 1 Preparation of K-Fe Sulfide Catalyst 1000 g of iron oxide (Fe ₂ O ₃ ) and 580 g of potassium carbonate were combined with 412 g of deionized water to form a wet paste. The wet paste was dried at 200 ° C. to form an iron oxide / potassium carbonate mixture. The iron oxide / potassium carbonate mixture was calcined at 500 ° C. to form an iron oxide / potassium carbonate mixture. This iron oxide / potassium carbonate mixture was reacted with hydrogen to form a reduced intermediate solid containing iron metal. Hydrogenation was performed at 450 ° C. and 11.5 to 12.2 MPa (1665-1765 psi) for 48 hours. This intermediate solid was passed through a 40 mesh sieve with minimal force.

  The intermediate solid was incrementally added to the 100 ° C. VGO / m-xylene / elemental sulfur mixture at a rate that controlled the generation of heat and the gas produced. After the addition of the intermediate solid, the resulting mixture was incrementally heated to 300 ° C. and maintained at this temperature for 1 hour. The solvent / catalyst mixture was cooled to below 100 ° C. and the sulfurized catalyst was separated from the mixture. The sulfided catalyst was isolated by filtration in an atmosphere of argon in a dry box and washed with m-xylene to produce 544.7 g of K-Fe sulfide catalyst. The K-Fe sulfide catalyst was pulverized through a 40 mesh sieve.

The obtained K-Fe sulfide catalyst was analyzed by X-ray diffraction. By analysis of the X-ray diffraction spectrum, the catalyst contained trolite (FeS), K—Fe sulfide (KFeS ₂ ), pyrorhotite and iron oxide (eg, magnetite, Fe ₃ O ₄ ). No peaks associated with iron disulfide (eg pyrite, FeS ₂ ) were observed in the X-ray diffraction spectrum.

Example 2: Contact between crude oil raw material and hydrogen supply source in the presence of K-Fe sulfide catalyst 600 mL continuous stirred tank reactor (made of 316 stainless steel), bottom raw material inlet, single outlet steam port, inside reactor Three arranged thermocouples and a shaft-driven 1.25 inch diameter 6 blade Rushion turbine were installed.

A K-Fe sulfide catalyst (110.3 g) prepared as described in Example 1 was charged to the reactor. Hydrogen gas was metered into an 8,000 Nm ³ / m ³ (50,000 SCFB) reactor and mixed with bitumen (Lloydminster region of Canada). This bitumen was introduced into the reactor from the bottom feed inlet to form a hydrogen / crude feed mixture. During the 185 hour reaction run, hydrogen gas and crude feed were continuously fed into the reactor and the product was continuously removed from the reactor outlet steam port. The crude feed was fed at a rate of 67.0 g / hr to maintain the crude feed liquid level at 60% of the reactor volume. A 50 millicurie ¹³⁷ Cs gamma source and a sodium iodide scintillation detector were used to measure the liquid level in the reactor.

  This hydrogen gas / crude feed was contacted with the catalyst at a reactor average internal temperature of 430 ° C. The entire product was produced in the reactor effluent vapor by contacting the hydrogen / crude feed and the catalyst. The reactor effluent vapor exited the reactor from a single top outlet. The reactor tower top was electrically heated to 430 ° C. to prevent internal condensation of the reactor effluent vapor on the tower top.

  After exiting the reactor, the reactor effluent vapor was cooled and separated in a high pressure gas / liquid separator and a low pressure gas / liquid separator to produce a liquid and gas stream. The gas stream was sent to a countercurrent caustic scrubber to remove acid gases and then quantified using standard chromatographic techniques. The total product each contained 0.918 g of crude product and 0.089 g of noncondensable hydrocarbon gas per gram of total product. 0.027 g of solid remained in the reactor per gram of total product. The characteristics and composition of the crude product and non-condensable hydrocarbon gas produced by this method are shown in Table 1 of FIG. 8, Table 2 of FIG. 9, and Table 3 of FIG.

  This example illustrates a process in which a crude feed is contacted with hydrogen in the presence of a transition metal sulfide catalyst to produce the entire product with minimal concomitant generation of coke. The total product contains a crude product that is a liquid mixture at STP and has no more than 0.1 g of non-condensable hydrocarbon gas per gram of total product.

  Table 1 compares the MCR content (13.7 wt%) for the crude feed with the solids formed during the process (2.7 wt%), and the combination of controlled conditions and the catalyst shows that ASTM It can be seen that a smaller amount of coke was produced than the amount indicated by method D4530.

Non-condensable hydrocarbons _contained a C 2, _{C 3} and _{C 4} hydrocarbons. From the total weight ratio (%) of C ₂ hydrocarbons shown in Table 2 (20.5 g), the ethylene content per gram of total C ₂ hydrocarbons can be calculated. The C ₂ hydrocarbon in the hydrocarbon gas contained 0.073 g of ethylene per gram of total C ₂ hydrocarbon. From the total weight ratio (23.9 g) of C ₃ hydrocarbons shown in Table 2, the propene content per gram of total C ₃ hydrocarbons can be calculated. The C ₃ hydrocarbon in the hydrocarbon gas contained 0.21 g of propene per gram of total C ₃ hydrocarbon. The weight ratio of C ₄ hydrocarbons in non-condensable hydrocarbons to isobutane to n-butane was 0.2.

  In this example, 0.001 g or more of hydrocarbon having a boiling range distribution of 204 ° C. (400 ° F.) or less at 0.101 MPa, and 0.001 g of hydrocarbon having a boiling range distribution of 204 to 300 ° C. at 0.101 MPa. More than 0.001 g of hydrocarbon having a boiling range distribution of 300 to 400 ° C. at 0.101 MPa and 0.001 g of hydrocarbon having a boiling range distribution of 400 to 538 ° C. (1000 ° F.) at 0.101 MPa The manufacturing method of the crude product containing above is shown. Hydrocarbons having a boiling range distribution below 204 ° C. contained isoparaffins and n-paraffins, and the weight ratio of isoparaffin to n-paraffin was 1.4 or less.

