EA009091B1 - Method of production a catalyst, a catalyst, method of production a crude product and crude product - Google Patents

Abstract

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

Description

The present invention relates generally to methods for processing crude oil production processes, to compositions, and to a method for producing a catalyst. More specifically, embodiments of the invention described relate to methods for converting a crude feed that has a residue content of at least 0.2 g residue per gram of crude feed into a crude product that is: (a) a liquid mixture at a temperature of 25 ° C and a pressure of 0.101 MPa normal pressure temperature (NTD), and (b) has one or more characteristics that are improved compared with similar characteristics of the raw material.

Description of the level of technology

Untreated raw materials that have one or more inappropriate characteristics that do not allow them to be economically transported or processed using traditional equipment are usually referred to as unprofitable raw materials.

Disadvantaged raw materials often contain a relatively large amount of residue. Such raw materials usually lead to difficulties, and its transportation and / or processing with the help of traditional equipment is costly. High residue feedstocks can be processed at high temperatures to convert these raw materials into coke. As a typical alternative, high residue feedstocks are treated with water at high temperatures to obtain less viscous feedstock and / or feedstocks. During processing, the removal of water from less viscous feedstock and / or raw mixes can be difficult using traditional means.

Disadvantaged raw materials may include hydrocarbons with a lack of hydrogen. When processing hydrocarbons with hydrogen deficiency, it is usually necessary to add appropriate amounts of hydrogen, especially if unsaturated compounds are formed as a result of the 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 its transportation to plants for processing.

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

Disadvantaged raw materials may include acidic components that contribute to the total acid number (TAN) of the raw material. Unprofitable raw materials with relatively high SCC may contribute to the corrosion of metal parts during transport and / or processing of unprofitable raw materials. Removal of acidic components from unfavorable raw materials may include chemical neutralization of acidic components with various bases. Alternatively, corrosion resistant metals can 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 way to inhibit corrosion may include the addition of corrosion inhibitors to unprofitable raw materials before transporting and / or processing unprofitable raw materials. The use of corrosion inhibitors can adversely affect the equipment used to process raw materials, and / or the quality of products derived from such raw materials.

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

Disadvantaged raw materials often include organically bound heteroatoms (for example, sulfur, oxygen, and nitrogen). In some cases, organically bound heteroatoms can have a detrimental effect on catalysts. In the process of residue desulfurization, 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 efficiency of demetallization, the formation of practically inseparable mixtures of salts with hydrocarbons, the use of large quantities of gaseous hydrogen and / or relatively high hydrogen pressures.

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

In US patent No. 3,136,714 (O1b8OI and others); 3,558,747 (О1е1ш and others); 3,847,797 (RaZegiak et al.); 3,948,759 (Kshd and others); 3,957,620 (Rickshaw et al.); 3,960,706 (MsSo11it and others); 3,960,708 (MsSo11it and others); 4,119,528 (Bai, 1g, etc.); 4,127,470 (Vibe, 1g, etc.); 4,224,140 (Firth et al.); 4,437,980 (Negebou and others); 4,591,426 (Kgakik et al.); 4,665,261 (Mahigek); 5,064,523 (Kgebsitag and others); 5,166,118 (Kegseitag et al.); 5,288,681 (Oaby); 6,547,957 (8bjakag and others); and in published applications US No. 20030000867 (Reu

- 1 009091 ηοΐάδ) and 20030149317 (Vepbta) described the various methods and systems used to process the raw material. However, the methods, systems, and catalysts described in these patents have limited applicability, due to the many technical problems outlined above.

As a result, disadvantageous raw materials usually have undesirable characteristics (for example, a relatively high residue content, 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 TAN, organically bound heteroatoms and / or polluting metals). Such characteristics usually lead to problems in conventional transport and / or problems for process equipment, including problems of increased corrosion, reduced catalyst life, process blocking 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 raw materials into unpurified products having more desirable characteristics.

Disclosure of the invention

In general, the invention described herein relates to systems and methods for contacting a crude feed with one or more catalysts in order to produce a total product containing the crude product and, in some embodiments, a non-condensable gas. In addition, the invention described herein generally relates to compositions that have new combinations of components. Such compositions can be obtained using the systems and methods described in the invention.

The invention has developed a method for producing a crude product, which consists in contacting the crude raw material with a hydrogen source in the presence of one or more catalysts in order to obtain a crude product in which one or more catalysts is a catalyst containing K ₃ Fe ₁₀ 8 ₁₄ .

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or more catalysts in order to obtain a total product that includes the crude product, the crude product being a liquid mixture at 25 ° C and a pressure of 0.101 MPa (NTD), at least one of the catalysts contains one or more transition metal sulphides, while the crude feed has a content of about Tatka at least 0.2 g of residue per 1 g of the crude feed, as determined by the method A8TM Ό5307; and adjusting the contact conditions such that the crude product has at most 0.05 grams of coke per gram of crude product, the crude product has at least 0.001 grams of naphtha per gram of crude product, and naphtha has an octane rating of at least 70.

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or more catalysts in order to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa , at least one of the catalysts contains one or more transition metal sulphides, the crude raw material having a residue content of at least 0.2 g of residue per 1 g of crude Nogo raw materials, as determined by the method A8TM Ό5307; and adjusting the contact conditions such that the crude product contains kerosene, having at least 0.2 g of aromatic hydrocarbons per g of kerosene, as determined by the A8TM method Ό5186, and kerosene has a freezing point at a temperature of at most -30 ° C, as determined by the A8TM method Ό2386, and the crude product has at most 0.05 g of coke per 1 g of the crude product.

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or more catalysts in order to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa , at least one of the catalysts contains one or more transition metal sulphides, the crude raw material having a residue content of at least 0.2 g of residue per 1 g of crude Nogo material; and adjusting the contact conditions such that the crude product contains at most 0.05 g coke per gram of crude product, the weight ratio of atomic hydrogen to atomic carbon (H / C) in the crude product is at most 1.75, which is determined according to A8TM method Ό6730.

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or more catalysts in order to obtain a total product that includes the crude product, in which the crude product is a liquid mixture at 25 ° C and 0.101 MPa, at least one of the catalysts contains one or more transition metal sulphides, and the crude feed has a residue content of at least 0.2 g residue per g crude

- 2,009,091 raw materials, which is determined by the LBTM method Ό5307, and the weight ratio of atomic hydrogen to atomic carbon (H / C) in the raw material is at least 1.5; and adjusting the contact conditions such that the crude product has an H / C atomic ratio of 80-120% of the H / C atomic ratio for the crude raw material, and the crude product has a residue content of at most 30% of the residue content for the crude raw material, As determined by the LBTM method Ό5307, the crude product has at least 0.001 g naphtha per gram of crude product, and naphtha has an octane number of at least 70.

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or more catalysts in order to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa , at least one of the catalysts contains one or more transition metal sulphides, the crude raw material having a residue content of at least 0.2 g of residue per 1 g of crude Nogo raw materials, as determined by the method LBTM Ό5307; and adjusting the contact conditions such that the crude product contains, per g of the crude product: at least 0.001 g of naphtha, with naphtha having an octane number of at least 70; at least 0.001 g of kerosene, and the content of aromatic hydrocarbons in kerosene is at least 0.2 g of aromatic hydrocarbons per 1 g of kerosene, which is determined by the LBTM method Ό5186, and kerosene has a freezing point at a temperature of at most -30 ° C, what is determined by the LBTM method Ό 2386; at least 0.001 g of vacuum gas oil (VGO), and VGO has at least 0.3 g of aromatic hydrocarbons per 1 g of VGO, which is determined by the method 368/90; and at most 0.05 g of residue, as determined by the LBTM method Ό5307.

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or more catalysts containing a catalyst, a transition metal sulfide, to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the catalyst is a transition metal sulphide in total has at least 0.4 g of one or more transition metal sulphides per 1 of total catalyst, transition metal sulfide, the crude feed has a residue content of at least 0.2 g of residue per 1 g of the crude feed, as determined by the method LBTM Ό5307; and adjusting the contact conditions such that the crude product has at most 0.05 g of coke per 1 g of crude product, and the crude product has a residue content of at most 30% of the residue content of the raw material, as determined by the LBTM method Ό5307.

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or more catalysts containing a catalyst, a transition metal sulfide, to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the catalyst is a transition metal sulphide in total has at least 0.4 g of one or more transition metal sulphides per 1 catalyst transition metal sulfide, the crude feed has a nitrogen content of at least 0.001 grams of nitrogen per 1 g of the crude feed and the crude feed has a residue content of at least 0.2 g of residue per 1 g of the crude feed; and adjusting the contact conditions such that the crude product has a nitrogen content of at most 90% of the nitrogen content of the crude raw material, and the crude product has a residue content of at most 30% of the residue content of the crude raw material, where the nitrogen content is determined by the LBTM method Ό5762, and the residue content is determined by the LBTM method Ό5307.

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or more catalysts containing a catalyst, a transition metal sulfide, to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the catalyst is a transition metal sulphide in total has at least 0.4 g of one or several transition metal sulphides per g the amm of the catalyst of transition metal sulfides, the crude feed has a total Νί / ν / Re content of at least 0.0001 g Νί / ν / Fe per 1 g of crude raw materials, and the crude feed has a residue content of at least 0.2 g of residue to 1 g crude raw materials; and adjusting the contact conditions such that the crude product contains at most 0.05 g of coke per gram of crude product, the crude product has a total content of Νί / ν / Re at most 90% of the content of / ν / Re for the crude raw material , the crude product has a residue content of at most 30% of the residue content for the raw material and where the Νί / ν / Fe content is determined by the LBTM method Ό5863, and the residue content is determined by the LBTM method 305307.

In addition, the invention provides a method of obtaining a crude product, which consists in contacting the crude raw material with a source of hydrogen in the presence of one or not

- 3 009091 how many catalysts containing a catalyst - transition metal sulfide to obtain a total product, which includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the catalyst - transition metal sulfide has at least 0.4 g of one or more transition metal sulphides per 1 g of catalyst of transition metal sulphides, the crude feed has a sulfur content of at least 0.001 grams of sulfur per 1 g of crude feed, and the crude feed has a residual content and at least 0.2 gms of 1 g of the crude feed; and adjusting the contact conditions such that the crude product has a sulfur content of at most 70% of the sulfur content of the crude feed, and the crude product has a residue content of at most 30% of the residue content of the crude feed, and where the sulfur content is determined by the method L8TM Ό4294 and the residue content is determined by the method L8TM Ό5307.

In addition, the invention provides a method for producing a catalytic composition of transition metal sulfides, which consists in mixing a transition metal oxide and a metal salt to form a mixture of a transition metal oxide and a metal salt; a mixture of a transition metal oxide with a metal salt reacts with hydrogen to form an intermediate; and this intermediate compound reacts with sulfur in the presence of one or more hydrocarbons in order to obtain a transition metal sulfide catalyst.

The invention also provides a method for producing a crude product comprising contacting a crude raw material with a source of hydrogen in the presence of one or more catalysts containing a catalyst, a transition metal sulfide, to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, the catalyst — a transition metal sulfide contains a transition metal sulfide, and the crude feed has a residue content of at least 0.2 g residue per 1 g of crude raw materials, which is determined by the method L8TM Ό5307; adjusting the contact conditions such that the crude product has a residue content of at most 30% of the residue content for the crude material; and in which the catalyst is a transition metal sulfide can be obtained by: mixing the transition metal oxide and the metal salt to form a mixture of the transition metal oxide with the metal salt; the interaction of a mixture of a transition metal oxide and a metal salt with hydrogen, forming an intermediate compound; and reacting the intermediate with sulfur in the presence of one or more hydrocarbons to form a transition metal sulfide catalyst.

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a hydrogen source in the presence of one or more catalysts, to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude the raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, which is determined by the L8TM method Ό5307; obtaining at least part of the total product in the form of vapor; condensation of at least part of the vapor at 25 ° C and 0.101 MPa; and the formation of the crude product, in which the crude product contains per 1 g of the crude product at least 0.001 g of naphtha, and naphtha has an octane number of at least 70; at least 0.001 g of VGO, and VGO has at least 0.3 g of aromatic hydrocarbons per 1 g of VGO, which is determined by the method 368/90; and at most 0.05 g of residue, as determined by the L8TM method Ό5307.

The invention also provides a method for producing a crude product, comprising contacting a crude raw material with a hydrogen source in the presence of an inorganic salt catalyst, to obtain a total product that includes a crude product in which the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw materials, which is determined by the method L8TM Ό5307; the crude product is a liquid mixture at 25 ° C and 0,011 MPa, and the crude product contains 1 g of the crude product at least 0.001 g of naphtha, and naphtha has at least 0.001 g of monocyclic aromatic hydrocarbons per g of naphtha, which is determined by the method L8TM Ό6730; at least 0.001 g of distillate and at most 0.05 g of residue, as determined by the method Л8ТМ Ό5307.

The invention also provides a method for producing a crude product, comprising contacting a crude raw material with a hydrogen source in the presence of an inorganic salt catalyst, to obtain a total product that includes a crude product in which the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw materials, which is determined by the method L8TM Ό5307; the crude product is a liquid mixture at 25 ° C and 0.101 MPa, and the crude product contains at least 1 g of crude product at least 0.001 g of diesel fuel, and diesel fuel contains at least 0.3 g of aromatic hydrocarbons per 1 g of diesel fuel, what is determined by the method 368/90; at least 0.001 g of VGO, and VGO has at least 0.3 g of aromatic hydrocarbons per 1 g of VGO, which is determined by the method 368/90; and at most 0.05 g of residue, as determined by the L8TM method Ό5307.

- 4 009091

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, as determined by A8TM method Ό5307, and the crude raw material has a monocyclic aromatic content for hydrocarbons at most 0.1 g of monocyclic aromatic hydrocarbons per gram of crude feed; and adjusting the conditions of contact in such a way that, during contacting, at the most, 0.2 g of hydrocarbons, which are not condensed at 25 ° C and 0.101 MPa, which is determined by the material balance, is formed per 1 g of crude raw material, and thus, that the crude product has a content of monocyclic aromatic hydrocarbons at least 5% more than the content of monocyclic aromatic hydrocarbons for crude raw materials, where the content of monocyclic aromatic hydrocarbons is determined by Method L8TM Ό6730.

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude feed, as determined by the L8TM method Ό5307, and the crude feed has an olefin content, expressed in grams mmah olefin per 1 g of the crude feed; and adjusting the contacting conditions so that the crude product has an olefin content of at least 5% more than the olefin content of the raw material, where the olefin content is determined by the method L8TM 306730.

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, and for the inorganic salt catalyst, there is an inflection point when gas is released at a rate of The temperature range is between 50 and 500 ° C, which is determined by the method of time analysis of products (VAP) and adjusting the contact conditions such that the crude product has a residue content expressed in grams of residue per 1 g of the crude product, at most 30% of the residue content for the crude raw material, where the residue content is determined by the A8TM method Ό5307.

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, the inorganic salt catalyst contains at least two inorganic metal salts, and for inorganic salt catalyst, there is an inflection point when gas is released in the temperature range, which is determined by the Temporary Product Analysis Method (VAP), and the inflection point during gas evolution is in the temperature range between: (a) differential scanning calorimetry (DSC) temperature, at least measure one of the two inorganic metal salts and (b) the temperature of the DSC inorganic salt catalyst; and adjusting the contact conditions such that the crude product has a residue content expressed in grams of residue per 1 g of the crude product, at most 30% of the residue content for the crude raw material, where the residue content is determined by the A8TM method Ό5307.

In addition, the invention provides a method of obtaining a crude product, comprising contacting the crude raw material with a hydrogen source in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, as determined by the A8TM method Ό 5307, and for the inorganic salt catalyst is observed the inflection point in the evolution of gas in the temperature range between 50 and 500 ° C, which is determined by the method of the Temporary analysis of products (VAP); and obtaining a crude product in such a way that the volume of the crude product obtained is at least 5% larger than the volume of the crude raw material, and the volumes are measured at a temperature of 25 ° C and a pressure of 0.101 MPa.

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, and for the inorganic salt catalyst, there is an inflection point when gas is released at a rate of the range of between

- 5 009091 and 500 ° C, which is determined by the method of temporary analysis of products (VAP); and adjusting the conditions of contact in such a way that during contacting at most 0.2 g of hydrocarbons are formed, which do not condense at 25 ° C and 0.01 MPa, per 1 g of crude raw material, which is determined by the material balance.

The invention also provides a method for preparing a crude product, comprising contacting the crude raw material with a hydrogen source in the presence of an inorganic salt catalyst, to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, and the inorganic salt catalyst has a thermal transition temperature in the range between 200 ° C 500 ° C as determined by differential scanning calorimetry (DSC) at a heating rate of 10 ° C per minute; and adjusting the conditions of contact in such a way that the crude product has a residue content expressed in grams of residue per 1 g of crude product at most 30% of the residue content for the crude raw material, where the residue content is determined by the L8TM I5307 method.

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, and the inorganic salt catalyst has ionic conductivity, which is shey least the ionic conductivity of at least one of the inorganic salts of the inorganic salt catalyst at a temperature in the range of from 300 to 500 ° C; and adjusting the contact conditions such that the crude product has a residue content expressed in grams of residue per 1 g of the crude product, at most 30% of the residue content for the crude raw material, where the residue content is determined by the L8TM I5307 method.

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, and the inorganic salt catalyst contains alkali metal salts, where at least one salt l alkali metal is an alkali metal carbonate, and the alkali metal has an atomic number of at least 11, and an atomic ratio of at least one of the alkali metals 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; and adjusting the contact conditions such that the crude product has a residue content of at most 30% of the residue content for the crude raw material, where the residue content is determined by the method L8TM I5307.

The invention also provides a method for producing a crude product comprising contacting a crude raw material with a hydrogen source in the presence of an inorganic salt catalyst to obtain a total product, the crude raw material having a residue content of at least 0.2 g residue per 1 g of crude raw material, inorganic salt catalyst contains alkali metal salts, where at least one alkali metal salt is an alkali metal hydroxide, and the alkali metal has an atomic nom ep is at least 11, and the atomic ratio of at least one of the alkali metals 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; obtaining at least part of the total product in the form of vapor; condensation of at least part of the vapor at 25 ° C and 0.101 MPa; and the formation of the crude product, where the crude product has a residue content of at most 30% of the residue content for the crude material.

