NL1027775C2 - Systems and methods for preparing a crude product. - Google Patents

Abstract

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

Description

- 1 -

SYSTEMS AND METHODS FOR PREPARING A RAW

PRODUCT

FIELD OF THE INVENTION

The present invention relates generally to systems and methods for treating a crude feed, and to compositions prepared, for example, by using such systems and methods. More specifically, the embodiments described in this patent relate to systems and methods for converting a crude feed with a residual content of at least 0.2 grams of residue per gram of crude feed into a product which (a) is liquid is at 25 ° C and 0.101 MPa, and (b) has one or more properties that are improved over the same properties of the crude feed.

15 DESCRIPTION OF THE RELATED ART

Crude oils that have one or more unsuitable properties that make it impossible for them to be transported at low cost, or processed with the aid of conventional installations, are often referred to as "less useful crude oils".

Less useful crude oils often contain a relatively high residue content. Such crude oils are often difficult and only at high costs to transport and / or to process with the aid of conventional devices. Crude oils with a high residue content can be treated at high temperatures, so that the crude oil is converted to coke. Alternatively, the crude oils with a high residue content are often treated with water at high temperatures, so that less viscous crude oils and / or blends of crude oils are obtained. During processing it can be difficult to remove water from the less viscous crude oils and / or blends of crude oils using conventional devices.

Less useful raw oils can contain hydrocarbons with a shortage of hydrogen. When hydrocarbons with a hydrogen deficiency are processed, corresponding amounts of hydrogen should generally be added to the. especially if unsaturated fragments are prepared that come from cracking processes. In order to prevent unsaturated fragments from forming coke, hydrogenation during processing may generally be necessary, which hydrogenation generally involves the use of an active hydrogenation catalyst. It is expensive to prepare hydrogen and / or expensive to transport hydrogen to treatment plants. During the processing of less useful crude oils, coke can form at a high speed and / or can be deposited at a high speed on the surfaces of catalysts. It can be expensive to regenerate the catalytic activity of a coke contaminated catalyst. Due to the high temperatures used during regeneration, the activity of the catalyst can also be reduced and / or the catalyst can also deteriorate.

Less useful raw oils can have acidic components that contribute to the total acid value ("TAN") of the crude feed. Less usable crude oils with a relatively high TAN can contribute to the corrosion of metal components during transport and / or processing of the less useful crude oils. The removal of acid components from less useful crude oils may involve the chemical neutralization of acid components with different bases. Alternatively, corrosion-resistant metals may be used for the transport device and / or the processing device. The use of corrosion-resistant metal often entails considerable costs, and therefore the use of corrosion-resistant metal in an existing device may not be desirable. Another method for preventing corrosion may involve the addition of corrosion inhibitors to the less useful crude oils for transporting and / or processing the less useful crude oils. The use of corrosion inhibitors can have a negative effect on the device used to process the crude oils and / or on the quality of products prepared from the crude oils.

Less useful crude oils can contain relatively large amounts of metal contaminants, for example nickel, vanadium and / or iron. During the processing of such crude oils, metal impurities and / or compounds of metal impurities can deposit on a surface of the catalyst or in the void space of the catalyst. Such deposits can cause a decrease in the activity of the catalyst.

Less useful crude oils often contain organically bound heteroatoms (for example sulfur, oxygen and nitrogen). Organically bound heteroatoms can in some cases have an adverse effect on 1027775 "- 4 - catalysts. In processes for removing the residue from sulfur, alkali metal salts and / or alkaline earth metal salts are used. In these processes, the efficiency of removing sulfur is often poor. 5. oil-insoluble sludge is often formed, the metal stripping efficiency is often poor, salt-oil mixtures that are essentially indivisible are often used, large amounts of hydrogen gas are often used and / or high hydrogen pressures are often used.

Some processes for improving the quality of a crude oil involve the addition of a diluent to the less useful crude oil, so that the weight percentage of components is reduced which contributes to the disadvantageous properties. However, by adding diluent, the cost of treating less usable crude oils is generally increased because the diluent entails costs and / or the handling costs of the less useful crude oils increase. Adding a diluent to a less useful crude oil can in some cases degrade the stability of such a crude oil.

In U.S. Patent Nos. 3,136,714 to Gibson et al .; 3,558,747 to Gleim et al .; 3,847,797 to Pasternak et al .; 3,948,759 to King et al .; 3,957,620 to Fukui et al .; 3,960,706 to McCollum et al .; 3,960,708 to McCollum et al .; 4,119,528 to Baird. Jr. et al .; 4,127,470 to Baird. Jr. et al .; 4,224,140 to Fujimori et al .; 4,437,980 to Heredy et al .; 4,591,426 to Krasuk et al .; 4,665,261 to Mazurek; 5,064,523 to Kretschmar et al .; 5,166,118 to Kretschmar et al .; 5,288,681 to Gatsis; No. 1,027,775 "to Sudhakar et al.; And U.S. Patent Applications Nos. 20030000867 to Reynolds and 20030149317 to Rendina, describe various methods and systems used to treat crude oils. The methods, systems, and catalysts however, those described in these patents have limited applicability due to many of the above technical problems.

In summary, less useful crude oils generally have undesirable properties (for example, a relatively high residue content, the tendency to corrode devices and / or the tendency to use relatively large amounts of hydrogen during their treatment) . Other undesirable properties include relatively large amounts of undesirable components (e.g., a relatively high TAN, organically bound heteroatoms, and / or metal-containing contaminants). Such properties often cause problems in conventional transport and / or treatment devices, including increased corrosion, shorter catalyst life, clogging of the device and / or increased use of hydrogen during the treatment.

In view of the costs and in the technical field, there is therefore a clear need for improved systems, processes and / or catalysts for converting less usable crude oils into crude products with properties that are more desirable.

SUMMARY OF THE INVENTION

The inventions described in this patent generally relate to systems and methods for contacting a crude 1027775 "- 6 - feed with one or more catalysts, thereby obtaining a total product comprising a crude product and, in some embodiments , non-condensable gas. The inventions described in this patent generally also relate to compositions with novel combinations of components therein. Such compositions can be obtained by using the systems and methods described in this patent.

The invention provides a process for preparing a crude product comprising contacting a crude feed with a source of hydrogen in the presence of one or more catalysts, so that the crude product is formed, one or more of the catalysts include a catalyst containing K3 Fe10 Si4.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts to obtain a total product containing the crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein at least one of the catalysts comprises one or more transition metal sulfides, and wherein the crude feed has a residue content determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of raw food; and controlling the contact conditions such that the crude product contains at most 0.05 grams of coke per gram of crude product, wherein the crude product contains at least 0.001 grams of naphtha per gram of crude product, and the naphtha has an octane number of at least 70 .