The crude product has a boiling range associated with naphtha, kerosene, diesel oil and VGO. The crude product contained 0.001 g or more of naphtha, and the octane number of the naphtha portion of the crude product was 70 or more. The benzene content in the naphtha portion of the crude product was 0.01 g or less per gram of naphtha. The naphtha portion of the crude product contained no more than 0.15 g olefin per naphtha. The naphtha portion of the crude product contained 0.1 g or more of monocyclic aromatic per naphtha.
The crude product contained 0.001 g or more of kerosene. The freezing point of the kerosene part of the crude product was less than -30 ° C. The kerosene portion of the crude product contained aromatics, and the aromatic content of the kerosene portion of the crude product was 0.3 g or more per gram of kerosene. The kerosene portion of the crude product contained 0.2 g or more of monocyclic aromatic per gram of kerosene.

The crude product contained 0.001 g or more of diesel oil. The crude product diesel fraction contained aromatics, and the aromatic content of the diesel fraction portion of the crude product was 0.4 g or more per gram of diesel oil.
The crude product contained 0.001 g or more of VGO. The VGO portion of the crude product contained aromatics, and the aromatic content of the VGO portion was 0.5 g or more per gram of VGO.

Example 3: Preparation of K-Fe sulfide catalyst in the absence of hydrocarbon diluent 1000 g of iron oxide and 173 g of potassium carbonate were combined with 423 g of deionized water to form a wet paste. This wet paste was processed as described in Example 1 to form an intermediate solid. This intermediate solid was passed through a 40 mesh sieve with minimal force.

  Contrary to Example 2, the intermediate solid was mixed with elemental sulfur in the absence of a hydrocarbon diluent. The intermediate solid was mixed with powdered elemental sulfur in a dry box using an argon atmosphere, placed in a sealed carbon steel cylinder, heated to 400 ° C. and maintained at this temperature for 1 hour. The sulfurization catalyst was recovered as a solid from the carbon steel cylinder. The potassium-iron sulfide catalyst was crushed into powder using a mortar and pestle so that the resulting catalyst powder could pass through a 40 mesh sieve.

The obtained potassium-iron sulfide catalyst was analyzed by X-ray diffraction method. The catalyst contained pyrite (FeS ₂ ), iron sulfide (FeS), and pyrotite (Fe _1-x S) by analysis of the X-ray diffraction spectrum. No mixed potassium-iron sulfide or iron oxide species were observed in the X-ray diffraction spectrum.

Example 4: Contact of crude feed with hydrogen source at high gaseous hydrogen to crude feed ratio in the presence of K-F sulfide catalyst The hydrogen to crude feed ratio is 16,000 Nm ³ / m ³ (100,000 SCFB) Other than that, the apparatus, the crude oil feed, and the reaction method are the same as in Example 2. 75.0 g of the K—F sulfide catalyst prepared as described in Example 3 was charged to the reactor.

  The properties of the crude product produced by this method are summarized in Table 1 of FIG. 8 and Table 3 of FIG. The weight percentage (%) of the VGO produced in Example 4 is greater than the weight percentage of the VGO produced in Example 2. The weight percentage (%) of the distillate produced in Example 4 is less than the weight percentage of the distillate produced in Example 2. The API specific gravity of the crude product produced in Example 4 is lower than the API specific gravity of the crude product produced in Example 2. A high API specific gravity indicates that a hydrocarbon having a large carbon number was produced.

After contact with the crude feed, the TMS catalyst in the reactor was analyzed. From this analysis, the transition metal sulfide catalyst contained K ₃ Fe ₁₀ S ₁₄ since crude oil feedstock and hydrogen were present.

Example 5: K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; TAP Test of Catalyst and Individual Inorganic Salts For any TAP test, a 300 g sample was taken from room temperature (27 ° C.) in a TAP system reactor. Heat to 500 ° C. at a rate of 50 ° C. per minute. The water vapor and carbon dioxide released were monitored using a TAP system mass spectrometer.

K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ supported on alumina; catalyst is 0.2 V of current inflection point of carbon dioxide released from inorganic salt at 360 ° C. and current of released water The inflection point was higher than 0.01 volts. The minimum TAP temperature was 360 ° C., and ion current vs. temperature was measured by natural log plot. FIG. 11 is a graph in which K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; ion current (“logarithm (I)”) of a gas released from a catalyst is naturally logarithmically plotted with respect to temperature (“T”). It is. Curves 168 and 170 are logarithmic values of ion currents for water and CO ₂ released from the inorganic salt catalyst. A sharp inflection point occurs at 360 ° C. with respect to the water and CO ₂ discharged from the inorganic salt catalyst.

K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; in contrast to the catalyst, potassium carbonate and cesium carbonate cannot detect the current inflection point at 360 ° C for both released water and released carbon dioxide It was.
K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; The significant increase in emissions from the catalyst means that the inorganic salt catalyst composed of two or more different inorganic salts is more than the individual pure inorganic salts. It also shows that it can be disordered.

Example 6: DSC test of inorganic salt catalyst and individual inorganic salt All DSC tests used a differential scanning calorimeter (DSC) model DSC-7 (Perkin-Elmer, Norwalk, Connecticut, USA) to prepare a 10 mg sample. Heated to 520 ° C. at a rate of 10 ° C. per minute, cooled from 520 ° C. to 0.0 ° C. at a rate of 10 ° C. per minute, and then heated from 0 ° C. to 600 ° C. at a rate of 10 ° C. per minute .

K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; In the DSC analysis of the catalyst, during the second heating of the sample, this salt mixture exhibited a wide range of thermal transition temperatures from 219 to 260 ° C. The midpoint of this temperature range was 250 ° C. The area of the thermal transition curve was calculated to be -1.75 joules / g. The onset of crystal disorder was measured to begin at the lowest DSC temperature of 219 ° C. Contrary to these results, no clear thermal transition was observed for cesium carbonate.

In DSC analysis of a mixture of Li ₂ CO ₃ , Na ₂ CO ₃ and K ₂ CO ₃ , during the second heating cycle, the Li ₂ CO ₃ / Na ₂ CO ₃ / K ₂ CO ₃ mixture is between 390 and 400 ° C. And showed a sharp thermal transition. The midpoint of this temperature range was 385 ° C. The portion of the thermal transition curve was calculated to be -182 Joule / g. The onset of mobility was measured to start at the lowest DSC temperature of 390 ° C. This sharp thermal transition indicates an almost homogeneous salt mixture.

