EA010396B1 - A crude product of oil production and a method for treating thereof - Google Patents

Abstract

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

Description

FIELD OF THE INVENTION

The present invention generally relates to a crude product formed by processing crude oil from oil production processes to produce a crude product that has improved characteristics compared to similar characteristics of a crude feed. More specifically, the invention relates to a crude product obtained from a crude feed, which includes hydrocarbons and a catalyst, the crude product having at least 0.05 g of residue per 1 g of crude feed and at least 0.001 g of hydrocarbons with a boiling range distribution above 204 ° C, with a distribution of the boiling range between 204 and 300 ° C and with a distribution of the boiling range between 400 and 538 ° C at a pressure of 0.101 MPa, and the catalyst contains one or more alkali metals. The crude product is used to produce products such as transport and boiler fuels, a lubricant, or chemicals.

State of the art

Unrefined raw materials that have one or more inappropriate characteristics that do not allow economically transporting or processing these raw materials using conventional equipment are usually called disadvantageous raw materials.

Unfavorable raw materials often contain a relatively large amount of residue. Such raw materials usually lead to difficulties, and their transportation and / or processing using traditional equipment are expensive. High-residue feeds can be processed at high temperatures to turn these feeds into coke. As a typical alternative, high-residue feeds are treated with water at high temperatures to obtain less viscous feeds and / or feed mixes. During processing, the removal of water from less viscous raw materials and / or raw mixes can be difficult using conventional means.

Unfavorable feedstocks may include hydrogen-deficient hydrocarbons. In the processing of hydrogen-deficient hydrocarbons, it is usually necessary to add appropriate amounts of hydrogen, especially if unsaturated compounds are formed as a result of cracking processes. To prevent the formation of coke from unsaturated compounds during processing, hydrogenation may be required, for which an active hydrogenation catalyst should usually be used. Hydrogen production is expensive, as is transporting it to processing plants.

During processing of disadvantageous raw materials, coke can form and / or precipitate at a high rate on the catalyst surface. Regenerating the catalytic activity of a catalyst contaminated with coke can be expensive. In addition, the high temperatures used during regeneration can reduce the activity of the catalyst and / or cause its destruction.

Unfavorable feedstocks may include acidic components that contribute to the total acid number (TAC) of the crude feed. Unfavorable raw materials with a relatively high SKH can contribute to the corrosion of metal parts during transportation and / or processing of unfavorable raw materials. Removing acidic components from disadvantageous materials may include chemical neutralization of the acidic components with various bases. Alternatively, corrosion resistant metals may be used in transport equipment and / or processing equipment. The use of corrosion resistant metals often leads to significant costs and, therefore, the use of corrosion resistant metals in existing equipment may be undesirable. Another method of suppressing corrosion may include adding corrosion inhibitors to the unfavorable feedstock prior to transporting and / or processing the unfavorable feedstock. The use of corrosion inhibitors can adversely affect equipment used for processing raw materials and / or the quality of products derived from such raw materials.

Unfavorable raw materials may contain relatively high amounts of contaminating metals, for example nickel, vanadium and / or iron. During the processing of such raw materials, polluting metals and / or compounds of polluting metals can be deposited on the surface of the catalyst or in the volume of the voids of the catalyst. Such deposits can cause a decrease in catalyst activity.

Unfavorable feedstocks often include organically bound heteroatoms (e.g., sulfur, oxygen, and nitrogen). In some cases, organically bound heteroatoms can have a detrimental effect on the catalysts. In the processes for the desulfurization of the residue, alkali metal salts and / or alkaline earth metal salts are used. For these processes, there is a tendency for low desulfurization efficiency, they lead to the formation of sludge insoluble in hydrocarbons, low demetallization efficiency, to the formation of practically inseparable mixtures of salts with hydrocarbons, to the use of large quantities of hydrogen gas and / or relatively high hydrogen pressures.

Some ways to improve the quality of raw materials include adding a diluent to disadvantageous raw materials in order to reduce the mass fraction of components that contribute to disadvantageous characteristics. However, the addition of a diluent usually increases the cost of processing disadvantageous raw materials due to the cost of the diluent and / or increase the cost of handling unfavorable raw materials. Adding a diluent to an unfavorable raw material may in some cases reduce the stability of such a raw material.

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U.S. Patent Nos. 3,136,714 (Spedp e! A1.); 3558747 (C1e e! A1.); 3,847,797 (Ra§! Ehpak e! A1.); 3948759 (Kshd e! A1.); 3957620 (Rickshaw e! A1.); 3960706 (McCo11it e! A1.); 3960708 (McCo11it e! A1.); 4119528 (Wapb, 1g.e! A1.); 4127470 (Ba1gb, 1g.e! A1.); 4,224,140 (Ritztop e! A1.); 4,437,980 (Negebu e! A1.); 4,591,426 (Kgakik e! A1.); 4,665,261 (Mahigek); 5064523 (Kge! Xttag e! A1.); 5166118 (Kge! Xttag e! A1.); 5,288,681 (Ca! K1k); 6,547,957 (8ibyakag e! A1.) And US Published Application Nos. No. 20030000867 (Beupo1bq) and 20030149317 (Wepbsha) describe various methods and systems used to process crude feed. However, the compositions described in these patents have limited applicability, due to the many technical problems set forth above.

As a result, unfavorable raw materials usually have undesirable characteristics (for example, a relatively high content of residue, a tendency to corrosion of equipment and / or a tendency to consume relatively large amounts of hydrogen during processing). Other undesirable characteristics include a relatively high content of undesirable components (for example, a relatively high value of TCR, organically bound heteroatoms and / or contaminating metals). Such characteristics usually lead to problems in traditional transportation and / or problems for process equipment, including problems of increased corrosion, reduced catalyst life, blocking of the process and / or increased hydrogen consumption during processing. Thus, there is a significant economic and technical need for improved systems, methods, and / or catalysts for converting disadvantageous feeds into crude products having more desirable characteristics.

Disclosure of the invention

The invention generally relates to crude product compositions that have new combinations of components. The basis of the invention is a crude product, which is a composition containing hydrocarbons and a catalyst, the crude product having a distribution of boiling ranges above 204 ° C, between 204 and 300 ° C at 0.01 MPa, between 300 and 400 ° C and between 400 and 538 ° C at a pressure of 0.01 MPa, and the catalyst contains one or more alkali metals.

More specifically, the invention describes a crude composition, which contains per 1 g of composition:

at most 0.05 g of residue;

at least 0.001 g of hydrocarbons with a boiling range distribution of at least 204 ° C (400 ° P) at 0.101 MPa; at least 0.001 g of hydrocarbons with a boiling range distribution between 204 and 300 ° C at 0.101 MPa of at least 0.001 g of hydrocarbons with a distribution of the boiling range between 300 and 400 ° C at 0.101 MPa and at least 0.001 g of hydrocarbons with a distribution of the range of boiling between 400 and 538 ° C (1000 ° P) at 0.101 MPa;

more than 0 g, but less than 0.01 g of one or more catalysts, where the catalyst contains at least one or more alkali metals.

In some embodiments, the invention also describes a K ₃ Fe1 ₀ §1 ₄ catalyst or a transition metal sulfide catalyst that:

(a) in total, has at least 0.4 g, at least 0.6 g, or at least 0.8 g of at least one transition metal sulfide per 1 g of K ₃ P _{! 0} 81 ₄ catalyst or sulfide catalyst transition metal;

(b) has an atomic ratio of transition metal to sulfur in a K ₃ Fe1 ₀ §1 ₄ catalyst or a transition metal sulfide catalyst in the range of 0.2 to 20;

(c) additionally contains one or more alkali metals, one or more compounds of one or more alkali metals, or mixtures thereof;

(b) additionally contains one or more alkaline earth metals, one or more compounds of one or more alkaline earth metals, or mixtures thereof;

(f) additionally contains one or more alkali metals, one or more compounds of one or more alkali metals, or mixtures thereof, where the atomic ratio of the transition metal to sulfur in the K ₃ Fe _{! 0} 81 ₄ catalyst or the transition metal sulfide catalyst is from 0, 5 to 2.5 and the atomic ratio of alkali metal to transition metal is from above 0 to 1;

(ί) additionally contains one or more alkaline earth metals, one or more compounds of one or more alkaline earth metals, or mixtures thereof, wherein the atomic ratio of the transition metal to sulfur in the K ₃ Fe1 ₀ §1 ₄ catalyst or the transition metal sulfide catalyst ranges from 0.5 to 2.5 and the atomic ratio of alkaline earth metal to transition metal is from above 0 to 1;

(e) additionally contains zinc;

(11) additionally contains Kre ₂ 8 ₃ ;

(ί) additionally contains Kre8 ₂ and / or (ί) is non-acid.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a K ₃ Fe1 ₀ 81 ₄ catalyst that is formed by ίη 8II.

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In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, one or more transition metal sulfides, which (or in which):

(a) contain one or more transition metals from groups 6-10 of the Periodic Table of the Elements, one or more compounds of one or more transition metals from groups 6-10, or mixtures thereof;

(b) contain one or more iron sulfides;

(c) contain Re8;

(b) contain Fe8 ₂ ;

(e) contain a mixture of iron sulfides, where iron sulfides are represented by the formula Pe ( _1-b ) 8, where b is in the range from above 0 to 0.17;

(I) additionally contain K ₃ Re ₁₀ 8 ₁₄ after contact with the crude feed;

(e) at least one transition metal in one or more transition metal sulfides is iron and / or (II) deposited on a support and catalyst — the transition metal sulfide has at least 0.25 g of total support per 100 g of catalyst.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method for forming a transition metal sulfide catalyst composition, which comprises mixing a transition metal oxide and a metal salt to form a mixture of the transition metal oxide and a metal salt;

reacting a mixture of a transition metal oxide and a metal salt with hydrogen to form an intermediate compound; and the interaction of the intermediate compound with sulfur in the presence of one or more hydrocarbons to obtain a transition metal sulfide catalyst:

(a) the metal salt contains alkali metal carbonate;

(b) which further includes dispersing the intermediate in one or more liquid hydrocarbons when it interacts with sulfur;

(c) in which one or more hydrocarbons have a boiling point of at least 100 ° C;

(b) in which one or more hydrocarbons are VGO, xylene or mixtures thereof;

(e) in which mixing the transition metal oxide and the metal salt includes mixing the transition metal oxide and the metal salt in the presence of deionized water to form a wet paste; drying the wet paste at a temperature in the range from 150 to 250 ° C; and calcining the dried paste at a temperature in the range from 300 to 600 ° C;

(1) wherein the interaction of the intermediate with sulfur is to heat the intermediate in the presence of at least one hydrocarbon to a temperature in the range of 240 to 350 ° C. and / or (e) which further includes contacting the catalyst composition with the crude feed, which contains sulfur and a source of hydrogen.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, an inorganic salt catalyst, which includes:

(a) one or more alkali metal carbonates, one or more alkaline earth metal carbonates, or mixtures thereof;

(b) one or more alkali metal hydroxides, one or more alkaline earth metal hydroxides, or mixtures thereof;

(c) one or more alkali metal hydrides, one or more alkaline earth metal hydrides, or mixtures thereof;

(b) one or more sulfides of one or more alkali metals, one or more sulfides of one or more alkaline earth metals, or mixtures thereof;

(e) one or more amides of one or more alkali metals, one or more amides of one or more alkaline earth metals, or mixtures thereof;

(1) one or more metals from groups 6-10 of the Periodic Table, one or more compounds of one or more metals from groups 6-10 of the Periodic Table, or a mixture thereof;

(e) one or more inorganic metal salts and in which at least one of the inorganic metal salts forms a hydride during use of the catalyst;

(1) sodium, potassium, rubidium, cesium, or mixtures thereof;

(ί) calcium and / or magnesium;

(ί) a mixture of sodium salt and potassium salt, and the potassium salt contains potassium carbonate, potassium hydroxide, potassium hydride or mixtures thereof, and the sodium salt contains sodium carbonate, sodium hydroxide, sodium hydride or mixtures thereof and / or

- 3 010396 (k) mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, an inorganic salt catalyst that includes alkali metals in which:

(a) the atomic ratio of an alkali metal having an atomic number of at least 11 to an alkali metal having an atomic number of more than 11 is in the range from 0.1 to 4;

(b) at least two alkali metals are sodium and potassium, and the atomic ratio of sodium to potassium is in the range from 0.1 to 4;

(c) at least three alkali metals are sodium, potassium and rubidium, and each of the atomic ratios of sodium to potassium, sodium to rubidium and potassium to rubidium is in the range from 0.1 to 5;

(b) at least three alkali metals are sodium, potassium and cesium, and each of the atomic ratios of sodium to potassium, sodium to cesium and potassium to cesium is in the range from 0.1 to 5;

(e) at least three alkali metals are potassium, cesium, rubidium, and each atomic ratio of potassium to cesium, potassium to rubidium and cesium to rubidium is in the range from 0.1 to 5.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, an inorganic salt catalyst that includes a support material and:

(a) the support material contains zirconium oxide, calcium oxide, magnesium oxide, titanium oxide, hydrotalcite, aluminum oxide, germanium oxide, iron oxide, nickel oxide, zinc oxide, cadmium oxide, antimony oxide, or mixtures thereof, and / or (b) the material one or more metals from groups 6-10 of the Periodic Table, one or more compounds of one or more metals from groups 6-10 of the Periodic Table, one or more alkali metal carbonates, one or more alkali metal hydroxides, one or more alkali meta hydrides are introduced llov, 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.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a method that comprises contacting the crude feed with an inorganic salt catalyst, wherein:

(a) the catalytic activity of the inorganic salt catalyst is practically unchanged in the presence of sulfur; and / or (b) the inorganic salt catalyst is continuously added to the crude feed.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, an inorganic salt catalyst for which there is:

(a) the inflection point of the gas evolution is in the temperature range of the time analysis of products (VAP), and the gas emitted contains water vapor and / or carbon dioxide;

(b) the thermal transition lies in the range between 200 and 500 ° C, 250-450 ° C or 300-400 ° C, which is determined by the method of differential scanning calorimetry (DSC) at a heating rate of 10 ° C / min;

(c) DSC temperature is in the range between 200 and 500 ° C or 250-450 ° C;

(b) at a temperature of at least 100 ° C, the peaks in the radiograph are wider than the peaks in the radiograph of the inorganic salt catalyst below 100 ° C; and / or (e) after conditioning, the ionic conductivity at 300 ° C. is less than the ionic conductivity of the inorganic salt catalyst before conditioning.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions according to the invention, an inorganic salt catalyst for which the inflection point for gas evolution lies in a temperature range that is determined by the VAP method and, in addition, the contact conditions are chosen such so that the contact temperature lies:

(a) above T ₁ , where Τι lies 30, 20 or 10 ° C below the VAP of the temperature of the inorganic salt catalyst;

(b) at (or above) the VAP temperature and / or (c) at least at the VAP temperature of the inorganic salt catalyst.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, an inorganic salt catalyst which (or in which):

(a) is a liquid or pseudo-liquid, at least at the VAP temperature of the inorganic salt catalyst, and the inorganic salt catalyst is practically insoluble in the crude feed, at least at the VAP temperature, where the VAP temperature is the minimum temperature at which the inorganic salt catalyst has an inflection point at

- 4 010396 gas evolution;

(b) is a mixture of a liquid phase and a solid phase at a temperature in the range of 50 to 500 ° C. and / or (c) at least one of the two inorganic salts has a DSC temperature above 500 ° C.

In some embodiments, the invention also provides, in combination with one or more of the methods or compositions of the invention, a crude product that has at least one of the catalysts containing one or more alkali metals, wherein: (a) at least one of the alkali the metal is potassium, rubidium or cesium, or mixtures thereof and / or (b), at least one of the catalysts further comprises a transition metal, a transition metal sulfide and / or bartonite.

Brief Description of the Drawings

The advantages of the present invention will become apparent to those skilled in the art using the following detailed description and with reference to the accompanying drawings, in which:

FIG. 1 is a schematic embodiment of a system for contacting a crude feed with a hydrogen source in the presence of one or more catalysts in order to obtain a total product;

FIG. 2 is another schematic embodiment of a system for contacting a crude feed with a hydrogen source in the presence of one or more catalysts in order to obtain a total product;

FIG. 3 is a schematic embodiment of a separation zone in combination with a contacting system;

FIG. 4 is a schematic embodiment of a mixing zone in combination with a contacting system;

FIG. 5 is a schematic embodiment of a separation zone, a contacting system, and a mixing zone;

FIG. 6 is a schematic embodiment of composite contacting systems;

FIG. 7 is a schematic embodiment of an ionic conductivity measurement system;

FIG. 8 is a table of the characteristics of the crude feed and the characteristics of the crude products obtained for various options for contacting the crude feed with a catalyst — transition metal sulfides;

FIG. 9 is a table of the composition of the crude feed and the composition of non-condensable hydrocarbons obtained for various options for contacting the crude feed with a catalyst — transition metal sulfides;

FIG. 10 is a table of the characteristics and composition of the crude products obtained for various options for contacting the crude feed with a catalyst — transition metal sulfides;

FIG. 11 - graphical dependence of the ion current (decimal logarithm) of the gases emitted for an inorganic salt catalyst on temperature, which is determined by the VAP method;

FIG. 12 is a graph of the resistance (decimal logarithm) of inorganic salt catalysts and inorganic salt relative to the temperature resistance of potassium carbonate;

FIG. 13 - graphical dependence of the resistance (decimal logarithm) of the catalyst

Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ relative to potassium carbonate resistance versus temperature;

FIG. 14 is a graphical weight percent of the obtained coke, liquid hydrocarbons and gas for various hydrogen sources for embodiments of contacting the crude feed with an inorganic salt catalyst;

FIG. 15 is a graph depicting the mass percent of the obtained crude products on the number of carbon atoms for various contacting crude materials with an inorganic salt catalyst;

FIG. 16 is a table of components obtained for various options for contacting a crude feed with inorganic salt catalysts, a metal salt, or silicon carbide.

Although this invention is susceptible to various modifications and alternative forms, its specific embodiments are shown by way of examples, in the drawings and will be described in detail in the invention. Drawings may not be drawn to scale. It should be understood that the drawings and, in addition, the detailed description are not intended to limit this invention to the described specific forms, but rather, this invention will protect all modifications, equivalents and alternatives that are related to the intent and scope of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

Some embodiments of the invention are described in more detail in this invention. The terms used in it mean the following.

The term alkali metal (s) refers to one or more metals from the first group of the Periodic Table, to one or more compounds of one or more metals from the first group of the Periodic Table, or mixtures thereof.

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The term alkaline earth metal (s) refers to one or more metals from the second group of the Periodic Table, to one or more compounds of one or more metals from the second group of the Periodic Table, or mixtures thereof.

The term AEM refers to an atomic unit of mass.

The term A8TM refers to the American Society for Testing Materials.

The term C ₅ asphaltenes refers to asphaltenes that are insoluble in pentane. The content of C ₅ asphaltenes is determined by the method A8TM Ό2007.

The percentage of atomic hydrogen and the percentage of atomic carbon for crude feed, crude product, naphtha, kerosene, diesel fuel and VGO is determined by the method A8TM Ό5291.

The term AP1 density refers to the density of AP1 at 15.5 ° C. The density of AR1 (in degrees) is determined by the method A8TM Ό6822.

The term bitumen refers to one type of raw material mined and / or distilled from a hydrocarbon formation in a retort.