1027775 * - 7 -

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts to obtain a total product containing the crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein at least one of the catalysts comprises one or more transition metal sulfides, and wherein the crude feed has a content of residue 10, determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of raw food; and controlling the contact conditions such that the crude product comprises petroleum, wherein the petroleum, determined according to the ASTM method D5186, contains at least 0.2 grams of aromatics per gram of petroleum, wherein the petroleum has a freezing point determined according to the ASTM method D2386, of no more than -30 ° C, and wherein the crude product contains no more than 0.05 grams of coke per gram of crude product.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts to obtain a total product containing the crude product wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein at least one of the catalysts comprises one or more transition metal sulfides, and wherein the crude feed has a residue content of at least 0.2 grams of residue per gram raw food; and controlling the contact conditions such that the crude product contains at most 0.05 grams of coke per gram of crude product, wherein the weight ratio of hydrogen atoms to carbon atoms (H / C) of the crude product, determined according to the ASTM method D6730, is no more than 1.75.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts to obtain a total product containing the crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein at least one of the catalysts comprises one or more transition metal sulfides, and wherein the crude feed has a residue content, determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of crude feed, and wherein the weight ratio of hydrogen atoms to carbon atoms (H / C) of the crude feed is at least 1.5; and controlling the contact conditions such that the crude product has an H / C atomic ratio of 80-120% of the H / C atomic ratio of the crude feed, wherein the crude product has a residue content determined according to the ASTM method D5307, of a maximum of 30% of the residual content of the crude feed, the crude product containing at least 0.001 grams of naphtha per gram of crude product, and wherein the naphtha has an octane number of at least 70.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts to obtain a total product containing the crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein at least one of the catalysts comprises one or more transition metal sulfides 1027775 "- 9 -, and wherein the crude feed has a residue content determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of raw food; and controlling the contact conditions such that the crude product, per gram of crude product: contains at least 0.001 gram of naphtha, wherein the naphtha has an octane number of at least 70; contains at least 0.001 grams of petroleum, the petroleum comprising aromatics, wherein the petroleum, determined according to the ASTM method D5186, contains at least 0.2 grams of aromatics per gram of petroleum, and wherein the petroleum has a freezing point determined according to the ASTM method D2386, of a maximum of -30 ° C; contains at least 0.001 vacuum gas oil (VGO), wherein the VGO, determined according to the IP method 368/90, contains at least 0.3 grams of aromatics per gram of VGO; and, determined by the ASTM method D5307, contains no more than 0.05 grams of residue.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts comprising a transition metal sulfide-containing catalyst, so that a total product is obtained that the crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein the transition metal sulfide-containing catalyst comprises a total of at least 0.4 grams of one or more transition metal sulfides per gram of the total transition metal sulfide-containing catalyst wherein the crude feed has a residue content, determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of raw feed; and controlling the contact conditions such that the crude product contains no more than 0.05 grams of coke per gram of crude product, and that the crude product has a content of 10277 75 * - 10 - residue, determined according to the ASTM method D5307, of at most 30% of the residual content of the crude feed.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts comprising a transition metal sulfide-containing catalyst, so that a total product is obtained containing the crude product, the crude product being a liquid mixture at 25 ° C and 0.101 MPa, wherein the transition metal sulfide-containing catalyst contains a total of at least 0.4 grams of one or more transition metal sulfides per gram of the transition metal sulfide-containing catalyst, wherein the crude feed has a nitrogen content of at least 0.01 grams of nitrogen per gram of raw feed, and wherein the crude feed has a residue content of at least 0.2 grams of residue per gram of raw feed; and controlling the contact conditions such that the crude product has a nitrogen content of at most 90% of the nitrogen content of the crude feed, and that the crude product has a residue content of at most 30% of the residue content of the crude feed, wherein the nitrogen content is determined according to the ASTM method D5672 and the content of residue is determined according to the ASTM method D5307.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts comprising a transition metal sulfide-containing catalyst, so that a total product is obtained that the crude 1027775 product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein the transition metal sulfide-containing catalyst contains a total of at least 0.4 grams of one or more transition metal sulfides per gram of the total transition metal sulfide-containing catalyst, wherein the crude feed has a total Ni / V / Fe content of at least 0.0001 grams of Ni / V / Fe per gram of crude feed, and wherein the crude feed has a residual content of at least 0.2 grams of residue per gram of crude feed; and controlling the contact conditions such that the crude product contains at most 0.05 grams of coke per gram of crude product, that the crude product has a total Ni / V / Fe content of at most 90% of the Ni / V / Fe content of the crude feed, and that the crude product has a residual content of at most 30% of the residual content of the raw feed, the Ni / V / Fe content being determined according to the ASTM method D5863 and the residue content is determined according to the ASTM method D5307.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts comprising a transition metal sulfide-containing catalyst, so that a total product is obtained containing the crude product, the crude product being a liquid mixture at 25 ° C and 0.101 MPa, wherein the transition metal sulfide-containing catalyst contains a total of at least 0.4 grams of one or more transition metal sulfides per gram of the total transition metal sulfide-containing catalyst, wherein the crude feed has a content of sulfur of at least 0.001 grams of sulfur per gram of raw feed, and wherein the crude feed has a content of 1027775 "- 12 - of residue of at least 0.2 grams of residue per gram of raw feed; and controlling the contact conditions such that the crude product has a sulfur content that is at most 70% of the sulfur content of the crude feed, and that the crude product has a residue content of at most 30% of the residual content of the crude feed, the content of sulfur being determined according to the ASTM method D4294 and the. residue content is determined according to the ASTM method D5307.

The invention also provides a process for preparing a transition metal sulfide-containing catalyst composition, comprising: mixing a transition metal oxide and a metal salt so that a transition metal oxide / metal salt mixture is obtained;

reacting the transition metal oxide / metal-salt mixture with hydrogen to form an intermediate; and reacting the intermediate with sulfur, in the presence of one or more hydrocarbons, so that the transition metal sulfide-containing catalyst is obtained.

The invention also provides a process for preparing a crude product, comprising: contacting a raw feed with a source of hydrogen in the presence of one or more catalysts comprising a transition metal sulfide-containing catalyst, so that a total product is obtained containing the crude product, the crude product being a liquid mixture at 25 ° C and 0.101 MPa, wherein the transition metal-containing sulfide-containing catalyst contains a transition metal sulfide, the crude feed having a residue content determined according to ASTM method D5307, of at least 0.2 grams of residue per gram of raw food; controlling the contact conditions such that the crude product has a residual content of at most 30% of the residual content of the crude feed; wherein the transition metal sulfide-containing catalyst can be obtained by: mixing a transition metal oxide and a metal salt so that a transition metal oxide / metal salt mixture is obtained, reacting the transition metal oxide / metal salt mixture with hydrogen to form an intermediate, and reacting the intermediate with sulfur in the presence of one or more hydrocarbons the transition metal sulfide-containing catalyst is obtained.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts, so that a total product is obtained containing the crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, and wherein the crude feed, determined according to the ASTM method D5307, contains at least 0.2 grams of residue per gram of crude feed; preparing at least a portion of the total product as a vapor; allowing at least a portion of the vapor to condense at 25 ° C and 0.101 MPa; and forming the crude product, wherein the crude product contains per gram of crude product: at least 0.001 gram of naphtha, wherein the naphtha has an octane number of at least 70; contains at least 0.001 gram of VGO, the VGO, determined according to the IP method 368/90, containing at least 0.3 gram of aromatics per gram of VGO; and, determined by the ASTM method D5307, contains no more than 0.05 grams of residue.