The invention also provides a method for preparing a crude product, comprising contacting a crude raw material with a hydrogen source in the presence of an inorganic salt catalyst to obtain a total product, the crude raw material having a residue content of at least 0.2 g residue per 1 g of crude raw material, inorganic salt catalyst contains alkali metal salts, where at least one alkali metal salt is an alkali metal hydride, and the alkali metal has an atomic number at least about 11, and the atomic ratio of at least one alkali metal having an atomic number of at least 11 to an alkali metal having an atomic number greater than 11 is in a range from 0.1 to 10; obtaining at least part of the total product in the form of vapor; condensation of at least part of the vapor at 25 ° C and 0.101 MPa; and the formation of the crude product, where the crude product has a residue content of at most 30% of the residue content for the crude material.

The invention also provides a method for producing a crude product, comprising contacting a crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst, to obtain a total product that includes the crude product,

- 6 009091 tory is a liquid mixture at 25 ° C and 0,011 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, and the inorganic salt catalyst contains one or more alkali metal salts, one or several alkaline earth metal salts, or mixtures thereof, where one of the alkali metal salts is an alkali metal carbonate, where the alkali metals have an atomic number of at least 11; and adjusting the contact conditions such that the crude product has a residue content of at most 30% of the residue content for the crude raw material, where the residue content is determined by the A8TM method Ό5307.

The invention also provides a method for preparing a crude product, comprising contacting the crude raw material with a hydrogen source in the presence of an inorganic salt catalyst, to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude feed, and the inorganic salt catalyst contains one or more alkali metal hydroxides, o the bottom or several salts of alkaline-earth metal, or mixtures thereof, where the alkali metal has an atomic number of at least 11; and adjusting the contact conditions such that the crude product has a residue content of at most 30% of the residue content for the crude raw material, where the residue content is determined by the L8TM method Ό5307.

The invention also provides a method for producing a crude product, comprising contacting the crude raw material with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g of residue per 1 g of crude raw material, and the inorganic salt catalyst contains one or more alkali metal hydrides, one or several alkaline earth metal salts, or mixtures thereof, where the alkali metal has an atomic number of at least 11; and adjusting the contact conditions such that the crude product has a residue content expressed in grams of residue per gram of crude product at most 30% of the residue content for the crude raw material, where the residue content is determined by the L8TM method Ό5307.

In addition, the invention provides a method for producing hydrogen gas comprising contacting a crude feed with one or more hydrocarbons in the presence of an inorganic salt catalyst and water, the number of carbon atoms in the hydrocarbon is in the range from 1 to 6, the crude feed has a residue content of at least 0 , 2 g of residue per 1 g of crude raw materials, and for the inorganic salt catalyst, there is an inflection point when gas is emitted in a temperature range between 50 and 500 ° C, which is determined by etsya method of temporal analysis of products (VAP); and it turns out gaseous hydrogen.

In addition, the invention provides a method for producing a crude product, comprising contacting a first crude raw material with an inorganic salt catalyst in the presence of water vapor to form a gas stream that includes hydrogen, in which the first crude raw material has a residue content of at least 0.2 g residue per 1 g of the first crude raw material, which is determined by the A8TM method Ό5307, and for the inorganic salt catalyst, there is an inflection point during the evolution of gas in the temperature range in the range between 50 and 500 ° С, which is determined by the method of temporary analysis of products; contacting the second crude feed with a second catalyst in the presence of at least a portion of the formed gas stream to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa; and adjusting the contact conditions such that one or more characteristics of the crude product is changed by at least 10% relative to one or more of the respective characteristics of the second raw material.

In addition, the invention provides a method for producing a gas stream that comprises contacting a crude feed with an inorganic salt catalyst in the presence of water vapor, in which the crude feed has a residue content of at least 0.2 g residue per 1 g of crude feed, which is determined by A8TM method 305307; and producing a gas stream that contains hydrogen, carbon monoxide and carbon dioxide, and in which the molar ratio of carbon monoxide to carbon dioxide is at least 0.3.

In addition, the invention provides a method for producing a crude product, comprising conditioning an inorganic salt catalyst; contacting the crude with a source of hydrogen in the presence of a conditioned inorganic salt catalyst to obtain a total product that includes the crude product, which is a liquid mixture at 25 ° C and 0.101 MPa, and the crude raw material has a residue content of at least 0.2 g residue per 1 g of crude raw materials; and adjusting the contact conditions such that the crude product has a residue content expressed in grams of residue per 1 g

- 7 009091 of the crude product, at most 30% of the residue content for the crude raw material, where the residue content is determined by the method L8TM 5307.

In addition, the invention provides a crude composition that includes hydrocarbons having a boiling range distribution between 30 and 538 ° C (1000 ° P) at 0.101 MPa, and these hydrocarbons contain isoparaffins and n-paraffins with a weight ratio of isoparaffins to n-paraffins equal to at most 1.4, which is determined by the method L8TM 306730.

In addition, the invention provides a crude composition that contains per g of composition at least 0.001 g of hydrocarbons with a boiling range distribution, at most 204 ° C (400 ° P) at 0.101 MPa, at least 0.001 g of hydrocarbons with boiling range 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 ° P) at 0,101 MPa, and where hydrocarbons, which have The boiling range distribution is at most 204 ° C, contains isoparaffins and nparaffins with a weight ratio of isoparaffins to n-paraffins at most 1.4, which is determined by the L8TM method Ό6730.

In addition, the invention provides a crude composition that contains per gram of composition at least 0.001 g of naphtha, which has an octane number of at least 70, and naphtha contains at most 0.15 g of olefins per gram of naphtha, which is determined by the method L8TM Ό6730; at least 0.001 g of kerosene, which contains at least 0.2 g of aromatic hydrocarbons per 1 g of kerosene, which is determined by L8TM method Ό5186, and kerosene has a freezing point at a temperature of at most -30 ° C, which is determined by L8TM method Ό 2386; and at most 0.05 g of residue, as determined by the L8TM method Ό5307.

The invention also provides a crude composition that contains per gram of composition at most 0.15 g of hydrocarbon gas that does not condense at 25 ° C and 0.101 MPa, this non-condensable hydrocarbon gas contains at most 0.3 g of hydrocarbons with carbon atoms. from 1 to 3 (C ₁ -C ₃ ), per 1 g of non-condensable hydrocarbon gas; at least 0.001 g of naphtha, which has an octane rating of at least 70; at least 0.001 g of kerosene, which has a freezing point at a temperature of at most -30 ° C, which is determined by the method L8TM Ό 2386, and kerosene has at least 0.2 g of aromatic hydrocarbons per 1 g of kerosene, which is determined by the method L8TM Ό5186; and at most 0.05 g of residue, as determined by the L8TM method Ό5307.

The invention also provides a crude composition that contains per gram of composition at most 0.05 g of residue, as determined by the L8TM method М5307; at least 0.001 g of hydrocarbons with a boiling range distribution, 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; at least 0.001 g of hydrocarbons with a boiling range distribution between 300 and 400 ° C at 0.101 MPa; at least 0.001 g of hydrocarbons with a boiling range distribution between 400 and 538 ° C (1000 ° P) at 0.101 MPa; moreover, hydrocarbons with a boiling range distribution between 20 and 204 ° C contain olefins having terminal double bonds, and olefins having internal double bonds, with a molar ratio of olefins having terminal double bonds, to olefins having internal double bonds of at least 0 , 4, which is determined by the method L8TM Ό6730.

The invention also provides a crude composition that contains per gram of composition at most 0.05 g of residue, as determined by the L8TM method М5307; at least 0.001 g of a mixture of hydrocarbons, which has a boiling range distribution between 20 ° C and 538 ° C (1000 ° P), which is determined by the L8TM method Ό5307, and the hydrocarbon mixture contains per g of hydrocarbon mixture at least 0.001 g of paraffins, what is determined by the method L8TM Ό6730; at least 0.001 g of olefins, as determined by the L8TM Ό6730 method, and the olefins contain at least 0.001 g of terminal olefins per 1 g of olefins, which is determined by the L8TM method Ό6730; at least 0.001 g of naphtha; at least 0.001 g of kerosene, and kerosene has at least 0.2 g of aromatic hydrocarbons per 1 g of kerosene, which is determined by the method L8TM Ό5186; at least 0.001 g of diesel fuel, with diesel fuel having at least 0.3 g of aromatic hydrocarbons per 1 g of diesel fuel, which is determined by the method ΙΡ 368/90; and at least 0.001 g of vacuum gas oil (VGO), and VGO has at least 0.3 g of aromatic hydrocarbons per 1 g of VGO, which is determined by the method 368/90.

Besides? the invention provides a crude composition that contains per gram of composition at most 0.05 g of residue, as determined by the L8TM method 305307; 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, 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, which is determined by the L8TM method Ό2887; and

- 8 009091 where hydrocarbons, which have a boiling range distribution of at most 204 ° C, have a boiling range distribution of at most 204 ° C, per g of hydrocarbons of at least 0.001 g of olefins, which is determined by the method L8TM Ό6730; and at least 0.001 g of paraffins, and the paraffins contain isoparaffins and n-paraffins with a weight ratio of isoparaffins to nparaffins of at most 1.4, which is determined by the L8TM method Ό6730.

In addition, the invention provides a crude composition that contains, per g of composition, at most 0.05 g of residue, as determined by the method L8TM No. 5307; and 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 ° C 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 ° P) at 0.101 MPa, which is determined by the L8TM method Ό2887; and where the hydrocarbons, which have a boiling range distribution between -10 and 204 ° C, contain compounds with carbon number 4 (C ₄ ), while the C ₄ compounds contain at least 0.001 g of butadiene per 1 g of C4 compounds.

In addition, the invention provides a crude composition that contains per gram of composition 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, 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 ° P) at 0.101 MPa; and 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 provides, in combination with one or more methods or compositions according to the invention, the crude raw material that: (a) has not been processed in a refinery, is not distilled, and / or is not subjected to fractional distillation; (B) contains components having a carbon number higher than 4, and this crude raw material has at least 0.5 g of such components per gram of crude raw material; (c) contains hydrocarbons, of which a part has a boiling range distribution below 100 ° C at 0.101 MPa, a boiling range distribution between 100 and 200 ° C at 0.101 MPa, a boiling range distribution between 200 and 300 ° C at 0.101 MPa, a boiling range distribution between 300 and 400 ° C at 0.101 MPa, and the distribution of boiling range between 400 and 700 ° C at 0.101 MPa; (d) contains per 1 g of crude feed: at least 0.001 g of hydrocarbons having a boiling range distribution below 100 ° C at 0.101 MPa, at least 0.001 g of hydrocarbons having a boiling range distribution between 100 and 200 ° C at 0.101 MPa , at least 0.001 g of hydrocarbons having a boiling range distribution between 200 and 300 ° C at 0.101 MPa, at least 0.001 g of hydrocarbons having a boiling range distribution between 300 and 400 ° C at 0.101 MPa, and at least 0.001 g of hydrocarbons having a boiling range distribution between 400 and 700 ° C at 0.101 MPa; (e) has a SCS; (1) has from 0.2 to 0.99 g, 0.3-0.8 g, or 0.4-0.7 g of residue per 1 g of crude raw material; (e) contains nickel, vanadium, iron, or mixtures thereof; (d) contains sulfur; and / or (ί) nitrogen-containing hydrocarbons.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a source of hydrogen that: (a) is gaseous; (B) contains molecular hydrogen; (c) contains light hydrocarbons; (d) contains methane, ethane, propane, or mixtures thereof; (e) contains water; and / or (1) mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a method that includes conditioning an inorganic salt catalyst, in which the conditions for the inorganic catalyst include: (a) heating the inorganic salt catalyst to a temperature at least 300 ° C; and / or (b) heating the inorganic salt catalyst to a temperature of at least 300 ° C, and cooling the inorganic salt catalyst to a temperature of at most 500 ° C.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a method that involves contacting the crude feed with one or more catalysts and controlling the contact conditions: (a) so that during the contact at most 0.2 g, at most 0.15 g, at most 0.1 g, or at most 0.05 g of hydrocarbons that do not condense at 25 ° C and 0.101 MPa per 1 g of crude feed, determined by using material balance; (B) such that the contact temperature is in the range of from 250 to 750 ° C or between 260 and 550 ° C; (c) the pressure is in the range from 0.1 to 20 MPa; (d) in such a way that the ratio of the gaseous source of hydrogen to the crude feed is in the range of 1 to 16,100 or 5-320 normal cubic meters (Nm ³ ) of the source of hydrogen per cubic meter of neo

- 9 009091 raw materials; (e) to inhibit coke formation; (ί) to inhibit coke formation in the total product or in the crude feed during the contacting; (e) such that the crude product also has at most 0.05 g, at most 0.03 g, at most 0.01 g, or at most 0.003 g of coke per 1 g of the crude product; (B) in such a way that at least part of the inorganic salt catalyst is a pseudo-liquid or liquid under such conditions of contact; (ί) such that the crude product has an SCF, at most 90% of the ACQ for the crude raw material; (]) such that the crude product has a total content of содержание / ν / Re at most 90%, at most 50% or at most 10% of the content of Νί / ν / Re for the raw material; (j) such that the crude product has a sulfur content of at most 90%, at most 60% or at most 30% of the sulfur content of the crude raw material; (1) such that the crude product has a nitrogen content of at most 90%, at most 70%, at most 50%, or at most 10% of the nitrogen content of the raw material; (t) such that the crude product has a residue content of at most 30%, at most 10% or at most 5% of the residue content for the crude material; (p) in such a way that ammonia is produced along with the crude product; (o) such that the crude product contains methanol, and the method further includes recovering methanol from the crude product; combining the recovered methanol with an additional amount of crude feed to form an additional mixture of crude feed with methanol; and heating the additional mixture of the crude raw material with methanol so that the TAN of the additional crude raw material is reduced below 1; (p) such that one or more characteristics of the crude product changes by at most 90% relative to the corresponding one or several characteristics of the crude raw material; (c) in such a way that the amount of catalyst in the contact zone varies from 1 to 60 g of total catalyst per 100 g of raw material; and / or (d) such that a source of hydrogen is added to the crude feed prior to or during contacting.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, contacting conditions which include: (a) mixing the inorganic salt catalyst with the crude raw material at a temperature below 500 ° C, and the inorganic salt catalyst is practically does not dissolve in raw material; (B) mixing the inorganic catalyst in the crude feed; and / or (c) contacting the crude raw material with an inorganic salt catalyst in the presence of water and / or steam in order to obtain a total product, which includes the crude product, which is a liquid mixture under NTD.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a method that includes contacting a crude raw material with an inorganic salt catalyst and which furthermore includes: (a) providing water vapor in contact area before or during contacting; (B) the formation of the emulsion of the crude raw material with water before contacting the crude raw material with an inorganic salt catalyst and a source of hydrogen; (c) spraying the raw material in the contact zone; and / or (s) contacting water vapor with an inorganic salt catalyst to at least partially remove coke from the surface of the inorganic salt catalyst.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a method that comprises contacting a crude raw material with an inorganic salt catalyst in order to obtain a total product, in which at least a part of the total product is obtained as vapor, and the method also includes the condensation of at least part of the vapor at 25 ° C and 0.101 MPa, with the formation of the crude product, while the contact conditions of the regulator Coziness in such a way that: (a) the crude product additionally contains components with a selected boiling range distribution; and / or (B) the crude product contains components having a given density in degrees.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a method that includes contacting a crude feed with one or more catalysts, one or more catalysts being non-acidic.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a K ₃ Pe1 ₀ 81 ₄ catalyst or a transition metal sulfide catalyst that: (a) has a total of at least 0.4 g, at least 0.6 g or at least 0.8 g, of at least one transition metal sulphide per 1 g of K ₃ P ₁₀ § ₁₄ catalyst or of a transition metal sulphide catalyst; (B) has the atomic ratio of transition metal to sulfur in the K ₃ Fe1 ₀ 81 ₄ catalyst or the catalyst — a transition metal sulfide, in the range from 0.2 to 20; (c) additionally contains one or more alkali metals, one or more

- 10 009091 compounds of one or more alkali metals, or mixtures thereof; (ά) additionally contains one or more alkaline-earth metals, one or more compounds of one or several alkaline-earth metals, or a mixture thereof; (e) 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 catalyst is ₁₀ 8 ₁₄ or the transition metal sulfide catalyst is in the range from 0.5 to 2.5 and the atomic ratio of alkali metal to transition metal is in the range from above 0 to 1; (ί) additionally contains one or more alkaline-earth metals, one or several compounds of one or several alkaline-earth metals, or mixtures thereof, the atomic ratio of transition metal to sulfur in the catalyst K ₃ Its ₁₀ 8 ₁₄ or the catalyst - transition metal sulfide, in the range from 0.5 to 2.5; and the atomic ratio of alkaline earth metal to transition metal is in the range from above 0 to 1; (e) additionally contains zinc; (11) additionally contains KEE ₂ 8 ₃ ; (ί) additionally contains KEE8 ₂ ; and / or ()) is non-acidic.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a catalyst K ₃ E ₁₀ 8 ₁₄ , which is formed by 1H 8I.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to 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 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 Her8; (ά) comprise Ee8 _2; (e) contain a mixture of iron sulfides, where iron sulfides are represented by the formula E ( _1-b ) 8, where b is in the range from above 0 to 0.17; (ί) additionally contain K ₃ E ₁₀ 8 ₁₄ after contact with the raw material; (e) at least one transition metal in one or more transition metal sulfides is iron; and / or (1) precipitated on a carrier, and the catalyst — a transition metal sulphide has at most 0.25 g of total carrier per 100 g of catalyst.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a method of forming a catalytic composition of transition metal sulfides, this method involves mixing a transition metal oxide and a metal salt to form a mixture of transition metal oxide with a metal salt; reacting a mixture of a transition metal oxide and a metal salt with hydrogen to form an intermediate; and reacting the intermediate with sulfur in the presence of one or more hydrocarbons to form a catalyst — a transition metal sulfide: (a) the metal salt contains an alkali metal carbonate; (B) which additionally comprises dispersing the intermediate in one or more liquid hydrocarbons when it reacts with sulfur; (c) in which one or more hydrocarbons have a boiling point of at least 100 ° C; (ά) in which one or more of the hydrocarbons is VGO, xylene, or mixtures thereof; (e) in which the mixing of the transition metal oxide and the metal salt comprises 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 of 300 to 600 ° C; (ί) the interaction of the intermediate with sulfur consists in heating the intermediate in the presence of at least one hydrocarbon to a temperature in the range from 240 to 350 ° C; and / or (e) which additionally comprises contacting the catalytic composition with a crude feed that contains sulfur and a source of hydrogen.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, an inorganic salt catalyst that includes: (a) one or more alkali metal carbonates, one or more alkaline earth metal carbonates, or mixtures; (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; (ά) one or more sulphides of one or more alkali metals, one or more sulphides 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; (ί) 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 mixtures thereof; (e) one or more inorganic metal salts, and in which at least one of the inorganic metal salts forms a hydride during the use of the catalyst; (1) sodium, potassium, rubidium, cesium, or mixtures thereof; (ί) calcium and / or magnesium; O) a mixture of sodium salt and potassium salt, and the potassium salt contains potassium carbonate, potassium hydroxide, potassium hydride, or