The distribution of the boiling range for the crude feed and / or the total product is determined by the method A8TM Ό5307, unless otherwise indicated. The content of hydrocarbon components, such as paraffins, isoparaffins, olefins, naphthenes and aromatic hydrocarbons in naphtha is determined by the method A8TM Ό6730. The content of aromatic hydrocarbons in diesel fuel and VGO is determined according to method 1P 368/90. The content of aromatic hydrocarbons in kerosene is determined by the method A8TM Ό5186.

The term acid Br6pk1eb-Eo ^ gu refers to a molecular object capable of transferring a proton to another molecular object.

The term Bgbieb-Lobetu base refers to a molecular object that is capable of receiving protons from another molecular object. Examples of the base of Br6pk1eb-Eo ^ gy include hydroxide (OH ^- ), water (H2O), carboxylate (PCO2 ^- ). halide (Br ^- , C1 ^- , P ^- , I ^- ), bisulfate (Н8О4 ^- ) and sulfate (8О ₄ ² ).

The term number of carbon atoms refers to the total number of carbon atoms in a molecule.

The term coke refers to a solid substance containing carbonaceous solids that do not evaporate under process conditions. The coke content is determined using material balance. Coke mass is the total mass of solid matter minus the total mass of introduced catalysts.

The term “content” refers to the weight of a component in a substrate (for example, in a crude feed, a total product or in a crude product), expressed as a weight fraction or weight percentage based on the total weight of the substrate. Weight. ppm refers to parts per million by weight.

The term diesel fuel refers to hydrocarbons with a boiling range distribution between 260 and 343 ° C (500-650 ° P) at 0.101 MPa. The diesel content is determined by the method A8TM Ό2887.

The term distillate refers to hydrocarbons with a boiling range distribution between 204 and 343 ° C (400-650 ° P) at 0.101 MPa. The distillate content is determined by the method A8TM Ό2887. The distillate may include kerosene and diesel.

The term DSC refers to differential scanning calorimetry.

The term freezing point refers to the temperature at which crystalline particles form in a liquid. The freezing point is determined by the method A8TM Ό2386.

The term GC / MS refers to gas chromatography in combination with mass spectrometry.

The term “rigid base” refers to the anions described by Pearson in article 1oigia1 o £ Ashepsap Syet1ea1 8os1e1u, 1963, 85, p. 3533.

The H / C ratio refers to the weight ratio of atomic hydrogen to atomic carbon. The N / C ratio is determined using the measured values of the weight percent hydrogen and weight percent carbon according to A8TM Ό5291.

The term heteroatoms refers to oxygen, nitrogen and / or sulfur, which are contained in the molecular structure of a hydrocarbon. The content of heteroatoms is determined by the methods A8TM E385 for oxygen, Ό5762 for nitrogen and Ό4294 for sulfur.

The term hydrogen source refers to hydrogen and / or a compound and / or compounds that, in the presence of a crude feed and a catalyst, react to provide hydrogen for one or more compounds in the raw feed. The hydrogen source may include, but is not limited to, hydrocarbons (e.g., C ₁ -C ₆ hydrocarbons such as methane, ethane, propane, butane, pentane, naphtha), water, or mixtures thereof. Material balance is reduced in order to estimate the total amount of hydrogen provided for one or more compounds in the crude feed.

The term inorganic salt refers to a compound that consists of a metal cation and an anion.

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The term ΙΡ refers to the Institute of Petroleum, currently Eeegdu Bolshe ί о ί иб иб иб иб, И И Н Н бот бот бот бот бот.

The term isoparaffins refers to branched chain saturated hydrocarbons.

The term kerosene refers to hydrocarbons with a boiling range distribution between 204 and 260 ° C (400-500 ° P) at 0.101 MPa. Kerosene content is determined by the method A8TM Ό2887.

The term Lewis acid refers to a compound or material capable of accepting one or more electrons from another compound.

The term Lewis base refers to a compound or material capable of transferring one or more electrons to another compound.

The term light hydrocarbons refers to hydrocarbons having a carbon number of 1 to 6.

The term liquid mixture refers to a composition that includes one or more compounds that are liquid at normal temperature and pressure (25 ° C, 0.101 MPa, hereinafter referred to as NTD) or a composition that includes a combination of one or more compounds which are liquid in STD with one or more compounds that are solid in STD.

The term microcarbon residue (WMD) refers to the amount of carbon residue remaining after evaporation and pyrolysis of a substance. The content of WMD is determined by the method A8TM Ό4530.

The term naphtha refers to hydrocarbon components with a boiling range distribution between 38 and 204 ° C (100-400 ° P) at 0.101 MPa. The naphtha content is determined by the method A8TM Ό2887.

The term Νί / ν / Pe refers to nickel, vanadium, iron, or combinations thereof.

The term Νί / ν / Pe content refers to the content of Νί / ν / Pe in the substrate. The content of Νί / ν / Pe is determined by the method A8TM Ό5863.

The term Nm ³ / m ³ refers to normal cubic meters of gas per 1 cubic meter of crude feed.

The term non-acidic refers to the characteristics of the Lewis base and / or the base of Brbiebobo ^ gu.

The term non-condensable gas refers to components and / or mixtures of components that are gases at normal temperature and pressure (25 ° C, 0.101 MPa, hereinafter referred to as NTD).

The term n-paraffins refers to normal (straight chain) saturated hydrocarbons.

The term octane number refers to the calculated numerical representation of the antiknock characteristics of motor fuel compared to a standard reference fuel. The estimated octane number of naphtha is determined by the method A8TM Ό6730.

The term olefins refers to compounds with non-aromatic carbon-carbon double bonds. Types of olefins include, but are not limited to, cis, trans, terminal, internal, branched and linear olefins.

The term Periodic Table refers to the Periodic Table of the Elements, which is defined by the organization 1i1egia1uia1 Itoi οί Riga aib ArrNeb S’yetMgu (GORAS), November 2003.

The term polyaromatic compounds refers to compounds that include two or more aromatic rings. Examples of polyaromatic compounds include, but are not limited to, indene, naphthalene, anthracene, phenanthrene, benzothiophene, and dibenzothiophene.

The term residue refers to components that have a boiling range distribution above 538 ° C (1000 ° P) at 0.101 MPa, which is determined by the A8TM Ό5307 method.

The term pseudo-fluid refers to a phase of a substance that has the characteristics of a liquid phase and a solid phase of a substance. Examples of pseudo-liquid inorganic salt catalysts include a suspension and / or phase, which has the consistency of, for example, toffee, dough or toothpaste.

The term SKFB refers to standard cubic feet of gas per barrel of crude feed.

The term superbase refers to a material that can deprotonate hydrocarbons such as paraffins and olefins under reaction conditions.

The term SKH refers to the total acid number expressed in milligrams (mg) KOH per 1 gram (g) of sample. SKH is determined by the method A8TM Ό664.

The term VAP refers to a temporary analysis of products.

The term SPM refers to a transition metal sulfide.

The term VGO (vacuum gas oil) refers to components with a boiling range distribution between 343 and 538 ° C (650-1000 ° P) at 0.101 MPa. The content of VGO is determined by the method A8TM Ό2887.

In the context of this invention, it should be understood that if the value obtained for characterizing the tested composition is outside the scope of the tested method, this method can be re-calibrated to test such a characteristic. It should be understood that other standardized test methods that are considered equivalent to the reference test methods may be used.

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Raw materials can be extracted and / or distilled from hydrocarbon containing formations and then stabilized. Typically, the feed may be a solid, semi-solid and / or liquid. Raw materials may include crude oil. Stabilization may include, but is not limited to, removing non-condensable gases, water, salts, or combinations thereof from the feed to obtain a stabilized feed. Often, such stabilization can be performed near or at the site of production and / or distillation in a retort.

Typically, stabilized feeds are not subjected to distillation and / or fractional distillation in a processing plant in order to obtain constituents with a specific distribution of boiling ranges (e.g., naphtha, distillates, VGO and / or lubricating oils). Distillation includes (but is not limited to) atmospheric distillation methods and / or vacuum distillation methods. The non-refluxed and / or unfractionated stabilized feed may include components that have a carbon number greater than 4 in an amount of at least 0.5 g of components per 1 g of feed. Examples of stabilized feedstocks include whole feedstocks, stripped feedstocks, desalted feedstocks, desalinated stripped feedstocks, or combinations thereof.

The term topped refers to raw materials that are processed in such a way that at least part of the components having a boiling point below 35 ° C at 0.101 MPa is removed. Typically, the stripped feed has a content of such components of at most 0.1 g, at least 0.05 g, or at most 0.02 g per 1 g of stripped feed.

Some types of stabilized raw materials have such characteristics that stabilized raw materials can be transported to conventional processing units using vehicles (for example, pipelines, tankers or tankers). Other types of raw materials have one or more inappropriate characteristics that make them disadvantageous. Unfavorable raw materials may be unacceptable for vehicles and / or processing equipment, thus reducing the economic importance of unfavorable raw materials. This economic value may be such that it is considered impractical to extract, transport and / or process raw materials from the reservoir, which includes disadvantageous raw materials.

Characteristics of disadvantageous raw materials may include, but are not limited to:

a) an SKH of at least 0.5;

b) a viscosity of at least 0.2 Pa-s;

c) density ΑΡΙ, at most 19 °;

6) the total content of Νί / ν / Her, at least 0.00005 g or at least 0.0001 g Νί / ν / Her per 1 g of raw materials;

e) the total content of heteroatoms, at least 0.005 g of heteroatoms per 1 g of raw materials;

I) a residue content of at least 0.01 g of residue per 1 g of raw material;

d) the content of asphaltenes, at least 0.04 g of asphaltenes per 1 g of raw materials;

II) the content of WMD, at least 0.02 g of WMD per 1 g of raw materials or

ί) their combinations.

In some embodiments, the disadvantageous feed may include, per gram of disadvantageous feed, at least 0.2 g of a residue, at least 0.3 g of a residue, at least 0.5 g of a residue, or at least 0.9 g of a residue . In certain embodiments, the disadvantageous feed has 0.2-0.99 g, 0.3-0.9 g, or 0.4-0.7 g of residue per 1 g of the unfavorable feed. In certain embodiments, the disadvantageous feed may have a sulfur content of at least 0.001 g, at least 0.005 g, at least 0.01 g, or at least 0.02 g per 1 g of disadvantageous feed.

Unfavorable feedstocks may include a hydrocarbon mixture having a boiling range. Unfavorable raw materials may include, per 1 g of unfavorable raw materials, at least 0.001 g, at least 0.005 g, or at least a distribution of the boiling range between 200 and 300 ° C at 0.101 MPa;

at least 0.001 g, at least 0.005 g, or at least a boiling range distribution between 300 and 400 ° C. at 0.101 MPa, and at least 0.001 g, at least 0.005 g, or at least a boiling range distribution between 400 and 700 ° C at 0.101 MPa

0.01

0.01

0.01 hydrocarbons hydrocarbons hydrocarbons or combinations thereof.

In some embodiments, the disadvantageous feed can also include, per gram of disadvantageous feed, at least 0.001 g, at least 0.005 g, or at least 0.01 g of hydrocarbons with a boiling range of at least 200 ° C. at 0.101 MPa in addition to components with a high boiling point. Typically, the unfavorable feed has a content of such hydrocarbons of at most 0.2 g or at most 0.1 g per 1 g of unfavorable feed.

In certain embodiments, the disadvantageous feed can include up to 0.9 g or up to 0.99 g of hydrocarbons per gram of disadvantageous feed with a boiling range of at least 300 ° C. In certain embodiments, the disadvantageous feed may also include, per gram of disadvantageous feed, at least 0.001 g of hydrocarbons with a boiling range of at least 650 ° C. In certain embodiments, the disadvantageous feed may include up to 0.9 g or up to 0.99 g of hydrocarbons per 1 g of the unfavorable feed with a boiling range of between 300 and 1000 ° C.

Examples of disadvantageous raw materials that can be processed using the methods described in this invention include, but are not limited to, raw materials from the following countries and regions of these countries: A1bet1a province (Canada), Opposo province (Venezuela), southern California and northern slope of Alaska (USA), Gulf of Satresie. 8ap 1otde basin (Argentina), 8ai1o8 and Satrok pools (Brazil), Βοϊιαί Bay (China), Kagatau (China), Ζ; · ΐβΐΌ5 (Iraq), Caspian Sea (Kazakhstan), marine fisheries in Nigeria, in the North Sea (Great Britain ), northwestern Madagascar, Oman, and 8cióupebék (Netherlands).

Processing disadvantageous raw materials can improve its characteristics so that the raw materials become acceptable for transportation and / or processing. Raw materials and / or disadvantageous raw materials to be processed may be referred to as raw materials. This crude feed may be stripped as described in the invention. The crude product obtained by processing the crude feed using the methods described in the invention is suitable for transportation and / or processing. The characteristics of the crude product are more reminiscent of the corresponding characteristics of East Texas intermediate raw materials than the raw crude or closer to the corresponding characteristics of the Vtep1 brand raw materials than the raw crude, and therefore the product has an increased economic value compared to the economic value of the crude raw material. Such a crude product can be processed with or without less pretreatment, thereby increasing the efficiency of oil refining. Pretreatment may include desulfurization, demetallization and / or atmospheric distillation in order to remove impurities from the crude product.

Methods for contacting the crude feed according to the invention are described in the invention. Additionally described are embodiments for producing products with various concentrations of naphtha, kerosene, diesel fuel and / or VGO, which are usually not obtained in conventional processes.

The crude feed can be brought into contact with a hydrogen source in the presence of one or more catalysts in the contacting zone and / or in combinations of two or more contacting zones. In some embodiments, a hydrogen source is formed. The production of a hydrogen source ίη 8Yi may include the interaction of at least a portion of the crude feed with an inorganic salt catalyst at a temperature in the range of 200-500 ° C or 300-400 ° C with the formation of hydrogen and / or light hydrocarbons. The production of hydrogen ίη zi may include the interaction of at least a portion of an inorganic salt catalyst, which includes, for example, alkali metal formate.

Typically, the total product contains gas, vapors, liquids or mixtures thereof formed during contacting. The total product includes the crude product, which is a liquid mixture in the STD and, in some embodiments, hydrocarbons that do not condense in the STD. In some embodiments, the total product and / or the crude product may include solids (such as inorganic solids and / or coke). In certain embodiments, solids can be entrained in liquid and / or vapor generated during contacting.

The contacting zone typically includes a reactor, part of a reactor, constituent parts of a reactor, or constituent reactors. Examples of reactors that can be used to contact the crude feed with a hydrogen source in the presence of a catalyst include a multi-layer reactor, a fixed-bed reactor, a continuous mixing reactor (RNP), a spray reactor, a piston flow reactor, and a liquid contact apparatus /liquid. Examples of NPS include a fluidized bed reactor and a fluidized bed reactor.

Contact conditions typically include temperature, pressure, flow rate of the crude feed, flow rate of the total product, residence time, flow rate of the hydrogen source, or a combination thereof. Contact conditions can be adjusted to obtain a crude product with specific characteristics.

The contact temperature can vary in the range of 200-800 ° C, 300-700 ° C or 400-600 ° C. In embodiments where the hydrogen source is supplied in the form of a gas (e.g., gaseous hydrogen, methane or ethane), typically the ratio of gas to crude feed may vary from 1 to 16100 Nm / m, from 2 to 8000 Nm / m, from 3 to 4000 Nm / m or from 5 to 300 Nm / m. Contacting is usually carried out in the pressure range of 0.1-20 MPa, 1-16 MPa, 2-10 MPa or 4-8 MPa. In some embodiments in which water vapor is added, the ratio of steam to crude feed is in the range of 0.01-3 kg, 0.03-2.5 kg, or 0.1-1 kg of steam per 1 kg of crude feed. The flow rate of the crude feed may be sufficient to maintain the volume of the crude feed in the contact zone at least 10%, at least 50%, or at least 90% of the total volume of the contact zone. Typically, the volume of crude feed in the contact zone is

- 9 010396 et 40, 60 or 80% of the total volume of the contact zone. In some embodiments, contacting may be carried out in the presence of additional gas, for example argon, nitrogen, methane, ethane, propane, butanes, propylene, butylenes, or combinations thereof.

FIG. 1 is a schematic embodiment of a contacting system 100 used to produce a total product in the form of vapors. The crude feed leaves the feed feed assembly 101 and enters the contacting zone 102 through line 104. The amount of catalyst used in the contacting zone can vary from 1 to 100 g, from 2 to 80 g, from 3 to 70 g, or from 4 to 60 g per 100 g of crude feed in the contact zone. In certain embodiments, a diluent may be added to the crude feed in order to reduce the viscosity of the crude feed. In some embodiments, the crude feed enters the lower portion of the contacting zone 102 through conduit 104. In certain embodiments, the crude feed can be heated to a temperature of at least 100 ° C or at least 300 ° C before and / or during the introduction of the crude feed to the contacting zone 102. Typically, the crude feed can be heated to a temperature in the range of 100-500 ° C or 200-400 ° C.

In some embodiments, the catalyst is combined with the crude feed and pumped to the contact zone 102. The mixture of the crude feed with the catalyst can be heated to a temperature of at least 100 ° C or at least 300 ° C before being introduced into the contact zone 102. Typically, the crude feed can be heated to a temperature in the range of 200-500 ° C or 300-400 ° C. In some embodiments, the mixture of the crude feed with the catalyst is a suspension. In certain embodiments, the CCR value of the crude feed can be reduced prior to the introduction of the crude feed into the contact zone. For example, when a mixture of crude feed with a catalyst is heated at a temperature in the range of 100-400 ° C or 200-300 ° C, alkali metal salts with acidic components in the crude feed can form. Due to the formation of these alkaline salts, it is possible to remove some acidic components from the crude feed and reduce the CKP of the crude feed.

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

In some embodiments, the crude feed and / or a mixture of the crude feed with an inorganic salt catalyst is introduced into the contact zone as an emulsion. This emulsion can be prepared by combining a mixture of an inorganic salt catalyst and water with a mixture of crude feed and surfactant. In some embodiments, a stabilizer is added to the emulsion. The emulsion may remain stable for at least 2 days, at least 4 days, or at least 7 days. Typically, the emulsion can remain stable for 30, 10, 5, or 3 days. Surfactants may include, but are not limited to, organic polycarboxylic acids (Tepah 2010; MsabKhUSyuaso 8pcc1a11u Rgobis! Stair; Syabschop. 8oy1y Satoysha, I8A),

With ₂₁ dicarboxylic fatty acids (O1ACS 1550; MsabKhUSyuaso 8pcc1a11u Rgobis! Scoir), petroleum sulphonates (Noyarit 8A8 30; S1apsp1 Sotrotabop, Soyagosum, Sulfuricobactylbenzoate; I8A) or mixtures thereof.

Stabilizers include (but are not limited to) diethyleneamine (A1bps11 C11c1shsa1 Co .; Mi ^ aikss, UESopyp, I8A) and / or monoethanolamine (1.T. Vaxg; RYShkItd, No. \ ν 1st8su, IZA).

A recirculation conduit 106 may connect conduit 108 and conduit 104. In some embodiments, the recirculation conduit 106 may enter and exit the contacting area 102 directly. The recirculation pipe 106 may include a flow control valve 110. This control valve 110 may recycle at least a portion of the material from conduit 108 to conduit 104 and / or contact area 102. In some embodiments, a condensation assembly may be located in conduit 108 by allowing condensation of at least a portion of the material and its recirculation to the contacting zone 102. In certain embodiments, the recirculation conduit 106 may be a line w recirculation gas. Flow control valves 110 and 110 'may be used to control flow to and from the contact zone 102 so as to maintain a constant volume of liquid in the contact zone. In some embodiments, in the contact zone 102, it is possible to maintain a fluid volume in a substantially predetermined range. The volume of raw materials in the contact zone 102 can be controlled using standard devices

- 10 010396 moat. A gas inlet 112 may be used to provide a source of hydrogen and / or additional gases to the crude feed when the crude feed enters the contacting zone 102. In some embodiments, the steam inlet 114 may be used to provide added water vapor to the zone contacting 102. In certain embodiments, a stream of water is introduced into contacting area 102 through a steam inlet 114.