1027775 * 5 - 14 -

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, so that a total product is obtained that the crude product contains, wherein the crude feed has a residue content, determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of crude feed, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, and wherein the crude product, per gram of crude product: contains at least 0.001 gram of naphtha, wherein the naphtha determined according to the ASTM method D6730 contains at least 0.001 gram of aromatics consisting of a monocyclic ring; contains at least 0.001 grams of distillate; and, determined by the ASTM method D5307, contains no more than 0.05 grams of residue.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, so that a total product is obtained that the crude product contains, wherein the crude feed has a residue content, determined according to the ASTM method D5307, of at least 0.2 grams of residue per 25 grams of crude feed, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, and wherein the crude product, per gram of crude product: contains at least 0.001 gram of diesel, wherein the diesel, determined according to the IP method 368/90, contains at least 0.3 gram of aromatics per gram of diesel; contains at least 0.001 grams of VGO, the VGO, determined according to the IP method 369/90, containing at least 0.3 grams of aromatics per gram of VGO; and, determined by the ASTM method D5307, contains no more than 0.05 grams of residue.

10277751 - 15 -

The invention also provides a method for. preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product containing the crude product, the crude product at 25 ° C and 0.101 MPa is a liquid mixture in which the crude feed has a residue content, determined according to the ASTM method D5307, of at least 10 0.2 grams of residue per gram of raw feed, and wherein the raw feed has a content of has aromatics consisting of a monocyclic ring, determined according to the ASTM method D5307, of no more than 0.1 gram aromatics consisting of a monocyclic ring per gram of raw food; and controlling the contact conditions such that during contacting, determined on the basis of the mass balance, per gram of raw feed a maximum of 0.2 gram of hydrocarbons is formed which cannot be condensed at 25 ° C and 0.101 MPa, and that the crude product has a monocyclic ring aromatics content that is at least 5% greater than the monocyclic ring aromatics content of the crude feed, wherein the monocyclic ring aromatics content is determined according to the ASTM method D6730.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, so that a total product is obtained that the crude product product, where the crude product is a liquid mixture at 25 ° C and 0.101 MPa, where the crude feed has a residue content, determined according to the ASTM method D5307, of at least 0.2 grams residue per gram of crude feed, and the crude feed has an olefins content, expressed in grams of olefins per gram of raw feed, and controlling the contact conditions such that the crude product has an olefins content that is at least 5% higher then the olefins content of the crude feed, wherein the olefins content is determined according to the ASTM-10 method D6730.

The invention also provides a method for preparing a crude product, comprising: the. presence of an inorganic salt catalyst contacting a crude feed with a source of hydrogen to obtain a total product containing the crude product, the crude product being a liquid mixture at 25 ° C and 0.101 MPa, wherein the crude feed has a residue content of at least 0.2 grams of residue per gram of crude feed, and wherein the inorganic salt catalyst exhibits an inflection of the gas released, determined by Temporal Analysis of Products (TAP) , in a temperature range between 50 ° C and 500 ° C; and controlling the contact conditions such that the crude product has a residue content, expressed in grams of residue per gram of crude product, of at most 30% of the residue content of the crude feed, the residue content being determined according to the ASTM method D5307.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst to produce a total product. 1027775 17 - obtained containing the crude product, the crude product being a liquid mixture at 25 ° C and 0.101 MPa, the crude feed having a residual content of at least 0.2 grams of residue per gram of raw feeding, wherein 5 the inorganic salt comprises at least two inorganic metal salts, and the inorganic salt exhibits inflation of the released gas, determined by Temporal Analysis of Products (TAP), in a temperature range where the temperature range of the inflation of the released gas is is between (a) the DSC temperature of at least one of the two inorganic metal salts and (b) the DSC temperature of the inorganic salt catalyst; and controlling the contact conditions such that the crude product has a residue content, expressed in grams of residue per gram of crude product, of at most 30% of the residue content of the crude feed, the residue content being determined according to the ASTM method D5307.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, so that a total product is obtained that the crude product product, the crude product at 25 ° C and 0.101 MPa being a liquid mixture, the crude feed having a residual content, determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of raw feed and wherein the inorganic salt exhibits an inflection of the gas released 30, determined by Temporal Analysis or

Products (TAP), in a temperature range between 50 ° C and 500 ° C; and preparing the crude product such that> 1027775- the volume of the prepared crude product is at least 5% greater than the volume of the crude feed, the volumes being measured at 25 ° C and 0.101 MPa.

The invention also provides a process for the preparation of a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, so that a total product is obtained that the crude product product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, wherein the crude feed has a residual content of at least 0.2 grams of residue per gram of crude feed, and wherein the inorganic salt has an inflection of the gas released, determined by Temporal Analysis of Products (TAP), has a temperature range of 50 ° C to 500 ° C; and controlling the contact conditions such that during contacting, determined on the basis of the mass balance, per gram of crude feed a maximum of 0.2 gram of hydrocarbons is formed which cannot be condensed at 25 ° C and 0.101 MPa to become.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that contains crude product, the crude product being a liquid mixture at 25 ° C and 0.101 MPa, the crude feed having a residual content of at least 0.2 grams of residue per gram of crude feed, and the inorganic salt existing catalyst exhibits a heat transition determined by differential scanning calorimetry (DSC), at a rate of 10 ° C per minute, in a temperature range of 200 ° C to 500 ° C; and controlling the contact conditions such that the crude product has a residue content, expressed in grams of residue per gram of crude product, of at most 30% of the residue content of the crude feed, wherein the residue content is determined according to the ASTM method D5307.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, so that a total product is obtained that the crude product product, the crude product being at 25 ° C and. 0.01 MPa is a liquid mixture, the crude feed having a residue content of. at least 0.2 grams of residue per gram of crude feed, and wherein the inorganic salt catalyst has an ionic conductivity that is. is at least equal to the ionic conductivity of at least one of the inorganic salts of the inorganic salt catalyst at a temperature in the range of 300 ° C to 500 ° C; and controlling the contact conditions such that the crude product has a residue content, expressed in grams of residue per gram of crude product, of at most 30% of the residue content of the crude feed, the residue content being determined according to the ASTM method D5307.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed in the presence of an inorganic salt catalyst with a source of hydrogen to produce a total product the crude product is obtained, the crude product being a liquid mixture at 25 ° C and 0.101 MPa, the crude feed having a residual content of at least 0.2 grams of residue per gram of raw feeding, the inorganic salt catalyst comprises alkali metal salts, wherein at least one of the alkali metal salts is an alkali metal carbonate and the alkali metals have an atomic number of at least 11, 10 and wherein at least one atomic ratio of an alkali metal having an atomic number of at least 11, to an alkali metal with an atomic number greater than 11 is in the range of 0.1 to 10; and controlling the contact conditions such that the crude product has a residue content that is at most 30% of the residue content of the crude feed, the residue content being determined according to the ASTM method D5307.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst to form a total product, the crude product forming feed has a residue content of at least 0.2 grams of residue per gram of crude feed, wherein the inorganic salt catalyst comprises alkali metal salts, wherein at least one of the alkali metal salts is an alkali metal hydroxide and the alkali metals have an atomic number of at least 30 11, and at least one atomic ratio of an alkali metal having an atomic number of at least 11 to an alkali metal having an atomic number greater than 11 is in the range of 0.1 to 10; 11027775 preparing at least a portion of the total product as a vapor; allowing at least a portion of the vapor to condense at 25 ° C and 0.101 MPa; and forming the crude product, wherein the crude product 5 has a residue content that is at most 30% of the residue content of the crude feed.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst to form a total product, wherein the total product is formed, crude feed has a residue content of at least 0.2 grams of residue per gram of crude feed, wherein the inorganic salt catalyst comprises alkali metal salts, wherein at least one of the alkali metal salts is an alkali metal hydride and the alkali metals have an atomic number of at least 11, and at least one atomic ratio of an alkali metal with an atomic number of at least 11, relative to an alkali metal with an atomic number greater than 11, is in the range of 0.1 to 10; preparing at least a portion of the total product as a vapor; allowing at least a portion of the vapor to condense at 25 ° C and 0.101 MPa; and forming the crude product, wherein the crude product has a residue content that is at most 30% of the residue content of the crude feed.