Example 7: Comparison test of the ionic conductivity of an inorganic salt catalyst or individual inorganic salt with K ₂ CO ₃ However, it was carried out in a quartz container with platinum or copper wire immersed in a sample in a muffle furnace. These wires were connected to a 9.55 volt dry cell and a 220,000 ohm current limiting resistor. The muffle furnace was heated to 600 ° C., and the current was measured with a microampere meter.

FIG. 12 is a graph plotting logarithmically versus temperature (“T”), comparing the resistance of the sample to that of potassium carbonate (“logarithm (rK ₂ CO)”). Curves 172, 174, 176, 178, 180 are respectively K ₂ CO resistance, CaO resistance, K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalytic resistance, Li ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst resistance, Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst resistance are shown.

CaO (curve 174) exhibits a relatively large and stable resistance compared to K ₂ CO ₃ (curve 172) at temperatures in the range of 380-500 ° C. A stable resistance indicates that the ordered structure and / or ions are difficult to move away 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 (curves 176, 178, 180, respectively) shows a sharp decrease in resistance compared to K ₂ CO ₃ at temperatures in the range of 380-500 ° C. In general, a decrease in resistance indicates that a current was detected while applying a voltage to a wire embedded in an inorganic salt catalyst. From the data in FIG. 12, it can be seen that inorganic salt catalysts are more mobile than pure inorganic salts at temperatures in the range of 350-600 ° C.

FIG. 13 compares the resistance of Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst with the resistance of K ₂ CO ₃ (“logarithm (rK ₂ CO)”) and the temperature ( It is the graph which carried out the logarithm plot about "T"). Curve _{182, Na 2 CO 3 / K 2} CO 3 / Rb 2 CO 3 / Cs 2 CO 3 during the heating of the _{catalyst, Na 2 CO 3 / K 2} CO 3 / Rb 2 CO 3 / Cs 2 CO 3 Catalyst resistor pairs FIG. 6 is a curve plotting the ratio of K ₂ CO ₃ resistance (curve 172) versus temperature (“T”). After heating, the Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst was cooled to room temperature and then heated in a conductivity apparatus. Curve 184 shows the resistance of this inorganic salt catalyst to that of K ₂ CO ₃ during heating of the Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst after cooling from 600 ° C. to 25 ° C. Is a logarithmically plotted curve for temperature ("T"). The ionic conductivity of the reheated Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst is the original Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ Increased compared to the catalyst.

  Due to the difference in ionic conductivity of the inorganic salt catalyst during the first heating and the second heating, the inorganic salt catalyst is different from the form before heating (first form) during cooling (second form). ).

Example 8: Flow characteristics 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 was placed in a quartz dish. The dish was placed in a furnace and heated at 500 ° C. for 1 hour. To measure the flow properties of the catalyst, the dish was tilted by hand in the oven after heating. The K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst did not flow. When pressed with a spatula, the catalyst had a taffy consistency. In contrast, the individual carbonates were powders that flow freely under the same conditions.
The K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst became liquid under the same conditions in the dish and flowed easily (eg, similar to water).

Example 9-10: The _{K 2 CO 3 / Rb 2 CO} 3 / Cs 2 CO 3 contact example of the crude feed with a hydrogen source in the presence of a catalyst and steam 9 to 27, except that described deformation is less The following equipment and general methods were used.
Reactor:
Mechanical stirrer in a 250 ml Hastelloy C Parr autoclave (Parr model # 4576) loaded at 500 ° C. and working pressure of 35 MPa (5000 psi); A Gaumer zone heater; gas inlet; steam inlet; outlet; and an internal temperature recording thermocouple were attached. Prior to heating, the top of the autoclave was insulated with a glass cloth.

Addition container:
Addition vessel (250 ml, 316 stainless steel vessel) with controlled heating system, appropriate gas control valve, pressure release device, thermocouple, pressure gauge, and hot viscous and / or pressurized crude feed stream from 0 to A high temperature control valve (Swagelok Valve # SS-4UW) adjustable at a flow rate of 500 g / min was attached. After charging the feedstock into the addition vessel, the outlet side of the high temperature control valve was attached to the first inlet of the reactor. Prior to use, the addition vessel line was insulated.

Product collection:
Reactor vapors exiting the reactor outlet were introduced into a series of cold traps (a series of 150 ml, dip tubes connected to a 360 stainless steel vessel) with decreasing temperature. The liquid from the vapor was condensed with a cold trap to form a gas stream and a liquid condensate stream. The vapor flow rate out of the reactor and through the cold trap was adjusted as needed. The flow rate and total gas volume of the gas stream exiting the cold trap was measured using a wet test meter (Ritter model #TG 05 wet test meter). After leaving the wet test meter, the gas stream was collected in an analytical gas bag (Tedler gas collection bag). The gas was analyzed using GC / MS (Hewlett-Packard model 5890, currently Agilent model 5890, Zion, Illinois, USA). The liquid condensate stream was removed from the cold trap and weighed. The crude product and water were separated from the liquid condensate stream. The crude product was weighed and analyzed.
Method:
137.5 g of Cerro Negro raw material was charged into the addition vessel. The API specific gravity of this crude raw material is 6.7. The crude feedstock has a sulfur content of 0.042 g, a nitrogen content of 0.001 g, and a total Ni / V content of 0.009 g per gram of crude feedstock. The crude feed was heated to 150 ° C. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst (31.39 g) was charged to the reactor.

_{K 2 CO 3 16.44g, Rb 2} CO 3 19.44g and Cs ₂ CO _3; by blending _{22.49g, K 2 CO 3 / Rb} 2 CO 3 / Cs 2 CO 3; catalyst was produced. K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ ; the minimum TAP temperature of the catalyst was 360 ° C., and the DSC temperature was 250 ° C. Individual salts (K ₂ CO ₃ , Rb ₂ CO ₃ , and Cs ₂ CO ₃ ;) showed no DSC temperature at temperatures in the range of 50-500 ° C. This TAP temperature is higher than the DSC temperature of the inorganic salt catalyst and lower than the DSC temperature of the individual metal carbonate.