In some embodiments, at least a portion of the total product is obtained in the form of steam from the contacting zones 102. In certain embodiments, the total product is formed in the form of steam and / or steam containing small amounts of liquid and solid substances leaving the top of the contacting zone 102. Steam is supplied to the separation zone 116 through the pipeline 108. The ratio of the hydrogen source to the crude feed in the contact zone 102 and / or the pressure in the contact zone can be varied in order to control the amount of aaric and / or liquid phase formed at the top of the contacting zone 102. In some embodiments, the vapor formed at the top of the contacting zone 102 includes at least 0.5 g, at least 0.8 g, at least 0.9 g or at least 0.97 g of crude product per 1 g of crude feed. In certain embodiments, the vapor generated at the top of the contact zone 102 includes from 0.8 to 0.99 g or 0.9-0.98 g of crude product per 1 g of crude feed.

Spent catalyst and / or solids may remain in the contacting zone 102 as by-products of the contacting process. Solids and / or spent catalyst may include residual crude feed and / or coke.

In the separation unit 116, the steam is cooled and separated, forming the crude product and gases, using standard separation techniques. The crude product leaves separation unit 116 and enters the crude product receiver 119 through line 118. The resulting crude product may be suitable for transportation and / or processing. The crude product receiver 119 may include one or more pipelines, one or more storage units, one or more containers for transportation, or a combination thereof. In some embodiments, the evolved gas (e.g., hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide or methane) is transported to other processing plants (e.g., for use in a fuel cell or in a sulfur recovery unit) and / or recycled to the contact zone 102 via conduit 120. In certain embodiments, solids and / or liquids entrained in the crude product can be removed using conventional physical separation methods (eg, filtration centrifugation or membrane separation).

In FIG. 2 shows a contacting system 122 for processing a crude feed with one or more catalysts to produce a total product, which may be a liquid or a liquid mixed with gaseous or solid substances. The crude feed may enter the contacting zone 102 through a conduit 104. In some embodiments, the crude feed comes from a raw feed source. The pipe 104 may include a gas inlet channel 112. In some embodiments, the gas inlet channel 112 may directly enter the contact area 102. In certain embodiments, the steam inlet channel 114 may be used to allow steam to be added to the contact area 102. The crude feed can be brought into contact with the catalyst in the contact zone 102 to obtain the total product. In some embodiments, conduit 106 recirculates at least a portion of the total product to the contact zone 102. A mixture that includes the total product and / or solids and / or unreacted crude feed leaves the contact zone 102 and enters the separation zone 124 through line 108. In some embodiments, a condensation unit may be located, for example, in line 106, allowing condensation of at least a portion of the mixture in the line and recirculating it to the contact zone anija 102 for subsequent processing. In certain embodiments, the recirculation pipe 106 may be a gas recirculation line. In some embodiments, conduit 108 may include a filter to remove particles from the total product.

In separation zone 124, at least a portion of the crude product may be separated from the total product and / or catalyst. In embodiments in which the total product contains solids, these solids can be separated from the total product using standard isolation techniques (e.g., centrifugation, filtration, decantation, membrane separation). Solids include, for example, a combination of catalyst, spent catalyst and / or coke. In some embodiments, a portion of the gases is released from the total product. In some embodiments, at least a portion of the total product and / or solids may be recycled to conduit 104 and / or in some embodiments to the contacting zone 102 via conduit 126. For example, the recycled portion may be combined with the crude feed and introduced into the contacting zone 102 for subsequent processing. The crude product may exit separation zone 124 via conduit 128. In certain embodiments

- 11 010396 embodiments of the crude product may be sent to the receiver of the crude product.

In some embodiments, the total product and / or the crude product may include at least a portion of the catalyst. Gases entrained with the total product and / or the crude product can be emitted using standard gas / liquid separation techniques such as bubbling, membrane separation and pressure reduction. In some embodiments, the evolved gas is sent to other process plants (for example, for use in a fuel cell, in a sulfur recovery plant, in other processing plants or a combination thereof) and / or is recycled to the contact zone.

In some embodiments, the separation of at least a portion of the crude feed is performed before the crude feed enters the contact zone.

FIG. 3 is a schematic embodiment of a separation zone in combination with a contacting system. The contacting system 130 may be a contacting system 100 and / or a contacting system 122 (shown in FIGS. 1 and 2). The crude feed enters separation zone 132 through a conduit 104. In separation zone 132, at least a portion of the crude feed is recovered using standard separation techniques to produce recovered crude feed and hydrocarbons. In some embodiments, the recovered crude feed includes a mixture of components with a boiling range distribution of at least 100 ° C, at least 120 ° C, or, in some embodiments, a boiling range distribution of at least 200 ° C. Typically, the selected crude feed includes a mixture of components with a distribution of the boiling range 100-1000 ° C, 120-900 ° C or 200-800 ° C. Hydrocarbons extracted from crude raw materials leave separation zone 132 via pipeline 134 and can be transported to other processing plants, storage equipment, or a combination thereof.

At least a portion of the recovered crude feed leaves separation zone 132 and enters the contacting system 130 via line 136 for subsequent processing to form a crude product that exits the contacting system 130 via line 138.

In some embodiments, the crude product obtained from the crude feed by any method described in the invention is mixed with a feed that is the same or different from the crude feed. For example, the crude product can be combined with a raw material having a different viscosity, resulting in a mixed product having an intermediate viscosity between the viscosity of the crude product and the viscosity of the raw material. The resulting mixed product may be suitable for transportation and / or processing.

FIG. 4 is a schematic diagram of a combination of a mixing zone 140 and a contacting system 130. In certain embodiments, at least a portion of the crude product leaves the contacting system 130 via line 138 and enters the mixing zone 140. In the mixing zone 140, at least a portion of the crude product is combined with one or more process streams (for example, a hydrocarbon stream obtained by separating one or more types of crude feed or naphtha), raw materials, raw feed silt mixtures thereof, to obtain a mixed product. Process streams, crude feed, raw materials or mixtures thereof are injected directly into the mixing zone 140 or to a point above the mixing zone via line 142. The mixing system can be located inside or near the mixing zone 140. The mixed product can meet the specifications for a particular product. Product-specific specifications include, but are not limited to, the range or density limit ΑΡΙ (in degrees), SKH, viscosity, or combinations thereof. The blended product leaves mixing zone 140 via conduit 144 and will be transported and / or processed.

In some embodiments, methanol is produced during the contacting process using the catalyst. For example, hydrogen and carbon monoxide can interact to produce methanol. The recovered methanol may contain dissolved salts, for example potassium hydroxide. The recovered methanol may be combined with additional crude feed to form a mixture of the crude feed with methanol. The combination of methanol with crude feed helps to reduce the viscosity of the crude feed. Heating a mixture of crude feed with methanol to at most 500 ° C can reduce the CKP of the crude feed to less than 1.

FIG. 5 is a schematic illustration of a separation zone in combination with a contacting system and in combination with a mixing zone. The crude feed enters the separation zone 132 through a conduit 104. The crude feed is separated, as described above, to form the recovered crude feed. This isolated crude feed enters the contacting system 130 through line 136. The crude product leaves the contacting system 130 and enters the mixing zone 140 through line 138. In the mixing zone 140, another process stream and / or raw materials introduced through line 142 are combined with the crude product forming a mixed product. This mixed product leaves mixing zone 140 via line 144.

FIG. 6 is a diagram of a composite contacting system 146. The contacting system 100 (shown in FIG. 1) may be located upstream of the contacting system 148. In an alternate embodiment, the arrangement of the contacting systems may be reversed. The contacting system 100 includes an inorganic salt catalyst. The contacting system 148 may include one or more catalysts. The catalyst in contacting system 148 may be an additional catalyst — an inorganic salt, a catalyst — transition metal sulfide, industrial catalysts, or mixtures thereof. The crude feed enters the contacting system 100 via line 104, where it is contacted with a hydrogen source in the presence of an inorganic salt catalyst in order to obtain a total product. This total product contains hydrogen and, in some embodiments, is a crude product. The total product can leave the contacting system 100 via line 108. The hydrogen obtained by contacting the inorganic salt catalyst with the crude feed can be used as a hydrogen source for the contacting system 148. At least a portion of the hydrogen produced is pumped to the contacting system 148 from the contacting system 100 by pipeline 150.

In an alternative embodiment, the hydrogen thus produced can be separated and / or processed, and then pumped to the contacting system 148 via conduit 150. In certain embodiments, the contacting system 148 can be part of the contacting system 100 so that the hydrogen produced directly comes from the contacting system 100 to the contacting system 148. In some embodiments, the vapor stream obtained from the contacting system 100 is directly mixed with the crude raw materials entering the contacting system 148.

The second crude feed stream enters the contacting system 148 via line 152. In the contacting system 148, when the crude feed contacts at least a portion of the hydrogen produced and the catalyst, a product is obtained. In some embodiments, this product is a total product. Product exits contacting system 148 via conduit 154.

In certain embodiments, a system that includes contact systems, contact zones, separation zones, and / or mixing zones, as shown in FIG. 1-6, may be located at the place of production or near the place of production of disadvantageous raw materials. After processing using a catalytic system, the crude feed can be considered suitable for transportation and / or for use in oil refining processes.

In some embodiments, the crude product and / or mixed product is transported to a refinery and / or to a processing device. The crude product and / or mixed product may be processed to produce industrial products such as transport fuels, boiler fuels, lubricants or chemicals. Processing may include distillation and / or fractional distillation of the crude product and / or mixed product to obtain one or more distillate fractions. In some embodiments, the crude product, mixed product, and / or one or more distillate fractions may be hydrotreated.

In some embodiments, the total product contains at least 0.05 g, at least 0.03 g, or at least 0.01 g of coke per 1 g of total product. In certain embodiments, the total product is substantially free of coke (i.e., no coke is detected). In some embodiments, the crude product may include at least 0.05 g, at least 0.03 g, at least 0.01 g, at least 0.005 g, or at most 0.003 g of coke per g of crude product. In certain embodiments, the crude product has a coke content in the range from above 0 to 0.05, 0.00001 to 0.03 g, 0.0001 to 0.01 g, or 0.001 to 0.005 g per 1 g of the crude product or no coke is detected.

In certain embodiments, the crude product has a WMD content of at least 90%, at least 80%, at least 50%, at least 30%, or at most 10% of the WMD content for the crude feed. In some embodiments, the crude product has a low WMD content. In some embodiments, the crude product contains, per gram of crude product, at least 0.05 g, at least 0.03 g, at least 0.01 g, or at most 0.001 g WMD. Typically, the crude product has from 0 to 0.04 g, 0.000001 to 0.03 g, or 0.00001 to 0.01 g WMD per 1 g of the crude product.

In some embodiments, the total product contains non-condensable gas. Non-condensable gas typically includes (but is not limited to) carbon dioxide, ammonia, hydrogen sulfide, hydrogen, carbon monoxide, methane, other hydrocarbons that do not condense during the NTP or a mixture thereof.

In certain embodiments, gaseous hydrogen, carbon dioxide, carbon monoxide, or combinations thereof, can form ίη 8uy as a result of contact of water vapor and light hydrocarbons with an inorganic salt catalyst. Typically, in thermodynamic conditions, the molar ratio of carbon monoxide to carbon dioxide is 0.07. In some embodiments, the molar ratio of carbon monoxide produced to carbon dioxide produced is at least 0.3, at least 0.5, or at least 0.7. In some embodiments, the molar ratio of carbon monoxide produced to carbon dioxide produced is

- 13 010396

0.3-1.0; 0.4-0.9 or 0.5-0.8. The ability to preferentially produce carbon monoxide relative to carbon dioxide ίη δίΐιι may be advantageous given other processes located in adjacent areas or upstream. For example, carbon monoxide produced can be used as a reducing agent in the processing of hydrocarbon formations or used in other processes, for example, in the production of synthesis gas.

In some embodiments, the total product that is obtained according to the invention may include a mixture of compounds that have a boiling range distribution between -10 and 538 ° C. This mixture may include hydrocarbons that have a carbon number of from 1 to 4. The mixture may include from 0.001 to 0.8 g, from 0.003 to 0.1 g, or from 0.005 to 0.01 g of C ₄ hydrocarbons per 1 g. such a mixture. C ₄ hydrocarbons may include from 0.001 to 0.8 g, from 0.003 to 0.1 g, or from 0.005 to 0.01 g of butadiene per 1 g of C ₄ hydrocarbons. In some embodiments, the weight ratio of the resulting isoparaffins to n-paraffins is at least 1.5, at least 1.4, at least 1.0, at least 0.8, at most 0.3, or greater least 0.1. In certain embodiments, the weight ratio of the resulting isoparaffins to n-paraffins is in the range from 0.00001 to 1.5, from 0.0001 to 1.0, or from 0.001 to 0.1. Paraffins may include isoparaffins and / or n-paraffins.

In some embodiments, the total product and / or the crude product may include olefins and / or paraffins in ratios or amounts that are not typically observed for oils recovered and / or distilled from the formation. Olefins include a mixture of olefins with terminal double bonds (alpha olefins) and olefins with internal double bonds. In certain embodiments, the olefin content of the crude product exceeds the olefin content of the crude feed by 2, 10, 50, 100 times, or at least 200 times. In some embodiments, the olefin content of the crude product is greater than the olefin content of the crude feed, at least 1000 times, at most 500, at least 300, or at most 250 times.

In certain embodiments, hydrocarbons with a boiling range distribution of 20-400 ° C. have olefins in the range of 0.00001 to 0.1 g, 0.0001 to 0.05 g, or 0.01 to 0.04 g per 1 g of hydrocarbons having a boiling point distribution in the range of 20-400 ° C.

In some embodiments, at least 0.001 g, at least 0.005 g, or at least 0.01 g of alpha olefins per gram of crude product can be obtained. In certain embodiments, the crude product contains from 0.0001 to 0.5 g, from 0.001 to 0.2 g, or from 0.01 to 0.1 g of alpha olefins per g of the crude product. In certain embodiments, hydrocarbons with a boiling range distribution of between 20 and 400 ° C. have an alpha olefin content in the range of 0.0001 to 0.08 g, 0.001 to 0.05 g, or 0.01 to 0.04 g per 1 g hydrocarbons with a distribution of the boiling range between 20 and 400 ° C.

In some embodiments, hydrocarbons with a boiling range distribution of between 20 and 204 ° C. have a weight ratio of alpha olefins to olefins with an internal double bond of at least 0.7, at least 0.8, at least 0.9, at least at least 1.0, at least 1.4, or at least 1.5. In some embodiments, hydrocarbons with a boiling range distribution of between 20 and 204 ° C. have a weight ratio of alpha olefins to olefins with an internal double bond in the range of 0.7 to 10, 0.8 to 5, 0.9 to 3, or from 1 to 2. The weight ratio of alpha-olefins to olefins with an internal double bond for raw materials and industrial products is usually at least 0.5. The possibility of obtaining an increased amount of alpha olefins relative to olefins with internal double bonds can contribute to the conversion of the crude product into industrial products.

In some embodiments, upon contacting the crude feed with a hydrogen source in the presence of an inorganic salt catalyst, hydrocarbons may form with a boiling range of between 20 and 204 ° C, which include linear olefins. These linear olefins have double bonds in the cis and trans positions. The weight ratio of linear olefins with trans double bonds to linear olefins with cis double bonds is at least 0.4, at least 1.0, or at most 1.4. In certain embodiments, the weight ratio of linear olefins with trans double bonds to linear olefins with cis double bonds is in the range of 0.001 to 1.4, 0.01 to 1.0, or 0.1 to 0.4.

In certain embodiments, hydrocarbons having a boiling range distribution between 20 and 204 ° C. have an n-paraffin content of at least 0.1 g, at least 0.15 g, at least 0.20 g, or at least at least 0.30 g per 1 g of hydrocarbons having a boiling range distribution in the range between 20 and 400 ° C. The content of n-paraffins in such hydrocarbons per 1 g of hydrocarbons may be in the range from 0.001 to 0.9 g, from 0.1 to 0.8 g, or from 0.2 to 0.5 g. In some embodiments, such hydrocarbons have the weight ratio of isoparaffins to n-paraffins is at least 1.5, at least 1.4, at least 1.0, at least 0.8, or at least 0.3. Given the content of n-paraffins in such hydrocarbons, it can be estimated that the content of n-paraffins in the crude product can range from 0.001 to

- 14 010396

0.9 g, 0.01 to 0.8 g, or 0.1 to 0.5 g per 1 g of crude product.

In some embodiments, the crude product has a total Νί / ν / Pe content of at most 90%, at least 50%, at least 10%, at least 5%, or at least 3% of the Νί / ν / Pe content in crude feed. In certain embodiments, the crude product contains, per gram of crude product, at least 0.0001 g, at least 1x10 ^-5 g, or at least 1x10 ^-6 g Νί / ν / Pe. In certain embodiments, the crude product has, on 1 g of the crude product, a total Νί / ν / Pe content in the range of 1x10 ^-7 to 5x10 ^-5 g, 3x10 ^-7 to 2x10 ^-5 g, or 1 x 10 ^-6 to 1 x 10 ^-5 g.

In some embodiments, the crude product has an SKH of at least 90%, at least 50%, or at most 10% of the SKH for the crude feed. In certain embodiments, the crude product may have an HCC of at least 1, at least 0.5, at most 0.1, or at most 0.05. In some embodiments, the CCR of the crude product may be in the range of 0.001 to 0.5, 0.01 to 0.2, or 0.05 to 0.1.

In certain embodiments, the density ΑΡΙ (in degrees) for the crude product is at least 10% higher, at least 50% higher, or at least 90% higher than the density ΑΡΙ for the crude feed. In certain embodiments, the density for the crude product is between 13 and 50, 15-30, or 16-20 ° ΑΡΙ.

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

The crude product may have a sulfur content of at most 90%, at least 70%, or at most 60% of the sulfur content for the crude feed. The sulfur content of the crude product per 1 g of the crude product may be at least 0.02 g, at least 0.008 g, at least 0.005 g, at most 0.004 g, at most 0.003 g, or at most 0.001 g. In certain embodiments, the crude product has a sulfur content per gram of crude product in the range of 0.0001 to 0.02 g, or 0.005 to 0.01 g.

In certain embodiments, the crude product may have a nitrogen content of at least 90% or at least 80% of the nitrogen content of the crude feed. The nitrogen content of the crude product per 1 g of the crude product may be at least 0.004 g, at least 0.003 g, or at most 0.001 g. In some embodiments, the crude product has a nitrogen content per 1 g of crude product in the range of 0.0001 up to 0.005 g or from 0.001 to 0.003 g.

In some embodiments, the crude product has 1.05 g of crude product from 0.05 to 0.2 g, or 0.09 to 0.15 g of hydrogen. The H / C ratio for the crude product may be at least 1.8, at least 1.7, at most 1.6, at least 1.5, or at most 1.4. In some embodiments, the H / C ratio for the crude product is 80-120% or 90-110% of the H / C ratio in the crude feed. In other embodiments, the H / C ratio for the crude product is 100-120% of the H / C ratio in the crude feed. The value of the N / C ratio for the crude product within 20% of the N / C ratio in the crude feed indicates the minimum absorption and / or consumption of hydrogen in the process according to the invention.