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, so that a total product is obtained that the crude product wherein the crude 1027775 product at 25 ° C and 0.101 MPa is a liquid mixture, the crude feed having a residual content of at least 0.2 grams of residue per gram of crude feed, the crude salt from inorganic salt existing catalyst comprises one or more alkali metal salts, one or more alkaline earth metal salts or a mixture thereof, wherein one of the alkali metal salts is an alkali metal carbonate, the alkali metals having an atomic number of at least 11; and controlling the contact conditions such that the crude product has a residue content of at most 30% of the residue content of the crude feed, wherein the residue content is determined according to the ASTM method D5307.

The invention also provides a method for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst to obtain a total product that the crude product wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture, wherein the crude feed has a residue content of at least 0.2 grams of residue per gram of crude feed, wherein the inorganic salt catalyst is one or more alkali metal hydroxides, one or more alkaline earth metal salts or a mixture thereof, wherein one of the alkali metal salts is an alkali metal carbonate, the alkali metals having an atomic number of at least 11; and controlling the contact conditions such that the crude product has a residue content of at most 30% of the residue content of the crude feed, the residue content being determined according to the ASTM method D5307.

1027775- 23 -

The invention also provides a process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of an inorganic salt catalyst, so that a total product is obtained that the crude product wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the crude feed having a residual content of at least 0. 2 grams of residue per gram of crude feed, wherein the inorganic salt catalyst is a or more alkali metal hydrides, one or more alkaline earth metal salts or a mixture thereof, wherein one of the alkali metal salts is an alkali metal carbonate, wherein the alkali metals have an atomic number of at least 11/11 and controlling the contact conditions such that the crude product has a residue content has a maximum of 30% of the residual content of the crude feed, the residual content being determined vo according to the ASTM method D5307.

The invention also provides a process for the preparation of hydrogen gas, comprising: contacting a crude feed with one or more hydrocarbons in the presence of an inorganic salt catalyst and water, the hydrocarbons having a number of carbon atoms in the range from 1 to 6, wherein the crude feed has a residue content of at least 0.2 grams of residue per gram of crude feed, and wherein the inorganic salt catalyst exhibits an inflection of the gas released, determined by means of Temporal Analysis of Products (TAP), in a temperature range of 50 ° C to 500 ° C; and preparing hydrogen gas.

1027775 - 24 -

The invention also provides a process for preparing a crude product, comprising: contacting a first crude feed in the presence of steam with an inorganic salt catalyst to form a gas stream, which gas stream comprises hydrogen, wherein the first crude feed has a residue content, determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of the first crude feed, and the inorganic salt catalyst exhibits an inflection of the gas released , determined by Temporal Analysis of Products (TAP), in a temperature range of 50 ° C to 500 ° C; contacting a second crude feed with a second catalyst in the presence of at least a portion of the formed gas stream, so that a total product is obtained containing the crude product, the crude product at 25 ° C and 0.101 MPa liquid mixture; and controlling the contact conditions such that one or more properties of the crude product change by at least 10% relative to the respective one or more properties of the second crude feed.

The invention also provides a method for generating a gas stream, comprising: contacting a crude feed in the presence of steam with an inorganic salt catalyst, wherein the crude feed has a residue content determined according to the ASTM method D5307, of at least 0.2 grams of residue per gram of raw food; and generating a gas stream, wherein the gas stream comprises hydrogen, carbon monoxide, and carbon dioxide, and wherein the molar ratio of the carbon monoxide to the carbon dioxide is at least 0.3.

The invention also provides a process for preparing a crude product, comprising: conditioning an inorganic salt catalyst; contacting a crude feed with a source of hydrogen in the presence of the conditioned inorganic salt catalyst to obtain a total product containing the crude product, wherein the crude product at 25 ° C and 0.101 MPa is a liquid mixture wherein the crude feed has a residue content of at least 0.2 grams of residue per gram of raw feed; and controlling the contact conditions such that the crude product has a residue content, expressed in grams of residue per gram of crude product, of at most 30% of the residue content of the crude feed, wherein the residue content is determined according to the ASTM method D5307.

The invention also provides a crude composition comprising hydrocarbons with a boiling range at 0.101 MPa between 30 ° C and 538 ° C (1000 ° F), wherein the hydrocarbons comprise isoparaffins and n-paraffins, the weight ratio of the isoparaffins to of the n-paraffins, determined according to the ASTM method D6730, is at most 1.4.

The invention also provides a crude composition with per gram of the composition: at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa to at most 204 ° C (400 ° F), at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 204 ° C and 300 ° C, at least 0.001 grams of hydrocarbons with a boiling range at 0.101 MPa between 300 ° C and 400 ° C, and at least 0.001 grams of hydrocarbons with a boiling range at 0.01 MPa between 400 ° C and 538 ° C (1000 ° F), wherein the hydrocarbons having a boiling range up to a maximum of 204 ° C comprise isoparaffins and n-paraffins with a weight ratio of the isoparaffins to the n-paraffins determined according to the ASTM method D6730, of no more than 1.4.

The invention also provides a crude composition with per gram of the composition: at least 0.001 gram of naphtha, wherein the naphtha has an octane number of at least 70, and the naphtha, as determined according to the ASTM method D6730, at most 0, Contains 15 grams of olefins per gram of naphtha; at least 0.001 grams of petroleum, wherein the petroleum, as determined according to ASTM D5186, contains at least 0.2 grams of aromatics per gram of petroleum, and the petroleum has a freezing point, as determined according to the ASTM method D2386, of at most -30 ° C; and, as determined by the ASTM method D5307, at most 0.05 grams of residue.