The catalyst was rapidly heated to 450 ° C. under an atmospheric flow of methane (250 cm ³ / min). After reaching the desired reaction temperature, water vapor was metered into the reactor at a rate of 0.4 mL / min and methane at a rate of 250 cm ³ / min. Steam and methane were continuously introduced into the reactor over 2.6 hours during the addition of the crude feed. The crude feed was infused for 16 minutes using 1.5 MPa (229 psi) CH ₄ . After the addition of the crude material was completed, the remaining crude material (0.56 g) remained in the addition container. It was observed that the temperature dropped to 370 ° C. during the addition of the crude feed.

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

Due to the weight difference between the initial catalyst and the coke / catalyst mixture, the coke remained in the reactor at 0.046 g / g crude feed. The total product contained 0.87 g of crude feed with an average API specific gravity of 13 and gas. The gas contained unreacted CH ₄ , hydrogen, C ₂ and C ₄ -C ₆ hydrocarbons, and CO ₂ (0.08 g CO ₂ per g gas).

Each crude product contained 0.01 g sulfur per gram crude product and 0.000005 g total Ni and V. The crude product was not analyzed further.
The reaction method, conditions, crude feed and catalyst in Example 10 are the same as in Example 9. The crude product of Example 10 was analyzed to determine their boiling range distribution. This reaction product contained 0.14 g of naphtha, 0.19 g of distillate, 0.45 g of VGO, and 0.001 g of residue per gram of reaction product, respectively, and no coke was detectable.

  Examples 9 and 10 are examples in which a crude product and a hydrogen source are contacted in the presence of 3 g of catalyst per 100 g of crude feed to produce a total product including a crude product that is liquid in STP. The residue content of all products was 30% or less with respect to the residue content of the crude oil feedstock. The sulfur content and the total Ni / V content of the crude product were 90% or less with respect to the sulfur content and the total Ni / V content of the crude raw material.

  This crude product has 0.001 g or more of hydrocarbons at 200 ° C. or less at a boiling point range distribution of 0.101 MPa, and 0.001 g or more of hydrocarbons at 200 to 300 ° C. at a boiling point range distribution of 0.101 MPa. Contained 0.001 g or more of hydrocarbon at 400 to 538 ° C. (1000 ° F.) at 0.101 MPa.

Examples 11-12: Contact of Crude Oil Feed with Hydrogen Source in the Presence of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ Catalyst and Water Steam Reaction Methods, Conditions, and K _{2 in} Examples 11 and 12 The CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst was the same as Example 9 except that 130 g of crude oil feed (Cerro Negro) and 60 g of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst were used. It is. In Example 11, methane was used as the hydrogen source. In Example 12, hydrogen gas was used as the hydrogen source. The amounts of non-condensable gas, crude product and coke are shown in the graph of FIG. Bars 186, 188 represent the weight percent of coke produced, bars 190, 120 represent the weight percent of produced liquid hydrocarbons, and bars 194, 196 represent the weight percent of produced gas relative to the weight of the crude feed. Represents.

In Example 11, 93% by weight of crude product (bar 192), 3% by weight of gas (bar 196), and 4% by weight of coke (bar 188) were produced, respectively, relative to the weight of the Cero Negro raw material.
In Example 12, the crude product (bar 190) was 84% by weight, the gas (bar 194) was 7% by weight, and the coke (bar 186) was 9% by weight, based on the weight of the Cero Negro feedstock.

  In Examples 11 and 12, a comparison between the case where methane is used as the hydrogen supply source and the case where hydrogen gas is used as the hydrogen supply source can be obtained. Methane is generally less expensive to produce and / or transport than hydrogen, and therefore a method that utilizes methane is desirable. As illustrated, methane is at least as effective as hydrogen gas as a hydrogen source when contacting crude oil feed in the presence of an inorganic salt catalyst to produce the entire product.

Examples 13-14: Production of crude product with selected API specific gravity The equipment, reaction method and inorganic salt catalyst are the same as in Example 9 except that the reaction pressure was varied.
In Example 13, the reactor pressure was 0.1 MPa (14.7 psi) during the contact period. A crude product with an API specific gravity of 15.5 ° C. and 25 was produced. All products contained hydrocarbons with a carbon number distribution ranging from 5 to 32 (curve 198 in FIG. 15).

  In Example 14, the reactor pressure was 3.4 MPa (514.7 psi) during the contact period. A crude product of 51.6 with an API specific gravity of 15.5 ° C. was produced. All products contained hydrocarbons with a carbon number distribution ranging from 5 to 15 (curve 200 in FIG. 15).

  These examples illustrate a method of producing a crude product having a selected API gravity by contacting a crude feed with hydrogen at various pressures in the presence of an inorganic salt catalyst. By changing the pressure, a crude product having a high or low API gravity was produced.

Example 15-16: The _{K 2 CO 3 / Rb 2 CO} 3 / Cs 2 CO 3 the presence of a catalyst or silicon carbide, the contact example of crude feed in the absence of external hydrogen source 15, apparatus, crude The raw materials and the reaction method are the same as in Example 9, except that the crude raw material and the catalyst (or silicon carbide) were directly and simultaneously charged into the reactor. Carbon dioxide (CO ₂ ) was used as the carrier gas. In Example 15, 138 g of Cerro Negro raw material was blended with 60.4 g of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst (the same catalyst as in Example 9). In Example 16, 132 g of Cero Negro raw material was blended with 83.13 g of silicon carbide (40 mesh, Stanford Materials; Aliso Viejo, CA). Such silicon carbide is believed to have poor catalytic properties (if any) under the process conditions described herein.

In each case, the mixture was heated to a reaction temperature of 500 ° C. for 2 hours. CO ₂ was metered into the reactor at a rate of 100 cm ³ / min. Vapor generated in the reactor was collected in a cold trap and gas bag using a back pressure of 3.2 MPa (479.7 psi). The crude product in the cold trap was solidified and analyzed.