The crude product includes components boiling over in the temperature range. In some embodiments, the crude product includes:

at least 0.001 g or from 0.001 to 0.5 g of hydrocarbons with a boiling range distribution of at most 200 ° C or at least 204 ° C at 0.101 MPa;

at least 0.001 g or from 0.001 to 0.5 g of hydrocarbons with a boiling range distribution between 200 and 300 ° C. at 0.101 MPa;

at least 0.001 g or from 0.001 to 0.5 g of hydrocarbons with a boiling range distribution between 300 and 400 ° C at 0.101 MPa and at least 0.001 g or from 0.001 to 0.5 g of hydrocarbons with a boiling range distribution between 400 and 538 ° C at 0.101 MPa.

In some embodiments, the crude product has a naphtha content per gram of crude product from 0.00001 to 0.2 g, 0.0001 to 0.1 g, or 0.001 to 0.05 g. In certain embodiments, the crude product has from 0.001 to 0.2 g or 0.01 to 0.05 g of naphtha. In some embodiments, the naphtha has at least 0.15 g, at least 0.1 g, or at least 0.05 g of olefins per g of naphtha. In certain embodiments, the crude product has from 0.00001 to 0.15 g, from 0.0001 to 0.1 g, or from 0.001 to 0.05 g of olefins per gram of crude product. In some embodiments, the naphtha has a benzene content per gram of naphtha of at least 0.01 g, at least 0.005 g, or at least 0.002 g. In certain embodiments, the naphtha

- 15 010396 has a benzene content that is not found, in the range from 1x10 ^-7 to 1x10 ^-2 g, from 1x10 ^-6 to 1 x 10 ^-5 g, from 5x10 ^-6 to 1 x 10 ^-4 g. Compositions, which contain benzene can be considered hazardous to handle, so for a crude product that has a relatively low benzene content, special handling may not be necessary.

In certain embodiments, naphtha may include aromatic compounds. Aromatic compounds may include monocyclic compounds and / or polycyclic ring compounds. Monocyclic compounds may include (but are not limited to) benzene, toluene, orthoxylene, methaxylene, paraxylene, 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; 2-ethyl-1,4-dimethylbenzene; 2-ethyl-2,4-dimethylbenzene; 1,2,3,4-tetramethylbenzene; ethylpentylmethylbenzene; 1,3-diethyl-2,4,5,6-tetramethylbenzene; triisopropylorthoxylene; substituted homologues of benzene, toluene, orthoxylene, methaxylene, paraxylene or mixtures thereof. Monocyclic aromatic hydrocarbons are used in a variety of industrial products and / or are sold as individual components. The crude product obtained as described in the invention typically has a high content of monocyclic aromatic hydrocarbons.

In certain embodiments, the crude product has a toluene content per gram of crude product from 0.001 to 0.2 g, 0.05 to 0.15 g, or 0.01 to 0.1 g. The crude product has a methaxylene content of 1 g the crude product from 0.001 to 0.1 g, from 0.005 to 0.09 g, or from 0.05 to 0.08 g. The crude product has an orthoxylol content per gram of crude product from 0.001 to 0.2 g, from 0.005 to 0 , 1 g or from 0.01 to 0.05 g. The crude product has a paraxylene content per g of crude product from 0.001 to 0.09 g, from 0.005 to 0.08 g, or from 0.001 to 0.06 g.

An increase in aromatic hydrocarbon content in naphtha usually increases the octane number of naphtha. The importance of oils can be estimated based on the gasoline potential of raw materials. The gas potential may include, but is not limited to, the calculated octane number for the oil naphtha fraction. Typically, the estimated octane number for raw materials is in the range of 35-60. High octane gasoline usually reduces the need for additives that increase the octane number of gasoline. In certain embodiments, the crude product includes naphtha that has an octane of at least 60, at least 70, at least 80, or at least 90. Typically, the octane number of naphtha is in the range from 60 to 99, from 70 to 98 or from 80 to 95.

In some embodiments, the crude product has an increased total aromatic content in hydrocarbons having a boiling range distribution of between 204 and 500 ° C. (sum of naphtha and kerosene), relative to the total aromatic hydrocarbon content of at least 5 total naphtha and kerosene for crude raw materials. %, at least 10%, at least 50%, or at least 99%. Typically, the total aromatic hydrocarbon content in the sum of naphtha and kerosene of the crude feed is 8, 20, 75, or 100% higher than the total aromatic hydrocarbon content in the sum of naphtha and kerosene for the crude feed.

In some embodiments, kerosene and naphtha may have a total content of polyaromatic compounds in the range from 0.00001 to 0.5 g, from 0.0001 to 0.2 g, or from 0.001 to 0.1 g per 1 g of the amount of kerosene and naphtha.

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

In some embodiments, the crude product contains, per gram of crude product, at least 0.001 g, from above 0 to 0.7 g, from 0.001 to 0.5 g, or from 0.01 to 0.1 g of kerosene. In certain embodiments, the crude product has from 0.001 to 0.5 g, or from 0.01 to 0.3 g of kerosene. In some embodiments, kerosene has an aromatic hydrocarbon content per g of kerosene of at least 0.2 g, at least 0.3 g, or at least 0.4 g. In certain embodiments, kerosene has an aromatic hydrocarbon content of 1 g of kerosene in the range from 0.1 to 0.5 g or from 0.2 to 0.4 g.

In certain embodiments, the freezing point of kerosene may be below -30, below -40, or below -50 ° C. An increase in the content of aromatic hydrocarbons in the kerosene fraction of the crude product usually leads to an increase in density and lowering the freezing point of the kerosene fraction of the crude product. A crude product with a kerosene fraction having a high density and low freezing point can be processed to produce fuel for aircraft turbines with the desired high density and low freezing characteristics.

In certain embodiments, the crude product has a diesel content per gram of crude product in the range of 0.001 to 0.8 g or 0.01 to 0.4 g. In certain embodiments, diesel fuel has an aromatic content of 1 g di

- 16 010396 diesel fuel of at least 0.1 g, at least 0.3 g, or at least 0.5 g. In some embodiments, diesel fuel has an aromatic hydrocarbon content per g of diesel fuel in the range of 0.1 up to 1 g, from 0.3 to 0.8 g or from 0.2 to 0.5 g.

In some embodiments, the crude product has a VGO content per gram of crude product in the range of 0.0001 to 0.99 g, 0.001 to 0.8 g, or 0.1 to 0.3 g. In certain embodiments, the VGO content in the crude product is in the range from 0.4 to 0.9 g or from 0.6 to 0.8 g per 1 g of the crude product. In certain embodiments, the VGO has an aromatic hydrocarbon content per gram of VGO in the range of 0.1 to 0.99 g, 0.3 to 0.8 g, or 0.5 to 0.6 g.

In some embodiments, the crude product has a residue content of at least 70%, at least 50%, at least 30%, at least 10%, or at least 1% of the crude feed. In certain embodiments, the crude product has a residue content per gram of crude product of at least 0.1 g, at least 0.05 g, at least 0.03 g, at most 0.02 g, at most 0 01 g, at least 0.005 g, or at most 0.001 g. In some embodiments, the crude product has a residue content per gram of crude product in the range of 0.000001 to 0.1 g, 0.00001 to 0.05 g, from 0.001 to 0.03 g or from 0.005 to 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 from more than 0, but less than 0.01 g, from 0.000001 to 0.001 g, or from 0.00001 to 0.0001 g of catalyst per 1 g of crude product. The catalyst can help stabilize the crude product during transportation and / or processing in process equipment. The catalyst may inhibit corrosion, inhibit friction, and / or promote the separation of water from the crude product. The crude product, which includes at least a portion of the catalyst, may be further processed to produce lubricants and / or other industrial products.

The catalyst used to process the crude feed in the presence of a hydrogen source to produce a total product may be an individual catalyst or multiple catalysts. The catalysts according to the invention may first be a catalyst precursor that is converted to a catalyst in the contact zone when hydrogen and / or crude feed containing sulfur is reacted with the catalyst precursor.

The catalysts used in contacting the crude feed with a hydrogen source in order to obtain the total product can help reduce the molecular weight of the crude feed. Regardless of the theory, it is believed that the catalyst, in combination with a hydrogen source, can reduce the molecular weight of the components in the crude feed as a result of exposure to the main (Lewis base or Br6 and 81Be-Liu) and / or superbasic components in the catalyst. Examples of catalysts that possess the characteristics of a Lewis base and / or Br6 and 81B-Tegue include the catalysts described in the invention.

In some embodiments, the catalyst is an SPM catalyst. This SPM catalyst includes a compound that contains a transition metal sulfide. For the purposes of the present invention, the mass of the transition metal sulfide in the SPM catalyst is determined by summing the total mass of the transition metal (s) with the total mass of sulfur in the catalyst. The atomic ratio of the transition metal to sulfur usually lies in the range from 0.2 to 20, from 0.5 to 10, or from 1 to 5. Examples of transition metal sulfides can be found in the book Chemistry of Inorganic Sulfur "(1 then 8yig Siesh181gu); edited by S. Nsk1ezz; E1zeu1eg Riysypd Sotrapu; At51gyat-Yopyop-No \ at Wogk; Sorupdy 1968; si. nineteen.

In certain embodiments, the PSD catalyst may total include at least 0.4 g, at least 0.5 g, at least 0.8 g, or at least 0.99 g of one or more transition metal sulfides per 1 g of catalyst. In certain embodiments, the SPM catalyst has a total content of one or more transition metal sulfides per gram of catalyst in the range of 0.4 to 0.999 g, 0.5 to 0.9 g, or 0.6 to 0.8 g.

The SPM catalyst includes one or more transition metal sulfides. Examples of transition metal sulfides include pentlandite (Her ₄ , ₅ No. ₄ , ₅ 8 ₈ ). Smith (Her ₆ , ₇ 5№ ₂ , ₂₅ 8c), Bravoite (Her ₀ , -W ₁₂ C.'o ₀ , | 8 ₂ ). makinavit (Her ₀ , ₇ 5№ ₀ , ₂₅ 8 ₀ , ₉ ), argentopentlandite (AdEe ₆ No. ₂ 8 ₈ ), isocubanite (CuEe ₂ 8 ₃ ), isochalcopyrite (Cu ₈ Her ₉ 81 ₆ ), sphalerite (2po, ₉₅ Her ₀ , ₀ 58), muoyhoekit (Si ₉ Her ₉ 81 ₆ ), chatkalit (SibEe8n ₂ 8 ₈ ), sternbergite (Adee ₂ 8 ₃ ), chalcopyrite (CuEe8 ₂ ), troilite (Eb8), pyrite (Eb8 ₂ ), pyrgotitis (Her ( _{1. x} ) 8 (x = 0-0.17)), cheazlevudit (Νί ₃ 8 ₂ ) or waesite (Νί8 ₂ ).

In some embodiments, the SPM catalyst includes one or more transition metal sulfides in combination with an alkali metal (s), alkaline earth metal (s), zinc, zinc compounds, or mixtures thereof. In some embodiments, the SPM catalyst is represented by the general chemical formula A _with [M _a 8 _b ] ₄ , in which A is an alkali metal, alkaline earth metal or zinc; M represents a transition metal from groups 6-10 of the Periodic table and 8 is gray. The atomic ratio of a to b is in the range from 0.5 to

- 17 010396

2.5 or from 1 to 2. The atomic ratio with to a is in the range from 0.0001 to 1, from 0.1 to 0.8, or from 0.3 to 0.5. In some embodiments, the transition metal is iron.

In some embodiments, the SPM catalyst may include well-known compounds of alkali and / or alkaline earth metals with transition metal sulfides (for example, bartonite (K ₃ Ee1 ₀ 81 ₄ ), raumbum (Kre ₂ 8 ₃ ), dierfisherite (K ₆ NaEe1 ₉ Cu ₄ M18 ₂₆ C1), chlorobartonite (K ₆ , ₁ Re ₂₄ Cu ₀ , ₂ 8 ₂₆ , 1C1 ₀ , ₇ ) and / or coyoteite (MaEe ₃ 8 ₅ - (H ₂ O) ₂ )). In some embodiments, the SPM catalyst includes bartonite prepared by ίη δίΐιι. Bartonite obtained by ίη δίΐιι. may be called synthetic bartonite. Natural and / or synthetic bartonite can be used as an SPM catalyst in the methods described in the invention.

In some embodiments, the SPM catalyst may include at least 25 g, at least 15 g, or at least 1 g of support material per 100 g of SPM catalyst. Typically, the SPM catalyst has from 0 to 25 g, from 0.00001 to 20 g, from 0.0001 g to 10 g of carrier material per 100 g of SPM catalyst. Examples of support materials that can be used with an SPM catalyst include refractory oxides, porous carbon materials, zeolites, or mixtures thereof. In some embodiments, the SPM catalyst is substantially free or free of carrier material.

The SPM catalyst, which includes alkali metal (s), alkaline earth metal (s), zinc, zinc compounds or mixtures thereof, may contain one or more transition metal sulfides, alkali metal transition metal bimetal sulfides, and transition metal sulfides of increased valencies, transition metal oxides or mixtures thereof, which are determined by x-ray diffraction. In some embodiments, a portion of the alkaline metal component (s), alkaline earth metal component (s), zinc component and / or part of the transition metal sulfide component of the SPM catalyst may be in the form of an amorphous composition not detectable by X-ray diffraction methods.

In some embodiments, the crystalline particles of the SPM catalyst and / or the mixture of crystalline particles of the SPM catalyst have a particle size of at most 10 ⁸ A, at least 10 ³ A, at least 100 A or at least 40 A. In normal operation, the size the crystalline particles of the SPM catalyst as a whole will be at least 10 A.

The SPM catalyst, which includes alkali metal (s), alkaline earth metal (s), zinc, zinc compounds or mixtures thereof, can be obtained by mixing a sufficient amount of deionized water, a given amount of transition metal oxide and a given amount of metal carbonates from groups 1-2, metal oxalates from groups 1-2, metal acetates from groups 1-2, zinc carbonate, zinc acetate, zinc oxalate or mixtures thereof to form a wet paste. This wet paste can be dried at a temperature of from 100 to 300 ° C or at 150-250 ° C to obtain a mixture of transition metal oxide and salt. This mixture of transition metal oxide and salt can be calcined at a temperature in the range from 300 to 1000 ° C, from 500 to 800 ° C, or from 600 to 700 ° C to form a mixture of transition metal oxide and metal salt. A mixture of a transition metal oxide and a metal salt can interact with hydrogen to form a solid reduced intermediate. The addition of hydrogen can be carried out at a flow rate that is sufficient to provide an excess amount of hydrogen relative to the mixture of transition metal oxide and metal salt. Hydrogen can be added to the mixture of transition metal oxide and metal salt for 10-50 hours or 20-40 hours to obtain a solid reduced intermediate compound that contains an elementary transition metal. The addition of hydrogen can be carried out at a temperature of 35-500 ° C, 50-400 ° C or 100-300 ° C and with a total pressure of 10-15 MPa, 11-14 MPa or 12-13 MPa. It should be borne in mind that the recovery time, reaction temperature, choice of reducing gas, pressure of the reducing gas and / or flow rate of the reducing gas, which are used to obtain a solid intermediate compound, often vary depending on the absolute mass of the selected transition metal oxide. In some embodiments, the solid reduced intermediate can be sieved through a 40 mesh (0.31 mm) sieve with minimal effort.

The solid reduced intermediate may be added in parts to a mixture of hot (e.g. 100 ° C.) diluent / elemental sulfur and / or one or more sulfur compounds at such a rate as to control heat generation and gas formation. Said diluent includes any suitable diluent providing a means for dissipating the heat of sulfidation. This diluent may include solvents with a boiling range distribution of at least 100 ° C, at least 150 ° C, at least 200 ° C, or at least 300 ° C. Typically, the diluent has a boiling range distribution between 100 and 500 ° C, 150-400 ° C or 200-300 ° C. In some embodiments, the diluent is VGO and / or xylenes. Sulfur compounds include, but are not limited to, hydrogen sulfide and / or thiols. The amount of sulfur and / or sulfur compounds may vary from 1 to 100 mol.%, From 2 to 80 mol.%, From 5 to 50 mol.%, From 10 to 30 mol.% Based on the number of moles of metal from groups 1- 2 or zinc in a metal salt of groups 1-2 or zinc salts. After adding the solid reduced intermediate to the diluent-elemental sulfur mixture, the resulting mixture can be gradually

- 18 010396 heat up to a final temperature of 200-500 ° C, 250-450 ° C or 300-400 ° C and maintain at a final temperature for at least 1 hour, at least 2 hours or at least 10 hours. Usually the final temperature is maintained for 15, 10, 5 or 1.5 hours. After heating the sulfidation reaction at an elevated temperature, the diluent-catalyst mixture can be cooled to a temperature in the range from 0 to 100 ° C, from 30 to 90 ° C or from 50 up to 80 ° C to facilitate the selection of the catalyst from the mixture. The sulfidated catalyst can be recovered from the diluent in an oxygen-free atmosphere using standard techniques and washed with at least a portion of a low boiling solvent (e.g., pentane, heptane or hexane) to obtain an SPM catalyst. This SPM catalyst can be pulverized using standard techniques.

In some embodiments, the catalyst is an inorganic salt catalyst. The inorganic salt catalyst anion may include an inorganic compound, an organic compound, or mixtures thereof. Inorganic salt catalyst includes alkali metal carbonates, alkali metal hydroxides, alkali metal hydrides, alkali metal amides, alkali metal sulfides, alkali metal oxalates, alkali metal formates, pyruvates (pyruvic acid salts) of alkali metals, alkali carbonates earth metals, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal amides, alkaline earth metal sulfides, alkaline earth acetates non ferrous metals, alkaline earth metal oxalates, alkaline earth metal formates, alkaline-earth metal pyruvates, or mixtures thereof.

Inorganic salt catalysts include, but are not limited to, mixtures of: HaOH / NbH / SCH; CON / NYON / SCON; Haon / Kon / Nyon; Haon / Kon / Skon; K; CO; / H; CO; / Ck _; WITH ;; Ha; O / K; O / K _; CO _; ; HaNSO; / JHCO; / Hb; CO _; ; H1SO _; / JISC _; / H _; CO _; ; KOH / NYON / SCON in combination with K2CO3 / K2COe / Sk2CO3 mixtures; K-CCK / CaCOa K _; WITH) _; / \ 1aCO _; ; SK-SOL aOa; SK-SOL aO; Ha _; CO _; / Ca (OH) _; ; KN / SKCOa KOSNO / CaO; CWO / CaCO ₃ ; SkOSNO / Ca (OCHO; HaHN; / _{K, CO;} / Hb; O; K2SO ₃ / CaCO ₃ / K2SO _3; K2SO ₃ / CaCO ₃ / Sk2SO _{3; K, CO;} / _ISSA; / Hb; _CO; and K ; CO _; / MaCO _; / Ck _; CO _; or Ca (OH) 2 in combination with a mixture of K2CO3 / K2CO3 / Sk2CO3.

In some embodiments, the inorganic salt catalyst contains at least 0.00001 g, at least 0.001 g, or at least 0.01 g lithium based on the weight of lithium, per 1 g of inorganic salt catalyst. In some embodiments, the inorganic salt catalyst has a lithium content of 0 g, but less than 0.01 g, 0.0000001-0.001 g, or 0.00001-0.0001 g, based on the weight of lithium, per 1 g of inorganic salt catalyst.