The invention also provides a crude composition with per gram of the composition: at most 0.15 grams of hydrocarbon gas that cannot be condensed at 25 ° C and 0.101 MPa, wherein the hydrocarbon gas that cannot be condensed, per gram of hydrocarbon gas that is not can be condensed, contains no more than 0.3 grams of hydrocarbons with a number of carbon atoms of 1 to 3 (C 1 to C 3); at least 0.001 gram of naphtha, wherein the naphtha has an octane number of at least 70; at least 0.001 gram of petroleum, the petroleum, as determined according to the ASTM method D2386, 1027775-27 - having a freezing point of at most -30 ° C, and the petroleum, as determined according to the ASTM method D5186 Contains 2 grams of aromatics per gram of petroleum; and, as determined by the ASTM method D5307, at most 0.05 grams of residue.

The invention also provides a crude composition with per gram of the composition: at most 0.05 grams of residue, determined according to the ASTM method D5307, at least 0.001 grams of hydrocarbons with a boiling range at 0.101 MPa to at most 204 ° C ( 400 ° F); at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 204 ° C and 300 ° C; at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 300 ° C and 400 ° C; at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 400 ° C and 538 ° C (1000 ° F); wherein the hydrocarbons with a boiling range between 20 ° C and 204 ° C comprise olefins with terminal double bonds and olefins with internal double bonds, the molar ratio of the olefins with terminal double bonds to the olefins with internal double bonds, determined according to the ASTM method D6730, is at least 0.4.

The invention also provides a crude composition with per gram of the composition: at most 0.05 grams of residue, determined according to the ASTM method D5307; and at least 0.001 gram of a mixture of hydrocarbons with a boiling range, determined according to the ASTM method D5307, between 20 ° C and 538 ° C (1000 ° F), wherein the hydrocarbon mixture per gram of hydrocarbon mixture: contains at least 0.001 gram of paraffins determined according to the ASTM method D6730; contains at least 0.001 gram of olefins, determined according to the ASTM method D6730, wherein the 1027775 * 28 olefins, determined according to the ASTM method D6730, contain at least 0.001 gram of terminal olefins per gram of olefins; contains at least 0.001 grams of naphtha; contains at least 0.001 grams of petroleum, wherein the petroleum, determined according to the ASTM method D5186, contains at least 0.2 grams of aromatics per gram of petroleum; contains at least 0.001 grams of diesel, the diesel, determined according to the IP method 368/90, containing at least 0.3 grams of aromatics per gram of diesel; and contains at least 0.001 grams of vacuum gas oil 10 (VGO), wherein the VGO, determined according to the IP method 368/90, contains at least 0.3 grams of aromatics per gram of VGO.

The invention also provides a crude composition with per gram of the composition: at most 0.05 grams of residue, determined according to the ASTM method D5307; at least

0.001 gram of hydrocarbons with a boiling range at 0.101 MPa to a maximum of 204 ° C (400 ° F); and at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 204 ° C and 300 ° C; at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 300 ° C

and 400 ° C; and at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 400 ° C and 538 ° C (1000 ° F), determined according to the ASTM method D2887; wherein the hydrocarbons with a boiling range up to at most 204 ° C, per gram of hydrocarbons with a boiling range up to at most 204 ° C: contain at least 0.001 gram of olefins, determined according to the ASTM method D6730; and contain at least 0.001 gram of paraffins, the paraffins comprising isoparaffins and n-paraffins, wherein the weight ratio of the isoparaffins to the n-paraffins determined according to the ASTM method D6730 is at most 1.4.

1,027,775 i -29

The invention also provides a crude composition with per gram of the composition: at most 0.05 grams of residue, determined according to the ASTM method D5307; and at least 0.001 gram of hydrocarbons with a boiling range 5 at 0.101 MPa of at most 204 ° C (400 ° F); at least

0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 204 ° C and 300 ° C; at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 300 ° C and 400 ° C; and at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 400 ° C

and 538 ° C (1000 ° F), determined according to the ASTM method D2887; and wherein the hydrocarbons with a boiling range between -10 ° C and 204 ° C include compounds with a number of carbon atoms of 4 (C4), wherein the C4-15 compounds contain at least 0.001 grams of butadiene per gram of C4 compounds.

The invention also provides a crude composition with per gram of the composition: at most 0.05 grams of residue, at least 0.001 grams of hydrocarbons with a boiling range at 0.101 MPa to at most 204 ° C

(400 ° F), at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 204 ° C and 300 ° C, at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 300 ° C and 400 ° C, and at least 25 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 400 ° C and 538 ° C; and more than 0 grams, but less than 0.01 grams of one or more catalysts, wherein the catalyst contains at least one or more alkali metals.

According to some embodiments, the invention, in combination with one or more of the 1027775 "processes or compositions of the invention, also provides a crude feed that: (a) has not been treated in a refinery, is not distilled and / (b) comprises constituents 5 having a number of carbon atoms greater than 4, the crude feed containing at least 0.5 grams of such constituents per gram of crude feed (c) hydrocarbons of which a portion: a boiling range has a boiling range at 0.101 MPa below 100 ° C, a boiling range at 0.101 MPa between 100 ° C and 200 ° C, a boiling range at 0.101 MPa has between 200 ° C and 300 ° C, a boiling range at 0.101 MPa has between 300 ° C and 400 ° C, and a boiling range at 0.01 MPa has between 400 ° C and 700 ° C. (d) per gram of crude feed: contains at least 15 0.001 grams of hydrocarbons with a boiling range at 0.101 MPa below 100 ° C, at least 0.001 gra m contains hydrocarbons with a boiling range at 0.101 MPa between 100 ° C and 200 ° C; contains at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 200 ° C and 300 ° C, contains at least 0.001 gram of hydrocarbons with a boiling range at 0.01 MPa between 300 ° C and 400 ° C and contains at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 400 ° C and 700 ° C; (e) has a TAN; (f) contains 0.2-0.99 25 grams, 0.3-0.8 grams or 0.4-0.7 grams of residue per gram of crude feed; (g) comprises nickel, vanadium, iron or a mixture thereof; (h) comprises sulfur; and / or (i) includes nitrogen-containing hydrocarbons.

According to some embodiments, the invention, in combination with one or more of the methods or compositions of the invention, also provides a source of hydrogen which: (a) is gaseous; (b) comprises molecular hydrogen; (c) comprises light hydrocarbons; (d) comprises methane, ethane, propane or a mixture thereof; (e) comprises water; and / or (f) a mixture thereof.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides a process which comprises, inter alia, conditioning the inorganic salt catalyst, wherein the conditions of conditioning the inorganic salt catalyst include, inter alia: (a) heating the inorganic salt catalyst to a temperature of 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.