In Example 15, 36.82 g of a colorless hydrocarbon liquid having an API specific gravity of 50 or more (26.68% by weight based on the weight of the crude feed) was produced by contacting the crude feed with the inorganic salt catalyst in a carbon dioxide atmosphere. It was.
In Example 16, 15.78 g of a yellow hydrocarbon liquid having an API specific gravity of 12 (11.95% by weight based on the weight of the crude feed) was produced by contacting the crude feed with silicon carbide in a carbon dioxide atmosphere.

  Although the yield of Example 15 is low, the in situ generation of the hydrogen source in the presence of the inorganic salt catalyst is more than the in situ generation of hydrogen under non-contact conditions. The yield of the raw product in Example 16 is ½ of the yield of the raw product in Example 15. Example 15 also shows that hydrogen is generated during the contact of the crude feed in the presence of an inorganic salt catalyst and in the absence of a gaseous hydrogen source.

Examples 17 to 20: Contact apparatus for crude oil raw material and hydrogen source in the presence of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst, calcium oxide, and silicon carbide at atmospheric pressure, crude oil raw material The reaction method and the inorganic salt catalyst are the same as in Example 9, except that the Cerro Negro raw material was directly added to the reactor instead of addition by the addition vessel, and hydrogen gas was used as the hydrogen supply source. The reactor pressure was 0.101 MPa (14.7 psi) during the contact period. The hydrogen gas flow rate is 250 cm ³ / min. The reaction temperature, water vapor flow rate, and the ratio (%) of produced crude product, gas, and coke are shown in Table 4 of FIG.

In Examples 17 and 18, a K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst was used. In Example 17, the contact temperature was 375 ° C. In Example 18, the contact temperature was in the range of 500-600 ° C.
As shown in Table 4 (FIG. 16), in Examples 17 and 18, gas production increased from 0.02 g to 0.05 g per gram of total product when the temperature was increased from 375 ° C. to 500 ° C. However, coke formation decreased from 0.17 g to 0.09 g / g crude feed at high temperatures. The sulfur content of the crude product also decreased from 0.01 g to 0.008 g per gram of crude product at high temperatures. Both crude products had an H / C of 1.8.

In Example 19, the crude feed was contacted with CaCO ₃ under conditions similar to those described in Example 18. The production ratio (%) of crude product, gas and coke is shown in Table 4 of FIG. In Example 19, the amount of gas produced increased compared to the amount of gas produced in Example 18. The crude feed de-flow was not as effective as in Example 18. The sulfur content of the crude product produced in Example 19 per gram of crude product was 0.01 g compared to 0.008 g per gram of crude product of the crude product produced in Example 18.

  Example 20 is a comparative example for Example 18. In Example 20, 85.23 g of silicon carbide was charged to the reactor instead of the inorganic salt catalyst. In Example 20, the amount of gas produced and the amount of coke produced were significantly increased compared to the amount of produced gas and coke produced in Example 18. Under these non-contact conditions, 0.22 g of coke, 0.25 g of non-condensable gas, and 0.5 g of crude product were produced per gram of crude product. The crude product produced in Example 20 contained 0.036 g of sulfur per gram of crude product compared to 0.01 g of sulfur per gram of crude product produced in Example 18.

These examples show that the catalysts used in Examples 17 and 18 give improved results over non-contact conditions and conventional metal salts. At a hydrogen flow rate of 250 cm ³ / min at 500 ° C., the production of coke and non-condensable gas was significantly less than the amount of coke and non-condensable gas produced under non-contact conditions.

  In the example using the inorganic salt catalyst (FIG. 16, Examples 17 to 18 in Table 4), the weight ratio of the generated gas compared to the gas generated during the control experiment (for example, Example 20 in FIG. 16 and Table 4). A decrease in (%) was observed. From the amount of hydrocarbons in the product gas, the thermal cracking of the crude feedstock is 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, based on the total amount of the crude feedstock contacted with the hydrogen source Or estimated to be none.

Examples 21 and 22: Contact of crude oil feed with gaseous hydrogen source in the presence of water and K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst or silicon carbide The apparatus in Examples 21 and 22 is hydrogen Example 9 is the same as Example 9 except that hydrogen gas was used as the supply source. In Example 21, 130.4 g of Cero Negro feed was blended with 30.88 g of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst to form a crude feed mixture. In Example 22, 139.6 g of Cero Negro feed was blended with 80.14 g of silicon carbide to form a crude feed mix.

The crude feed mixture was charged directly into the reactor. During the heating and holding period, hydrogen gas was introduced into the reactor at 250 cm ³ / min. The crude feed mixture was heated to 300 ° C. over 1.5 hours and maintained at this temperature for 1 hour. The reaction temperature was raised to 400 ° C. over 1 hour and maintained at this temperature for 1 hour. After the reaction temperature reached 400 ° C., water was introduced into the reactor at a rate of 0.4 g / min in combination with nitrogen. Water and hydrogen were charged to the reactor for the remainder of the heating and holding period. After maintaining the reaction mixture at 400 ° C., the reaction temperature was raised to 500 ° C. and maintained at this temperature for a time. Vapor generated in the reactor was collected in a cold trap and gas bag. The liquid product in the cold trap solidified and analyzed.

In Example 21, in a hydrogen atmosphere, 86.17 g of dark reddish brown hydrocarbon liquid (crude product) was added to the weight of crude feed by contacting the crude feed with K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst. 66.1% by weight) and 97.5 g of water formed as steam.

  In Example 22, water vapor and a small amount of gas were generated from the reactor. The reactor was examined and a dark brown viscous hydrocarbon liquid was removed from the reactor. A dark brown viscous liquid of less than 50% by weight was produced by contacting crude oil and silicon carbide in a hydrogen atmosphere. Compared to the yield of the crude product produced in Example 22, it was found that in Example 21, the yield of crude product was improved by 25%.

  Example 21 shows that the properties of the crude product produced using the method described herein are improved compared to the crude product produced using hot water. In particular, the crude product of Example 21 has a lower boiling point than the crude product produced in Example 22, as indicated by the hrm produced in Example 22 that cannot be produced as steam.