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

In some embodiments, the inorganic salt catalyst also includes metals from groups 8-10 of the Periodic Table, metal compounds from groups 8-10 of the Periodic Table, metals from group 6 of the Periodic Table, metal compounds from group 6 of the Periodic Table, or mixtures thereof. Metals from groups 8-10 include (but are not limited to) iron, ruthenium, cobalt or nickel. Metals from group 6 include (but are not limited to) chromium, molybdenum, or tungsten. In some embodiments, the inorganic salt catalyst includes 0.1-0.5 g or 0.2-0.4 g of Raney nickel per 1 g of inorganic salt catalyst.

In certain embodiments, the inorganic salt catalyst also includes metal oxides from groups 1-2 and / or group 13 of the Periodic Table. Metals from group 13 include (but are not limited to) boron or aluminum. Non-limiting examples of metal oxides include lithium oxide (L1 ₂ O), potassium oxide (K ₂ O), calcium oxide (CaO) or alumina (A1 ₂ O ₃ ).

In certain embodiments, the inorganic salt catalyst does not contain or substantially does not contain Lewis acid (e.g., BC1 ₃ , A1C1 ₃ and 8O ₃ ), Br6pc1eb-L0 ^ hu acid (e.g., H ₃ O ⁺ , H ₂ 8O ₄ , HC1 and HNO ₃ ), glass-forming compositions (for example, borates and silicates) and halides. Inorganic salt may contain, per 1 g of inorganic salt catalyst from 0 to 0.1 g, from 0.000001 to 0.01 g, or from 0.00001 to 0.005 g:

a) halides;

b) compositions that form glass at temperatures of at least 350 ° C or greater

- 19 010396 at least 1000 ° C;

c) Lewis acids;

6) acids of Bgpyeb-bo ^ gy or

e) mixtures thereof.

Inorganic salt catalyst can be obtained using standard techniques. For example, predetermined amounts of each catalyst component can be combined using standard mixing techniques (e.g., crushing and / or spraying). In other embodiments, the inorganic compositions are dissolved in a solvent (eg, water or a suitable organic solvent) to form a mixture of the inorganic composition and the solvent. The solvent can be removed using standard separation techniques in order to obtain an inorganic salt catalyst.

In some embodiments, inorganic salts of the inorganic salt catalyst may be incorporated into the carrier to form a supported inorganic salt catalyst. Examples of carriers include, but are not limited to, zirconia, calcium oxide, magnesium oxide, titanium oxide, hydrotalcite, alumina, germanium oxide, iron oxide, nickel oxide, zinc oxide, cadmium oxide, antimony oxide, and mixtures thereof. In some embodiments, the carrier may be impregnated with an inorganic metal salt from groups 6-10 and / or a metal compound from groups 6-10. Alternatively, inorganic salts can be melted or softened by heat and introduced into (and / or onto) a metal support or metal oxide support to form a supported inorganic salt catalyst.

The structure of the inorganic salt catalyst usually becomes heterogeneous, permeable, and / or mobile at a given temperature or in a temperature range in which a disorder in the structure of the catalyst occurs. The inorganic salt catalyst may become disordered without a significant change in composition (for example, without salt decomposition). Regardless of the theory, it is believed that the inorganic salt catalyst becomes disordered (mobile) as the distance between the ions in the lattice of the inorganic salt catalyst increases. As the distance between the ions increases, the crude feed and / or hydrogen source can penetrate the inorganic salt catalyst instead of moving along the surface of the inorganic salt catalyst. Penetration of the crude feed and / or hydrogen source through the inorganic salt often leads to an increase in the contact zone between the inorganic salt catalyst and the crude feed and / or hydrogen source. An increase in the contact zone and / or the reaction region of the inorganic salt catalyst can often increase the yield of the crude product, limit the formation of residue and / or coke and / or contribute to a change in the characteristics of the crude product relative to the same characteristics of the crude feed. The disordering of the inorganic salt catalyst (e.g., heterogeneity, permeability, and / or mobility) can be determined using DSC methods, ion conductivity measurements, VAP methods, visual inspection, X-ray diffraction methods, or a combination thereof.

The use of VAPs for characterizing catalysts is described in US Pat. Nos. 4,626,412 (Epeg e! A1.); 5039489 (61 eaue§ e! A1.) And 5264183 (Epee e! A1.). The VAP system can be obtained at the company MPNga Tespo1od1e8 (Eo1eu, McKosh, I8A). VAP analysis can be carried out in the temperature range from 25 to 850 ° C, from 50 to 500 ° C or from 60 to 400 ° C at a heating rate in the range from 10 to 50 ° C or from 20 to 40 ° C and in vacuum in range from 1x10 ^-13 to 1x10 ^-8 Torr. The analysis temperature may remain constant and / or increase as a function of time. When the temperature of the inorganic salt catalyst increases, the gas evolution from the inorganic salt catalyst is measured. Examples of gases that are released from the inorganic salt catalyst include carbon monoxide, carbon dioxide, hydrogen, water, or mixtures thereof. The temperature at which there is an inflection point (a sharp increase) in gas evolution from the inorganic salt catalyst is taken as the temperature at which the inorganic salt catalyst becomes disordered.

In some embodiments, the inflection point for gas evolution from the inorganic salt catalyst can be detected in a temperature range that is determined using a VAP. This temperature or temperature range is called the VAP temperature. The initial temperature of the temperature range determined using the VAP is called the minimum VAP temperature.

The inflection point during gas evolution observed for an inorganic salt catalyst suitable for contact with crude feed is in the range of VAP temperatures from 100 to 600 ° C, from 200 to 500 ° C, or from 300 to 400 ° C. Typically, VAP temperatures range from 300 to 500 ° C. In some embodiments, for other compositions of suitable inorganic salt catalysts, an inflection point is also observed during gas evolution, but at other VAP temperatures.

The magnitude of the ionization at the inflection point associated with the released gas may indicate the ordering of the particles in the crystal structure. For a highly ordered crystalline structure, ionic particles are usually directly associated, and more energy (i.e. more heat) is required to extract ions, molecules, gases, or combinations thereof from the structure. In not

- 20 010396 ordered crystalline structure of the ions are not as strongly associated with each other as ions in a highly ordered crystalline structure. Due to the reduced degree of ion association, less energy is usually required to separate ions, molecules and / or gases from the disordered crystal structure, and thus, the number of ions and / or gases extracted from the disordered crystal structure usually exceeds the number of ions and / or gases released from a highly ordered crystalline structure at a selected temperature.

In some embodiments, the heat of dissociation of the inorganic salt catalyst can be observed in the range of 50 to 500 ° C at a heating or cooling rate of 10 ° C and is determined using differential scanning calorimetry (DSC). In the DSC method, a sample can be heated to a first temperature, cooled to room temperature, and then heated a second time. The transitions observed during the first heating typically represent entrained water and / or solvent and may not be related to the heat of dissociation. For example, the easily identifiable drying heat of a wet or hydrated sample can usually be observed below 250 ° C, usually between 100 and 150 ° C. The transitions observed during the cooling and reheating cycle correspond to the heat of dissociation of the sample.

The term thermal transition refers to a process that occurs when ordered molecules and / or atoms in a structure become disordered with increasing temperature during DSC analysis. A transition upon cooling refers to a process that occurs when molecules and / or atoms in a structure become more uniform with decreasing temperature during DSC analysis. In some embodiments, the heating / cooling transition of the inorganic salt catalyst occurs in a temperature range that is detected using the DSC method. The temperature or temperature range in which the heat of transition of the inorganic salt catalyst is recorded during the second heating cycle is called DSC temperature. The lowest DSC temperature in the temperature range during the second heating cycle is called the minimum DSC temperature. For an inorganic salt catalyst, the observed thermal transition can be in the range between 200 and 500 ° C, 250-450 ° C, or 300-400 ° C.

In an inorganic salt that contains particles of inorganic salt, which are a relatively homogeneous mixture, the peak associated with the heat absorbed during the second heating cycle may be relatively narrow in shape. In an inorganic salt catalyst that contains particles of inorganic salt in a relatively heterogeneous mixture, the peak associated with the heat absorbed during the second heating cycle can be relatively wide in shape. The absence of peaks in the DSC spectrum indicates that the salt does not absorb or produce heat in the scanned temperature range. The absence of a temperature transition usually indicates that the structure of the sample does not change upon heating.

As the degree of homogeneity (homogeneity) of particles in a mixture of inorganic salts increases, the ability of the mixture to remain in a solid and / or pseudo-liquid state during heating decreases. The homogeneity of the inorganic mixture may be related to the ionic radius of the cations in the mixture. For cations with a smaller ionic radius, the ability of the cation to divide the electron density with the corresponding anion increases, and the acidity of the corresponding anion increases. In a series of ions of the same charge, a smaller ionic radius leads to increased forces of interionic attraction between the cation and the anion, if the anion is a rigid base. Increased forces of interionic attraction usually lead to higher thermal transition temperatures for the salt and / or a more homogeneous mixture of particles in salt (a more intense peak and an increased area under the DSC curve). Mixtures that include cations with a small ionic radius are usually more acidic than cations with a large ionic radius, and thus the acidity of the mixture of inorganic salts increases with decreasing cationic radius. For example, the contact of the crude feed with a hydrogen source in the presence of an inorganic mixture that includes lithium cations results in higher amounts of gas and / or coke compared to the contact of the crude feed with a hydrogen source in the presence of an inorganic salt catalyst that includes cations with a larger ionic radius than lithium. The ability to inhibit the formation of gas and / or coke leads to an increase in the overall yield of the liquid reaction product.

In certain embodiments, the inorganic salt catalyst may include two or more inorganic salts. For each of the inorganic salts, a minimum DSC temperature can be determined. This minimum DSC temperature of the inorganic salt catalyst may be lower than the minimum DSC temperature of at least one inorganic metal salt in the inorganic salt catalyst. For example, an inorganic salt catalyst may include potassium carbonate and cesium carbonate. Potassium carbonate and cesium carbonate have DSC temperatures higher than 500 ° C. Catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / CO _{3 2} Cg DSC temperature lies in the range from 290 to 300 ° C.

In some embodiments, the VAP temperature may be between the DSC temperature of at least one of the inorganic salts and the DSC temperature for the inorganic salt catalyst. For example, the VAP temperature of the inorganic salt catalyst may be in

- 21 010396 range from 350 to 500 ° C. The DSC temperature of the same inorganic salt catalyst may range from 200 to 300 ° C. and the DSC temperature of the individual salts may be at least 500 ° C. or at least 1000 ° C.

An inorganic salt catalyst that has a VAP and / or DSC temperature between 150 and 500 ° C, 200-450 ° C or 300-400 ° C and does not decompose at these temperatures, in many embodiments of the invention can be used to catalyze the conversion of compositions with high molecular weight and / or high viscosity (e.g., crude feed) into liquid products.

In certain embodiments, the inorganic salt catalyst may exhibit enhanced electrical conductivity relative to the individual inorganic salts during heating of the inorganic salt catalyst in a temperature range of 200 to 600 ° C, 300 to 500 ° C, or 350 to 450 ° C. The increased conductivity of the inorganic salt catalyst is usually explained by the fact that particles in the inorganic salt catalyst become mobile. The ionic conductivity of some inorganic salt catalysts changes at a lower temperature than the temperature at which the ionic conductivity of an individual component of the inorganic salt catalyst changes.

The ionic conductivity of inorganic salts can be determined using Ohm's law and = ΙΒ, where and means voltage;

I represents current;

B means resistance.

To measure ionic conductivity, the inorganic salt catalyst can be in a quartz cell with two wires (for example, copper wires or platinum wires) isolated from each other, but immersed in an inorganic salt catalyst.

FIG. 7 is a schematic embodiment of an ionic conductivity measurement system that can be used to measure ionic conductivity. A quartz cell 156 containing a sample 158 may be in a heating device and gradually heat up to a predetermined temperature. The voltage from source 160 is applied to wires 162 during heating. The resulting current in the wires 162 and 164 is measured using a measuring device 166. This measuring device 166 can be (but is not limited to) a universal measuring device or a Wheatstone bridge. When the sample 158 becomes less uniform (more mobile), in the absence of decomposition, the resistivity of the sample should decrease, and the current recorded by the measuring device 166 should increase. In some embodiments, at a predetermined temperature, the inorganic salt catalyst may have different ionic conductivity after heating, cooling, and subsequent heating. Different ionic conductivity may indicate that the crystalline structure of the inorganic salt catalyst has changed from the original form (first form) to another form (second form) during heating. It can be expected that the ionic conductivity after heating will be close or the same if its shape does not change during heating of the inorganic salt catalyst.

In certain embodiments, the inorganic salt catalyst has a particle size in the range of 10-1000 microns (microns), 20-500 microns, or 50-100 microns, as determined by sieve analysis of the inorganic salt catalyst using sieves or sieves.

Inorganic salt catalyst can soften when heated to temperatures above 50 and below 500 ° C. When the inorganic salt catalyst softens, liquid and catalyst particles can coexist in the inorganic salt catalyst matrix. In some embodiments, the catalyst particles can spontaneously deform under the influence of gravity or under pressure of at least 0.007 MPa or at least 0.101 MPa, when heated to a temperature of at least 300 ° C or at least 800 ° C so that the inorganic the salt catalyst passes 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 again take the first form of the inorganic salt catalyst. The temperature at which the inorganic salt passes from the first form to the second form is called the deformation temperature. This deformation temperature may be in the temperature range or is a specific temperature. In certain embodiments, the particles of the inorganic salt catalyst spontaneously deform under the influence of gravity or pressure when heated to a strain temperature below the strain temperature of any individual inorganic metal salt. In some embodiments, the inorganic salt catalyst includes two (or more) inorganic salts that have 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 salts.

In certain embodiments, the inorganic salt catalyst is a liquid and / or pseudo-liquid at VAP and / or DSC temperatures or higher than VAP and / or DSC temperatures. In some embodiments, the inorganic salt catalyst is a liquid

- 22 010396 bone or pseudo-fluid at the minimum temperature of the VAP and / or DSC. At a minimum temperature of VAP and / or DSC (or above these temperatures), a liquid or pseudo-liquid inorganic salt catalyst mixed with crude feed, in some embodiments, may form a phase separate from the crude feed. In some embodiments, the liquid or pseudo-liquid inorganic salt catalyst has low solubility in the crude feed (e.g., from 0 g to 0.5 g, from 0.0000001 to 0.2 g, or from 0.0001 to 0.1 g of inorganic salt catalyst per 1 g of crude feed) or does not have solubility in the crude feed (for example, from 0 to 0.05 g, from 0.000001 to 0.01 g, or from 0.00001 to 0.001 g of inorganic salt catalyst per 1 g of crude feed) at the minimum VAP temperature.

In some embodiments, powder X-ray diffraction methods are used to determine the spatial arrangement of atoms in an inorganic salt catalyst. The shape of the Ό ₀₀ ι peak in the X-ray spectrum can be analyzed and the relative ordering of the inorganic salt particles can be estimated. The peaks in the X-ray diffraction pattern correspond to various compounds of the inorganic salt catalyst. In X-ray diffraction by powder, Ό ₀₀₁ peak can be analyzed and the distance between the atoms can be estimated. In an inorganic salt catalyst that contains highly ordered atoms of an inorganic salt, the Ό ₀₀ ι peak shape is relatively narrow. In an inorganic salt catalyst (e.g., catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃₎ that contains randomly ordered inorganic salt atoms, the shape Ό ₀₀ ι peak may be relatively broad or ₀₀ Ό ι peak may be absent. In order to establish whether the disorder of the inorganic salt atoms changes during heating, the X-ray diffraction spectrum for the inorganic salt catalyst before heating can be recorded and compared with the X-ray diffraction spectrum after heating. The Ό ₀₀ ι peak (corresponding to inorganic salt atoms) in the X-ray diffraction spectrum recorded at temperatures above 50 ° C may be absent or broadened compared to the Ό ₀₀₁ peaks in the X-ray diffraction spectrum recorded at temperatures below 50 ° C. In addition, in the X-ray diffraction pattern for an individual inorganic salt, relatively narrow Ό ₀₀₁ peaks can be observed at the same temperatures.

Contact conditions can be controlled in such a way that the composition of the total product (and thus of the crude product) for a given crude feed can be changed, in addition to limiting and / or inhibiting the formation of by-products. The composition of the total product includes (but is not limited to) paraffins, olefins, aromatic hydrocarbons, or mixtures thereof. These compounds are included in the crude product and non-condensable hydrocarbon gases.

The regulation of the contacting conditions in combination with the catalyst described in the invention can provide a total product with a lower coke content than expected. Comparison of the content of WMD in different raw materials can provide ranking of raw materials based on its tendency to form coke. For example, it can be expected that more coke is formed from raw materials with a WMD content of 0.1 g WMD per 1 g of raw material than from raw materials with a WMD content of 0.001 g WMD per 1 g of raw material. Unfavorable raw materials usually have a WMD content of at least 0.05 g WMD per 1 g of disadvantaged raw materials.

In some embodiments, the residue and / or coke deposited on the catalyst during the process may be at least 0.1 g, at least 0.05 g, or at most 0.03 g of residue and / or coke per 1 g of catalyst. In certain embodiments, the mass of the residue and / or coke deposited on the catalyst is in the range of 0.0001 to 0.1 g, 0.001 to 0.05 g, or 0.01 to 0.03 g. In some embodiments the used catalyst contains practically no residue and / or coke. In certain embodiments, the contact conditions are controlled so that at least 0.015 g, at least 0.01 g, at least 0.005 g, or at most 0.003 g of coke per 1 g of crude product are formed. Contacting the crude feed with the catalyst under controlled contact conditions reduces the amount of coke and / or residue compared to the amount of coke and / or residue obtained by heating the crude feed in the presence of a processing catalyst or in the absence of a catalyst using the same contacting conditions.

In some embodiments, the contact conditions can be adjusted so that, per g of crude feed, at least 0.5 g, at least 0.7 g, at least 0.8 g, or at least 0 are converted to the crude product. 9 g of crude feed. Typically, during contacting, between 0.5 and 0.99 g, 0.6-0.9 g, or 0.7-0.8 g of crude product per 1 g of crude feed are obtained. The conversion of the crude feed into a crude product with a minimum yield of residue and / or coke (if any) into a crude product allows the crude product to be processed into industrial products with minimal involvement of pre-treatment processes at the refinery. In certain embodiments, at least 0.2 g, at least 0.1 g, at least 0.05 g, at least 0.03 g, or at most 0.01 g crude are converted per gram of crude feed. raw materials to non-condensing

- 23 010396 hydrocarbons. In some embodiments, from 0 to 0.2 g, from 0.0001 to 0.1 g, from 0.001 to 0.05 g, or from 0.01 to 0.03 g of non-condensable hydrocarbons per 1 g of crude feed are formed.

To maintain the desired process temperature, it is possible to control the temperature in the contact zone, the feed rate of the crude feed, the flow rate of the total product, the feed rate and / or the amount of catalyst supplied, or a combination thereof. In some embodiments, temperature control in the contact zone can be carried out by changing the flow of a gaseous source of hydrogen and / or inert gas through the contact zone in order to reduce the concentration of hydrogen and / or remove excess heat from the contact zone.

In some embodiments, the temperature in the contact zone can be adjusted so that the temperature in the contact zone is higher, lower, or corresponds to a predetermined temperature T1. In certain embodiments, the contact temperature is controlled so that the temperature of the contact zone is lower than the minimum VAP temperature and / or minimum DSC temperature. In certain embodiments, the T ₁ value may be 30 ° C lower, 20 ° C lower, or 10 ° C lower than the minimum VAP temperature and / or minimum DSC temperature. For example, in one embodiment, the contact temperature may be adjusted to 370, 380, or 390 ° C during the process when the minimum VAP temperature and / or minimum DSC temperature is 400 ° C.