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides a method comprising contacting a crude feed with one or more catalysts, and controlling the conditions of contacting: (a) such that during contacting, determined on the basis of the mass balance, per gram of raw food no more than 0.2 gram, no more than 0.15 gram, no more than 0.1 gram or no more than 0.05 grams is formed of hydrocarbons that cannot be condensed at 25 ° C and 0.101 MPa; (b) such that the contact temperature is in the range of 250-750 ° C or 1027775 - 32 - of 260-550 ° C; (c) such that the pressure is in the range of 0.1-20 MPa; (d) such that the ratio of a gaseous source of hydrogen to the crude feed is in the range of 1-516100 or 5-320 normal cubic meters of the source of hydrogen per cubic meter of the crude feed; (e) such that the formation of coke is prevented; (f) such that formation of coke in the total product or in the crude feed during contacting is prevented; (g) such that the crude product, per gram of crude product, contains no more than 0.05 grams, no more than 0.03 grams, no more than 0.01 grams or no more than 0.003 grams of coke; (h) such that at least a portion of the inorganic salt catalyst is, under contacting conditions, either semi-liquid or liquid; (i) such that the crude product has a TAN of up to 90% of the TAN of the crude feed; (j) such that the crude product has a total Ni / V / Fe content that is at most 90%, at most 50% or at most 10% of the Ni / V / Fe content of the crude feed; (k) 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 feed; (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 crude feed; (m) such that the crude product has a residue content of at most 30%, at most 10% or at most 5% of the residue content of the crude feed; (n) such that ammonia is produced together with the crude product; (o) such that the crude product comprises methanol and the process further comprises the steps of: recovering the methanol from the crude product; combining the recovered methanol with an additional crude feed so that an additional crude feed / methanol mixture is formed; and heating the extra crude feed / methanol mixture, so that the TAN of the extra crude feed is reduced to a value below 1; (p) such that one or more of the properties of the crude product change at most 90% with respect to the respective one or more properties of the crude feed; (q) such that the amount of the catalyst in the contacting zone ranges from 1-60 grams of total catalyst per 100 grams of crude feed; and / or (r) such that a source of hydrogen is added to the crude feed before or during contacting.

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides for contacting conditions,

20 comprising: (a) it at a temperature of less than 500 ° C

mixing the inorganic salt catalyst with the crude feed, wherein the inorganic salt catalyst is substantially insoluble in the crude feed; (b) stirring the inorganic salt catalyst in the crude feed; and / or (c) contacting the crude feed with the inorganic salt catalyst in the presence of water and / or steam, so that a total product is obtained which contains the crude product containing a liquid at standard temperature and pressure. mixture.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides a process comprising contacting a crude feed with an inorganic salt catalyst, which process further comprising the steps of: (a) supplying steam to the contact zone before or during contacting; (b) contacting the crude feed with the inorganic salt catalyst and the source of hydrogen to form an emulsion of the crude feed and water; (c) spraying the crude feed into the contact zone; and / or (d) contacting the inorganic salt catalyst with steam so that at least partially coke is removed from the surface of the inorganic salt catalyst.

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides a method comprising contacting a crude feed with an inorganic salt catalyst, so that a total product becomes wherein at least a portion of the total product is prepared as a vapor, the process further comprising condensing at least a portion of the vapor at 25 ° C and 0.101 MPa to form the crude product, the conditions of the contacting is controlled such that: (a) the crude product further comprises ingredients with a selected boiling range; and / or (b) the crude product comprises components with a selected API density.

. According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides a method comprising contacting a crude feed with one or more catalysts, wherein the one or more catalysts are not acidic.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides a K3 Fe10 Si4 catalyst or a transition metal sulfide containing catalyst which: (a) per gram of the K3 Fe10 Si4 catalyst or of the transition metal sulfide-containing catalyst contains a total of at least 0.4 grams, at least 0.6 grams or at least 0.8 grams of at least one of the transition metal sulfides; (b) has an atomic ratio of transition metal to sulfur in the K3 Fe10 Si4 catalyst or in the transition metal sulfide-containing catalyst in the range of 0.2 to 20; (c) further comprises one or more alkali metals, one or more compounds of one or more alkali metals, or a mixture thereof; (d) further comprises one or more alkaline earth metals, one or more compounds of one or more alkaline earth metals or a mixture thereof; (e) further comprising one or more alkali metals, one or more compounds of one or more alkali metals or a mixture thereof, wherein the atomic ratio of transition metal to sulfur in the K3Fei0Si4 catalyst or in the transition metal sulfide-containing catalyst 25 is in the range of 0.5-2.5, and the atomic ratio of the alkali metals to the transition metal is in the range of greater than 0 to 1; (f) further comprises one or more alkaline earth metals, one or more compounds of one or more alkaline earth metals or a mixture thereof, wherein the atomic ratio of transition metal to sulfur in the K3 Fe10 Si4 catalyst or in the transition metal sulfide-containing catalyst is in the range of 0 , 5-2.5; and the alkali metal to transition metal atomic ratio of 1027775 to 36 is in the range of greater than 0 to 1; (g) further comprises zinc; (h) further comprises KFe2S3; (i) further comprises KFeS2; and / or (j) is not acidic.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides a K3 Fe10 Si4 catalyst formed in situ.

According to some embodiments, the invention, in combination with one or more of the methods or compositions of the invention, also provides one or more transition metal sulfides which or wherein: (a) comprises one or more transition metals from groups 6-10 of the Periodic System, comprise one or more compounds of one or more transition metals from groups 6-10, or a mixture thereof; (b) include one or more iron sulfides; (c) include FeS; (d) include FeS2; (e) comprise a mixture of iron sulfides, the iron sulfides being represented by the formula Fe (i-b) S, wherein b is in the range of greater than 0 to 0.17; (f) further, after contact with the crude feedstock, comprise K3 Fe10 Si4; (g) at least one of the transition metals of the one or more transition metal sulfides is iron; and / or (h) are supported on a support, wherein the transition metal sulfide-containing catalyst contains at most 0.25 grams of the total support per 100 grams of catalyst.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides a process for forming a composition of a transition metal sulfide-containing catalyst, the process comprising the steps of: mixing 1027775- A transition metal oxide and a metal salt, so that a transition metal oxide / metal salt mixture is formed; reacting the transition metal oxide / metal-salt mixture with hydrogen to form an intermediate; and reacting the intermediate with sulfur in the presence of one or more hydrocarbons to form the transition metal sulfide-containing catalyst: (a) wherein the metal salt comprises an alkali metal carbonate; (b) wherein the intermediate product, while being reacted with the sulfur, is further dispersed in the one or more liquid hydrocarbons; (c) wherein one or more of the hydrocarbons have a boiling point of at least 100 ° C; (d) wherein one or more of the hydrocarbons is VGO, xylene or a mixture thereof; (e) wherein the mixing of the transition metal oxide and the metal salt comprises the following steps: mixing the transition metal oxide and the metal salt in the presence of deionized water to form a wet paste;