- 11 009091 mixture, and the sodium salt contains sodium carbonate, sodium hydroxide, sodium hydride, or mixtures thereof; and / or (k) mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, an inorganic salt catalyst that includes alkali metals in which: (a) an atomic ratio of an alkali metal having an atomic number of at least 11, an alkali metal having an atomic number greater than 11 is in the range of 0.1 to 4; (B) at least two alkali metals are sodium and potassium, and the atomic ratio of sodium to potassium is in the range 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; (ά) 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 of the atomic ratios 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 methods or compositions according to the invention, an inorganic salt catalyst that includes a carrier material and: (a) the carrier material contains zirconium oxide, calcium oxide, magnesium oxide, titanium oxide, hydrotalcite , alumina, germanium oxide, iron oxide, nickel oxide, zinc oxide, cadmium oxide, antimony oxide, or mixtures thereof; and / or (b) one or more of the metals from Groups 6–10 of the Periodic Table, one or more compounds of one or more metals from the Groups 6–10 of the Periodic Table; one or more alkali metal carbonates, one or more alkali metal hydroxides, one or more alkali metal hydrides, one or more alkaline earth metal carbonates, one or more alkaline earth metal hydroxides, one or more alkaline earth metal hydrides, and / or mixtures thereof.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a method that includes contacting a crude raw material with an inorganic salt catalyst, in which: (a) the catalytic activity of the inorganic salt catalyst is practically unchanged in the presence 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 methods or compositions according to the invention, an inorganic salt catalyst for which there is: (a) the inflection point during gas evolution is in the VAP temperature range, 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, as determined by the method of differential scanning calorimetry (DSC), at a heating rate of 10 ° C per minute: (s ) DSC temperature lies in the range between 200 and 500 ° C, or 250-450 ° C; (ά) 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, ionic conductivity at 300 ° C is less than ionic conductivity of the inorganic salt catalyst before conditioning.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, an inorganic salt catalyst for which the inflection point in the evolution of gas lies in the temperature range, which is determined by the VAP method, and in addition, the contact conditions are chosen as such the way that the contact temperature lies: (a) above Τι, where Τι lies 30, 20 ° C or 10 ° C below the VAP 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 methods or compositions according to 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 neor anichesky salt catalyst has an inflection point when evolution of gas; (B) is a mixture of the liquid phase and the solid phase at a temperature in the range from 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 methods or compositions according to the invention, an inorganic salt catalyst that when tested in the form of particles that can pass through a 1000 micron filter, is spontaneously deformed by gravity and / or under pressure of at least measure 0.007 MPa when heated to a temperature of at least 300 ° C, such that the inorganic salt kata

- 12 009091 the lyser goes from the first form to the second form, and the second form is unable to go into the first form when the inorganic salt catalyst is cooled to 20 ° C.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, an inorganic salt catalyst that contains per 1 g of inorganic salt catalyst: (a) at most 0.01 g of lithium, or lithium compounds, based on lithium mass; (B) at most 0.001 g of halide, based on the weight of the halogen; and / or (c) at most 0.001 g of glassy oxide compounds.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a total product that contains at least 0.8 g of a crude product per gram of total product.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a crude product that: (a) contains at most 0.003 g, at most 0.02 g, at most 0.01 g, at more than 0.05 g, extremely 0.001 g, from 0.000001-0.1 g, 0.00001-0.05 g or 0.0001-0.03 g of residue per 1 g of the crude product; (B) contains from 0 to 0.05 g, 0.00001-0.03 g or 0.0001-0.01 g coke per 1 g of the crude product; (c) has an olefin content of at least 10% higher than the olefin content of the crude feed; (b) has more than 0 g, but less than 0.01 g of total inorganic salt catalyst per gram of crude product, as determined by material balance; (e) has at least 0.1 g, from 0.00001 to 0.99 g, from 0.04 to 0.9 g, from 0.6 to 0.8 g of VGO, per 1 g of the crude product; (1) contains VGO and VGO contains at least 0.3 g of aromatic hydrocarbons per 1 g of VGO; (e) has 0.001 g or from 0.1 to 0.5 g of distillate; (d) the atomic ratio H / C is at most 1.4; (1) has an H / C atomic ratio of 90-110% of the H / C ratio for the crude feed; (]) has a content of monocyclic aromatic hydrocarbons at least 10% more than the content of monocyclic aromatic hydrocarbons for crude raw materials; (k) has monocyclic aromatic hydrocarbons that contain xylenes, ethylbenzene or ethylbenzene compounds; (1) contains per 1 g of the crude product at most 0.1 g of benzene, from 0.05 to 0.15 g of toluene, from 0.3 to 0.9 g of metaxylene, from 0.5 to 0.15 g of orthoxylene and from 0.2 to 0.6 g of para-xylene; (t) contains at least 0.0001 g or from 0.01 to 0.5 g of diesel fuel; (p) contains diesel fuel, and this diesel fuel has at least 0.3 g of aromatic hydrocarbons per 1 g of diesel fuel; (o) has at least 0.001 g, from above 0 to 0.7 g, or from 0.001 to 0.5 g of kerosene; (p) contains kerosene and kerosene has at least 0.2 g or at least 0.5 g of aromatic hydrocarbons per g of kerosene, and / or a freezing point at a temperature of at most -30 ° C, at most -40 ° C, or at most -50 ° C; (c |) has at least 0.001 g or at least 0.5 g of naphtha; (g) contains naphtha, which has at most 0.01 g, at most 0.05 g, or at most 0.002 g, of benzene per g of naphtha, an octane number of at least 70, at least 80, or at least 90, and / or isoparaffins and normal paraffins, with a weight ratio of isoparaffins to normal paraffins in naphtha at most 1.4; and / or (§) has a volume that is at least 10% larger than the volume of the raw material.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a method that includes contacting a crude raw material with a catalyst to obtain a total product containing the crude product, which further includes: (a) combining the crude product with a feed that is similar to or different from the crude feed to form a mixture suitable for transport; (B) combining the crude product with a feed that is similar or different from the crude to form a mixture suitable for processing equipment; (c) fractionation of the crude product; (b) the fractionation of the crude product, obtaining one or more distillate fractions, and obtaining transported fuel from at least one of the distillate fractions; and / or (e) when the catalyst is a transition metal sulphide, the processing of the catalyst is transition metal sulphides to extract metals from the catalyst - transition metal sulphides.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to the invention, a crude product that contains per gram of crude product: (a) at least 0.001 g of VGO, and VGO has at least 0.3 g of aromatic hydrocarbons per 1 g of VGO; (B) at least 0.001 g of diesel fuel, with diesel fuel having at least 0.3 g of aromatic hydrocarbons per g of diesel fuel; (c) at least 0.001 g of naphtha and this naphtha has at most 0.5 g of benzene per 1 g of naphtha, an octane number of at least 70 and / or isoparaffins and n-paraffins with a weight ratio of isoparaffins to n-paraffins for the most part least 1,4; (b) a total of at least 0.001 g of a mixture of components that have a boiling range distribution of at most 204 ° C (400 ° P), and this mixture has at most 0.15 g of olefins per 1 g of mixture; (e) the weight ratio of atomic hydrogen to atomic carbon in the composition is at most 1.75, or at most 1.8; (1) at least 0.001 g of kerosene, and this kerosene has at least 0.5 g of aromatic hydrocarbons per 1 g of kero

- 13 009091 sina, and / or has a freezing point at a temperature of at most -30 ° C; (e) from 0.09 to 0.13 g of atomic hydrogen per 1 g of the composition; (11) non-condensable hydrocarbon gases and naphtha, which, when combined, contain at most 0.15 g of olefins per 1 g of combined non-condensable hydrocarbon gases and naphtha; (ί) non-condensable hydrocarbon gases and naphtha, which, when combined, contain isoparaffins and n-paraffins with a weight ratio of isoparaffins to nparaffins in combined naphtha and non-condensable hydrocarbon gases at most 1.4; (ί) hydrocarbons with up to three carbon atoms, containing olefins and paraffins with carbon atoms 2 (C ₂ ) and 3 (C ₃ ), and the weight ratio of the combined C ₂ and C ₃ olefins to the combined C ₂ and C ₃ paraffins is at most 0.3; olefins and paraffins with the number of carbon atoms 2 (C ₂ ), in which the weight ratio of C2 olefins to C2 paraffins is at most 0.2; and / or olefins and paraffins with the number of carbon atoms 3 (C3), and the weight ratio of C3 olefins to C3 paraffins is at most 0.3; (k) has a butadiene content of at least 0.005 g; (1) has a density in degrees in the range of 15 to 30 at 15.5 ° C; (t) contains at most 0.00001 g of amount Νί / ν / Her per gram of composition; (p) the paraffin content of hydrocarbons having a boiling range distribution of at most 204 ° C is in the range of 0.7 to 0.98 g; (o) hydrocarbons with a boiling range distribution of at most 204 ° C, which contain per g of olefinic hydrocarbons having a boiling range distribution of at most 204 ° C, from 0.001 to 0.5 g of olefins; (p) hydrocarbons with a boiling range distribution of at most 204 ° C, which contain olefins, and these olefins have at least 0.001 g of terminal olefins per 1 g of olefins; (c |) hydrocarbons with a boiling range distribution of at most 204 ° C, which contain olefins, and these olefins have a molar ratio of terminal olefins to internal olefins of at least 0.4; and / or (g) from 0.001 to 0.5 g of olefins per 1 g of hydrocarbons in the distribution of boiling range between 20 and 204 ° C.

In some embodiments, the invention also provides, in combination with one or more methods or compositions according to 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 metals is a 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.

In additional embodiments, features of one particular embodiment of the invention may be combined with features of another embodiment of the invention. For example, features of one embodiment may be combined with features of any other embodiment.

In further embodiments, crude products may be obtained using any of the methods and systems described in this invention.

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

Brief Description of the Drawings

The advantages of the present invention will become apparent to those skilled in the art with 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 source of hydrogen in the presence of one or more catalysts to obtain a total product;

FIG. 2 is a diagram of another embodiment of a system for contacting a crude feed with a source of hydrogen 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 the mixing zone in combination with a contacting system;

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

FIG. 6 is a schematic of an embodiment of composite contacting systems; FIG. 7 is a schematic embodiment of an ion conductivity measurement system;

in fig. 8 shows a table of the characteristics of the crude raw materials and the characteristics of the crude products obtained for various options for contacting the crude raw materials with the catalyst — transition metal sulphides;

in fig. 9 shows a table of the composition of the crude feedstock and the composition of non-condensable hydrocarbons obtained for various options for contacting the crude feedstock with a catalyst with transition metal sulphides;

- 14 009091 in FIG. 10 shows a table of characteristics and composition of crude products obtained for various options for contacting the crude raw material with a catalyst — transition metal sulphides;

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

in fig. 12 shows the graphical dependence of the resistance (decimal logarithm) of inorganic salt catalysts and inorganic salt relative to the resistance of potassium carbonate to temperature;

in fig. 13 shows the graphical dependence of the resistance (decimal logarithm) of the catalyst Ia ₂ CO ₃ / K ₂ CO ₃ / Kb ₂ CO ₃ relative to the resistance of potassium carbonate to temperature;

in fig. 14 graphically presents the weight percentages of the coke, liquid hydrocarbons and gas obtained for various hydrogen sources, for embodiments in contacting the crude raw material with an inorganic salt catalyst;

in fig. 15 graphically shows the dependence of the weight percent of the crude products obtained on the number of carbon atoms for different variants of contacting the crude raw material with an inorganic salt catalyst;

in fig. 16 shows a table of components obtained for various options for contacting the raw material 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 means of examples, in the drawings, and will be described in detail in the invention. Drawings may not be to scale. It should be understood that the drawings and, furthermore, the detailed description are not intended to limit this invention to the specific forms described, but rather that this invention will protect all modifications, equivalents and alternatives that relate to the intent and scope of the present invention.

Detailed Description of the Invention

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

The term alkali metal (metals) 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 their mixtures.

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 their mixtures.

The term AEM refers to atomic mass units.

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 feedstock, crude product, naphtha, kerosene, diesel fuel, and VGO is determined using the A8TM method Ό5291.

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

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

The boiling range distribution for the crude feedstock and / or the total product is determined using A8TM method No. 5307, unless otherwise mentioned. The content of hydrocarbon components, for example, paraffins, isoparaffins, olefins, naphthenes and aromatic hydrocarbons in naphtha is determined by the A8TM method Ό6730. The content of aromatic hydrocarbons in diesel fuel and VGO is determined by the method of 1Р 368/90. The content of aromatic hydrocarbons in kerosene is determined according to A8TM method Ό5186.

The term Acid-Botegu acid refers to a molecular object that can transfer a proton to another molecular object.

The base of the Bridger-Botegu refers to a molecular object that is able to receive protons from another molecular object. Examples of GdbpCheb-Lotegu bases include hydroxide (OH ^- ), water (H2O), carboxylate (BCO2 ^- ), halide (Br ^- , C1 ^- , P ^- , I ^- ), bisulfate (H8O4 ^- ), and sulfate (8О4 ^{2 -} ).

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

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

- 00 009091

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

Diesel fuel refers to hydrocarbons with a boiling range distribution between 260 and 343 ° C (500-650 ° E) at 0.101 MPa. The content of diesel fuel is determined by the method A8TM Ό 2887.

The term distillate refers to hydrocarbons with a boiling range distribution between 204 and 343 ° C (400-650 ° E) at 0.101 MPa. The distillate content is determined by the method A8TM 88 2887. Distillate may include kerosene and diesel.

The term DSC refers to differential scanning calorimetry.

The freezing point refers to the temperature at which crystalline particles form in a liquid. The freezing point is determined by the A8TM method Ό 2386.

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

The term “rigid base” refers to the anions described by Pearson in article 1 of 1 about £ Lesnspar Silentus1 Sosteel, 1963, 85, p. 3533.

The ratio H / C refers to the weight ratio of atomic hydrogen to atomic carbon. The ratio H / C is determined using the measured values of the weight percentage of hydrogen and the weight percentage of carbon according to L8TM Ό 5291.

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 L8TM 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 interact in the presence of a crude feed and a catalyst, providing hydrogen for one or more compounds in the crude feed. The hydrogen source may include, but is not limited to, hydrocarbons (for example, C ₁ -C ₆ hydrocarbons, such as methane, ethane, propane, butane, pentane, naphtha), water, or mixtures thereof. The material balance is reduced in order to estimate the total amount of hydrogen provided for one or several compounds in the raw material.

Inorganic salt refers to a compound that consists of a metal cation and an anion.

The term ΙΡ refers to the Institute of Petroleum, currently Epetdu 1 on 81 £ 22b, Ipbeb Kshdbot.

The term isoparaffins refers to branched-chain saturated hydrocarbons.

Kerosene refers to hydrocarbons with a boiling range distribution between 204 and 260 ° C (400-500 ° E) at 0.101 MPa. The content of kerosene is determined by the method L8TM Ό2887.

The term Lewis acid refers to a compound or material capable of receiving 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.

Light hydrocarbons refers to hydrocarbons having a carbon number in the range from 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 that are liquid under NTD, with one or more compounds that are solid under NTD.

The carbon residue (OMU) 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.

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

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

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

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

The term non-acid refers to the characteristics of the Lewis base and / or the base of the Violent Note.

Non-condensable gas refers to components and / or a mixture 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 octane number refers to the calculated numerical representation of the anti-knock characteristics of motor fuels compared to standard reference fuels. The estimated octane number of naphtha is determined by the A8TM method Ό6730.

- 16 009091

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 1p! Yagpa!

Polyaromatic compounds refer to compounds that include two or more aromatic rings. Examples of polyaromatics include, but are not limited to, indene, naphthalene, anthracene, phenanthrene, benzothiophene, and dibenzothiophene.

The balance relates to components that have a boiling range distribution above 538 ° С (1000 ° Р) at 0.101 MPa, which is determined by the ABTM method Ό5307.

Pseudo-liquid refers to the 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 slurry and / or phase that has a consistency, for example, toffee, dough or toothpaste.

The term SKFB refers to standard cubic feet of gas per barrel of raw material.

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

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

The term VAP refers to the interim 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 ABTM Ό2887.

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

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

Usually, the stabilized feedstock is not subjected to distillation and / or fractional distillation in a processing plant in order to obtain composite components with a specific distribution of boiling ranges (for example, naphtha, distillates, VGO and / or lubricating oils). Distillation includes (but is not limited to) atmospheric distillation methods and / or vacuum distillation methods. Non-distilled and / or unfractionated stabilized raw materials may include components that have a carbon number above 4, in an amount of at least 0.5 g of components per 1 g of raw material. Examples of stabilized raw materials include whole raw materials, stripped raw materials, desalted raw materials, desalted raw materials, or combinations thereof. The term “stripped” refers to raw materials that are processed in such a way that at least part of the components that have a boiling point below 35 ° C at 0.101 MPa are removed. Usually stripped raw materials have a content of such components of at most 0.1 g, at most 0.05 g, or at most 0.02 g per 1 g of stripped raw material.

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

The characteristics of a disadvantageous raw material may include, but are not limited to: a) TAN at least 0.5; B) a viscosity of at least 0.2 Pa-s; c) density of AP1 is at most 19 °; b) the total content of Νί / ν / Re is at least 0.00005 g or at least 0.0001 g / ν / Re per g of raw material; e) the total content of heteroatoms of at least 0.005 g of heteroatoms per 1 g of raw material; ί) residue content of at least 0.01 g residue per 1 g of raw material; e) the content of asphaltenes is at least 0.04 g of asphaltenes per 1 g of raw material; B) the content of WMD at least 0.02 g of WMD per 1 g of raw material; or ί) combinations thereof. In some embodiments, the disadvantageous raw materials may include at least 0.2 g of residue, at least 0.3 g of residue, at least 0.5 g per 1 g of unfavorable raw material

- 17 009091 residue or at least 0.9 g residue. In certain embodiments, the disadvantageous raw material has 0.2-0.99 g, 0.3-0.9 g, or 0.4-0.7 g of residue per gram of unprofitable raw material. In certain embodiments, the disadvantageous feedstock 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 gram of unprofitable raw material.