Examples 23-24: Contact between crude oil feedstock and hydrogen source in the presence of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst compared to the amount (volume) of crude product produced under non-contact conditions The production equipment, crude oil raw material, inorganic catalyst and reaction method of the crude oil product increased by the same amount as in Example 9 except that the crude oil raw material was directly charged into the reactor and hydrogen gas was used as the hydrogen supply source. is there. Crude raw material (Cerro Negro) has an API specific gravity of 6.7 and a density of 1.02 g / mL at 15.5 ° C.

In Example 23, 102 g (102 mL) of crude feed and 31 g of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst were charged into the reactor. An 87.6 g (112 mL) crude product with an API gravity of 50 and a density of 0.7796 g / mL at 15.5 ° C. was produced.
In Example 24, 102 g (102 mL) of crude raw material and 80 g of silicon carbide were charged to the reactor. 70 g (70 mL) of crude product with an API specific gravity of 12 and density of 0.9861 g / mL at 15.5 ° C. was produced.

  Under these conditions, the volume of the crude product produced in Example 23 was about 10% greater than the volume of the crude feed. The volume of the crude product produced in Example 24 was significantly less (about 40% less) than that of the crude product produced in Example 23. A significant increase in product volume increases the manufacturer's ability to further increase the crude product volume per volume of input crude.

Example _{25: K 2 CO 3 / Rb} 2 CO 3 / Cs 2 CO 3 catalyst, the presence of sulfur and coke, contact apparatus and reaction procedure of crude feed and the hydrogen source, the reactor vapor at 300 cm 3 _/ min Example 9 is the same as Example 9, except that _{K 2 CO 3 / Rb 2 CO} 3 / Cs 2 CO 3 _{catalyst, K 2 CO 3 27.2g, Rb} 2 CO 3 32.2g and Cs ₂ CO _3; manufactured by blending 40.6 g.

The reactor was charged with 130.35 g of crude raw material and 31.6 g of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst. The Cero Negro raw material is 0.04 g of total aromatics having a boiling range distribution of 149 to 260 ° C. (300 to 500 ° F.), 0.000640 g of a combination of nickel and vanadium, and 0.042 g of sulfur per 1 g of this crude raw material. And 0.56 g of residue. The API specific gravity of this crude material is 6.7.

When the crude feed was contacted with methane in the presence of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst, 0.95 g total product and 0.041 g coke were produced per gram crude feed.
The total product contained 0.91 g of crude product and 0.028 g of hydrogen gas per gram of total product. All collected gases contain 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, respectively, by GC / MS measurement. Was. The balance of the gas is methane, air, carbon monoxide, and trace (0.004 mol) of evaporated crude feed.

  The crude product was analyzed by gas chromatography and mass spectrometry. The crude product contained a mixture of hydrocarbons having a boiling range of 100-538 ° C. The total liquid product mixture contained 0.006 g ethylbenzene (monocyclic compound having a boiling point of 136.2 ° C. at 0.101 MPa) per gram of the mixture. This product was not detected in the crude feed.

The spent catalyst (“first spent catalyst”) was removed from the reactor, weighed and then analyzed. The first spent catalyst had a weight increase from 31.6 g to a total weight of 37.38 g (18% weight increase relative to the weight of the original K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst) . The first spent catalyst is 0.15 g of additional coke, 0.0035 g of sulfur, 0.0014 g of Ni / V, and K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ per gram of spent catalyst. Of 0.845 g.

An additional 152.71 g of crude feed was contacted with 36.63 g of the first spent catalyst to produce 150 g of recovered total product after loss. The total product contained 0.92 g of liquid crude product, 0.058 g of additional coke, and 0.017 g of gas per gram of total product respectively. This gas per each gas 1 mol, 0.18 mol of hydrogen, carbon dioxide 0.07 g, and _C 2 -C ₆ hydrocarbons contained 0.035 mol. The balance of the gas is methane, nitrogen, some air, and trace amounts (<1% mol) of evaporated oil product.

  The crude product contained a mixture of hydrocarbons with a boiling range of 100-538 ° C. The portion of the mixture having a boiling range distribution of less than 149 ° C is 0.018 mol% ethylbenzene, 0.04 mol% toluene, 0.03 mol% m-xylene, and p- Xylene was contained in an amount of 0.060 mol% (a monocyclic compound having a boiling point of less than 149 ° C. at 0.101 MPa). These products were not detected in the crude feed.

The spent catalyst (“second spent catalyst”) was removed from the reactor, weighed and then analyzed. The second spent catalyst had a weight increase from 36.63 g to a total weight of 45.44 g (43 wt% increase relative to the weight of the original K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst) . The second used catalyst contained 0.32 g of coke, 0.01 g of sulfur and 0.67 g of sulfur per gram of the second used catalyst.

  An additional 104 g of crude crude feed was contacted with 44.84 g of second spent catalyst to produce 104 g total product per g crude feed and 0.114 g coke was collected. Part of the coke is attributed to the fact that 104.1 g of the 133 g of the crude oil raw material transferred was crude oil raw material, so that coke was formed in the addition vessel due to overheating of the addition vessel.

The total product contained 0.86 g of crude product and 0.025 g of hydrocarbon gas per gram of total product respectively. The total gas per each gas 1 mol, 0.18 mol of hydrogen, carbon dioxide 0.052 moles, and the _C 2 -C ₆ hydrocarbons contained 0.03 mol. The balance of the gas is methane, air, carbon monoxide, hydrogen sulfide and a small amount of evaporated oil.

  The crude product contained a mixture of hydrocarbons with a boiling range of 100-538 ° C. As described above, the mixture portion having a boiling point range distribution of less than 149 ° C. was 0.021 g of ethylbenzene, 0.027 g of toluene, 0.042 g of m-xylene, and 0.042 g of m-xylene per 1 g of the hydrocarbon mixture, respectively. It contained 0.020 g of p-xylene.

The spent catalyst (“third spent catalyst”) was removed from the reactor, weighed and then analyzed. The third spent catalyst had a weight increase from 44.84 g to a total weight of 56.59 g (79% weight increase relative to the weight of the original K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst) . Detailed elemental analysis was performed on the third spent catalyst. The third spent catalyst is 0.90 g of carbon, 0.028 g of hydrogen, 0.0025 g of oxygen, 0.046 g of sulfur, 0.017 g of nitrogen, and 0.17 g of vanadium per 1 g of matter. 0018 g, 0.0007 g nickel, 0.0015 g iron and 0.00025 g chloride, the balance being other transition metals such as chromium, titanium and zirconium.