It is at a temperature in the range of 150-250 ° C

drying the wet pasta; and calcining the dried pasta at a temperature in the range of 300-600 ° C; (f) wherein reacting the intermediate with sulfur comprises heating the intermediate in the presence of at least one of the hydrocarbons to a temperature in the range 240-350 ° C; and / or (g) wherein the catalyst composition is further contacted with a crude feed comprising sulfur and a source of hydrogen.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides an inorganic salt catalyst comprising: (a) one or more alkali metal carbonates, one or more alkaline earth metal carbonates or a mixture thereof; (b) one or more alkali metal hydroxides, one or more alkaline earth metal hydroxides or a mixture thereof; (c) one or more alkali metal hydrides, one or more alkaline earth metal hydrides or a mixture thereof; (d) one or more sulfides of one or more alkali metals, one or more sulfides of one or more alkaline earth metals or a mixture thereof; (e) one or more amides of one or more alkali metals, one or more amides of one or more alkaline earth metals or a mixture thereof: (fj one or more 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, or a mixture thereof: (g) one or more inorganic metal salts, wherein at least one of the inorganic metal salts forms a hydride during use of the catalyst; ) sodium, potassium, rubidium, cesium or a mixture thereof, (i) calcium and / or magnesium, (j) a mixture of a sodium salt and a potassium salt, wherein the potassium salt comprises potassium carbonate, potassium hydroxide, potassium hydride or a mixture thereof and the sodium salt, sodium carbonate, sodium hydroxide, sodium hydride or a mixture thereof, and / or (k) a mixture thereof.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides an inorganic salt catalyst comprising alkali metals, wherein: (a) the atomic ratio of an alkali metal. having an atomic number of at least 11 with respect to an alkali metal with an atomic number greater than 11 is in the range of 0.1 to 4; (B) at least two of the alkali metals are sodium and potassium and the atomic ratio of sodium to potassium is in the range of 0.1 to 4; (c) at least three of the alkali metals are sodium, potassium, and rubidium, with the atomic ratios of sodium to potassium, sodium to rubidium, and potassium to rubidium all in the range of 0.1 to 5; (d) at least three of the alkali metals are sodium, potassium and cesium, with the atomic ratios of sodium to potassium, sodium to cesium and potassium to cesium being in the range of 0.1 to 5; (e) at least three of the alkali metals are potassium, cesium, rubidium, wherein the atomic ratios of potassium to cesium, potassium to rubidium and cesium to rubidium are in the range of 0.1 to 5.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides an inorganic salt catalyst comprising a support material, wherein: (a) the support material is zirconium oxide, calcium oxide, magnesium oxide comprises titanium oxide, hydrotalcite, alumina, germanium oxide, iron oxide, nickel oxide, zinc oxide, cadmium oxide, antimony oxide or a mixture thereof; and / or (b) wherein the following substances are included in the carrier material: one or more metals from groups 6-10 of the Periodic Table, one or more compounds of one or more metals from groups 6-10 of the Periodic Table System; 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.

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

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides an inorganic salt catalyst which: (a) exhibits an inflation of the released gas in a TAP temperature range, wherein the released gas comprises water vapor and / or carbon dioxide; (b) a heat transition determined by differential scanning calorimetry with a heating rate of 10 ° C per minute, is in the range of 200-500 ° C, 250-450 ° C, or 300-400 ° C; (c) has a DSC temperature in a range of 200-500 ° C or 250-450 ° C; (d) exhibits an X-ray diffraction pattern wider than the X-ray diffraction pattern of the inorganic salt catalyst at a temperature lower than 100 ° C at a temperature of at least 100 ° C; and / or (e) after conditioning exhibits an ionic conductivity at 300 ° C that is less than the ionic conductivity of the inorganic salt conditioning catalyst.

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides an inorganic salt catalyst which, in a temperature range as determined by TAP, exhibits an inflation of the released gas, wherein the contact conditions are also controlled such that the contact temperature: (a) is higher than Ti if Ti is 30 ° C, 20 ° C or 10 ° C higher than the TAP temperature of the inorganic salt catalyst; (b) is equal to or higher than the TAP temperature; and / or (c) is at least equal to the TAP temperature of the inorganic salt catalyst.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides an inorganic salt catalyst which or wherein: (a) is liquid or semi-liquid at least at the TAP temperature of the inorganic salt catalyst, wherein the inorganic salt catalyst is substantially insoluble in the crude feed at least the TAP temperature, the TAP temperature being the minimum temperature at which the inorganic salt catalyst is an inflection of the gas released; (b) at a temperature in the range of 50 ° C to 500 ° C, a mixture of a liquid phase and a solid phase; and / or (c) at least one of the two inorganic salts has a DSC temperature in excess of 500 ° C.

1027775 * - 42 -

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides an inorganic salt catalyst which when tested in the form of particles that can pass through a 1000 micron filter , when heated to a temperature of at least 300 ° C, deforms itself under the influence of gravity and / or under the influence of a pressure of at least 0.007 MPa, so that the inorganic salt catalyst is converted from a first form in a second form, wherein the second form cannot cool back to the first form upon cooling the inorganic salt catalyst to 20 ° C.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides an inorganic salt catalyst with per gram of the inorganic salt catalyst: (a) at most 0, 01 grams of lithium, or of compounds of lithium, calculated as the weight of the lithium; (b) at most 0.001 grams of halide, calculated as the weight of the halogen, and / or (c) at most 0.001 grams of a glassy oxide compound.

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides the total product with at least 0.8 grams of crude product per gram of total product.

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides a crude product that: (a) at most 0.003 grams, at most 1027775 "- 43 - at most 0.02 grams, not more than 0.01 grams, not more than 0.05 grams, not more than 0.001 grams, 0.000001-0.1 grams, 0.00001-0.05 grams or 0.0001-0.03 grams of residue per gram of crude product contains; (b) contains 0 grams to 0.05 grams, 0.00001-0.03 5 grams or 0.0001-0.01 grams of coke per gram of crude product; (c) has an olefins content that is at least 10% higher than the olefins content of the crude feed; (d) contains more than 0 grams, but less than 0.01 grams, of the total amount of inorganic salt catalyst per gram of crude product, determined by the mass balance; (e) contains at least 0.1 grams, 0.00001-0.99 grams, 0.04-0.9 grams or 0.6-0.8 grams of VGO per gram of crude product; (f) VGO, wherein the VGO contains at least 0.3 grams of aromatics per gram of VGO; (g) contains 0.001 15 grams or 0.1-0.5 grams of distillate; (h) an H / C atomic ratio of at most 1.4; (i) has an H / C atomic ratio that is 90-110% of the H / C atomic ratio of the crude feed; (j) has a monocyclic ring aromatics content that is at least 10% greater than the monocyclic ring aromatics content of the crude feed; (k) a monocyclic ring containing aromatics comprising xylenes, ethylbenzene or compounds of ethylbenzene; (1) per gram of crude feed no more than 0.1 gram of benzene, 0.05-0.15 gram of toluene, 0, Ι Ο, 9 gram of metaxylene, 0.5-0.15 gram of orthoxylene and 0.2-0 Contains 6 grams of paraxylene; (m) contains at least 0.0001 grams or 0.01-0.5 grams of diesel; (n) comprises diesel, wherein the diesel contains at least 0.3 grams of aromatics per gram of diesel; (o) contains at least 0.001 grams, more than 0 to 0.7 grams or 0.001-0.5 grams of petroleum; (p) petroleum, wherein the petroleum contains at least 0.2 grams or at least 0.5 grams aromatics per gram of petroleum and / or wherein the petroleum has a freezing point of at most -30 ° C, at most -40 ° C or at most -50 ° C; (q) contains at least 0.001 grams or at least 0.5 grams of naphtha; (r) naphtha wherein the naphtha contains at most 0.01 grams, at most 0.05 grams or at most 0.002 grams of benzene per gram of naphtha, has an octane number of at least 70, at least 80 or at least 90, and / or contains isoparaffins and normal paraffins with a weight ratio of isoparaffins to normal paraffins in the naphtha of 1.4 at most; and / or (s) has a volume that is at least 10% greater than the volume of the crude feed.