Disadvantaged raw materials may include a mixture of hydrocarbons having a boiling range. A disadvantageous raw material may include per 1 g of unfavorable raw material at least 0.001 g, at least 0.005 g, or at least 0.01 g of hydrocarbons with a boiling range distribution between 200 and 300 ° C at 0.101 MPa; at least 0.001 g, at least 0.005 g, or at least 0.01 g of hydrocarbons with 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 0.01 g of hydrocarbons with a boiling range distribution between 400 and 700 ° C at 0.101 MPa, or a combination thereof.

In some embodiments, the disadvantageous feedstock may also include per gram of disadvantageous feedstock at least 0.001 g, at least 0.005 g, or at least 0.01 g of hydrocarbons with a boiling range distribution of at least 200 ° C at 0.101 MPa , in addition to components with a high boiling point. Usually disadvantageous raw materials have a content of such hydrocarbons at most 0.2 g or at most 0.1 g per 1 g of unprofitable raw materials.

In certain embodiments, the disadvantageous feedstock may include per g of unprofitable feeds up to 0.9 g or 0.99 g of hydrocarbons with a boiling range distribution of at least 300 ° C. In certain embodiments, the disadvantageous feedstock may also include per gram of disadvantageous feedstock at least 0.001 g of hydrocarbons with a boiling range distribution of at least 650 ° C. In certain embodiments, the disadvantageous feedstock may include per g of unprofitable feeds up to 0.9 g or up to 0.99 g of hydrocarbons with a boiling range distribution 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: L1bsgia Province (Canada), Opposo Province (Venezuela), Southern California and northern slope of Alaska (USA), Gulf of Mexico SatrssNs. Basin 8g Ocean (Argentina), Basin 8 and Satroz Basins (Brazil), Voia Bay (China), Kagatau (China), Ζαβκυκ (Iraq), Caspian Sea (Kazakhstan), marine fisheries in Nigeria, in the North Sea (United Kingdom), north West-Madagascar, Oman and Monument (Netherlands).

Processing unfavorable raw materials can improve the characteristics of unfavorable raw materials in such a way that the raw materials become acceptable for transport and / or processing. Raw materials and / or unfavorable raw materials that must be processed can be called as crude raw materials. This crude raw material may be stripped as described in the invention. The crude product obtained by processing the crude raw materials using the methods described in the invention is suitable for transport and / or processing. The characteristics of the crude product resemble the characteristics of East Texas intermediate raw materials more than the crude raw materials, or closer to the corresponding characteristics of the Vgep !, brand raw materials, and therefore the product has an increased economic value compared to the economic value of the crude raw materials. Such a crude product can be recycled with less or no pretreatment, thereby increasing the efficiency of refining. Pretreatment may include desulfurization, demetallization and / or atmospheric distillation in order to remove impurities from the crude product.

Methods for contacting the crude raw materials according to the invention are described in the invention. Additionally described variants of the embodiment for obtaining products with different concentrations of naphtha, kerosene, diesel fuel and / or VGO, which are usually not obtained in the processes of the traditional type.

The crude feed may be brought into contact with a source of hydrogen in the presence of one or more catalysts in the contact zone and / or in combinations of two or more contact zones. In some embodiments, a source of hydrogen is formed зη zyi. The production of a source of hydrogen ίη зйи may include the interaction of at least part of the crude raw material with an inorganic salt catalyst at a temperature in the range from 200-500 ° C or 300400 ° C, with the formation of hydrogen and / or light hydrocarbons. Hydrogen production may include the interaction of at least part of the inorganic salt catalyst, which includes, for example, an 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 under NTD and, in some embodiments, hydrocarbons that do not condense under NTD. 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 may be entrained in liquid and / or vapor formed during contacting.

- 18 009091

The contact zone typically includes a reactor, a portion of a reactor, reactor components, or composite reactors. Examples of reactors that can be used to contact raw materials with a source of hydrogen in the presence of a catalyst include a multi-layered reactor, a fixed-bed reactor, a continuous stirring reactor (RHP), a spray reactor, a piston flow reactor, and a liquid-type contact apparatus. /liquid. Examples of LDPs include a fluidized bed reactor and a fluidized bed reactor.

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

The temperature of contact may vary in the range of 200-800 ° C, 300-700 ° C or 400-600 ° C. In embodiments in which the source of hydrogen is supplied as a gas (for example, gaseous hydrogen, methane or ethane), the ratio of gas to crude raw material can usually vary from 1 to 16100 Nm ³ / m ³ , 2-8000 Nm ³ / m ³ , 3-4,000 Nm ³ / m ³ , or 5-300 Nm ³ / m ³ . The contacting is usually carried out in the pressure range between 0.1 and 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 raw materials is in the range of 0.01 to 3 kg, 0.03-2.5 kg, or 0.1-1 kg of steam per 1 kg of crude raw materials. The flow rate of the raw material may be sufficient to maintain the volume of the raw material 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 the raw material in the contact zone is 40, 60 or 80% of the total volume of the contact zone. In some embodiments, the contacting may be carried out in the presence of additional gas, for example, argon, nitrogen, methane, ethane, propane, butane, propylene, butylenes, or combinations thereof.

FIG. 1 is a schematic embodiment of a contact system 100 used to produce a total product in the form of vapor. Untreated raw material leaves the feed unit of raw raw material 101 and enters the contact zone 102 via pipeline 104. The amount of catalyst used in the contact zone can vary from 1 to 100 g, 2-80 g, 3-70 g or 4-60 g per 100 g of raw materials 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 contact zone 102 via conduit 104. In certain embodiments, the crude feed may be heated to at least 100 ° C or at least 300 ° C before and / or during the introduction of the crude feed in the contact zone 102. Usually the crude raw material can be heated to a temperature in the range from 100 to 500 ° C or 200-400 ° C.

In some embodiments, the catalyst is combined with the crude raw material and pumped to the contact zone 102. The mixture of the crude raw material with the catalyst may be heated to a temperature of at least 100 ° C or at least 300 ° C before being introduced into the contact zone 102. Usually the crude raw material may be heated to a temperature in the range of 200 to 500 ° C or 300-400 ° C. In some embodiments, the mixture of crude feedstock with catalyst is a slurry. In certain embodiments, the TAN of the crude raw material may be reduced before the crude raw material is introduced into the contact zone. For example, when a mixture of crude raw materials with a catalyst is heated at a temperature in the range of 100 to 400 ° C or 200300 ° C, alkali metal salts with acidic components in the crude raw material may form. Due to the formation of these alkali salts, it is possible to remove some acidic components from the crude feed and reduce the SCF of the crude feed.

In some embodiments, the crude feed is continuously added to the contact zone 102. Mixing in the contact zone 102 may be sufficient to prevent the release of the catalyst from the mixture of the crude feed to the catalyst. In certain embodiments, at least a portion of the catalyst may be removed from the contact 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 the mixture of crude feed with an inorganic salt catalyst is introduced into the contact area as an emulsion. This emulsion can be prepared by combining a mixture of inorganic salt catalyst and water with a mixture of crude raw material 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. Usually 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; MePAcChueo ZreeiAnHrgoia Cogeir; Syagjekiop, 8oiyy Sagoypa, I.8.L.), C ₂₁ dicarboxylic fatty acids (OAHPA4). Pgobia Skoir), petroleum sulphonates (Neuarig 8L8 30; Syapep

- 19 009091

SogroGabon. S11ag1o11e. Νοιίΐι Sagoypa, i.8.A.), Surface-active agent Tegdya1-40 (Ishop SagYbe; OpiBigu, Soppesynk I.8.A.), or their mixtures. Stabilizers include (but are not limited to) diethyleneamine (A1bps11 Sytka1 So .; Myahiko, Uysopyp, i.8.A.) and / or monoethanolamine (1. T. Wakeg; LISHA, No. \ ν 1ggee, I.8.A.).

A pipeline for recycling 106 may connect the pipeline 108 and the pipeline 104. In some embodiments, the pipeline for recycling 106 may directly enter the contact zone 102 and / or leave it. The recirculation pipeline 106 may include a flow control valve 110. This control valve 110 may recirculate at least part of the material from the pipeline 108 to the pipeline 104 and / or contact area 102. In some embodiments, the condensation unit may be located in the pipeline 108 , providing condensation of at least part of the material and its recirculation to the contact zone 102. In certain embodiments, the pipeline for recycling 106 may be a line w recirculation gas. Flow control valves 110 and 110 'can be used to regulate flow to and from the zone of contact 102 in such a way as to maintain a constant volume of fluid in the zone of contact. In some embodiments, in the contact zone 102, it is possible to maintain the volume of the liquid in substantially the predetermined range. The volume of raw materials in the contact zone 102 can be monitored using standard instruments. The inlet for gas 112 may be used to provide the addition of a source of hydrogen and / or additional gases to the raw feed when the crude feed enters the contact zone 102. In some embodiments, the steam inlet 114 may be used to add water vapor to the zone contacting 102. In certain embodiments, a stream of water is introduced into the contacting area 102 through the steam inlet channel 114.

In some embodiments, at least a portion of the total product is obtained in the form of steam from the contact 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 exiting from the top of the contact zone 102. Steam enters to the separation zone 116 via conduit 108. The ratio of the hydrogen source to the crude feed in the contact zone 102, and / or the pressure in the contact zone, may vary in order to regulate the amount steam and / or liquid phase formed at the top of the contact zone 102. In some embodiments, the steam formed at the top of the contact 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 the crude product per 1 g of the crude raw material. In certain embodiments, the steam formed at the top of the contact zone 102 comprises from 0.8 to 0.99 g or 0.9-0.98 g of the crude product per 1 g of the raw material.

Spent catalyst and / or solids may remain in the contact zone 102 as byproducts of the contact process. Solids and / or spent catalyst may include residual crude feeds and / or coke.

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

FIG. 2 depicts a contacting system 122 for processing crude raw materials 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 contact zone 102 via conduit 104. In some embodiments, the crude feed comes from the raw feed source. Pipeline 104 may include an inlet for gas 112. In some embodiments, the inlet for gas 112 may directly enter the contact zone 102. In certain embodiments, the steam inlet 114 may be used to add steam to the contact zone 102. Raw materials can be brought into contact with the catalyst in the contact zone 102 to obtain a 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 raw feed leaves the contact zone 102 and enters the separation zone 124 through pipeline

- 0109091 water 108. In some embodiments, the condensation unit may be located, for example, in the pipeline 106, providing condensation of at least part of the mixture in the pipeline and its recirculation to the contact zone 102 for further processing. In certain embodiments, the pipeline for recycling 106 may be a line for gas recycling. In some embodiments, conduit 108 may include a filter to remove particles from the total product.

In the separation zone 124, at least a portion of the crude product may be separated from the total product and / or catalyst. In embodiments in which the total product contains solids, these solids can be separated from the total product using standard isolation techniques (eg, 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 contact zone 102 via conduit 126. For example, the recycled portion may be combined with the raw material and introduced into contacting 102 for further processing. The crude product may exit separation zone 124 via conduit 128. In certain embodiments, 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 separated using standard gas / liquid separation techniques, such as sparging, membrane separation, and pressure reduction. In some embodiments, the released gas is sent to other process plants (for example, for use in a fuel cell, in a sulfur recovery unit, 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 carried out 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 via conduit 104. In separation zone 132, at least a portion of the crude feed is separated using standard separation techniques to obtain the separated crude feed and hydrocarbons. In some embodiments, the isolated 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 isolated crude feed includes a mixture of components with a boiling range distribution between 100 and 1000 ° C, 120-900 ° C or 200-800 ° C. Hydrocarbons separated from raw materials leave separation zone 132 via pipeline 134 and can be transported to other process plants, storage equipment, or combinations thereof.

At least a portion of the recovered raw material leaves the separation zone 132 and enters the contacting system 130 via line 136 for further processing to form a crude product, which leaves the contacting system 130 via line 138.

In some embodiments, the crude product obtained from the crude raw material by any method described in the invention is mixed with a raw material that is the same or different from the crude raw material. For example, a crude product may 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 transport and / or processing.

FIG. 4 is a schematic version of the combination of the mixing zone 140 and the contacting system 130. In certain embodiments, at least a portion of the crude product leaves the contact system 130 via conduit 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 feedstock or naphtha), feedstock, crude feedstock, or and their mixtures to get a mixed product. Process streams, unpurified raw materials, raw materials or their mixtures are injected directly into the mixing zone 140 or to a point above the mixing zone through a pipeline 142. The mixing system may be located inside or near the mixing zone 140. The mixed product may meet the specifications for a particular product. The technical conditions of a particular product include (but are not limited to) the range or density limit in degrees AP1, TAN, viscosity, or combinations thereof. The mixed product leaves the mixing zone 140 through conduit 144 and will be transported and / or processed.

- 21 009091

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

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

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

In an alternative embodiment, the hydrogen thus produced may be isolated and / or processed and then pumped to the contacting system 148 via conduit 150. In certain embodiments, the contacting system 148 may be part of the contacting system 100 so that the hydrogen produced is directly supplied from the contacting system 100 to the contacting system 148. In some embodiments, the steam flow obtained from the contacting system 100 is directly mixed with the uncleaned th raw material entering the contact system 148.

The second stream of crude raw material enters the contacting system 148 via conduit 152. In the contacting system 148, by contacting the crude raw material with at least part of the hydrogen produced and the catalyst, a product is obtained. In some embodiments, this product is a total product. The product leaves the contacting system 148 through conduit 154.

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

In some embodiments, the crude product and / or the mixed product are transported to a refinery and / or processing unit. The crude product and / or mixed product can be recycled to produce industrial products, such as transportation fuels, boiler fuels, lubricants or chemicals. The processing may include distillation and / or fractional distillation of the crude product and / or the mixed product to obtain one or more distillate fractions. In some embodiments, the crude product, the mixed product, and / or one or more distillate fractions may be hydrotreated.

In some embodiments, the total product contains at most 0.05 g, at most 0.03 g, or at most 0.01 g of coke per gram of total product. In certain embodiments, the total product is practically free of coke (i.e., no coke is detected). In some embodiments, the crude product may include at most 0.05 g, at most 0.03 g, at most 0.01 g, at most 0.005 g, or at most 0.003 g of coke per 1 g of unrefined product. In certain embodiments, the crude

- 22 009091 the product has a coke content in the range from above 0 to 0.05, from 0.00001 to 0.03 g, 0.0001-0.01 g, or 0.001-0.005 g per 1 g of the crude product, or coke is not detected .

In certain embodiments, the crude product has a WMD content that is at most 90%, at most 80%, at most 50%, at most 30%, or at most 10% of the content of WMD for the raw material. In some embodiments, the crude product has a low content of WMD. In some embodiments, the crude product contains per 1 g of the crude product, at most 0.05 g, at most 0.03 g, at most 0.01 g, or at most 0.001 g of WMD. Usually the crude product has from 0 to 0.04 g, 0.000001-0.03 g, or 0.00001-0.01 g of WMD per 1 g of the crude product.

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

In certain embodiments, gaseous hydrogen, carbon dioxide, carbon monoxide, or combinations thereof may be formed as a result of contact of water vapor and light hydrocarbons with an inorganic salt catalyst. Typically, under 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 in the range of 0.3 to 1.0, 0.4-0.9, or 0.5-0.8. The possibility of preferable carbon monoxide production relative to carbon dioxide ίη δίΐιι can be advantageous given other processes located in adjacent areas or higher in the processing chain. For example, the carbon monoxide produced may 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, which 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 number of carbon atoms in the range from 1 to 4. The mixture may include from 0.001 to 0.8 g, 0.003-0.1 g, or 0.005-0.01 g of C ₄ hydrocarbons per 1 g such a mixture. C4 hydrocarbons may include from 0.001 to 0.8 g, 0.003 to 0.1 g, or 0.005 to 0.01 g of butadiene per g of C4 hydrocarbons. In some embodiments, the weight ratio of isoparaffins to n-paraffins obtained is at most 1.5, at most 1.4, at most 1.0, at most 0.8, at most 0.3 or at most measure 0.1. In certain embodiments, the weight ratio of the isoparaffins to n-paraffins obtained is in the range of 0.00001 to 1.5, 0.0001-1.0, or 0.001-0.1. Paraffins may include isoparaffins and / or naraffins.

In some embodiments, the total product and / or the crude product may include olefins and / or paraffins in proportions or quantities that are not usually observed for oils extracted and / or distilled in a retort 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 in the crude product is 2, 10, 50, 100 times the olefin content in the crude feed, 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 most 1000 times, at most 500, at most 300, or at most 250 times.

In certain embodiments, hydrocarbons with a boiling range distribution between 20-400 ° C have an olefin content in the range of 0.00001 to 0.1 g, 0.0001-0.05 g or 0.01-0.04 g per 1 g hydrocarbons having a boiling point distribution in the range between 20 and 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 0.0001 to 0.5 g, 0.001-0.2 g, or 0.01-0.1 g alpha olefins per gram of crude product. In certain embodiments, hydrocarbons with a boiling range distribution between 20 and 400 ° C have an alpha-olefin content ranging from 0.0001 to 0.08 g, 0.001-0.05 g or 0.01-0.04 g per 1 g hydrocarbons with a boiling range distribution between 20 and 400 ° C.

In some embodiments, hydrocarbons with a boiling range distribution between 20 and 204 ° C. have a weight ratio of alpha olefins to internal double bond olefins of at least 0.7, at least 0.8, at least 0.9, at least 1.0, at least 1.4, or at least 1.5. In some embodiments, hydrocarbons with a boiling range distribution between 20 and 204 ° C have a weight ratio of alpha olefins to internal olefins in the range of 0.7 to 10, 0.8-5, 0.9-3, or 1- 2 The weight ratio of alpha-olefins to olefins with an internal double bond for raw materials and industrial products is usually about

- 23 009091 more than 0.5. The ability to produce an increased amount of alpha-olefins relative to olefins with internal double bonds can promote the conversion of the crude product to industrial products.

In some embodiments, by contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, hydrocarbons may form with a boiling range distribution 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 most, 0.4, at most 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 from 0.001 to 1.4, 0.01-1.0, or 0.1-0.4.

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 measure 0.30 g per 1 g of hydrocarbons having a boiling range distribution 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, 0.1-0.8 g, or 0.2-0.5 g. In some embodiments, such hydrocarbons have a weight ratio isoparaffins to nparaffins at most 1.5, at most 1.4, at most 1.0, at most 0.8, or at most 0.3. Considering the content of n-paraffins in such hydrocarbons, it can be estimated that the content of n-paraffins in the crude product can be in the range of 0.001 to 0.9 g, 0.01-0.8 g or 0.1-0.5 g on 1 g of the crude product.