  As shown in this example, the coke, sulfur and / or metal deposited on and / or in the inorganic salt catalyst is crude oil produced by contacting the crude feed with a hydrogen source in the presence of the inorganic salt catalyst. Does not affect the overall yield of product (over 80% for each experiment). The crude product has a monocyclic aromatic content that is at least 100 times the monocyclic aromatic content with a boiling range distribution of less than 149 ° C. contained in the crude feed.

  In these three experiments, the average yield of crude product (relative to the weight of crude feed) is 89.7% by weight (standard deviation: 2.6%), and the average yield of coke (relative to the weight of crude feed) Is 7.5% by weight (standard deviation: 2.7%), and the average yield of gaseous cracked hydrocarbons (relative to the weight of crude oil) is 2.3% by weight (standard deviation: 0.46%). there were. The reason why the standard deviation of both liquid and gas is relatively large is that the crude material in the addition vessel was overheated in the third experiment and the temperature controller of the feed vessel failed. Even so, even the large amount of coke tested here has no clear and noticeable negative impact on the activity of the catalyst system.

C ₂ olefins to total _{C 2} ratio was 0.19. The ratio of C ₃ olefin to total C ₃ was 0.4. The α-olefin to internal olefin ratio in the C ₄ hydrocarbon was 0.61. C ₄ cis / trans olefins ratio was 6.34. This ratio was substantially higher than the 0.68 of the estimated thermodynamic C ₄ cis / trans olefins ratio. The α-olefin to internal olefin ratio in the C ₅ hydrocarbon was 0.92. This ratio was greater than the estimated thermodynamic C ₅ α-olefin to C ₅ internal olefin ratio of 0.194. C ₅ cis / trans olefins ratio was 1.25. This ratio, this ratio was greater than 0.9 of the estimated thermodynamic C ₅ cis / trans olefins ratio.

Example 26: Contact of a crude feed containing a relatively large amount of sulfur with a hydrogen source in the presence of a K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst and a hydrogen source include crude feed, methane and Same as Example 9 except that water vapor was continuously fed to the reactor. The feed level in the reactor was monitored using the change in weight of the reactor. Methane gas was continuously introduced into the reactor at 500 cm ³ / min. Steam was metered continuously into the reactor at 6 g / min.

The inorganic salt catalyst was produced by blending 27.2 g of K ₂ CO _3, 32.2 g of Rb ₂ CO _{3 and} 40.6 g of Cs ₂ CO ₃ . 59.88 g of this K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst was charged into the reactor.

  A crude feedstock (bitumen, Lloydminster, Canada) having an API specific gravity of 9.4, 0.02 g sulfur per gram crude feed and 0.40 g residue was heated to 150 ° C. in an addition vessel. In an attempt to maintain the crude feed liquid level at 50% of the reactor volume, hot bitumen was metered continuously into the reactor at 10.5 g / min from the addition vessel, but at this rate the level was maintained. Was insufficient.

  The methane / steam / crude feed was contacted with the catalyst at an average reactor temperature of 456 ° C. The entire product was produced by contact of the methane / steam / crude oil feed with the catalyst (in this example in the form of reactor effluent steam).

1640 g of crude feed was processed over 6 hours. Due to the difference between the initial catalyst weight and the residue / catalyst mixture weight, 0.085 g coke per gram crude oil feed remained in the reactor. By contacting the crude raw material with methane in the presence of a K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst, 0.93 g of the entire product was produced per gram of the crude raw material. The total product, except for the amount of methane and water used in the reaction, contained 0.03 g of gas and 0.97 g of crude product per gram of total product, respectively.

  Each gas contained 0.014 g of hydrogen, 0.018 g of carbon monoxide, 0.08 g of carbon dioxide, 0.13 g of hydrogen sulfide, and 0.68 g of non-condensable hydrocarbon per 1 g of gas. . From the amount of hydrogen sulfide generated, it may be estimated that the sulfur content of the crude oil raw material has been reduced by 18% by weight. As shown in this example, hydrogen, carbon monoxide and carbon dioxide were produced. The molar ratio of carbon monoxide to carbon dioxide was 0.4.

C ₂ -C ₅ hydrocarbons each contain 0.30 g of C ₂ compound, 0.32 g of C ₃ compound, 0.26 g of C ₄ compound, and 0.10 g of C ₅ compound per gram of hydrocarbon. It was. The weight ratio of isopentane to n-pentane in the non-condensable hydrocarbon was 0.3. The weight ratio of isobutane to n-butane in the non-condensable hydrocarbon was 0.189. The C ₄ compound had a butadiene content of 0.003 g per gram of C ₄ compound. The weight ratio of α-C ₄ olefin to internal C ₄ olefin was 0.75. The weight ratio of α-C ₅ olefin to internal C ₅ olefin was 1.08.

  From the data of Example 25, even when a crude raw material containing a relatively large amount of sulfur is continuously treated with the same catalyst in the presence of coke, the activity of the inorganic salt catalyst is not reduced, and the crude oil is suitable for transportation. It can be seen that the product is manufactured.

Example 27: Contact apparatus and reaction method of crude feedstock and hydrogen source in the presence of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst and coke are as described in Example 26. 56.5 g of K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ catalyst was charged into the reactor. A total of 2550 g of crude feed was processed over 6 hours.
From the difference between the initial catalyst weight and the residue / catalyst mixture weight, 0.114 g of coke remained in the reactor per gram of crude feed, based on the weight of the crude feed. A total of 0.89 g of total product was produced per gram of crude feed. The total product contained 0.04 g of gas and 0.96 g of crude product per gram of total product, respectively, excluding the amount of methane and water used in the reaction.

  Each gas contained 0.021 g of hydrogen, 0.018 g of carbon monoxide, 0.052 g of carbon dioxide, 0.18 g of hydrogen sulfide, and 0.65 g of non-condensable hydrocarbon per 1 g of gas. . From the amount of hydrogen sulfide produced, it may be estimated that the sulfur content of the crude material is reduced by 14% by weight with respect to the weight of the crude material. As shown in this example, hydrogen, carbon monoxide and carbon dioxide were produced. The molar ratio of carbon monoxide to carbon dioxide was 0.6.