In other embodiments, the contact temperature is controlled so that the temperature is higher, lower, or VAP consistent with the catalyst temperature and / or DSC temperature of the catalyst. For example, the contact temperature can be adjusted at 450, 500 or 550 ° C during the process, when the minimum VAP temperature and / or minimum DSC temperature is 450 ° C. Controlling the contact temperature based on the VAP of the catalyst temperature and / or DSC of the catalyst temperature can provide an improvement in the performance of the crude product. For example, such regulation can reduce the amount of coke formed, the amount of non-condensable gas, or a combination thereof.

In certain embodiments, the inorganic salt catalyst may be conditioned prior to the addition of the crude feed. In some embodiments, conditioning may occur in the presence of crude feed. Conditioning the inorganic salt catalyst may include heating the inorganic salt catalyst to a first temperature of at least 100 ° C, at least 300 ° C, at least 400 ° C, or at least 500 ° C, followed by cooling of the inorganic salt catalyst to a second temperatures of at most 250 ° C, at least 200 ° C, or at most 100 ° C. In certain embodiments, the inorganic salt catalyst is heated to a temperature in the range of 150 to 700 ° C, 200 to 600 ° C, or 300 to 500 ° C, and then cooled to a second temperature in the range of 25 to 240 ° C, 30 to 200 ° C or from 50 to 90 ° C. The conditioning temperature can be determined by measuring ionic conductivity at various temperatures. In some embodiments, the conditioning temperature can be determined from the DSC values of the temperatures obtained for transitions in multiple heating / cooling cycles of the inorganic salt catalyst in DSC. The conditioning of the inorganic salt catalyst may allow contacting of the crude feed at a lower process temperature compared to temperatures used for conventional hydrotreating catalysts.

In some embodiments, the content of naphtha, distillate, VGO or mixtures thereof in the total product can be changed by varying the rate of removal of the total product from the contact zone. For example, a decrease in the rate of removal of the total product leads to an increase in the contact time of the crude feed with the catalyst. Alternatively, increasing the pressure relative to the initial pressure can increase the contact time, increase the yield of the crude product, increase the degree of hydrogen incorporation from the gases into the crude product at a given mass flow rate of the crude feed or a hydrogen source, or affect the combination of these effects. The increased contact time of the crude feed with the catalyst can lead to an increase in the amount of diesel fuel, kerosene or naphtha and a decrease in the amount of VGO compared to the amounts of diesel fuel, kerosene, naphtha and VGO obtained with shorter contact times. An increase in the contact time of the total product in the contact zone can also change the average number of carbon atoms in the crude product. An increased contact time can lead to an increased percentage (by weight) of components with fewer carbon atoms (and thus to an increased density of AP1 (in degrees)).

In some embodiments, the contact conditions may vary over time. For example, the contact pressure and / or contact temperature may be increased in order to increase the amount of hydrogen absorbed by the crude feed in order to obtain a crude product. The possibility of changing the amount of hydrogen absorbed by the crude feed, while improving other characteristics of the crude feed, expands the range of crude products that can be obtained from a separate crude feed. The ability to obtain a variety of crude products from separate raw materials can provide various

- 24 010396 specifications for transportation and / or processing.

Hydrogen absorption can be estimated by comparing the H / C ratio for the crude feed with the H / C value for the crude product. An increase in the H / C ratio for the crude product compared to H / C in the crude feed indicates the incorporation of hydrogen into the crude product from a hydrogen source. A relatively small increase in N / C for the crude product (20% compared to the crude feed) indicates a relatively low consumption of hydrogen gas during the process. It is desirable to significantly improve the performance of the crude product compared to the performance of the crude feed, achieved with minimal hydrogen consumption.

In addition, you can vary the ratio of the source of hydrogen to the crude feed in order to change the characteristics of the crude product. For example, an increase in the ratio of the source of hydrogen to the crude feed can give a crude product that has an increased VGO content per gram of crude product.

In certain embodiments, contacting the crude feed with an inorganic salt catalyst in the presence of light hydrocarbons and / or water vapor gives a higher yield of liquid hydrocarbons and less coke in the crude product than contacting the crude feed with an inorganic salt catalyst in the presence of hydrogen and steam. In embodiments that include contacting the crude feed with methane in the presence of an inorganic salt catalyst, at least a portion of the components of the crude product may include carbon and hydrogen atoms (from methane) that are incorporated into the molecular structures of the components.

In certain embodiments, the volume of the crude product obtained from the crude feed by contacting the feed with a hydrogen source in the presence of an inorganic salt catalyst exceeds at least 5%, at least 10%, or at least 15%, or at least 100% of the crude product obtained in the thermal process during scientific and technical documentation. The total volume of the crude product obtained by contacting the crude material with an inorganic salt catalyst may be at least 110 vol.% Of the volume of the crude material in the course of technical documentation. It is believed that this increase in volume is due to a decrease in density. Typically, a decrease in density, at least in part, may be caused by hydrogenation of the crude feed.

In certain embodiments, the crude feed having 1 g of raw feed at least 0.02 g, at least 0.05 g, or at least 0.1 g sulfur and / or at least 0.001 g Νί / U / Re, is in contact with a hydrogen source in the presence of an inorganic salt catalyst, without reducing the activity of the catalyst.

In some embodiments, the inorganic salt catalyst can be regenerated, at least in part, by removing one or more components that contaminate the catalyst. Contaminants include (but are not limited to) metals, sulfides, nitrogen, coke, or mixtures thereof. Polluting sulfides can be removed from the spent inorganic salt catalyst by contacting water vapor and carbon dioxide with the spent catalyst to produce hydrogen sulfide. Polluting nitrogen can be removed by contacting the spent inorganic salt catalyst with water vapor to produce ammonia. Contaminant coke can be removed from the spent inorganic salt catalyst by contacting the catalyst with water vapor and / or methane to produce hydrogen and carbon oxides. In some embodiments, one or more gases are produced from a mixture of spent inorganic salt catalyst and the remainder of the crude feed.

In certain embodiments, the spent mixture of inorganic salts (e.g., K ₂ CO _c / BL _of CO ₂ / CO _{2 of} Cg; KOH / A1 ₂ O _3; Cg ₂ CO ₃ / CaCO ₃ or №-1ON / 1 <OH / YON / 2gO ₂ ). unreacted crude feed and / or residue and / or coke can be heated to a temperature in the range from 700 to 1000 ° C or from 800 to 900 ° C until in the presence of water vapor, hydrogen, carbon dioxide and / or light hydrocarbons, the production of gas and / or liquid is minimal in order to obtain a liquid phase and / or gas. This gas may contain an increased concentration of hydrogen and / or carbon dioxide relative to the reacting gas. For example, a gas may include from 0.1 to 99 mol or from 0.2 to 8 mol of hydrogen and / or carbon dioxide per 1 mol of reacting gas. This gas may contain a relatively small amount of light hydrocarbons and / or carbon monoxide, for example, less than 0.05 g of light hydrocarbons per g of gas and less than 0.01 g of carbon monoxide per g of gas. The liquid phase may contain water, for example, more than 0.5-0.99 g or more than 0.9-0.9 g per 1 g of liquid.

In some embodiments, spent catalyst and / or solids in the contact zone may be treated to recover: metals (e.g., vanadium and / or nickel) from spent catalyst and / or solids. Spent catalyst and / or solids can be processed using well-known metal separation techniques, such as heating, chemical processing and / or gasification.

- 25 010396

Examples

The following are non-limiting examples of the preparation of catalysts, tests of catalysts and systems with controlled contact conditions.

Example 1. Obtaining a sulfide catalyst K-Pe.

The K-Fe sulfide catalyst is prepared by combining 1000 g of iron oxide (Fe ₂ O ₃ ) and 580 g of potassium carbonate with deionized water (412 g) to form a wet paste. The wet paste is dried at 200 ° C. to obtain a mixture of iron oxide and potassium carbonate. This mixture of iron oxide and potassium carbonate is calcined at 500 ° C. to obtain a mixture of iron oxide and potassium carbonate. This mixture of iron oxide and potassium carbonate reacts with hydrogen to form a reduced solid intermediate compound that includes metallic iron. The addition of hydrogen is carried out for 48 hours at 450 ° C and a pressure of 11.5-12.2 MPa (1665-1765 psi). The solid intermediate is sieved through a 40 mesh sieve (0.31 mm) with minimal effort.

The solid intermediate compound is added in portions to the mixture of VGO with m-xylene and elemental sulfur at 100 ° C. at such a rate as to regulate heat and gas generation. After adding the solid intermediate compound, the resulting mixture was gradually heated to 300 ° C and kept at 300 ° C for 1 h. The solvent mixture with the catalyst was cooled below 100 ° C and the sulfated catalyst was isolated from the mixture. This sulfidated catalyst was isolated by filtration in a dry box under argon and washed with methaxylol to obtain 544.7 g of K-Pe sulfide catalyst. This K-Pe sulfide catalyst is crushed by passing the catalyst through a 40 mesh sieve (0.31 mm).

The resulting K-Pe sulfide catalyst was analyzed using an X-ray diffraction method. From an analysis of the X-ray diffraction spectrum, it was found that this catalyst includes troilite (Fe8), K-Pe sulfide (Kre8 ₂ ), pyrrhotite, and iron oxides (e.g. magnetite, Fe3O4). No peak corresponding to iron disulfide was observed in the X-ray diffraction spectrum (e.g., pyrite, Fe8 ₂ ).

Example 2. Contacting the crude feed with a hydrogen source in the presence of K-Pe sulfide catalyst.

The continuous mixing reactor (600 ml capacity, made of 316 stainless steel) is equipped with a lower feed channel, one vapor outlet channel, three thermocouples located inside the reactor, and a KikYoi six-blade turbine with a drive shaft of 1.25 inches (3.17 cm in diameter) )

The K-Pe sulfide catalyst (110.3 g) obtained as described in Example 1 was charged to a reactor. Hydrogen gas is dosed at a ratio of 8,000 Nm ³ / m ³ (50,000 std. Cubic feet per barrel) to the reactor and mixed with bitumen (Schubtjeeg deposit, Canada). Bitumen enters the reactor through the lower feed channel to form a mixture of hydrogen with crude feed. During the course of the process, over 185 h, gaseous hydrogen and crude feed are continuously fed into the reactor and the product is continuously removed from the reactor through a vapor exit channel.

The crude feed is supplied at a rate of 67.0 g / h in order to maintain the volume of liquid crude feed at 60% of the reactor volume. To measure the liquid level in the reactor used ^Cg-137 gamma ray source (50 mCi) and sodium iodide scintillation detector.

A mixture of gaseous hydrogen and crude feed is contacted with the catalyst at an average temperature inside the reactor of 430 ° C. After the hydrogen / crude feed mixture is contacted with the catalyst, the total product is formed in the form of vapors leaving the reactor. Vapors from the reactor exit through a separate upper outlet channel. The reactor lid is electrically heated to 430 ° C. to prevent internal condensation of the vapors leaving the reactor on the reactor lid.

After leaving the reactor, the reaction vapors are cooled and separated in a gas / liquid high pressure separator and a gas / liquid low pressure separator to obtain a liquid stream and a gas stream. This gas stream is sent to a countercurrent scrubber with an alkali to remove acid gases and then subjected to quantitative analysis using standard chromatographic techniques. The total product includes, per 1 g of the total product, 0.918 g of the crude product and 0.089 g of non-condensable hydrocarbon gases. 0.027 g of solid per 1 g of crude material remains in the reactor. The characteristics and compositions of the crude product and non-condensable hydrocarbon gases formed in the method according to the invention are shown in table. 1 in FIG. 8, in table. 2 in FIG. 9 and tab. 3 in FIG. 10.

This example illustrates a method of contacting a crude feed with hydrogen in the presence of a transition metal sulfide catalyst to produce a total product with minimal formation of concomitant coke. The total product includes the crude product, which is a liquid mixture in the process of technical documentation and contains at least 0.1 g of non-condensable hydrocarbon gases per 1 g of the total product.

When comparing data on the content of WMD in crude raw materials (13.7 wt.%) In table. 1 with the amount of solid substance formed during the course of the process (2.7 wt.%), It can be understood that by combining controlled conditions and a catalyst, a smaller amount of coke can be obtained than

- 26 010396 this was detected by the method L8TM Ό4530.

Non-condensable hydrocarbons include C ₂ , C ₃ and C ₄ hydrocarbons. From the total content (percent by weight) of C2 hydrocarbons indicated in the table. 2 (20.5 g), it is possible to calculate the ethylene content per 1 g of total. C ₂ hydrocarbons from hydrocarbon gases include 0.073 g of ethylene per 1 g of total C2 hydrocarbon content. From the total content (percent by weight) of C ₃ hydrocarbons indicated in the table. 2 (23.9 g), the propylene content per 1 g of the sum of C3 hydrocarbons can be calculated. C3 hydrocarbons from non-condensable hydrocarbons include 0.21 g of propylene per 1 g of the sum of C ₃ hydrocarbons. C ₄ hydrocarbons from non-condensable hydrocarbon gases have a weight ratio of isobutane to n-butane of 0.2.

This example illustrates a method for producing a crude product, which includes at least 0.001 g of hydrocarbons with a boiling range distribution of at least 204 ° C. (400 ° E) at 0.101 MPa, at least 0.001 g of hydrocarbons with a boiling range distribution between 204 and 300 ° C at 0.101 MPa, at least 0.001 g of hydrocarbons with a boiling range distribution between 300 and 400 ° C at 0.101 MPa and at least 0.001 g of hydrocarbons with a boiling range distribution between 400 and 538 ° C (1000 ° E) at 0.101 MPa Hydrocarbons that have a boiling range distribution below 204 ° C include isoparaffins and n-paraffins, and the ratio of such isoparaffins to n-paraffins is at most 1.4.

The crude product has a boiling point distribution that is associated with naphtha, kerosene, diesel, and VGO. The crude product contains at least 0.001 g of naphtha, the naphtha fraction of the crude product having an octane of at least 70. The naphtha fraction of the crude product has a benzene content of at least 0.01 g benzene per 1 g of naphtha. The naphtha fraction from the crude product has a content of at most 0.15 g of olefins per 1 g of naphtha. The naphtha fraction from the crude product contains at least 0.1 g of monocyclic aromatic hydrocarbons per g of naphtha.

The crude product has at least 0.001 g of kerosene. The kerosene fraction of the crude product has a freezing point below -30 ° C. The kerosene fraction of the crude product includes aromatic hydrocarbons, wherein the kerosene fraction of the crude product has an aromatic hydrocarbon content of at least 0.3 g per 1 g of kerosene. The kerosene fraction of the crude product has at least 0.2 g of monocyclic aromatic hydrocarbons per 1 g of kerosene.

The crude product contains at least 0.001 g of diesel fuel. The diesel fuel fraction from the crude product includes aromatic hydrocarbons, the diesel fuel fraction from the crude product having an aromatic hydrocarbon content of at least 0.4 g per 1 g of diesel fuel.

The crude product contains at least 0.001 g of VGO. The VGO fraction of the crude product includes aromatic hydrocarbons, wherein the VGO has an aromatic hydrocarbon content of at least 0.5 g per 1 g of VGO.

Example 3. Obtaining K-Its sulfide catalyst in the absence of a hydrocarbon diluent.

K-Her sulfide catalyst is obtained by combining 1000 g of iron oxide and 173 g of potassium carbonate with 423 g of deionized water to form a wet paste. This wet paste is treated as described in Example 1 to obtain a solid intermediate. The solid intermediate is sieved through a 40 mesh sieve (0.31 mm) with minimal effort.

In contrast to Example 2, the solid intermediate compound is mixed with elemental sulfur in the absence of a hydrocarbon diluent. In a dry box using an argon atmosphere, the solid intermediate compound is mixed with powdered elemental sulfur, placed in a sealed carbon steel container, heated to 400 ° C and maintained at 400 ° C for 1 h. The sulfated catalyst is removed from the carbon steel reactor in solid condition. Potassium sulfide-iron catalyst is ground into powder using a pestle and mortar so that the resulting catalyst powder passes through a 40 mesh sieve (0.31 mm).

The resulting potassium sulfide-iron catalyst was analyzed using an X-ray diffraction method. From the analysis of the spectrum of X-ray diffraction found that the catalyst comprises pyrite (Ee8 _2), iron sulfide (Ee8) and pyrrhotite (Her _{1. X} 8). Using the X-ray diffraction method, particles of mixed potassium-iron sulfide or iron oxide were not detected.

Example 4. Contacting the crude feed with a hydrogen source in the presence of K-Its sulfide catalyst with an increased ratio of gaseous hydrogen to crude feed.

The apparatus, crude feed and process methodology were the same as in Example 2, except for the ratio of gaseous hydrogen to crude feed equal to 16,000 Nm ³ / m ³ (100,000 standard cubic feet per barrel). Sulfide K-Its catalyst (75.0 g), obtained as described in example 3, is loaded into the reactor.

- 27 010396

The characteristics of the crude product obtained by this method are summarized in table. 1 (Fig. 8) and in table. 3 (Fig. 10). The percentage of VGO (by weight) obtained in Example 4 is greater than the percentage of VGO (by weight) obtained in Example 2. The mass percentage of distillate obtained in Example 4 is less than the mass percentage of distillate obtained in Example 2 The density ΑΡΙ (in degrees) of the crude product obtained in Example 4 is lower than the density ΑΡΙ (in degrees) of the crude product obtained in Example 2. An increased density ΑΡΙ (in degrees) indicates the formation of hydrocarbons with an increased number of atoms gleroda.

After contacting with the crude feed, analyze the SPM catalyst from the reactor. According to this analysis, the sulfide transition metal catalyst after contacting with crude feed and hydrogen contains K ₃ Ee1 ₀ 81 ₄ .

Example 5. Investigation of VAP catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ and Individual Inorganic Salts.

In all VAP studies, a sample (300 mg) is heated in a VAP system reactor from room temperature 27 to 500 ° C at a rate of 50 ° C / min. The released water vapor and gaseous carbon dioxide are analyzed using a VAP mass spectrometer.

Catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO _3, supported on alumina, there is a current inflection point of more than 0.2 V for the evolved carbon dioxide and a current inflection point of 0.01 V for the precipitated water inorganic salt catalyst at 360 ° C. The minimum VAP temperature is 360 ° C, which is determined by constructing the temperature dependence of the logarithm (1 od 10) of the ion current. FIG. 11 is a plot of the logarithm of the ionic current gas provided from the catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ (1od (I)), the temperature (T). Curves 168 and 170 show the logarithm of the ion current of water and CO2 extracted from an inorganic salt catalyst. The sharp inflection point for the allocation of water and CO2 from an inorganic salt catalyst is at 360 ° C.

Unlike catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ for potassium carbonate and cesium carbonate was not observed current inflection point at 360 ° C for emitted water and carbon dioxide.

A significant increase in the amount of gases given off from the catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO _3, indicates that inorganic salt catalysts composed of two (or more) different inorganic salts, can be of great disorder than individual pure carbonate salts.

Example 6. The study of DSC inorganic salt catalyst and individual inorganic salts.

In all DSC studies, a sample (10 mg) is heated to 520 ° C at a rate of 10 ° C / min, cooled from 520 to 0 ° C at a rate of 10 ° C / min and then heated from 0 to 600 ° C at a rate of 10.0 ° C / min using a differential scanning calorimeter (DSC), model DSC-7, manufactured by Regkt-E1teg (Yogzha1k, SopesNsik I8A).