In some embodiments, the crude product has a total Νί / ν / Re content of at most 90%, at most 50%, at most 10%, at most 5%, or at most 3% of the content of Νί / ν / Re in raw material. In certain embodiments, the crude product contains, per g of the crude product, at most 0.0001 g, at most 1x10 ^-5 g, or at most 1x10 ^-6 g / ν / Fe. In certain embodiments of the embodiment, the crude product has per 1 g of the crude product, the total content of Νί / ν / Pe ranges from 1x10 ^-7 g to 5x10 ^-5 g, from 3x10 ^-7 g to 2x10 ^-5 g, or from 1x10 ^-6 g to 1x10 ^-5

In some embodiments, the crude product has an TAN of at most 90%, at most 50%, or at most 10% of TAN for the crude. In certain embodiments, the crude product may have an TAN of at most 1, at most 0.5, at most 0.1, or at most 0.05. In some embodiments, the embodiment of the SCCH of the crude product may be in the range of 0.001 to 0.5, 0.01 to 0.2, or 0.05-0.1.

In certain embodiments, the density in degrees AP1 for the crude product is at least 10% higher, at least 50% higher or at least 90% higher than the density of AP1 for the crude raw material. In certain embodiments, the density for the crude product is between 13 and 50, 15-30 or 16-20 ° AP1.

In some embodiments, the crude product has a total heteroatom content of at most 70%, at most 50%, or at most 30% of the total content of heteroatoms for the raw material. 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 raw material.

The crude product may have a sulfur content of at most 90%, at most 70%, or at most 60% of the sulfur content of the raw material. The sulfur content in the crude product per 1 g of the crude product can be at most 0.02 g, at most 0.008 g, at most 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 0.005-0.01 g.

In certain embodiments, the crude product may have a nitrogen content of at most 90% or at most 80% of the nitrogen content of the crude material. The nitrogen content in the crude product per 1 g of the crude product can be at most 0.004 g, at most 0.003 g or at most 0.001 g. In some embodiments, the crude product has a nitrogen content per 1 g of the crude product in the range of 0.0001 up to 0,005 g or 0,001-0,003 g

In some embodiments, the crude product has from 0.05 to 0.2 g or 0.09-0.15 g of hydrogen per 1 g of the crude product. The H / C ratio for the crude product can be at most 1.8, at most 1.7, at most 1.6, at most 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 raw material. 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 ratio H / C for the crude product is within 20% of the ratio

- 24 009091

H / C in the crude feed indicates minimum absorption and / or consumption of hydrogen in the process according to the invention.

The crude product includes components boiling away over a range of temperatures. In some embodiments, the crude product comprises at least 0.001 g or 0.001 to 0.5 g of hydrocarbons with a boiling range distribution of at most 200 ° C or at most 204 ° C at 0.101 MPa; at least 0.001 g or 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 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 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, 0.0001-0.1 g, or 0.001-0.05 g. In certain embodiments, the crude product has from 0.001 to 0.2 g or 0.01-0.05 g naphtha. In some embodiments, naphtha has at most 0.15 g, at most 0.1 g, or at most 0.05 g of olefins per gram of naphtha. In certain embodiments, the crude product has from 0.00001 to 0.15 g, 0.0001-0.1 g, or 0.001-0.05 g of olefins per gram of crude product. In some embodiments, naphtha has a benzene content, per gram of naphtha, at most 0.01 g, at most 0.005 g or at most 0.002 g. In certain embodiments, naphtha has benzene content that is not detectable or in the range from 1x10 ^-7 g to 1x10 ^-2 g, from 1x10 ^-6 g to 1x10 ^-5 g, from 5x10 ^-6 g to 1x10 ^-4 g. Compositions that contain benzene can be considered dangerous in circulation, thus, for unpurified A product that has a relatively low benzene content may not require special handling.

In certain embodiments, naphtha may include aromatics. Aromatic compounds can include monocyclic compounds and / or polycyclic ringed compounds. Monocyclic compounds may include (but are not limited to) benzene, toluene, orthoxylene, metaxylene, para-xylene, ethylbenzene, 1-ethyl-3-methylbenzene; 1-ethyl-2methylbenzene; 1,2,3-trimethylbenzene; 1,3,5-trimethylbenzene; 1-methyl-3-propylbenzene; 1-methyl-2propylbenzene; 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 homologs of benzene, toluene, orthoxylene, metaxylene, paraxylene, or mixtures thereof. Monocyclic aromatic hydrocarbons are used in a variety of industrial products and / or sold as individual components. The crude product, obtained as described in the invention, usually 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 grams, 0.05-0.15 grams or 0.01-0.1 grams. The crude product has a metaxylene content per gram of crude product from 0.001 to 0.1 g, 0.005-0.09 g or 0.05-0.08 g. The crude product has an orthoxylene content per g of the crude product from 0.001 to 0.2 g, 0.0050.1 g or 0.01-0.05 g. The crude product has a para-xylene content per gram of crude product from 0.001 to 0.09 g, 0.005-0.08 g, or 0.001-0.06 g.

Increasing the content of aromatic hydrocarbons in naphtha usually increases the octane number of naphtha. The significance of oils can be estimated based on the gasoline potential of the feedstock. The gasoline potential may include, but is not limited to, the estimated octane number for the naphtha oil fraction. Typically, the calculated octane number for raw materials lies in the range of 35-60. A high octane number of gasoline usually reduces the need for additives that increase the octane number of gasoline. In certain embodiments of the embodiment, the crude product includes naphtha, which has an octane number 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, 70-98 or 80-95.

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

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

The crude product has a distillate content per 1 g of the 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. 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.

- 25 009091

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

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

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

In some embodiments, the crude product has a VGO content per 1 g of the 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 0.6-0.8 g per 1 g of the crude product. In certain embodiments, the VGO has an aromatic hydrocarbon content per 1 g of VGO in the range of 0.1 to 0.99 g, 0.3-0.8 g, or 0.5-0.6 g.

In some embodiments, the crude product has a residue content of at most 70%, at most 50%, at most 30%, at most 10%, or at most 1% of the raw material. In certain embodiments, the crude product has a residue content of 1 g of the crude product of at most 0.1 g, at most 0.05 g, at most 0.03 g, at most 0.02 g, at most 0 , 01 g, at most 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, 0.00001-0. 05 g, 0.001-0.03 g or 0.005-0.04 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 g, but less than 0.01 g, 0.000001-0.001 g, or 0.00001-0,0001 g of catalyst per gram of crude product. The catalyst may contribute to the stabilization of the crude product during transportation and / or processing in process equipment. The catalyst can inhibit corrosion, inhibit friction, and / or promote the separation of water from the crude product. A crude product that includes at least a portion of the catalyst can be further processed to produce lubricants and / or other industrial products.

The catalyst used for treating a crude feed in the presence of a hydrogen source to produce a total product can be an individual catalyst or multiple catalysts. The catalysts of the invention may first be a catalyst precursor, which is converted to a catalyst in the contact zone when hydrogen and / or crude feed containing sulfur reacts with the catalyst precursor.

Catalysts used in contacting a crude feed with a source of hydrogen to produce a total product can reduce the molecular weight of the crude feed. Regardless of theory, it is believed that the catalyst in combination with a source of hydrogen can reduce the molecular weight of the components in the crude feedstock as a result of the action of the main (Lewis base or Bg6i81e-b) and / or superbase components in the catalyst. Examples of catalysts that have the characteristics of Lewis bases and / or Vgbiey-go'thu include the catalysts described in the invention.

In some embodiments, the catalyst is a SPM catalyst. This SPM catalyst comprises a compound that contains a transition metal sulphide. 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 transition metal to sulfur usually lies in the range from 0.2 to 20, 0.5-10 or 1-5. Examples of transition metal sulphides can be found in the book Chemistry of Inorganic Sulfur ”(1 then 8 and 1 Rig Syeschgu); edited by 6. MSK88; Ecology marketing; Atyygat-Eopyop-Ute Wogk; Soruda 1968; chapter 19.

In certain embodiments, the PSD catalyst may 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

- 26 009091 several transition metal sulfides per 1 g of catalyst. In certain embodiments, the SPM catalyst has a total content of one or more transition metal sulphides per gram of catalyst, ranging from 0.4 to 0.999 g, 0.5-0.9 g, or 0.6-0.8 g.

The catalyst SPM includes one or more transition metal sulphides. Examples of transition metal sulfides include pentlandite (Ee ₄ , ₅ no. ₄ , ₅ 8 ₈ ). smith (Re ₆ , 75 # ₂ , ₂₅ 8 c), bravoite (Pe ₀ , ₇ № ₀ , ₂ Co ₀ , 18 ₂ ), makinavit (Pe ₀ , ₇ 5 № ₀ , ₂₅ 8 ₀ , 9), argentopentlandite (AdRe ₆ No. ₂ 8 ₈ ), isocubanite (Cire ₂ 8 ₃ ), isochalcopyrite (C ₈ Re ₉ 81 ₆ ), sphalerite (2po, 9 ₅ Re ₀ , ₀ 58), muoichoit (Cire ₉ 81 ₆ ), chatkalit (SibRe8p ₂ 8 ₈ ), sternbergite (AdRe ₂ 8 ₃ ), chalcopyrite (CuRe8 ₂ ), troilite (Pe8), pyrite (Pe8 ₂ ), pyrgotite (Be ( _{1. X} ) 8 (x = 0 to 0.17)), hezlevudit (Νί ₃ 8 ₂ ) or vaazit (Νί8 ₂ ).

In some embodiments, the SPM catalyst includes one or more transition metal sulfides in combination with 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 _c [M _a 8 _b ] ₄ , in which A is an alkali metal, alkaline earth metal or zinc; M is 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 2.5, or from 1 to 2. The atomic ratio of c 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 PSM catalyst may include well-known alkali and / or alkaline earth metal compounds with transition metal sulphides (for example, bartonite (K ₃ Fe1 ₀ 81 ₄ ), dissolve (KPe ₂ 8 ₃ ), dyurfisherite (K ^ aRe19Ci ₄ №8 ₂₆ С1), chlorobartonite (К ₆ , 1Ре ₂₄ Cu ₀ , ₂ 8 ₂₆ , 1С1 ₀ , ₇ ) and / or coyoteite (№ 1Ее ₃ 8- (Н ₂ О) ₂ )). In some embodiments, the SPM catalyst includes bartonite obtained from WI. Bartonite, obtained by WI, can be called synthetic bartonite. Natural and / or synthetic bartonite can be used as a PSM catalyst in the methods described in the invention.

In some embodiments, the PSD catalyst may include at most 25 g, at most 15 g, or at most 1 g of support material per 100 g of PSA catalyst. Usually, the SPM catalyst has from 0 to 25 g, from 0.00001 to 20 g, from 0.0001 to 10 g of support material per 100 g of SPM catalyst. Examples of support materials that can be used with a PSD include refractory oxides, porous carbon materials, zeolites, or mixtures thereof. In some embodiments, the PSD catalyst is substantially free or does not contain support material.

SPM catalyst, which includes alkali metal (metals), alkaline earth metal (metals), zinc, zinc compounds, or mixtures thereof, may contain one or more transition metal sulfides, bimetallic alkali metal - transition metal sulfides, transition metal sulfides high valence, oxides of transition metals or mixtures thereof, which are determined using x-ray diffraction. In some embodiments, a portion of the alkali metal component (s), the alkaline earth metal component (s), the zinc component, and / or a portion of the transition metal sulfide component of the SPM catalyst may be in the form of an amorphous composition that is not detected 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 most of 10 ³ A, at most of 100 A, or at most of 40 A. In normal operation the size of the crystalline particles of the SPM catalyst as a whole will be at least 10 A.

The catalyst SPM, which includes alkali metal (metals), alkaline earth metal (metals), 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 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 moist 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, 500-800 ° C or 600-700 ° C with the formation of a mixture of transition metal oxide and metal salt. The mixture of the transition metal oxide and the metal salt can react 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 the transition metal oxide and the metal salt. Hydrogen can be added to a mixture of a transition metal oxide and a metal salt for 10-50 hours or 2040 hours to form a solid reduced intermediate that contains an elemental transition metal. Adding hydrogen can be carried out at a temperature of 35-500 ° C, 50-400 ° C or 100-300 ° C, and at a total pressure of 10-15 MPa, 11-14 MPa or 12-13 MPa. It should be borne in mind that the reduction time, the reaction temperature, the choice of the reducing gas, the pressure of the reducing gas and / or the flow rate of the reducing gas used for

- 27 009091 obtain solid intermediate compounds, often vary depending on the absolute mass of the selected oxide of the transition metal. 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 can be added in portions to a mixture of hot (for example, 100 ° C) diluent / elemental sulfur, and / or one or more sulfur compounds, at such a rate as to control heat generation and gas formation. The specified 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, 150400 ° 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 can vary from 1 to 100 mol.%, 2-80 mol.%, 5-50 mol.%, 10-30 mol.%, Based on the number of moles of metal from Groups 1-2 or zinc in the metal salt of Groups 1-2 or zinc salts. After adding the solid reduced intermediate to the mixture of diluent with elemental sulfur, the resulting mixture can be gradually heated to a final temperature of 200-500 ° C, 250-450 ° C or 300-400 ° C and maintained at the 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 at an elevated temperature of the sulphidation reaction, the mixture of diluent and catalyst can be cooled to in di in the range from 0 to 100 ° С, 30-90 ° С or 50-80 ° С to facilitate the separation of the catalyst from the mixture. The sulphided catalyst can be removed from the diluent in an oxygen-free atmosphere using standard techniques and washed with at least a portion of the low-boiling solvent (for example, pentane, heptane, or hexane) to obtain a PSM catalyst. This SPM catalyst can be pulverized using standard techniques.

In some embodiments, the catalyst is an inorganic salt catalyst. The anion of the inorganic salt catalyst 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 acetates, alkali metal oxalates, alkali metal formates, pyruvates (salts of pyruvic acid) alkali metals, alkali metal carbonates alkaline-earth metal hydroxides, alkaline-earth metal hydrides, alkaline-earth metal amides, alkaline-earth metal sulphides, 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: ^ OH / NBON / COH; KOH / NBON / SNOP; ΝαΟΗ / KOH / NBON; ΝαΟΗ / ΚΟΗ / ΟδΟΗ; K ₂ CO ₃ / NB ₂ CO ₃ / C8 ₂ CO ₃ ; Νη ₂ 0 / Κ ₂ 0 / Κ ₂ 00 ₃ ; \ anso _; / Cso _; / Hb _; WITH _; ; YNSO ₃ / KHCO ₃ / NB ₂ CO _3; KOH / NBON / ScON in combination with mixtures of KAO-NASO-SUSO ;; K2CO ₃ / CaCO ₃ ; K.AO-MdSO) ;; SCAO-CaCO) ;; SCAO-CaO; Kaaos (OH) 2; KN / SkSO ₃ ; KOSNO / CaO; SKOSNO / CaCO ₃ ; BOTTOM / CA (CAP) <ACC-CAO-NY); K ₂ CO ₃ / CaCO ₃ / КБ2СО ₃ ; AO-CASO) AKAOA AO-MdSO-NBAO) ;; K AOAACOAOKAOA or Ca (OH) 2 in combination with a mixture of K ₂ CO ₃ / NB ₂ CO ₃ / Ck ₂ CO ₃ .

In some embodiments, the inorganic salt catalyst contains at most 0.00001 g, at most 0.001 g, or at most 0.01 g lithium, based on the weight of lithium per 1 g of the inorganic salt catalyst. In some embodiments, the inorganic salt catalyst has a lithium content of from 0 g, but less than 0.01 g, 0.0000001-0.001 g, or 0.00001-0,0001 g, based on the mass of lithium, per 1 g of inorganic salt catalyst .

In certain embodiments, the inorganic salt catalyst contains one or more alkali metal salts, which include alkali metals with atomic numbers of at least 11. In some embodiments, the atomic ratio of alkali metal having atomic number at least 11 to 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, the inorganic salt catalyst may include sodium, potassium, and rubidium salts, the sodium to potassium ratio being in the range of 0.1 to 6; the ratio of sodium to rubidium is in the range from 0.1 to 6; and the potassium to rubidium ratio is in the range from 0.1 to 6. In another example, the inorganic salt catalyst comprises a sodium salt and a potassium salt, and 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, compounds of metals from Groups 8-10 of the Periodic Table, metals from Group 6 of the Periodic Table, compounds of metals from Group 6 of the Periodic Table, or mixtures thereof. Metals from Groups 8-10 include (but are not limited to)

- 28 009091 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 comprises 0.1-0.5 g or 0.2-0.4 g 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 ( _{1 2} O), potassium oxide (K ₂ O), calcium oxide (CaO), or aluminum oxide (A1 ₂ Oz).

In certain embodiments, the inorganic salt catalyst contains no, or substantially free, of a Lewis acid (e.g., BC1 _s, A1C1 _h and 8o ₃₎ acid Vgbpyeb-Lq ^ iy (e.g., H ₃ O ^+, H ₂ 8o _4, HC1 and ΗΝΟ ₃ ), glass-forming compositions (for example, borates and silicates) and halides. Inorganic salt may contain, per 1 g of inorganic salt catalyst: from 0 g to 0.1 g, 0.000001-0.01 g or 0.00001-0.005 g: a) halides; (B) compositions that form glass at temperatures of at least 350 ° C or at most 1000 ° C; c) Lewis acids; b) Vgbpieb-bo ^ gu acids; 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 (for example, crushing and / or spraying). In other embodiments, the inorganic compositions are dissolved in a solvent (for example, in water or a suitable organic solvent) to form a mixture of inorganic composition and 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 added to the support to form a supported inorganic salt catalyst. Examples of carriers include (but are not limited to) zirconium oxide, calcium oxide, magnesium oxide, titanium oxide, hydrotalcite, aluminum oxide, 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 metal compounds from Groups 6-10. Alternatively, inorganic salts may be melted or softened by heat and introduced into (and / or on) a metal carrier or a metal oxide carrier 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 temperature range in which disruptions in the order of the catalyst structure occur. The inorganic salt catalyst may become disordered without significant changes in the composition (for example, without decomposition of the salt). Regardless of theory, it is believed that the inorganic salt catalyst becomes disordered (mobile) when the distance between the ions in the lattice of the inorganic salt catalyst increases. As the distance between ions increases, the crude raw material and / or source of hydrogen can penetrate the inorganic salt catalyst instead of moving along the surface of the inorganic salt catalyst. Penetration of a crude feed and / or hydrogen source through an inorganic salt often results in an increase in the contact area between the inorganic salt catalyst and the crude feed and / or hydrogen source. Increasing the contact area and / or 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 characteristics in the crude product relative to the same characteristics of the crude material. The disordering of the inorganic salt catalyst (for example, heterogeneity, permeability, and / or mobility) can be determined using DSC methods, ion conductivity measurements, VAP methods, visual examination, X-ray diffraction methods, or a combination of these.