C ₂ -C ₆ hydrocarbons are 0.44 g of C ₂ compound, 0.31 g of C ₃ compound, 0.19 g of C ₄ compound, and 0 of C ₅ compound per 1 g of C ₂ -C ₆ hydrocarbon, respectively. Contained 0.068 g. The weight ratio of isopentane to n-pentane in the non-condensable hydrocarbon was 0.25. The weight ratio of isobutane to n-butane in the non-condensable hydrocarbon was 0.15. The C ₄ compound had a butadiene content of 0.003 g per gram of C ₄ compound.

  This example shows that even when a crude raw material containing a relatively large amount of sulfur (crude raw material 2550 g) is repeatedly treated with the same catalyst (56.5 g) in the presence of coke, the activity of the inorganic salt catalyst is not reduced. It shows that a crude product suitable for transportation is produced.

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

1 is a schematic diagram of one embodiment of a contact system for contacting a crude feed with a hydrogen source in the presence of one or more catalysts to produce a total product. FIG. FIG. 3 is a schematic diagram of another embodiment of a contact system for contacting a crude feed with a hydrogen source in the presence of one or more catalysts to produce a total product. FIG. 3 is a schematic view of one embodiment of a separation band in combination with a contact system. 1 is a schematic view of one embodiment of a blending band in combination with a contact system. FIG. 1 is a schematic view of one embodiment of a separation zone, a contact zone, and a blending zone. 1 is a schematic diagram of one embodiment of a multiple contact system. FIG. 1 is a schematic diagram of one embodiment of an ionic conductivity measurement system. 2 is a table showing the characteristics of crude feed and the characteristics of the crude product obtained in one embodiment of contacting the crude feed with a transition metal sulfide catalyst. It is a table | surface which shows the composition of a crude feedstock, and the composition of the non-condensable hydrocarbon obtained by the embodiment which makes a crude feedstock contact with a transition metal sulfide catalyst. 2 is a table showing the properties and composition of crude product obtained in an embodiment in which a crude feed is contacted with a transition metal sulfide catalyst. It is the graph (measured by TAP) which plotted the ionic current about the generated gas of an inorganic salt catalyst by the natural logarithm about temperature. It is the graph which compared the resistance of the inorganic salt catalyst and the inorganic salt with the resistance of potassium carbonate, and plotted logarithmically about temperature. The resistance of _{Na 2 Co 3 / K 2 CO} 3 / Rb 2 CO 3 catalyst as compared to the resistance of potassium carbonate, a graph logarithmically plotted for temperature. It is a graph which shows the weight ratio (%) with respect to the various hydrogen supply sources of the coke produced | generated in the embodiment which contacts a crude oil raw material with an inorganic salt catalyst, and a gas. It is a graph which shows the weight ratio (%) with respect to carbon number of the crude product manufactured by the embodiment which contacts a crude-oil raw material with an inorganic salt catalyst. It is a table | surface which shows the component produced | generated in the embodiment which contacts a crude oil raw material with an inorganic salt catalyst, a metal salt, or a silicon carbide.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Contact system 101 Crude oil supply part 102 Contact zone 116 Separation unit 119 Crude material receiver 122 Contact system 124 Separation zone 130 Contact system 132 Separation zone 140 Compounding zone 148 Contact system

Claims (11)

Each non-condensable hydrocarbon is less than 0.15 g of non-condensable hydrocarbons at 25 ° C. and 0.101 MPa per gram of crude product. _-3 (C ₁ -C ₃ ) hydrocarbons in an amount of 0.3 g or less]; Kerosene having an octane number of 70 or more naphtha of 0.001 g or more and a freezing point of -30 ° C. or less (measured by ASTM method D2386) However, a crude product containing 0.001 g or more of aromatics per 1 g of kerosene (measured by ASTM method D5186) and 0.05 g or less of residues (measured by ASTM method D5307).   The crude oil product contains not less than 0.001 g of diesel oil per gram of crude oil product, and the diesel oil contains not less than 0.3 g of aromatics (measured by IP method 368/90) per gram of diesel oil. The crude product described in 1.   The crude product contains not less than 0.001 g of VGO per gram of crude product, and VGO contains not less than 0.3 g of aromatics per gram of VGO (measured by IP method 368/90). The described crude product.   The crude product according to any one of claims 1 to 3, wherein the naphtha contains 0.01 g or less of benzene per 1 g of naphtha (measured by ASTM method D6730).   When naphtha and non-condensable hydrocarbon gas are combined, the naphtha and non-condensable hydrocarbon gas are combined in an isoparaffin to n-paraffin weight ratio of 1. The crude product according to any one of claims 1 to 4, which contains 4 or less (measured by ASTM method D6730) and 0.15 g or less per 1 g of a combination with a non-condensable hydrocarbon gas. Having 3 or less hydrocarbon carbon, 2 carbons _{(C 2)} and 3 together containing olefins and paraffins _{(C 3),} C 2 -C ₃ olefin to _C 2 -C ₃ paraffins weight ratio of (ASTM Method measured in D6730) is 0.3 or less, and the weight ratio of _{C 2} olefins versus _{C 2} paraffin 0.2 or less, and _{C 3} weight ratio of olefin to _{C 3} paraffins (measured by ASTM method D6730) 0 The crude product according to any one of claims 1 to 5, which is .3 or less.   The crude product according to any one of claims 1 to 6, wherein the crude product contains 0.09 to 0.13 g of hydrogen atoms per gram of crude product.   The crude product according to any one of claims 1 to 7, wherein the crude product has a weight ratio of hydrogen atoms to carbon atoms of 1.75 or less.   A method for producing a transportation fuel, a heating fuel, a lubricant or a chemical, comprising a step of treating the crude product according to any one of claims 1 to 8 or a blend of the crude product and crude oil.   The method of claim 9, wherein the treating step comprises distilling the crude product or blend into one or more distillate fractions.   11. A method according to claim 9 or 10, wherein the processing step comprises distilling the crude product or blend into one or more distillate fractions.