According to DSC analysis of the catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ during the second heating of the sample was found that there is a wide transition area for the salt mixture at a temperature between 219 and 260 ° C. The midpoint of this temperature range is at 250 ° C. The calculated area under the transition temperature curve is 1.75 J / g. It was found that the onset of crystal disorder occurs at a minimum DSC temperature of 219 ° C.

In contrast to these results, no specific thermal transition is observed for cesium carbonate.

A DSC analysis of the mixture of L1 ₂ CO ₃ , Ia ₂ CO ₃ and K ₂ CO ₃ during the second heating cycle showed that for the mixture L1 ₂ CO ₃ / Ka ₂ CO ₃ / K ₂ CO ₃ a sharp transition temperature between 390 and 400 ° FROM. The midpoint of this temperature range is at 385 ° C. The calculated area under the transition temperature curve is 182 J / g. It was found that the onset of crystal disorder occurs at a minimum DSC temperature of 390 ° C. The temperature of the abrupt transition indicates an almost uniform mixture of salts.

Example 7. The study of the ionic conductivity of inorganic salt catalysts or individual inorganic salts in comparison with K2CO3.

All studies are carried out by placing 3.81 cm (1.5 in) of inorganic salt catalysts or individual inorganic salts in a quartz ampoule with platinum or copper wires isolated from each other, but immersed in a sample in a muffle furnace. The wires are connected to a dry cell with a potential of 9.55 V and to a resistor (220,000 Ohms) limiting the electric current.

The muffle furnace is heated to 600 ° C and the current is measured using a microammeter.

In FIG. Figure 12 shows the graphical dependence of the logarithm of the resistance of the sample relative to the resistance of potassium carbonate (1ode (g K ₂ CO ₃ )) on temperature (T). Curves 172, 174, 176, 178, and 180 represent the dependences of the decimal logarithm of the resistance of K ₂ CO ₃ , CaO resistance, and the resistance of the catalyst K ₂ CO ₃ / K ₂ CO ₃ / C ₂ CO ₃ , b _{1 2} CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / C8 ₂ CO ₃ and the resistance of the catalyst Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / C8 ₂ CO _3, respectively.

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The CaO sample (curve 174) has a relatively large stable resistance to K ₂ CO ₃ (curve 172) at temperatures in the range between 380 and 500 ° C. Stable resistance indicates an ordered structure and / or that when heated, ions do not acquire the ability to move relative to each other. For catalyst K ₂ CO ₃ / B ₂ CO ₃ / C ₂ CO ₃ , catalyst L ₂ CO ₃ / K ₂ CO ₃ / B ₂ CO ₃ / C ₂ CO ₃ and catalyst Ba ₂ CO ₃ / K ₂ CO ₃ / K b ₂ CO ₃ / Sk ₂ CO ₃ (see curves 176, 178 and 180) there is a sharp decrease in resistivity relative to K2CO3 at temperatures in the range from 350 to 500 ° C. A decrease in resistivity usually indicates that an electric current occurs when voltage is applied to wires immersed in an inorganic salt catalyst. The data in FIG. 12 indicate that the mobility of ions in inorganic salt catalysts is usually greater than in pure inorganic salts at temperatures in the range from 350 to 600 ° C.

In FIG. 13 is a graph of the logarithm of the CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO _3, Na ₂ catalyst resistance relative to potassium carbonate resistance (1od (g K ₂ CO ₃₎₎ of the temperature (T). Curve 182 represents the dependence of CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO _3, Na ratio catalyst resistance ₂ Resistance K ₂ CO ₃ (curve 172) versus the temperature by heating Na catalyst ₂ CO ₃ / K ₂ CO ₃ / K ₂ CO ₃ / CK ₂ CO ₃ . After heating, the catalyst Ma ₂ CO ₃ / K ₂ CO ₃ / B ₂ CO ₃ / Ck ₂ CO _{3 is} cooled to room temperature and then heated in a conductivity measuring cell. Curve 184 is a plot of the logarithm of the resistance of the catalyst Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO ₃ with respect to resistance K ₂ CO ₃ the temperature during heating of the inorganic salt catalyst after being cooled from 600 to 25 ° C. . Ionic conductivity reheated Na catalyst ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO ₃ is increased relative to the ionic conductivity of the original catalyst Vi ₂ CO ₃ / K ₂ CO ₃ / BL ₂ CO ₃ / Ch ₂ CO _3.

Differences in the ionic conductivity of the inorganic salt catalyst during the first heating and the second heating suggest that the inorganic salt catalyst forms a different form (second form) upon cooling, which is not identical to the form (first form) before any heating.

Example 8. The study of the fluidity of the inorganic salt catalyst.

A layer of powdered catalyst K ₂ CO ₃ / B ₂ CO ₃ / Sk ₂ CO ₃ with a thickness of 1-2 cm is placed in a quartz cup. This cup is introduced into the furnace and heated to 500 ° C. for 1 hour. To determine the flow behavior of the catalyst after heating, the cup in the furnace is tilted by hand. The catalyst K ₂ CO ₃ / B ₂ CO ₃ / CK ₂ CO ₃ does not move. When compressed with a spatula, the catalyst has a toffee consistency.

Individual carbonate salts, in contrast, are free flowing powders under the same conditions.

Catalyst Na ₂ CO ₃ / K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO ₃ becomes liquid and flows easily (e.g., such as water) in the dish under the same conditions.

Examples 9, 10. Contacting the crude feed with a hydrogen source in the presence of a catalyst K ₂ CO ₃ / B ₂ CO ₃ / C ₂ CO ₃ and water vapor.

In examples 9-27, the following equipment and general procedure are used, with the exception of the variations that are described.

Reactor. The Ragg autoclave (volume 250 ml, made of Nak! E11ou C alloy (Ragg model No. 4576)), designed for an operating pressure of 35 MPa (5000 psi) at 500 ° C, is equipped with a mechanical stirrer and a Saiteg belt heater with a power of 800 W with an EigoShegt controller capable of maintaining the autoclave temperature with an accuracy of ± 5 ° C from room temperature to 625 ° C, a gas inlet channel, a water vapor inlet channel, one outlet channel and a thermocouple recording the internal temperature. Before heating, the lid of the autoclave is insulated with fiberglass.

The reservoir to add. The addition tank (250 ml capacity, made of aged 316 stainless steel) is equipped with an adjustable heating system, a suitable gas distribution system, a pressure relief system, a thermocouple, a pressure meter and a high temperature control valve (8teade1ok valve No. 88-4I ^), providing flow control hot, viscous and / or compressed raw materials at a flow rate of 0 to 500 g / min. On the downstream side, a high temperature control valve is connected to the first inlet of the reactor after loading the crude feed into the addition tank. Before operation, isolate the tank lines for addition.

Product collection. Steam from the reactor leaves the outlet of the reactor and enters a series of cooled traps having a lower temperature (immersion pipes connected to a set of tanks (150 ml) made of aged 316 stainless steel). The vapor stream liquid condenses in cooled traps to form a gas stream and a liquid condensate stream. The vapor flow rate from the reactor and through the cooled traps, if necessary, is controlled using an inverse pressure regulator. The flow rate and the total gas volume for the gas stream leaving the cooled traps are measured using a wet gas meter (Kgbeg Mobe1 # TC 05 \ 7e1 Tek! Instrument). After exiting the wet gas meter, a stream is taken into the gas chamber (Tb1ag gas sampling chamber) for analysis. Gas is analyzed using a gas chromatograph / mass spectrometer system (Nete1ei-Raskagb Mob! 5890, currently Adbe! Mob1 5890;

- 29 010396 manufactured by AdjeSh Teskpo1od1e5, Ζίοη ΙΙΙίηοίδ, I.8.A.). The liquid condensate stream is removed from the cooled traps and weighed. The crude product and water are recovered from the liquid condensate stream. The crude product is weighed and analyzed.

Methodology Seggo Ndgo raw materials (137.5 g) are loaded into the addition tank. This crude feed has a density of 6.7 ° ΑΡΙ (1023.9 kg / m ³ ). The crude feed has a sulfur content of 0.042 g, a nitrogen content of 0.011 g and a total content of Νί / ν of 0.009 g per 1 g of crude feed. The crude feed is heated to 150 ° C. The reactor is charged with Catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ (31.39 g).

Catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ was prepared by combining 16.44 g of K ₂ CO _3, 19.44 g of Rb ₂ CO ₃ and 24.49 g of Cg ₂ CO _3. Catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ has a minimum VAP temperature of 360 ° C. Catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ has a DSC temperature of 250 ° C. For individual salts (K ₂ CO _3, Rb ₂ CO ₃ and Cg ₂ CO ₃₎ in the range from 50 to 500 ° C is identified DSC temperature. This VAP temperature exceeds the DSC temperature of the inorganic salt catalyst and is below the DSC temperature of the individual metal carbonates.

The catalyst is quickly heated to 450 ° C at atmospheric pressure in a methane stream of 250 cm ³ / min. After reaching the desired reaction temperature, steam is dispensed into the reactor at a rate of 0.4 ml / min and methane at a rate of 250 cm ³ / min. Water vapor and methane are continuously dosed during the addition of crude feed to the reactor for 2.6 hours. Crude feed is fed to the reactor under a methane pressure of 1.5 MPa (229 psi) for 16 minutes. The remainder of the crude feed (0.56 g) remains in the addition tank after completion of the addition of the crude feed. During the addition of crude feed, a decrease in temperature to 370 ° C is observed.

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

The difference between the initial mass of the catalyst and the mass of the mixture of coke with the catalyst determines the amount of coke (0.046 g) remaining in the reactor per 1 g of crude feed. The total product contains 0.87 g of the crude product with an average density of 13 ° ΑΡΙ (979.2 kg / m ³ ) and gas. Gas includes unreacted CH4, hydrogen, C2 and C4-C6 hydrocarbons, and CO2 (0.08 g CO2 per 1 g of gas).

The crude product contains 0.01 g of sulfur and 0.000005 g of the sum of Νί and ν per 1 g of the crude product. This crude product is not subjected to subsequent analysis.

In Example 10, the methodology and process conditions, the crude feed and the catalyst were the same as in Example 9. The crude product of Example 10 was analyzed to determine the distribution of the boiling range for the crude product. The crude product contains 0.14 g of naphtha, 0.19 g of distillate, 0.45 g of VGO per 1 g of the crude product and has a residue content of 0.001 g and an undetectable amount of coke.

Examples 9 and 10 demonstrate that upon contacting the crude feed with a hydrogen source in the presence of at least 3 g of catalyst per 100 g of the crude feed, a total product is formed that includes the crude product, i.e. liquid mixture at NTD. The crude product has a residue content of at most 30% of the residue content of the crude feed. The crude product has a sulfur content and total содержание / ν content of at most 90% of the sulfur content and Νί / ν content for the crude feed.

The crude product includes at least 0.001 g of hydrocarbons with a boiling range distribution of at least 200 ° C at 0.101 MPa, at least 0.001 g of hydrocarbons with a boiling range distribution between 200 and 300 ° C at 0.101 MPa of at least 0.001 g hydrocarbons with a distribution of the boiling range between 400 and 538 ° C (1000 ° P) at 0.101 MPa.

Examples 11, 12. Contacting the crude feed with a hydrogen source in the presence of a catalyst K ₂ CO ₃ / K ₂ CO ₃ / C ₂ CO ₃ and water vapor.

In Examples 11 and 12, methodologies and process conditions, the crude feed and catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ were the same as in Example 9 except for using the 130 grams of crude feed (cerr Ngo) and 60 g of the catalyst K ₂ CO ₃ / K ₂ CO ₃ / C ₂ CO ₃ . In Example 11, methane was used as a hydrogen source. In Example 12, hydrogen gas was used as a source of hydrogen. In FIG. 14 graphically shows the amounts of non-condensable gas, crude product and coke. Lanes 186 and 188 represent the mass percent of the obtained coke, strips 190 and 192 depict the mass percent of the obtained liquid hydrocarbons, and strips 194 and 196 show the mass percent of the obtained gas based on the weight of the crude feed.

In Example 11, 93 wt.% Of the crude product (lane 192), 3 wt.% Gas (lane 196) and 4 wt.% Coke (lane 188) are calculated based on the weight of Seggo No. dgo.

In Example 12, 84 wt.% Of the crude product (lane 190), 7 wt.% Gas (lane 194) and 9 wt.% Coke (lane 186) are obtained based on the weight of Seggo No. dgo.

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Examples 11 and 12 provide a comparison of the use of methane as a source of hydrogen relative to the use of gaseous hydrogen as a source of hydrogen. Typically, methane is less expensive to produce and / or transport than hydrogen, so a methane process is desirable. As shown, methane is at least as effective as hydrogen gas as a source of hydrogen when contacting the crude feed in the presence of an inorganic salt catalyst in order to obtain a total product.

Examples 13, 14. Obtaining a crude product with a given density AP1.

The apparatus, process methodology and inorganic salt catalyst were the same as in example 9, with the exception of variable pressure in the reactor.

In Example 13, the pressure in the reactor was 0.1 MPa (14.7 psi) during the contacting period. A crude product is obtained with a density of 25 ° AP1 (904.2 kg / m ³ ) at 15.5 ° C. The total product contains hydrocarbons with a distribution of the number of carbon atoms in the range from 5 to 32 (see curve 198 in FIG. 15).

In Example 14, during the contacting period, the pressure in the reactor was 3.4 MPa (514.7 psi). A crude product is obtained with a density of 51.6 ° AP1 (772.8 kg / m ³ ) at 15.5 ° C. The total product contains hydrocarbons with a distribution of the number of carbon atoms in the range from 5 to 15 (see curve 200 in FIG. 15).

These examples demonstrate methods of contacting the crude feed with hydrogen in the presence of an inorganic salt catalyst at various pressures to obtain a crude product with a given density AP1. Due to the change in pressure, a crude product with an increased or decreased density of AP1 is obtained.

Examples 15, 16. Contacting the crude feed in the presence of a catalyst

K ₂ CO _c / Rb ₂ CO _s / Cg CO ₂ or _of silicon carbide in the absence of external hydrogen source.

In Examples 15 and 16, the apparatus, crude feed and process methodology were the same as in Example 9, except that the crude feed and catalyst (or silicon carbide) were directly charged to the reactor at the same time. Carbon dioxide (CO ₂ ) is used as the carrier gas. Example 15 Raw Ssggo №dgo (138 g) is combined with catalyst K ₂ CO _c / Rb ₂ CO _s / Cg _of CO ₂ (60.4 g, similar to the catalyst in Example 9). In Example 16, the raw materials of SSGGO Ndgo (132 g) were combined with silicon carbide (83.13 g, 40 mesh, 81apGogb Ma1spa15; ANyo U1c) o, CA). It is believed that such silicon carbide has low catalytic activity (if any) under the process conditions described in the invention.

In each example, the mixture is heated for 2 hours to a reaction temperature of 500 ° C. The reactor was metered CO ₂ at 100 cm ³ / min. Vapors exiting the reactor are collected in cooled traps and a gas chamber using a back pressure of 3.2 MPa (479.7 psi). The crude product from refrigerated traps is combined and analyzed.

In Example 15, upon contacting the crude feed with an inorganic salt catalyst in an atmosphere of carbon dioxide, 36.82 g (26.68 wt% based on the weight of the crude feed) of a colorless hydrocarbon liquid with a density of at least 50 ° AP1 (779.6 kg / m ³ ).

In example 16, by contacting the crude feed with silicon carbide in an atmosphere of carbon dioxide, 15.78 g (11.95 wt.% Based on the weight of the crude feed) of a yellow hydrocarbon liquid with a density of 12 ° AP1 (986.1 kg / m ³ ) are obtained .

Although the yield in Example 15 is small, the formation of a hydrogen source in the presence of an inorganic salt catalyst is greater than the formation of hydrogen under non-catalytic conditions. The yield of the crude product in Example 16 is half the yield of the crude product in Example 15. In addition, Example 15 shows that during the contacting of the crude feed in the presence of an inorganic salt, hydrogen is produced even in the absence of a gaseous hydrogen source.

Examples 17-20. Contacting a crude feed with a hydrogen source in the presence of a catalyst _of K ₂ CO / Rb ₂ CO _z / CO ₂ Cg _of calcium oxide and silicon carbide in atmospheric conditions.

The apparatus, process methodology, crude feed and inorganic salt catalyst are the same as in Example 9, except that the Csgggo Ndgo feed is added directly to the reactor, instead of being added through the addition tank, and hydrogen gas is used as a hydrogen source. During the contacting period, the pressure in the reactor is 0.101 MPa (14.7 psi). The hydrogen gas flow rate is 250 cm ³ / min. The data of the process temperature, the flow rate of water vapor and the percentage of the resulting crude product, gas and coke are summarized in table. 4 in FIG. sixteen.

In Examples 17 and 18 used Catalyst K ₂ CO _c / Rb ₂ CO _c / C8 ₂ CO _s. In example 17, the contact temperature is 375 ° C. In example 18, the contact temperature is in the temperature range from 500 to 600 ° C.

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As shown in the table. 4 (Fig. 16), for examples 17 and 18, when the temperature rises from 375 to 500 ° C, the formation of gas increases from 0.02 to 0.05 g of gas per 1 g of total product. However, coke formation decreases from 0.17 to 0.09 g of coke per 1 g of crude feed at elevated temperature. The sulfur content in the crude product also decreases from 0.01 to 0.008 g of sulfur per 1 g of the crude product at elevated temperature. Both crude products have an H / C ratio of 1.8.

In example 19, the crude feed is in contact with CaCO3 under conditions similar to the conditions described for example 18. Data on the percentage of the resulting crude product, gas and coke are summarized in table. 4 (Fig. 16). The gas production in Example 19 is increased compared to the gas production in Example 18. The desulphurization of the crude feed is not as effective as that of Example 18. The crude product obtained in Example 19 contains 0.01 g of sulfur per gram of crude product compared to the sulfur content 0.008 g per 1 g of crude product for the crude product obtained in example 18.

Example 20 is comparative for example 18. In example 20, 83.13 g of silicon carbide is loaded into the reactor instead of an inorganic salt catalyst. The formation of gas and coke in Example 20 increases significantly compared to the formation of gas and coke in Example 18. Under these non-catalytic conditions, 0.22 g of coke per 1 g of crude product, 0.25 g of non-condensable gas and 0.5 g of crude product are formed. The crude product obtained in Example 20 contains 0.036 g of sulfur per 1 g of crude product, compared with 0.01 g of sulfur per 1 g of the crude product obtained in Example 18.

These examples demonstrate that the catalysts used in examples 17 and 18 provide improved results compared to non-catalytic conditions and traditional metal salts. At 500 ° C and a hydrogen flow rate of 250 cm ³ / min, the amounts of coke and non-condensable gases were significantly lower than the amounts of coke and non-condensable gases obtained under non-catalytic conditions.

In the examples using inorganic salt catalysts (see examples 17-18 in table. 4, Fig. 16), a decrease in the gas produced (in wt.%) Is observed compared to the amount of gas generated during the controlled experiment (for example, see the example 20 in table 4 in Fig. 16). From the amount of hydrocarbons in the produced gas, it is possible to estimate the fraction of thermal cracking of the crude feed, comprising at least 20 wt.%, At least 15 wt.%, At least 10 wt.%, At least 5 wt.% (Or there is no cracking ) based on the total amount of crude feed in contact with a hydrogen source.

Examples 21, 22. Contacting the crude feed with a gaseous source of hydrogen in the presence of water and a catalyst K ₂ CO ₃ / K ₂ CO ₃ / Cz ₂ CO ₃ or silicon carbide.