The use of VAP to characterize catalysts is described in US Pat. Nos. 4,626,412 (Ebpeg et al.); 5,039,489 (C1ate5 et al.); and 5,264,183 (EB Peg et al.). The VAP system can be obtained at MieEga TesNpo1od1e5 (Eoile, M188oip, I.8.A.). VAP analysis can be carried out in the temperature range from 25 to 850 ° С, 50-500 ° С or 60-400 ° С, at a heating rate in the range from 10-50 ° С, or 20-40 ° С and in vacuum, range from 1x10 ^-13 to 1x10 ^-8 Torr. The temperature of the analysis may remain constant and / or increase as a function of time. When the temperature of the inorganic salt catalyst increases, the evolution of gas from the inorganic salt catalyst is measured. Examples of gases that are emitted from an 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 the evolution of gas from an inorganic salt catalyst is taken to be the temperature at which the inorganic salt catalyst becomes disordered.

In some embodiments, the inflection point when gas is released from the inorganic salt catalyst can be detected in the temperature range, which is determined using

- 29 009091

WAP. This temperature or temperature range is called VAP temperature. The initial temperature of the temperature range determined using VAP is called the minimum VAP temperature.

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

The magnitude of the ionization at the inflection point associated with the emitted gas may indicate the orderliness of the particles in the crystal structure. For a highly ordered crystalline structure, ionic particles are usually directly associated, and more energy is required to release ions, molecules, gases, or their combinations from the structure (that is, more heat). In a disordered crystal structure, ions are not as strongly associated with each other as ions in a highly ordered crystal structure. Due to the reduced degree of ion association, less energy is usually required to separate the ions, molecules and / or gases from the disordered crystal structure, and thus the number of ions and / or gases separated from the disordered crystal structure usually exceeds the number of ions and / or gases extracted from 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 from 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, the sample can be heated to the first temperature, cooled to room temperature, and then it is heated a second time. The transitions observed during the first heating usually represent entrained water and / or solvent and may not be related to the heat of dissociation. For example, the easily identifiable heat of drying 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 cycles correspond to the heat of dissociation of the sample.

The term thermal transition refers to the process that occurs when ordered molecules and / or atoms in a structure become disordered with increasing temperature during the DSC analysis. The transition during cooling refers to the process that occurs when the molecules and / or atoms in the structure become more homogeneous with decreasing temperature during the DSC analysis. In some embodiments, the transition when heated / cooled inorganic salt catalyst occurs in the 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 the 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 may be in the range between 200 and 500 ° C, 250-450 ° C or 300-400 ° C.

In an inorganic salt that contains particles of an 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, which contains particles of an inorganic salt in a relatively heterogeneous mixture, the peak associated with the heat absorbed during the second heating cycle may be relatively broad in shape. The absence of peaks in the DSC spectrum indicates that the salt does not absorb or does not generate heat in the scanned temperature range. The absence of a temperature transition usually indicates that the structure of the sample does not change when heated.

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 interionic attraction forces between the cation and anion, if the anion is a rigid base. Increased inter-ionic attraction forces usually lead to higher thermal transition temperatures for 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 in the case of cations with a large ionic radius, and thus the acidity of the mixture of inorganic salts increases with decreasing cationic radius. For example, contacting a crude feed with a source of hydrogen in the presence of an inorganic mixture that includes lithium cations results in increased amounts of gas and / or coke compared to contacting the crude feed with a source of hydrogen in the presence of an inorganic salt catalyst.

- 30 009091 ry includes cations with a large 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, the minimum DSC temperature can be determined. This minimum DSC temperature of the inorganic salt catalyst may be below the minimum DSC temperature of at least one inorganic metal salt in the inorganic salt catalyst. For example, the inorganic salt catalyst may include potassium carbonate and cesium carbonate. Potassium carbonate and cesium carbonate have a DSC temperature higher than 500 ° C. For catalyst K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ DSC, the temperature lies in the range from 290 to 300 ° C.

In some embodiments of the VAP, the 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 the range of 350 to 500 ° C.

The DSC temperature of the same inorganic salt catalyst may be in the range of 200 to 300 ° C, and the DSC temperature of the individual salts may be at least 500 ° C or at most 1000 ° C.

Inorganic salt catalyst, which 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 transformation of the compositions high molecular weight and / or high viscosity (for example, crude feed) to liquid products.

In certain embodiments, the inorganic salt catalyst may exhibit increased electrical conductivity relative to individual inorganic salts during heating of the inorganic salt catalyst in the temperature range from 200 to 600 ° C, 300-500 ° C or 350-450 ° C. The increased electrical conductivity of the inorganic salt catalyst is usually due to the fact that the 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: V = ΙΚ, where V means voltage, I represents current, and K means resistance. To measure ionic conductivity, the inorganic salt catalyst may be located 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 ion conductivity measurement system that can be used to measure ion conductivity. A quartz cell 156 containing sample 158 may be in a heating device and gradually heated to a predetermined temperature. The voltage from the source 160 is supplied to the wires 162 during heating. The resulting current in 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 sample 158 becomes less uniform (more mobile), in the absence of decomposition, the resistivity of the sample should decrease, and the current detected by the measuring device 166 should increase. In some embodiments, embodiments at a given temperature, the inorganic salt catalyst may have different ionic conductivities after heating, cooling, and subsequent heating. Different ionic conductivities may indicate that the crystal structure of the inorganic salt catalyst has changed from the original form (first form) to the other form (second form) during heating. It can be expected that the ionic conductivity after heating will be close or the same if, during the heating of the inorganic salt catalyst, its shape does not change.

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

Inorganic salt catalyst can soften when heated to temperatures above 50 ° C 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 may spontaneously deform under the action of gravity or under pressure of at least 0.007 MPa or at most 0.101 MPa when heated to a temperature of at least 300 ° C or at most 800 ° C, so that the inorganic the salt catalyst passes from the first form to the second form. When cooling the inorganic salt catalyst to 20 ° C, the second form of the inorganic salt catalyst cannot take on again 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 strain temperature. This deformation temperature may be in the temperature range or it is a specific temperature. In certain embodiments, the particles of the inorganic salt catalyst spontaneously deform under the action of gravity or pressure when heated to a deformation temperature below the deformation temperature of any individual inorganic metal salt. In some embodiments, the inorganic salt catalyst comprises two (or more) inorganic salts that have different deformation temperatures. In some embodiments, the strain temperature of the inorganic salt catalyst is different from the strain 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 or pseudo-liquid with a minimum VAP and / or DSC temperature. At the minimum temperature of the VAP and / or DSC (or above these temperatures), the liquid or pseudo-liquid inorganic salt catalyst mixed with the crude raw material may, in some embodiments, form a phase separate from the crude raw material phase. In some embodiments, the liquid or pseudo-liquid inorganic salt catalyst has a low solubility in the crude feed (for example, from 0 to 0.5 g, 0.0000001-0.2 g or 0.0001-0.1 g inorganic salt catalyst per 1 g raw materials) or does not have solubility in raw materials (for example, from 0 g to 0.05 g, 0.000001-0.01 g or 0.00001-0.001 g of inorganic salt catalyst per 1 g of raw material) at the minimum VAP temperature .

In some embodiments, x-ray powder diffraction techniques are used to determine the spatial arrangement of atoms in the 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 particles of the inorganic salt can be estimated. The peaks in the X-ray diffractogram correspond to the various compounds of the inorganic salt catalyst. By powder X-ray diffraction, a Ό ₀₀₁ peak can be analyzed and the distance between atoms can be estimated. In the inorganic salt catalyst, which contains highly ordered atoms of the inorganic salt, the peak shape Ό ₀₀ ι is relatively narrow. In an inorganic salt catalyst (for example, a K ₂ CO ₃ / KH ₂ CO ₃ / Ck ₂ CO ₃ catalyst), which contains arbitrarily ordered atoms of the inorganic salt, the shape of the Ό ₀₀ ι peak may be relatively broad or Ό ₀₀ ι the peak may be absent. In order to establish whether the disorder of the inorganic salt atoms changes during heating, one can record the X-ray diffraction spectrum for the inorganic salt catalyst before heating and compare it with the X-ray diffraction spectrum after heating. Peak Ό ₀₀ ι (corresponding to the atoms of the inorganic salt) in the X-ray diffraction spectrum recorded at a temperature above 50 ° C may be absent or broadened compared to Ό ₀₀₁ peaks in the X-ray diffraction spectrum recorded at a temperature below 50 ° C. In addition, in the radiograph for an individual inorganic salt, relatively narrow Ό ₀₀₁ peaks can be observed at the same temperatures.

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

Regulation of the conditions of contact, in combination with the catalyst described in the invention, can provide a total product with a lower content of coke, compared with the expected. Comparison of the content of WMD in different raw materials can ensure the ranking of raw materials based on their tendency to form coke. For example, it can be expected that from raw materials with a WMD content of 0.1 g of OMU, more coke is produced per 1 g of raw material than from raw materials with a WMD content of 0.001 g of OMU per 1 g of raw material. A disadvantageous raw material usually has a WMD content of at least 0.05 g of OMU per gram of unprofitable raw material.

In some embodiments, the residue content and / or coke content deposited on the catalyst during the process can be at most 0.1 g, at most 0.05 g or at most 0.03 g, of the residue and / or coke per g of catalyst. In certain embodiments, the weight of the residue and / or coke deposited on the catalyst is in the range from 0.0001 to 0.1 g, 0.0010.05 g, or 0.01-0.03 g. In some embodiments, the catalyst used is practically does not contain residue and / or coke. In certain embodiments, the contacting conditions are adjusted such that at most 0.015 g, at most 0.01 g, at most 0.005 g, or at most 0.003 g of coke per gram of crude product is formed. Contacting the raw material with a catalyst under controlled contact conditions reduces the amount of coke and / or residue, compared with the amount of coke and / or residue, obtained by heating the ne

- 32 009091 raw materials in the presence of a processing catalyst, or in the absence of a catalyst, using the same contact conditions.

In some embodiments, the contacting conditions can be adjusted such that, per 1 g of the crude raw material, at least 0.5 g, at least 0.7 g, at least 0.8 g, or at least 0 are converted into a crude product. , 9 g of crude raw materials. Usually 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 raw material are obtained. The transformation of the raw material into the crude product with a minimum yield of residue and / or coke (if any) into the crude product allows you to process the crude product into industrial products with minimal involvement of pre-treatment processes at the refinery. In certain embodiments, at least 0.2 g, at most 0.1 g, at most 0.05 g, at most 0.03 g, or at most 0.01 g are converted into 1 g of crude raw materials crude feed to non-condensable hydrocarbons. In some embodiments, from 0 to 0.2 g, 0.0001 to 0.1 g, 0.001 to 0.05 g, or 0.010.03 g of non-condensable hydrocarbons per 1 g of crude feed are formed.

To maintain the desired process temperature, it is possible to regulate the temperature in the contact zone, the feed rate of the crude material, the flow rate of the total product, the feed rate and / or the amount of catalyst fed, or a combination thereof. In some embodiments, temperature control in the contact zone can be performed by changing the flow of gaseous hydrogen source and / or inert gas through the contact zone in order to reduce the hydrogen concentration 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 adjusted such that the temperature of the contact zone is below the minimum VAP temperature and / or minimum DSC temperature. In certain embodiments of the embodiment, the value of T ₁ may be 30 ° C lower, 20 ° C lower or 10 ° C below the minimum VAP temperature and / or minimum DSC temperature. For example, in one embodiment, the contact temperature can be controlled at 370, 380 or 390 ° C during the process, when the minimum VAP temperature and / or the minimum DSC temperature is 400 ° C.

In other embodiments, the contacting temperature is adjusted so that the temperature is higher, lower or corresponds to the VAP of the catalyst and / or DSC temperature of the catalyst. For example, the contact temperature can be regulated at 450, 500 or 550 ° C during the process, when the minimum VAP temperature and / or minimum DSC temperature is 450 ° C. Regulation of the contact temperature based on the catalyst VAP and / or DSC temperature of the catalyst can improve the characteristics of the crude product. For example, such regulation may 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, the conditioning may proceed in the presence of a 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 the inorganic salt catalyst to a second temperature, at most 250 ° C, at most 200 ° C or at most 100 ° C. In certain embodiments, the inorganic salt catalyst is heated to a temperature in the range from 150 to 700 ° C, 200-600 ° C or 300-500 ° C and then cooled to a second temperature in the range from 25 to 240 ° C, 30-200 ° C or 50-90 ° C. The conditioning temperature can be determined by measuring the ionic conductivity at various temperatures. In some embodiments, the conditioning temperature can be determined from the DSC temperature values obtained for transitions with multiple heating / cooling cycles of the inorganic salt catalyst with DSC. Conditioning the inorganic salt catalyst can ensure that the raw material is contacted at a lower process temperature than the temperatures used for traditional hydrotreating catalysts.

In some embodiments, the content of naphtha, distillate, VGO, or mixtures thereof in the total product may vary by varying the rate of removal of the total product from the contact zone. For example, a decrease in the removal rate of the total product leads to an increase in the time of contacting the raw material with the catalyst. Alternatively, increasing the pressure relative to the initial pressure may increase the contact time, may increase the yield of the crude product, may increase the incorporation of hydrogen from the gases into the crude product at a given mass flow rate of the crude raw material or source of hydrogen, or may affect a combination of these effects. Increased time of contacting the raw material with the catalyst can give an increase in the amount of diesel fuel, kerosene or naphtha and a decrease in

- 33 009091 the amount of VGO compared with the quantities 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, increased density in degrees AP1).

In some embodiments, the contacting conditions may vary over time. For example, the contact pressure and / or the contact temperature may be increased in order to increase the amount of hydrogen absorbed by the crude feed to obtain a crude product. The ability to change the amount of hydrogen absorbed by the crude feedstock while improving other characteristics of the crude feedstock expands the range of crude products that can be obtained from individual crude feedstocks. The ability to produce a variety of unpurified products from separate unpurified raw materials can ensure the fulfillment of various technical conditions for transportation and / or processing.

Hydrogen uptake can be estimated by comparing the H / C ratio for the crude feed to the H / C ratio for the crude product. An increase in the H / C ratio for the crude product compared to the H / C in the crude feed indicates the incorporation of hydrogen into the crude product from a hydrogen source. A relatively small increase in H / C for the crude product (20%, compared to the crude feed) indicates a relatively low consumption of hydrogen gas during the process. Desirable is a significant improvement in the characteristics of the crude product compared with the characteristics of the crude raw material, achieved with minimal consumption of hydrogen.

In addition, you can vary the ratio of the source of hydrogen to the crude raw material 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 raw material may yield a crude product that has an elevated content of VGO per gram of crude product.

In certain embodiments, contacting a crude feed with an inorganic salt catalyst in the presence of light hydrocarbons and / or water vapor produces 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 involve contacting a crude feed with methane in the presence of an inorganic salt catalyst, at least some 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 is greater than at least 5%, at least 10% or at least 15%, or at most 100% more than the volume of the crude product obtained in the thermal process at NTD. The total volume of the crude product obtained by contacting the crude raw material with an inorganic salt catalyst may be at least 110 vol.% Of the volume of the crude raw material at the regulatory document. It is believed that this increase in volume is due to a decrease in density. Usually, a decrease in density, at least in part, can be caused by the hydrogenation of the raw material.

In certain embodiments, a crude raw material having 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 / ν / E per raw material g 1 of crude raw material , is in contact with a source of hydrogen in the presence of an inorganic salt catalyst, without reducing the activity of the catalyst.

In some embodiments, the inorganic salt catalyst may 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. Contaminated sulphides can be removed from spent inorganic salt catalyst by contacting water vapor and carbon dioxide with spent catalyst, to produce hydrogen sulfide. Contaminant nitrogen can be removed by contacting the spent inorganic salt catalyst with water vapor to produce ammonia. Contaminant coke can be removed from 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, a mixture of waste inorganic salt (for example, K ₂ CO _h / KL ₂ CO _h / C _{2 2} CO _h ; kOn / Al ₂ O ₃ ; C _{2 2} CO ₃ / CaCO ₃ ; or ΝαΟΗ / ΚΟΗ / ΕίΟΗ / ΖτΟ ₂ ), unreacted raw material, 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, as long as in the presence of water vapor, hydrogen, carbon dioxide

- 34 009091 kind and / or light hydrocarbons, the production of gas and / or liquid is minimal 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, the gas may include from 0.1 to 99 moles or from 0.2 to 8 moles of hydrogen and / or carbon dioxide per mole of reactant 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 1 g of gas and less than 0.01 g of carbon monoxide per 1 g of gas. The liquid phase may contain water, for example, more than 0.5-0.99 g or more than 0.9-0.99 g of water per g of liquid.

In some embodiments, spent catalyst and / or solids in the contact zone may be treated to extract metals (eg, vanadium and / or nickel) from the spent catalyst and / or solids. Spent catalyst and / or solids can be processed using well-known metal separation techniques, for example, heating, chemical processing and / or gasification.

Examples

Below are non-limiting examples of the preparation of catalysts, testing of catalysts and systems with controlled contact conditions.

Example 1. Getting sulfide catalyst To-Her.

The K-E sulfide catalyst is obtained by combining 1000 g of iron oxide (E ₂ O ₃ ) and 580 g of potassium carbonate with deionized water (412 g) to form a moist 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 that includes metallic iron. 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 is added in portions to a mixture of VGO with m-xylene and elemental sulfur at 100 ° C at such a rate as to regulate the evolution of heat and the formation of gas. After the solid intermediate is added, the resulting mixture is gradually heated to 300 ° C and maintained at 300 ° C for 1 hour. The mixture of solvent and catalyst is cooled below 100 ° C and the sulfided catalyst is separated from the mixture. This sulfided catalyst is isolated by filtration in a dry box under an argon atmosphere and washed with mA-xylene to obtain 544.7 g of the K-E sulfide catalyst. This K-E sulfide catalyst is crushed by passing the catalyst through a 40 mesh sieve (0.31 mm).

The resulting K-ee sulphide catalyst is analyzed using the X-ray diffraction method. From the analysis of the X-ray diffraction spectrum, it was established that this catalyst includes troilite (EE3), K-Her sulphide (KEZ ₂ ), pyrrhotite, and iron oxides (for example, magnetite, E ₃ O ₄ ). The X-ray diffraction spectrum was not observed a peak corresponding iron disulfide (for example, pyrite, EeZ _2).

Example 2. Contacting the raw material with a source of hydrogen in the presence of K-Her 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 inside the reactor, and a six-blade Kikyop turbine with a 1.25-inch drive shaft. ).

The K-Eue sulfide catalyst (110.3 g), prepared as described in Example 1, is loaded into the reactor. Hydrogen gas is dosed at a ratio of 8000 Nm ³ / m ³ (50,000 standard cubic feet per barrel) into the reactor and mixed with bitumen (HoubtchTeg. Canada deposit). Bitumen enters the reactor through the lower feed channel to form a mixture of hydrogen and crude feed. During the process run for 185 hours, hydrogen gas and crude feedstock continuously enter the reactor, and the product is continuously removed from the reactor through the vapor exit channel. The crude feed is fed at a rate of 67.0 g / h to maintain the volume of liquid crude feed at 60% of the reactor volume. To measure the liquid level in the reactor, ¹³⁷ Cg-gamma-radiation source (50 milli- curie) and a sodium iodide scintillation detector were used.

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

After leaving the reactor, the reaction vapors are cooled and separated in a high pressure gas / liquid separator and a low pressure gas / liquid separator to obtain a liquid flow and gas flow. This gas stream is sent to a countercurrent alkali scrubber to remove acid gases, and then subjected to quantitative analysis using standard methods.

- 35 009091 mov chromatography. The total product includes, for 1 g of the total product, 0.918 g of the crude product and 0.089 g of non-condensable hydrocarbon gases. In the reactor, 0.027 g of solid matter per 1 g of crude feed remains. The characteristics and compositions of the crude product and non-condensable hydrocarbon gases formed in the process according to the invention are listed in table. 1 in FIG. 8, in table. 2 in FIG. 9 and in table. 3 in FIG. ten.

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

When comparing data on the content of WMD in the raw material (13.7 wt.%) In the table. 1 with the amount of solid formed during the process (2.7 wt.%), It can be understood that due to a combination of controlled conditions and a catalyst, a smaller amount of coke can be obtained than was detected by the A8TM Ό4530 method.

Non-condensable hydrocarbons include C2, C3 and C4 hydrocarbons. From the sum of the percentage (by weight) of the C2 hydrocarbons indicated in Table. 2 (20.5 g), you can calculate the ethylene content per 1 g of the amount. C2 hydrocarbons from hydrocarbon gases include 0.073 grams of ethylene per gram of total C2 hydrocarbons. Of the total content (percentage by weight) of C3 hydrocarbons, indicated in Table. 2 (23.9 g), it is possible to calculate the content of propylene per 1 g of the sum of C3 hydrocarbons. C3 hydrocarbons from non-condensable hydrocarbons include 0.21 grams of propylene per gram of C3 hydrocarbons. C4 hydrocarbons from non-condensable hydrocarbon gases have an isobutane to n-butane weight ratio of 0.2.

This example illustrates a method for producing a crude product that includes at least 0.001 g of hydrocarbons with a boiling range distribution, at most 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 fuel and VGO. The crude product contains at least 0.001 g of naphtha, and the naphtha fraction of the crude product has an octane number of at least 70. The naphtha fraction of the crude product has a benzene content of at most 0.01 g of benzene per gram of naphtha. The crude naphtha fraction of the crude product has a content of at most 0.15 g of olefins per gram of naphtha. The crude naphtha fraction from the crude product contains at least 0.1 g of monocyclic aromatic hydrocarbons per gram 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, and the kerosene fraction of the crude product has an aromatic content of at least 0.3 g of aromatic hydrocarbons per 1 g of kerosene. The kerosene fraction of the crude product has at least 0.2 grams of monocyclic aromatic hydrocarbons per gram of kerosene.

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

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

Example 3. Getting To-Her sulfide catalyst in the absence of a hydrocarbon diluent.

The K-E 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 moist 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.

Unlike Example 2, the solid intermediate is mixed with elemental sulfur in the absence of a hydrocarbon diluent. In a dry box using an argon atmosphere, the solid intermediate is mixed with powdered elemental sulfur, placed in a sealed carbon steel cylinder, heated to 400 ° C, and held at 400 ° C for 1 hour. Sulfided catalyst is removed from the carbon steel reactor in solid condition. Potassium-sulphide-iron catalyst is pulverized with a pestle and mortar in such a way that the resulting catalyst powder passes through a 40 mesh sieve (0.31 mm).

- 36 009091

The resulting potassium sulphide-iron catalyst is analyzed using the X-ray diffraction method. From the analysis of the X-ray diffraction spectrum, it was found that the catalyst contains pyrite (E8 ₂ ), iron sulfide (E8) and pyrrhotite (E _{1. X} 8). Using the X-ray diffraction method, no particles of mixed potassium-iron sulphide or iron oxide were detected.

Example 4. Contacting the raw material with a source of hydrogen in the presence of K-Her sulfide catalyst with an increased ratio of hydrogen gas to the raw material.

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

The characteristics of the crude product obtained by this method are summarized in table. 1 in FIG. 8 and in table. 3 in FIG. 10. The percentage of VGO (by mass) obtained in Example 4 is greater than the percentage of VGO (by mass) 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 in degrees AP1 of the crude product obtained in Example 4 is less than the density in degrees AP1 of the crude product obtained in Example 2. The increased density in degrees AP1 indicates the formation of hydrocarbons with an increased number of carbon atoms. kind.

After contacting the crude feed, analyze the SPM catalyst from the reactor. According to this analysis, the sulfide catalyst of the transition metal, after contacting with crude raw materials and hydrogen, contains K ₃ E1 ₀ 81 ₄ .

Example 5. The study of the VAP for the catalyst K ₂ CO ₃ / KH ₂ CO ₃ / C3 ₂ CO ₃ and individual inorganic salts.

In all VAP studies, the sample (300 mg) is heated in a VAP reactor from room temperature (27 ° C) to 500 ° C at a rate of 50 ° C per minute. Released water vapor and carbon dioxide gas are analyzed using a VAP mass spectrometer.

For the K ₂ CO ₃ / KH ₂ CO ₃ / Cz ₂ CO ₃ catalyst supported on alumina, there is a current bending point greater than 0.2 V for evolved carbon dioxide and a current bending point of 0.01 V for evolved water from inorganic salt catalyst at 360 ° C. The minimum VAP temperature is 360 ° C, which is determined by plotting the dependence of the logarithm (1 to 10) of the ion current on temperature. FIG. 11 is a graphical dependence of the logarithm of the ionic current of gases emitted from the K ₂ CO ₃ / KL ₂ CO ₃ / Cz ₂ CO ₃ , (1 (I)) catalyst on temperature (T). Curves 168 and 170 show the logarithm of the ion current of water and CO2, isolated from an inorganic salt catalyst. The sharp inflection point for the separation of water and CO2 from the inorganic salt catalyst is at 360 ° C.

In contrast to the K ₂ CO ₃ / KH ₂ CO ₃ / Cz ₂ CO ₃ catalyst, for the potassium carbonate and cesium carbonate, no current inflection point is observed at 360 ° C for the emitted water, as well as for carbon dioxide.

A significant increase in the amount of gases emitted from the K ₂ CO ₃ / KH ₂ CO ₃ / Cz ₂ CO ₃ catalyst indicates that inorganic salt catalysts consisting of two (or more) different inorganic salts may have a greater disorder than individual pure carbonate salts.

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

In all DSC studies, the sample (10 mg) is heated to 520 ° C at a rate of 10 ° C per minute, cooled from 520 to 0.0 ° C at a rate of 10 ° C per minute, and then heated from 0 to 600 ° C at a rate of 10 , 0 ° C per minute using a differential scanning calorimeter (DSC), model DSK7, manufactured by Regk1p-E1teg (No. g \ ha1k. CoppesEsi !, I.8.A.).

According to the DSC analysis of the K ₂ CO ₃ / KH ₂ CO ₃ / Cz ₂ CO ₃ catalyst during the second heating of the sample, it was found that there is a wide transition region for the salt mixture at a temperature between 219 ° C 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 with a minimum DSC temperature of 219 ° C.

In contrast to these results, a certain thermal transition is not observed for cesium carbonate.

DSC analysis mixtures L1 ₂ CO _3, Na ₂ CO ₃ and K ₂ CO ₃ during the second heating cycle shows that for a mixture of N ₂ CO ₃ / Na ₂ CO ₃ / K ₂ CO ₃ there is a sharp transition temperature between 390 and 400 ° WITH. 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 with a minimum DSC temperature of 390 ° C. The temperature of the abrupt transition indicates a practically homogeneous mixture of salts.

- 37 009091

Example 7. The study of the ionic conductivity of inorganic salt catalysts or individual inorganic salts compared to K ₂ CO ₃ .

All studies are carried out by placing 3.81 cm (1.5 inches) of inorganic salt catalysts or individual inorganic salts in a quartz ampoule with platinum or copper wires, insulated from each other, but immersed in a sample that is in a muffle furnace. The wires are connected to a dry cell with a potential of 9.55 V and to a resistor (220000 Ohm) that limits the current flow. The muffle furnace is heated to 600 ° C and the current is measured using a microammeter.

FIG. 12 shows the graphical dependence of the logarithm of the sample resistance relative to the resistance of potassium carbonate (1 year (g K ₂ CO ₃ )) on temperature (T). Curves 172, 174, 176, 178 and 180 are dependences of the decimal logarithm of resistance K ₂ CO ₃ , resistance CaO, catalyst resistance K ₂ CO ₃ / КЬ ₂ CO ₃ / С§ ₂ CO ₃ , Ы ₂ CO ₃ / K ₂ CO ₃ / КЬ ₂ СО ₃ / С§ ₂ CO ₃ and catalyst resistances Ла ₂ СО ₃ / К ₂ СО ₃ / КЬ ₂ СО ₃ / С8 ₂ СО ₃ , respectively.

The CaO sample (curve 174) has a relatively large stable resistance relative 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, the ions do not acquire the ability to move relative to each other. For catalyst K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ , catalyst L ₂ CO ₃ / K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ and catalyst Ia ₂ CO ₃ / K ₂ CO ₃ / КЬ ₂ СО ₃ / С8 ₂ СО ₃ (see curves 176, 178 and 180) there is a sharp decrease in the specific resistance relative to K2CO3 at temperatures in the range from 350 to 500 ° C. The decrease in resistivity usually indicates that an electric current occurs when voltage is applied to the wires immersed in the 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.

FIG. Figure 13 shows the graphical dependence of the logarithm of the catalyst resistance Ia ₂ CO ₃ / K ₂ CO ₃ / KH ₂ CO ₃ / C _{8 2} CO ₃ relative to the resistance of potassium carbonate (1 year (g K ₂ CO ₃ )) on temperature (T). Curve 182 is the dependence of the ratio of the catalyst resistance, Ia ₂ CO ₃ / K ₂ CO ₃ / Kb ₂ CO ₃ / C8 ₂ CO ₃ to the resistance K ₂ CO ₃ (curve 172), as a function of the temperature during heating of the catalyst Ia ₂ CO ₃ / K ₂ CO ₃ / КЬ ₂ СО ₃ / С8 ₂ СО ₃ . After heating, the catalyst Ia ₂ CO ₃ / K ₂ CO ₃ / KH ₂ CO ₃ / C8 ₂ CO _{3 is} cooled to room temperature and then heated in a conductivity measurement cell. Curve 184 is the dependence of the logarithm of the catalyst resistance Ie ₂ CO ₃ / K ₂ CO ₃ / Ib ₂ CO ₃ / C8 ₂ CO ₃ relative to the resistance K ₂ CO ₃ on temperature during heating of the inorganic salt catalyst after it cools from 600 ° C to 25 ° s The ionic conductivity of the re-heated catalyst Na ₂ CO ₃ / K ₂ CO ₃ / KH ₂ CO ₃ / C _{8 2} CO ₃ increases relative to the ionic conductivity of the initial catalyst Oa ₂ CO ₃ / K ₂ CO ₃ / Kb ₂ CO ₃ / C _{8 2} CO ₃ .

From the difference in ionic conductivity of the inorganic salt catalyst during the first heating and the second heating, it can be concluded 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 / KH ₂ CO ₃ / C 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 characteristics of the catalyst after heating, the cup in the furnace is tilted by hand. Catalyst K ₂ CO ₃ / КЬ ₂ CO ₃ / С§ ₂ CO ₃ does not move. When pressed with a spatula, the catalyst has a toffee consistency.

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

The catalyst Na ₂ CO ₃ / K ₂ CO ₃ / Kb ₂ CO ₃ / C8 ₂ CO ₃ becomes liquid and easily flows (for example, like water) in a cup under the same conditions.

Examples 9-10. Contacting the raw material with a source of hydrogen in the presence of a catalyst K ₂ CO ₃ / KL ₂ CO ₃ / C ₂ CO ₃ and water vapor.

Examples 9-27 use the following equipment and general procedure, except for the variations that are described.

Reactor. The 250 ml autoclave Ragg of Na51e11ou C alloy (Regga model No. 4576), designed for a working pressure of 35 MPa (5000 psi) at 500 ° C, is equipped with a 800 W mechanical heater and Saiteg tape heater with an Eigoscheg regulator capable of maintain the temperature of the autoclave with an accuracy of ± 5 ° С from room temperature to 625 ° С, a gas inlet channel, a water vapor inlet channel, one outlet channel and a thermocouple recording the internal temperature. Before heating, the cover of the autoclave is insulated with fiberglass.

Reservoir to add. The reservoir for adding (volume 250 ml, made of 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 distribution valve (valve of the company No. 88-4 and ^) ^ providing regulation of the flow of hot, viscous and / or compressed raw materials at a flow rate of from 0 to 500 g / min. With the day off

- 38 009091 side high-temperature distribution valve connected to the first inlet channel of the reactor after loading the raw material into the tank to add. Before use, isolate the tank lines to be added.

Collect the product. The vapor from the reactor leaves the outlet of the reactor and enters a series of cooled traps having a lower temperature (immersion tubes connected to a set of tanks (150 ml) from aged 316 stainless steel). The liquid vapor stream is condensed in cooled traps with the formation of a gas stream and a stream of liquid condensate. The flow rate of vapor from the reactor and through the cooled traps, if necessary, regulate using a reverse pressure regulator. The flow rate and the total gas volume for the gas flow leaving the cooled traps is measured using a wet gas meter (KgReg егοάе1 # TS 05 \ Ve1 TECh meter). After exiting the wet gas meter, a stream is taken to the gas chamber (Te-1a ^ gas sampling chamber) for analysis. The gas is analyzed using a gas chromatograph / mass spectrometer system (NeMay-Raskay, Μοάе1 5890, currently Adyep! Άοάе1 5890; manufactured by Adyep! Tesypo1, 8, οη ηοίδ, I.8.A.). The stream of liquid condensate is removed from the cooled traps and weighed. The crude product and water are separated from the liquid condensate stream. The crude product is weighed and analyzed.

The technique. In the tank for adding feed raw materials Seggo Jedgo (137.5 g). This raw material has a density of 6.7 degrees AP1 (1023.9 kg / m ³ ). The crude feed has, per g of crude feed, a sulfur content of 0.042 g, a nitrogen content of 0.011 g and a total content of Νί / ν 0.009 g. The crude feed is heated to 150 ° C. Catalyst K ₂ CO ₃ / HL ₂ CO ₃ / C ₂ CO ₃ (31.39 g) was charged to the reactor.

Catalyst K ₂ CO ₃ / YA ₂ CO ₃ / C8 ₂ CO _{3 is} obtained by combining 16.44 g K ₂ CO ₃ , 19.44 g YAH ₂ CO _3, and 24.49 g Cg ₂ CO ₃ . Catalyst K ₂ CO ₃ / ЯЬ ₂ CO ₃ / C8 ₂ CO ₃ has a minimum VAP temperature of 360 ° C. Catalyst K ₂ CO ₃ / ЯЬ ₂ CO ₃ / C8 ₂ CO ₃ has a DSC temperature of 250 ° C. For individual salts (K ₂ CO ₃ , YA ₂ CO _3, and C ₂ CO ₃ ) in the range from 50–500 ° C, no DSC temperatures were detected. 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 rapidly heated to 450 ° C at atmospheric pressure in a stream of methane of 250 cm ³ / min. After reaching the desired reaction temperature, water vapor is metered into the reactor at a rate of 0.4 ml / min and methane at a rate of 250 cm ³ / min. Steam and methane are continuously metered during the addition of the crude feed to the reactor for 2.6 hours. The crude feed is fed to the reactor under a pressure of 1.5 MPa methane (229 psi) for 16 minutes. The remainder of the crude raw material (0.56 g) remains in the tank for addition after the completion of the addition of the crude raw material. During the addition of the crude material, a decrease in temperature to 370 ° C is observed.

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

The difference between the initial mass of the catalyst and the mass of the mixture of coke with a catalyst determines the amount of coke (0.046 g) remaining in the reactor per 1 g of the raw material. The total product contains 0.87 g of crude product with an average density of 13 degrees AP1 (979.2 kg / m ³ ) and gas. The gas includes unreacted CH4, hydrogen, C2 and C4-C6 hydrocarbons, and CO2 (0.08 g CO2 per g of gas).

The crude product contains on 1 g of the crude product 0.01 g of sulfur and 0.000005 g of the sum of N1 and V. This crude product is not subjected to subsequent analysis.

In Example 10, the methods 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 boiling range distribution for the crude product. The crude product contains per g of crude product 0.14 g of naphtha, 0.19 g of distillate, 0.45 g of VGO and has a residue content of 0.001 g and a non-detectable amount of coke.

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

The crude product includes at least 0.001 g of hydrocarbons with a boiling range distribution of at most 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, at least 0.001 g hydrocarbons with a boiling range distribution between 400 and 538 ° С (1000 ° Е) at 0.101 MPa.

Examples 11-12. Contacting the raw material with a source of hydrogen in the presence of a catalyst K ₂ CO ₃ / HL ₂ CO ₃ / C ₂ CO ₃ and water vapor.

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In examples 11 and 12, the methods and process conditions, the crude raw material and the catalyst K ₂ CO _s / KL ₂ CO _s / C§ ₂ CO _s were the same as in example 9, except that 130 g of the raw material was used (Seggo No. DGO) and 60 g of catalyst K ₂ CO ₃ / KH ₂ CO ₃ / C? ₂ CO ₃ . In example 11, methane is used as a source of hydrogen. In example 12, hydrogen gas is used as the source of hydrogen. FIG. 14 graphically represents the amounts of non-condensable gas, crude product and coke. Lanes 186 and 188 represent the weight percentages of coke produced, lanes 190 and 192 represent the mass percentages of the resulting liquid hydrocarbons, and lanes 194 and 196 depict the mass percentages of the gas produced, based on the weight of the crude material.