The apparatus in examples 21 and 22 was the same as in example 9, except that hydrogen gas was used as a hydrogen source. In Example 21, 130.4 g of raw material were combined cerr №dgo with catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ (30.88 g) to form the crude feed mixture. In Example 22, 139.6 g of Seggo Ndgo feedstock with silicon carbide (80.14 g) was combined to form a mixture of crude feed.

The crude feed mixture is charged directly to the reactor. Hydrogen gas is metered into the reactor at a rate of 250 cm ³ / min over a period of heating and aging. The crude mixture is heated to 300 ° C for 1.5 hours and kept at 300 ° C for 1 hour. The reaction temperature is raised to 400 ° C for 1 hour and kept at 400 ° C for 1 hour. After reaching the temperature reaction equal to 400 ° C., water is introduced into the reactor at a rate of 0.4 g / min in combination with hydrogen gas. Water and hydrogen are metered into the reactor during the remaining periods of heating and aging. After keeping the reaction mixture at 400 ° С, the reaction temperature is increased to 500 ° С and kept at 500 ° С for 2 hours. The vapors formed in the reactor are collected in cooled traps and in a gas chamber. The liquid product from the cooled traps is combined and analyzed.

In Example 21 by contacting the crude feed with catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cs ₂ CO ₃ in an atmosphere of hydrogen obtained 86.17 g (66.1 wt.% Based on the weight of the crude feed) of dark red-brown hydrocarbon liquids (crude product) and water (97.5 g) as vapors.

In Example 22, water vapor and a small amount of gas are released from the reactor. Upon examination of the reactor, a viscous, dark brown hydrocarbon liquid was removed from it. Upon contacting the crude feed with silicon carbide in a hydrogen atmosphere, less than 50% by weight of a viscous, dark brown liquid is formed. In example 21 there is an increase in the yield of the crude product by 25% compared with the yield of the crude product in example 22.

Example 21 demonstrates the improvement in the performance of a crude product obtained using the methods described in the invention compared to a crude product obtained using hot water. Specifically, in Example 21, the crude product boils lower than the crude product of Example 22, which demonstrates the crude product obtained in Example 22, which cannot be obtained as vapor. The crude product obtained in example 21 has improved flow characteristics compared to the crude product obtained in example 22, which is determined by visual inspection.

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Examples 23, 24. The contacting of the crude feed with a hydrogen source in the presence of a catalyst of K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO ₃ in order to obtain more volume of crude product as compared with the crude product obtained in the non-catalytic conditions.

The apparatus, the crude feed, the inorganic catalyst, and the process procedure were the same as described in Example 9, except that the crude feed was directly charged to the reactor and hydrogen gas was used as a hydrogen source. The crude Seggo Yedgo raw material has a density of 6.7 ° AP1 (1023.9 kg / m ³ ) and a density of 1.02 g / ml at 15.5 ° C.

In Example 23 the reactor was charged 102 grams of crude feed (100 mL of crude feed) and 31 g of catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO _3. A crude product (87.6 g) was obtained with a density of 50 ° AP1 (779.6 kg / m ³ ) and a density of 0.7796 g / ml at 15.5 ° C (112 ml).

In Example 24, 102 g of crude feed (100 ml of crude feed) and 80 g of silicon carbide were charged to the reactor. A crude product (70 g) was obtained with a density of 12 ° AP1 (986.1 kg / m ³ ) and a density of 0.9861 g / ml at 15.5 ° C (70 ml).

Under these conditions, the volume of the crude product obtained in Example 23 is approximately 10% greater than the volume of the crude feed. The volume of the crude product obtained in example 24 was significantly less (40%) than the volume of the crude product obtained in example 23. A significant increase in the volume of the product increases the ability of the refinery to produce a larger volume of crude product per unit volume of feed.

Example 25. Contacting the crude feed with a hydrogen source in the presence of a catalyst K ₂ CO ₃ / K ₂ CO ₃ / C ₂ CO ₃ sulfur and coke.

The apparatus and methodology of the process were the same as in Example 9, except that water vapor was dosed into the reactor at a rate of 300 cm ³ / min. Catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO ₃ was prepared by combining 27.2 g of K ₂ CO _3, 32.2 g of Rb ₂ CO ₃ and 40.6 g Ck ₂ CO _3.

The crude feed (130.35 g) and catalyst K ₂ CO ₃ / K ₂ CO ₃ / Ck ₂ CO ₃ (31.6 g) were charged into the reactor. Seggo Yedgo raw materials contain 0.04 g of aromatic hydrocarbons per 1 g of crude raw material, distributed in the boiling range between 149 and 260 ° С (300-500 ° Р), 0.000640 g of nickel and vanadium, 0.042 g of sulfur and 0, 56 g of residue. The density of raw AP1 raw materials (in degrees) is 6.7 (1023.9 kg / m ³ ).

Contacting the crude feed with methane in the presence of a catalyst of K ₂ CO ₃ / Rb ₂ CO ₃ / Ch ₂ CO ₃ gives 0.95 g of total product and 0.041 grams of coke per 1 g of the crude feed.

The total product includes 0.91 g of crude product and 0.028 g of hydrocarbon gas per 1 g of total product. The resulting gas amount includes, per 1 mol of gas, 0.16 mol of hydrogen, 0.045 mol of carbon dioxide and 0.025 mol of hydrocarbons C ₂ and C ₄ -C ₆ , which is determined by the GC / MS method. The gas balance is methane, air, carbon monoxide and traces (0.004 mol) of the vapor of the crude product.

The crude product is analyzed using a combination of gas chromatography and mass spectrometry methods. The crude product includes a mixture of hydrocarbons with a boiling range between 100 and 538 ° C. The total mixture of liquid products includes 0.006 g of ethylbenzene (a monocyclic compound with a boiling point of 136.2 ° C at 0.101 MPa) per 1 g of the mixture. This product was absent in crude feed.

Spent catalyst (first spent catalyst) is removed from the reactor, weighed and then analyzed. The mass of the first spent catalyst increases from 31.6 g to a total mass of 37.38 g (an increase of 18 wt.% Based on the weight of the initial catalyst K ₂ CO ₃ / K ₂ CO ₃ / C ₂ CO ₃ ). The first spent catalyst includes 0.15 g of additional coke, 0.0035 g of sulfur, 0.0014 g of V / V and 0.845 g of K ₂ CO ₃ / K ₂ CO ₃ / C ₂ CO ₃ per 1 g of spent catalyst.

An additional amount of crude feed (152.71 g) is contacted with the first spent catalyst (36.63 g) in order to obtain 150 g of the recovered total product, taking into account losses. This total product contains 0.92 g of liquid crude product, 0.058 g of additional coke and 0.017 g of gas per 1 g of total product. This gas includes, per 1 mol of gas, 0.18 mol of hydrogen, 0.07 g of carbon dioxide and 0.035 mol of C ₂ -C ₆ hydrocarbons. The gas balance is methane, nitrogen, some air and traces of vapor of the hydrocarbon product (<1 mol.%).

The crude product includes a mixture of hydrocarbons with a boiling range between 100 and 538 ° C. A part of this mixture with a boiling range distribution below 149 ° C includes 1 mol of the sum of liquid hydrocarbons 0.018 mol.% Ethylbenzene, 0.04 mol.% Toluene, 0.03 mol.% Metaxylene and 0.060 mol.% Paraxylene (monocyclic compounds with a boiling point below 149 ° C at 0.101 MPa). These products were absent from the crude feed.

The spent catalyst (second spent catalyst) is removed from the reactor, weighed and then analyzed. The mass of the second spent catalyst increases from 36.63 g to a total mass of 45.44 g (an increase of 43 wt.% Based on the weight of the original K ₂ CO ₃ / K ₂ CO ₃ / C ₂ CO ₃ catalyst). This second spent catalyst includes 0.32 g of coke, 0.01 g of sulfur and 0.67 g of K ₂ CO ₃ / K ₂ CO ₃ / C ₂ CO ₃ per 1 g of the second spent catalyst.

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An additional amount of crude feed (104 g) is contacted with a second spent catalyst (44.84 g) in order to obtain 104 g of the total product per 1 g of crude feed and 0.114 g of coke is collected. Part of this coke is associated with the formation of coke in the reservoir for addition due to overheating of this reservoir, when 104.1 of 133 g of the pumped crude feed are raw feed.

The total product includes 0.86 g of crude product and 0.025 g of hydrocarbon gas per 1 g of total product. The total gas includes, per 1 mol of gas, 0.18 mol of hydrogen, 0.052 mol of carbon dioxide and 0.03 mol of C ₂ -C ₆ hydrocarbons. The gas balance is methane, air, carbon monoxide, hydrogen sulfide, and a small admixture of hydrocarbon vapors.

The crude product includes a mixture of hydrocarbons with a boiling range between 100 and 538 ° C. Part of the mixture with a boiling range distribution below 149 ° C includes, per 1 g of a mixture of hydrocarbons, 0.021 g of ethylbenzene, 0.027 g of toluene, 0.042 g of methaxylene and 0.020 g of paraxylene, which are determined by GC / MS as described above.

Spent catalyst (third spent catalyst) is removed from the reactor, weighed and then analyzed. The weight of the third spent catalyst increases from 44.84 g to a total mass of 56.59 g (an increase of 79 wt.% Based on the weight of the original K ₂ CO ₃ / B ₂ CO ₃ / C8 ₂ CO ₃ catalyst). A detailed elemental analysis of the third spent catalyst was carried out. The third spent catalyst includes 1 g of additional substance 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, 0.0018 g of vanadium, 0.0007 g of nickel, 0.0015 g of iron and 0.00025 g of chloride, the balance being other transition metals such as chromium, titanium and zirconium.

As demonstrated in this example, coke, sulfur and / or metals deposited on (and / or in) the inorganic salt catalyst do not affect the total yield of the crude product (at least 80% in each experiment) obtained by contacting the crude feed with a hydrogen source in the presence of an inorganic salt catalyst. The crude product has a content of monocyclic aromatic hydrocarbons at least 100 times greater than the content of monocyclic aromatic hydrocarbons in the crude feed, distributed in the boiling range below 149 ° C.

For these three experiments, the average yield of the crude product (based on the weight of the crude feed) is 89.7 wt.% With a standard deviation of 2.6%; the average yield of coke is 7.5 wt.% (based on the weight of the crude feed) with a standard deviation of 2.7% and the average yield of mass of gaseous cracked hydrocarbons is 2.3 wt.% (based on the weight of the crude feed) with a standard deviation of 0 , 46%. The relatively large standard deviation for both liquid and coke is due to the third test, in which the poor operation of the temperature controller in the feed tank led to overheating of the crude feed in the addition tank. Despite this, apparently, there is no significant harmful effect of even large quantities of coke, as defined here, on the activity of the catalytic system.

The ratio of C ₂ olefins to the sum of C ₂ hydrocarbons is 0.19. The ratio of C ₃ olefins to the sum of C3 hydrocarbons is 0.4. The ratio of alpha olefins to internal olefins in C ₄ hydrocarbons is 0.61. The ratio of C ₄ cis / trans olefins is 6.34. This ratio is significantly higher than the thermodynamically predicted C4 ratio of cis / trans olefins, equal to 0.68. The ratio of alpha olefins to internal olefins in C5 hydrocarbons is 0.92. This ratio is significantly higher than the thermodynamically predicted ratio of C5 alpha olefins to internal C ₅ olefins, equal to 0.194. The ratio of C ₅ cis / trans olefins is 1.25. This ratio is higher than the thermodynamically predicted C5 ratio of cis / trans olefins, equal to 0.9.

Example 26 Contacting of the crude feed with a relatively high sulfur content with a hydrogen source in the presence of a catalyst of K ₂ CO ₃ / BL ₂ CO ₃ / C8 ₂ CO _3.

The apparatus and methodology of the process were the same as described in example 9, except that the crude feed, methane and water vapor were continuously fed into the reactor. The level of raw materials in the reactor is recorded by the change in the mass of the reactor. Methane gas is continuously dosed into the reactor at a rate of 500 cm ³ / min. Water vapor is continuously metered into the reactor at a rate of 6 g / min.

An inorganic salt catalyst is obtained by combining 27.2 g of K ₂ CO ₃ , 32.2 g of B ₂ CO ₃ and 40.6 g of C ₂ CO ₃ . Catalyst K ₂ CO ₃ / B ₂ CO ₃ / Cg ₂ CO ₃ (59.88 g) was charged to the reactor.

Crude raw materials (bitumen, Yubstysg. Sapaba), having a density of 9.4 ° ΑΡΙ (1004.3 kg / m ³ ), sulfur content of 0.02 g of sulfur and a residue content of 0.40 g per 1 g of crude raw material, is heated in a tank to add up to 150 ° C. Hot bitumen is continuously dosed at a rate of 10.5 g / min from the reservoir to be added to the reactor in order to maintain a level of liquid crude feed of 50% of the volume of the reactor, but this rate was insufficient to maintain such a level.

A mixture of methane, water vapor and crude feed is contacted with the catalyst at an average temperature inside the reactor of 456 ° C. When a mixture of methane, water vapor and crude feed is contacted with a catalyst, the total product is obtained (in this example, in the form of steam leaving the reactor).

- 34 010396

Within 6 hours, a total of 1,640 g of crude feed was processed. The difference between the initial mass of the catalyst and the mass of the mixture of the residue with the catalyst determines the amount of coke (0.085 g) remaining in the reactor per 1 g of crude feed. By contacting the crude feed with methane in the presence of a catalyst of K ₂ CO ₃ / Rb ₂ CO ₃ / Cg ₂ CO ₃ produced 0.93 g of total product per 1 g of the crude feed. The total product contains 0.03 g of gas and 0.97 g of crude product per 1 g of the total product, with the exception of the amount of methane and water used in this process.

Gas includes 1 g of gas, 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 hydrocarbons. By the amount of hydrogen sulfide obtained, it can be calculated that the sulfur content in the crude feed is reduced by 18 wt.%. As shown in this example, hydrogen, carbon monoxide, and carbon dioxide are obtained. The molar ratio of carbon monoxide to carbon dioxide is 0.4.

C ₂ -C ₅ hydrocarbons include, per 1 g of hydrocarbons, 0.30 g of C ₂ compounds, 0.32 g of C ₃ compounds, 0.26 g of C ₄ compounds, and 0.10 g of C ₅ compounds. The weight ratio of isopentane to n-pentane in non-condensable hydrocarbons is 0.3. The weight ratio of isobutane to n-butane in condensable hydrocarbons is 0.189. Compounds C ₄ have a butadiene content of 0.003 g per 1 g of compounds C _4. The weight ratio of C4 alpha olefins to C4 internal olefins is 0.75. The weight ratio of C5 alpha olefins to C5 internal olefins is 1.08.

The data in Example 25 demonstrate that with the continuous processing of crude feed with a relatively high sulfur content with the same catalyst in the presence of coke, the activity of the inorganic salt catalyst does not decrease, and a crude product suitable for transportation is obtained.

Example 27 Contacting of the crude feed with a hydrogen source in the presence of catalyst K cos ₂ / Rb ₂ CO _3/2 cos C8 and coke.

The apparatus and process procedure are carried out using the conditions described in example 26. The catalyst (56.5 g) is loaded into the reactor. Within 6 hours, a total of 2550 g of crude feed is processed. The difference between the initial mass of the catalyst and the mass of the mixture of the residue with the catalyst determines the amount of coke (0.114 g) remaining in the reactor, based on the weight of the crude feed. A total of 0.89 g of total product is obtained per 1 g of crude feed. The total product includes 0.04 g of gas and 0.96 g of crude product per 1 g of the total product, excluding the amount of methane and water used in this process.

Gas includes, per 1 g of gas, 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 hydrocarbons. According to the amount of hydrogen sulfide obtained, it can be calculated that the sulfur content in the crude feed is reduced by 14 wt.% Based on the weight of the crude feed. As shown in this example, hydrogen, carbon monoxide, and carbon dioxide are obtained. The molar ratio of carbon monoxide to carbon dioxide is 0.6.

Hydrocarbons C2-C6 include 0.44 g of compounds C2, 0.31 g of compounds C ₃ , 0.19 g of compounds C ₄ and 0.068 g of compounds C ₅ per 1 g of hydrocarbons C2-C6. The weight ratio of isopentane to n-pentane in non-condensable hydrocarbons is 0.25. The weight ratio of isobutane to n-butane in condensable hydrocarbons is 0.15. Compounds C ₄ have 1 g of compounds C ₄ butadiene content of 0.003 g

This example demonstrates that the reprocessing of raw crude (2550 g of raw material) with a relatively high sulfur content with the same catalyst (56.5 g) in the presence of coke does not reduce the activity of the inorganic salt catalyst and a crude product suitable for transportation is obtained.

The invention has developed a method for the practical use of the crude product, which consists in obtaining transport or boiler fuels, lubricants or chemicals, which includes processing the resulting crude product or a mixture of the crude product with raw materials.

Further modifications and alternative embodiments of various aspects of this invention will be apparent to those skilled in the art in view of the present description. Therefore, this description should be considered only as illustrative, which is given for the purpose of recommendations for specialists in this field of technology on the General method of carrying out the invention. It should be understood that the forms of the invention demonstrated and described herein may be taken as examples of its embodiment. The elements and materials shown and described herein can be replaced and some features of the invention can be used independently, all this is obvious to specialists in this field of technology after recognizing the advantages of this invention. Changes may be made to the elements described herein without departing from the spirit and scope of the invention, as described in the following claims.

Claims (9)

CLAIM 1. The crude product formed in the processes of oil production, which is a liquid at normal pressure temperature (NTD) and contains 1 g of crude product: at most 0.05 g of residue; at least 0.001 g of hydrocarbons with a boiling range distribution of at most 204 ° C (400 ° P) at 0.101 MPa, at least 0.001 g of hydrocarbons with a boiling range distribution between 204 and 300 ° C at 0.101 MPa of at least 0.001 g hydrocarbons with a boiling range distribution between 300 and 400 ° C at 0.101 MPa and at least 0.001 g of hydrocarbons with a boiling range distribution between 400 and 538 ° C (1000 ° P) at 0.101 MPa; more than 0 g, but less than 0.01 g of one or more catalysts, where at least one of the catalysts contains one or more alkali metals; where the crude product is a liquid at NTD. 2. The crude product according to claim 1, in which at least one of the catalysts there is an inflection point on the dependence of the ion current of the emitted gas for the inorganic salt catalyst in the temperature range between 50 and 500 ° C, which is determined by the method of temporary analysis of products (VAP ) and / or has a peak thermal transition in the temperature range between 200 and 500 ° C, which is determined by the method of differential scanning calorimetry at a heating rate of 10 ° C / min. 3. The crude product according to claim 1 or 2, in which at least one of the catalysts further includes a transition metal. 4. The crude product according to any one of claims 1 to 3, in which at least one of the catalysts also includes a transition metal sulfide. 5. The crude product according to claim 4, in which the atomic ratio of alkali metal to transition metal is in the range from above 0 to 1. 6. The crude product according to any one of claims 1 to 5, in which the alkali metal includes sodium, potassium, rubidium, cesium, or mixtures thereof. 7. The crude product according to any one of claims 1 to 6, in which at least one of the catalysts includes bartonite. 8. The crude product according to any one of claims 1 to 7, in which at least one of the catalysts further includes an alkaline earth metal and / or zinc. 9. A method of obtaining a transport fuel, boiler fuel, lubricants or chemicals, which includes the processing of the crude product according to any one of claims 1 to 8 or a mixture of the crude product with raw materials.