In Example 11, 93 wt.% Crude product (lane 192), 3 wt.% Gas (lane 196) and 4 wt.% Coke (lane 188) are calculated, based on the weight of Seggo # dgo.

In example 12, 84% by weight of the crude product (lane 190), 7% by weight of gas (lane 194) and 9% by weight of coke (lane 186) are obtained, based on the weight of Seggo # dgo.

Examples 11 and 12 provide a comparison of the use of methane as a source of hydrogen relative to the use of hydrogen gas as a source of hydrogen. Methane is usually less expensive to produce and / or transport than hydrogen, so a methane process is desirable. As has been demonstrated, methane is at least as effective as hydrogen gas as a hydrogen source when contacting a crude raw material in the presence of an inorganic salt catalyst in order to produce a total product.

Examples 13-14. Obtaining the crude product with a given density of AP1.

The apparatus, the process procedure and the inorganic salt catalyst were the same as in Example 9, except for the variable pressure in the reactor.

In example 13, the pressure in the reactor is 0.1 MPa (14.7 psi) during the contacting period. A crude product is obtained with a density of 25 degrees AP1 (904.2 kg / m ³ ) at 15.5 ° C. The total product contains hydrocarbons with a distribution 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 is 3.4 MPa (514.7 psi). A crude product is obtained with a density of 51.6 degrees AP1 (772.8 kg / m ³ ) at 15.5 ° C. The total product contains hydrocarbons with a distribution of carbon atoms in the range of 5 to 15 (see curve 200 in Fig. 15).

These examples demonstrate methods for contacting a crude feed with hydrogen in the presence of an inorganic salt catalyst at different pressures to obtain a crude product with a predetermined density of AP1. By changing the pressure, a crude product is obtained with a higher or lower density of AP1.

Examples 15-16. Contacting the crude raw material in the presence of a catalyst K ₂ CO _h / HL ₂ CO _h / C _{2 2} CO _h or silicon carbide in the absence of an external source of hydrogen.

In Examples 15 and 16, the apparatus, the crude feed, and the process method were the same as in Example 9, except that the crude feed and the catalyst (or silicon carbide) were directly loaded into the reactor at the same time. Carbon dioxide (CO ₂ ) is used as a carrier gas. In example 15, the raw material Seggo Ngr (138 g) is combined with the catalyst K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ (60.4 g, similar to the catalyst in example 9). In example 16, the raw materials of Seggo Ngr (132 g) are combined with silicon carbide (83.13 g, 40 mesh, 81gg Marte15; Anho U1e_) o, CA). Such a silicon carbide is believed to have a 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. CO2 is metered into the reactor at a rate of 100 cm ³ / min. The 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 the cooled traps combine and analyze.

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

In example 16, when contacting the crude raw material with silicon carbide in an atmosphere of carbon dioxide, 15.78 g (11.95 wt.% Based on the weight of the crude raw material) of a yellow hydrocarbon liquid with a density of 12 degrees 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 more than ίπ-δίΐΓΐ in 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 demonstrated that during the contacting of the crude raw material in the presence of an inorganic salt, hydrogen is produced 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 / Rh _of CO ₂ / CO _{2 of} Cg, calcium oxide and silicon carbide in atmospheric conditions.

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

In examples 17 and 18, a K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ catalyst is used. 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.

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

In Example 19, the crude feed is contacted with CaCO3 under conditions similar to those described for Example 18. These percentages of the resulting crude product, gas, and coke are summarized in table. 4 in FIG. 16. The formation of gas in example 19 is increased compared with the formation of gas in example 18. Desulphurisation of the crude feed is not as effective as in Example 18. The crude product obtained in Example 19 contains 1.01 g of crude product, 0.01 g of sulfur compared to with a sulfur content of 0.008 g per 1 g of the 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 the inorganic salt catalyst. The formation of gas and coke in example 20 is significantly increased compared with 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. Obtained in example 20, the crude product contains per 1 g of the crude product, 0,036 g of sulfur compared to 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 produced 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 is observed (in wt.%) Compared to the amount of gas produced in a controlled experiment (for example, see Example 20 in Table 4, Fig. 16). From the amount of hydrocarbons in the resulting gas, it is possible to estimate the proportion of thermal cracking of the crude feed, which is at most 20% by weight, at most 15% by weight, at most 10% by weight, at most 5% by weight (or there is no cracking ), based on the total amount of crude raw material that has come into contact with a source of hydrogen.

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

The apparatus in examples 21 and 22 was the same as in example 9, except that hydrogen gas was used as the source of hydrogen. In example 21, 130.4 g of raw material Seggo Jedgo is combined with a K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ catalyst (30.88 g) to form a mixture of crude raw materials. In Example 22, 139.6 g of Seggo Yedgo raw material is combined with silicon carbide (80.14 g) to form a mixture of crude raw materials.

The mixture of raw materials is loaded directly into the reactor. Hydrogen gas is metered into the reactor at a rate of 250 cm ³ / min during the period of heating and aging. The mixture of crude raw materials is heated to 300 ° C for 1.5 hours and maintained at 300 ° C for 1 hour. The reaction temperature is raised to 400 ° C for 1 hour and maintained at 400 ° C for 1 hour. the reaction is equal to 400 ° C, water is introduced into the reactor at a rate of 0.4 g / min, in combination with gaseous hydrogen. Water and hydrogen are metered into the reactor during the remaining heating and holding periods. After keeping the reaction mixture at 400 ° C, the reaction temperature is raised to 500 ° C and maintained at 500 ° C 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 combine and analyze.

In Example 21, when contacting the crude feed with the K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ catalyst in a hydrogen atmosphere, 86.17 g (66.1 wt.%, Based on the weight of the crude feed) of the dark red are obtained. brown hydrocarbon liquid (crude product) and water (97.5 g) as vapors.

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In Example 22, water vapor and a small amount of gas are released from the reactor. During the examination of the reactor, a viscous, dark brown hydrocarbon liquid was removed from it. When the raw material is contacted 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 characteristics of the crude product obtained using the methods described in the invention, compared with the crude product obtained using hot water. Specifically, in Example 21, the crude product boils lower than the crude product from Example 22, as demonstrated by the crude product obtained in Example 22, which cannot be obtained as vapors. The crude product obtained in example 21, has improved flow characteristics, compared with the crude product obtained in example 22, which is determined by the method of visual inspection.

Examples 23-24. Contacting the crude feed with a source of hydrogen in the presence of a K ₂ CO ₃ / KL ₂ CO ₃ / C ₂ CO ₃ catalyst in order to obtain a larger volume of the crude product compared to the volume of the crude product obtained under non-catalytic conditions.

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

In example 23, 102 g of crude raw materials (100 ml of crude raw materials) and 31 g of K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ catalyst are charged to the reactor. A crude product (87.6 g) is obtained with a density of 50 degrees (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 raw materials (100 ml of crude raw materials) and 80 g of silicon carbide are loaded into the reactor. A crude product (70 g) is obtained with a density of 12 degrees (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% higher 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 product volume increases the ability of the refinery to produce a larger volume of crude product per unit volume of feed.

Example 25. Contacting the raw material with a source of hydrogen in the presence of a catalyst K ₂ CO ₃ / KL ₂ CO ₃ / C ₂ CO ₃ , sulfur and coke.

The apparatus and procedure were the same as in Example 9, except that the water vapor was metered into the reactor at a speed of 300 cm ³ / min. Catalyst K ₂ CO ₃ / Rb ₂ CO ₃ / Cg 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 of Cg ₂ CO _3.

The crude feed (130.35 g) and the catalyst K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ (31.6 g) are loaded into the reactor. The raw material of Seggo Ngo contains, for 1 g of crude raw materials, 0.04 g of the sum of aromatic hydrocarbons distributed in the boiling range between 149 and 260 ° C (300-500 ° P), 0.000640 g of the amount of nickel and vanadium, 0.042 g of sulfur and 0.56 g of residue. The density of the raw material in degrees is 6.7 (1023.9 kg / m ³ ).

Contacting the raw material with methane in the presence of a catalyst K ₂ CO ₃ / KL ₂ CO ₃ / C ₂ CO ₃ gives 0.95 g of the total product and 0.041 g of coke per 1 g of the raw material.

The total product includes 1 g of total product, 0.91 g of crude product and 0.028 g of hydrocarbon gas. The resulting amount of gases 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 crude product vapor.

The crude product is analyzed using a combination of gas chromatography and mass spectrometry. The crude product includes a mixture of hydrocarbons with a boiling range of 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 the raw material.

The 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% by weight, based on the mass of the initial catalyst K ₂ CO ₃ / KL 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 U / ν, and 0.845 g K ₂ CO ₃ / KH ₂ CO ₃ / C ₂ CO ₃ per 1 g of the spent catalyst.

An additional amount of the raw material (152.71 g) is contacted with the first spent catalyst (36.63 g) in order to obtain 150 g of the extracted total product, taking into account losses. This total product contains, per 1 g total product, 0.92 g of liquid crude product, 0.058 g of additional coke and 0.017 g of gas. This gas includes 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 hydrocarbon product vapors (<1 mol.%).

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The crude product includes a mixture of hydrocarbons with a boiling range of between 100 and 538 ° C. 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 in the raw material.

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% by weight based on the mass of the initial K ₂ CO ₃ / KH ₂ CO ₃ / Ck 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 / KH ₂ CO ₃ / Ck ₂ CO ₃ per 1 g of the second spent catalyst.

An additional amount of the crude feed (104 g) is contacted with the second spent catalyst (44.84 g) to obtain 104 g of the total product per 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 tank for adding due to the overheating of this tank, when 104.1 g out of 133 g of the pumped raw raw material are raw raw material.

The total product includes 1 g of the total product, 0.86 g of the crude product and 0.025 g of hydrocarbon gas. The total gas includes 0.18 mol of hydrogen, 0.052 mol of carbon dioxide and 0.03 mol of C2-C6 hydrocarbons per 1 mol of gas. The gas balance is methane, air, carbon monoxide, hydrogen sulfide, and a small amount of hydrocarbon vapor.

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

The spent catalyst (the third spent catalyst) is removed from the reactor, weighed and then analyzed. The mass 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 mass of the initial K ₂ CO ₃ / KH ₂ CO ₃ / Ck ₂ CO ₃ catalyst). Conducted a detailed elementary analysis of the third spent catalyst. The third spent catalyst includes, for 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, and the remainder is in 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 raw material with source of hydrogen 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 raw materials, 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 raw material) is 89.7% by weight, with a standard deviation of 2.6%; the average coke yield is 7.5 wt.% (calculated on the mass of the crude feed) with a standard deviation of 2.7% and the average mass yield of cracked hydrocarbon gas is 2.3 wt.% (calculated 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 unsatisfactory performance of the temperature controller in the supply tank led to overheating of the raw material in the addition tank. Despite this, it appears that there is no significant adverse effect of even large amounts 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 C ₃ hydrocarbons is 0.4. The ratio of alpha-olefins to internal olefins in C ₄ hydrocarbons is 0.61. The C ₄ cis / trans olefin ratio is 6.34. This ratio is significantly higher than the thermodynamically predicted C4 cis / trans olefins ratio of 0.68. The ratio of alpha-olefins to internal olefins in C5 hydrocarbons is 0.92. This ratio is significantly higher than the predicted thermodynamic C5 ratio of alpha olefins to internal olefins of C ₅ equal to 0.194. The C ₅ cis / trans olefin ratio is 1.25. This ratio is higher than the thermodynamically predicted C5 ratio of cis- / trans-olefins, equal to 0.9.

Example 26. Contacting the raw material with a relatively high sulfur content with a source of hydrogen in the presence of a catalyst K ₂ CO ₃ / KH ₂ CO ₃ / Ck ₂ CO ₃ .

The apparatus and process method were the same as described in Example 9, except that crude raw materials, methane and steam are continuously fed to the reactor. The level of raw materials in the reactor is recorded by the change in mass of the reactor. Methane gas is continuously metered into the reactor at a rate of 500 cm ³ / min. Steam is continuously metered into the reactor at a rate of 6 g / min.

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The inorganic salt catalyst is obtained by combining 27.2 g of K ₂ CO ₃ , 32.2 g of KH ₂ CO _3, and 40.6 g of C _{2 2} CO ₃ . Catalyst K ₂ CO _c / Rb ₂ CO _s / Cg _of Co ₂ (59.88 g) was charged to the reactor.

Untreated raw materials (bitumen, Mowbstzieg, Sapaba), having a density of 9.4 degrees (1004.3 kg / m ³ ), a sulfur content of 0.02 g of sulfur and a residue content of 0.40 g per 1 g of raw material, are heated in a tank to add up to 150 ° C. Hot bitumen is continuously metered at a rate of 10.5 g / min from the reservoir to be added to the reactor in order to maintain the level of liquid crude raw material at 50% of the reactor volume, but this rate was not sufficient to maintain this level.

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

Over the course of 6 hours, a total of 1640 g of crude raw materials were 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 the raw material. When the raw material is contacted with methane in the presence of a K ₂ CO ₃ / KL ₂ CO ₃ / C ₂ CO ₃ catalyst, 0.93 g of the total product is produced per 1 g of the raw material. The total product contains per 1 g of the total product, 0.03 g of gas and 0.97 g of the crude product with the exception of the amount of methane and water used in this process.

The gas includes per 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% by weight. 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 0.30 g of compounds C ₂ , 0.32 g of compounds C3, 0.26 g of compounds C4 and 0.10 g of compounds C5 per 1 g of hydrocarbons. 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 of C ₄ have, per g of compounds of C ₄ , a butadiene content of 0.003 g. The weight ratio of alpha olefins of C ₄ to internal olefins of C ₄ is 0.75. The weight ratio of alpha-olefins C5 to internal olefins C5 is 1.08.

The data in Example 25 demonstrates that with continuous processing of crude raw materials with 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 is obtained that is suitable for transportation.

Example 27. Contacting the crude raw material with a source of hydrogen in the presence of a catalyst K ₂ CO ₃ / kL ₂ CO ₃ / C ₂ CO ₃ and coke.

The apparatus and the process procedure are carried out using the conditions described in Example 26. The catalyst (56.5 g) is loaded into the reactor. Over the course of 6 hours, a total of 2550 g of crude raw materials are 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 raw material. In total, 0.89 g of total product per 1 g of crude feed is obtained. The total product includes per gram of total product, 0.04 g of gas and 0.96 g of crude product, excluding the amount of methane and water used in this process.

The gas includes per 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. By 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, for 1 g of hydrocarbons C2-C6, 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 . 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 per g gram of compounds C _{4 the} content of butadiene is 0.003 g.

This example demonstrates that when recycling raw raw materials (2550 g raw materials) with a relatively high sulfur content with the same catalyst (56.5 g) in the presence of coke does not decrease the activity of the inorganic salt catalyst and produce a crude product suitable for transportation.

Further modifications and alternative embodiments of various aspects of this invention will be apparent to those skilled in the art in light of the present disclosure. Therefore, this description should be considered only as illustrative, which is given with 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 shown and described herein may be taken as examples of its implementation. Items and materials shown and described herein may be replaced.

- 44 009091, parts and processes can be changed and some features of the invention can be used independently, all this is obvious to those skilled in the art 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 (17)

CLAIM 1. A method of obtaining a crude product formed during oil production, in which the crude feed is in contact with a hydrogen source in the presence of one or more catalysts containing K ₃ Fe1 ₀ §1 ₄ . 2. The method according to claim 1, in which K ₃ Re1 ₀ §1 ₄ is formed in the hydrogenation zone. 3. The method according to claim 1 or 2, in which one or more catalysts contain at least one other transition metal sulfide. 4. The method according to any one of claims 1 to 3, in which at least one of the transition metal sulfides contains one or more transition metals from groups 6-10 of the Periodic table of elements, one or more compounds of one or more transition metals from groups 6- 10 of the Periodic Table or mixtures thereof. 5. The method according to any one of claims 3 or 4, wherein at least one of the transition metals in the sulfides of the transition metals is iron. 6. The method according to any one of claims 3 to 5, in which the atomic ratio of the transition metal to sulfur in at least one of the sulfides of the transition metals is in the range from 0.5 to 10. 7. The method according to any one of claims 3 to 6, in which the catalyst containing a transition metal sulfide further comprises at least one alkali metal, at least one alkali metal compound, at least one alkaline earth metal, at least one alkaline earth metal compound, zinc, at least one zinc compound or mixtures thereof. 8. The method according to claim 7, in which the atomic ratio of an alkali metal, alkaline earth metal or zinc to a transition metal is in the range from above 0 to 1. 9. The method according to any one of claims 1 to 8, in which, in addition, the contact conditions, which are temperature, pressure, flow rate of the hydrogen source, flow rate of the crude feed, or combinations thereof, are controlled in such a way that 1 g of crude feed at least 0.2 g, at least 0.15 g, or at most 0.1 g of hydrocarbons are formed, which do not condense at 25 ° C and 0.101 MPa, which is determined using the material balance. 10. The method according to any one of claims 1 to 9, in which the contact conditions, which are the temperature, pressure, flow rate of the hydrogen source, the flow rate of the crude feed or a combination thereof, are controlled so that at least part of the total product is obtained in the form steam, wherein at least a portion of the steam is condensed at 25 ° C. and 0.101 MPa to obtain a crude product. 11. The method according to any one of claims 1 to 10, in which the temperature, pressure, flow rate of the hydrogen source, the flow rate of the crude feed or combinations thereof are controlled so that the crude product has from 0.00001 to 0.03 g or from 0 , 0001 to 0.01 g of coke per 1 g of crude product. 12. The method according to any one of claims 1 to 11, in which the temperature, pressure, flow rate of the hydrogen source, the flow rate of the crude feed or combinations thereof are controlled so that the crude product has from 0.00001 to 0.05 g of a residue, from 0.001 to 0.99 g of vacuum gas oil, from 0.001 to 0.9 g of distillate and from 0.001 to 0.2 g of naphtha or mixtures thereof per 1 g of crude product and the crude product also has from 0.01 to 0.4 g of diesel fuel per 1 g of crude product. 13. The method according to any one of claims 1 to 12, in which the crude product has from 0.2 to 0.99 g or 0.30.8 g of residue per 1 g of crude feed. 14. The method according to any one of claims 1 to 13, in which further combine the crude product with a raw material that is the same or different from the crude raw material to obtain a mixture. 15. The method according to any one of claims 1 to 14, which further includes the step of processing the crude product or mixture in order to obtain transport fuel, boiler fuel, lubricants or chemicals. 16. The method according to clause 15, in which the processing includes distillation of the crude product or mixture to obtain one or more distillate fractions. 17. The method according to 14 or 15, in which the processing includes hydrotreating.