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides a method comprising contacting a crude feed with a catalyst to form a total product comprising a crude product which method further comprises the steps of: (a) combining the crude product with a crude oil that is the same as or different from the crude feed so as to form a mixture suitable for transport; (b) combining the crude product with a crude oil that is the same or different from the crude feed so as to form a mixture suitable for treatment in a treatment plant; (c) fractionating the crude product; (d) fractionating the crude product into one or more distillate fractions, and preparing fuel for transport vehicles from at least one of the distillate fractions; and / or (e) if the catalyst is a transition metal sulfide-containing catalyst, treating the transition metal sulfide-containing catalyst such that metals are recovered from the transition metal sulfide-containing catalyst.

According to some embodiments, the invention, in combination with one or more of the methods or compositions according to the invention, also provides a crude product which, per gram of crude product: (a) contains at least 0.001 gram of VGO, the VGO comprising at least Contains 0.3 grams of aromatics per gram of VGO; (b) contains at least 0.001 grams of diesel, wherein the diesel contains at least 0.3 grams of aromatics per gram of diesel; (c) contains at least 0.001 gram of naphtha, wherein the naphtha: contains at most 0.5 gram of benzene per gram of naphtha, has an octane number of at least 70 and / or isoparaffins and n-paraffins, the weight ratio of the isoparaffins being Is no more than 1.4 with respect to the n-paraffins; (d) contains a total of at least 0.001 grams of a mixture of ingredients with a boiling range that extends to at most 204 ° C (400 ° F), wherein the mixture contains at most 0.15 grams of olefins per gram of mixture; (e) 20 has a weight ratio of hydrogen atoms to carbon atoms in the composition of at most 1.75 or at most 1.8; (f) contains at least 0.001 grams of petroleum, wherein the petroleum contains: 0.5 grams of aromatics per gram of petroleum and / or has a freezing point of at most -30 ° C; (g) contains 0.09-0.13 grams of hydrogen atoms per gram of composition; (h) contains non-condensable hydrocarbon gases and naphtha, which substances together contain a maximum of 0.15 grams of olefins per gram of the combined amount of the non-condensable hydrocarbon gases and the naphtha; (i) contains non-condensable hydrocarbon gases and naphtha which together contain an amount of isoparaffins and n-paraffins such that the weight ratio of the isoparaffins to n-paraffins in the joint amount of the naphtha and the non-condensable hydrocarbon gases is at most 1.4; (j) contains hydrocarbons having a number of 5 to 3 carbon atoms, comprising: olefins and paraffins having a number of 2 (C2) and 3 (C3) carbon atoms, the weight ratio of the combined amount of C2 and C3 olefins to the combined amount of C2 and C3 paraffins is 0.3 at most; olefins and paraffins with a number of carbon atoms of 2 (C2), the weight ratio of the C2 olefins to the C2 paraffins being at most 0.2; and / or olefins and paraffins with a number of carbon atoms of 3 (C3), wherein the weight ratio of the C3 olefins to the C3 paraffins is at most 0.3, (k) has a butadiene content of at least 0, 05 grams; (1) has an API at 15.5 ° C in the range of 15 to 30, (m) contains a total of at most 0.00001 grams of Ni / V / Fe per gram of the composition; (n) has a paraffin content of the hydrocarbons with a boiling range of up to 204 ° C in the range of from 0.7-0.98 grams; (o) contains hydrocarbons with a boiling range up to a maximum of 204 ° C with 0.001-0.5 grams of olefins per gram of olefinic hydrocarbons with a boiling range up to a maximum of 204 ° C; (p) contains hydrocarbons with a boiling range of up to 204 ° C comprising olefins, wherein the olefins contain at least 0.0001 grams of terminal olefins per gram of olefins; (q) contains hydrocarbons with a boiling range up to a maximum of 204 ° C comprising olefins, wherein the olefins have a molar ratio of terminal olefins to internal olefins 1027775 "- 47 - of at least 0.4; and / or (r) contains 0.001-0.5 grams of olefins per gram of hydrocarbons with a boiling range between 20 ° C and 204 ° C.

According to some embodiments, the invention, in combination with one or more of the processes or compositions according to the invention, also provides a crude product with at least one of the catalysts comprising one or more alkali metals, wherein: (a) at least one of the alkali metal is potassium, rubidium or cesium or a mixture thereof; and / or (b) at least one of the catalysts further comprises a transition metal, a transition metal sulfide and / or bartonite.

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

In other embodiments, crude products can be obtained by any of the methods and systems described in this patent.

In other embodiments, certain features may be added to certain embodiments described in this patent specification.

BRIEF DESCRIPTION OF THE DRAWINGS

Those skilled in the art will appreciate the advantages of the present invention with reference to the following detailed description and with reference to the accompanying drawings, in which: FIG. 1 schematically shows an embodiment of a contact system for contacting the crude feed 1027775 "- 48 - with a source of hydrogen in the presence of one or more catalysts, so that a total product is obtained.

FIG. 2 schematically shows another embodiment of a contact system for contacting the crude feed with a source of hydrogen in the presence of one or more catalysts, so that a total product is obtained.

FIG. 3 schematically shows an embodiment of a separation zone that is combined with a contact system.

FIG. 4 schematically shows an embodiment of a mixing zone that is combined with a contact system.

FIG. 5 schematically shows an embodiment of a separation zone, a contact system and a mixing zone.

FIG. 6 schematically shows an embodiment of a plurality of contact systems.

FIG. 7 schematically shows an embodiment of a measuring system for measuring the ionic conductivity.

FIG. 8 is a table of the properties of the crude feed and of the properties of the crude products obtained in contacting embodiments of the crude feed with the transition metal sulfide-containing catalyst.

FIG: 9 is a table of the composition of the crude feed and of the composition of non-condensed hydrocarbons obtained in embodiments of contacting the crude feed with the transition metal sulfide-containing catalyst.

FIG. 10 is a table of the properties and composition of crude products obtained in contacting embodiments of the crude feed with the transition metal sulfide-containing catalyst.

FIG. 11 is a graphical representation of the curve obtained by plotting the 10 logarithm of the ion stream 5 of gases released by an inorganic salt catalyst against the temperature as determined by TAP.

FIG. 12 is a graphical representation of the curve obtained by plotting the logarithm of the resistance of the inorganic salt catalysts and of an inorganic salt to the resistance of potassium carbonate against the temperature.

FIG. 13 is a graphical representation of the curve obtained by plotting the logarithm of the resistance of a Na 2 CO 3 / K 2 CO 3 / Rb 2 CO 3 catalyst against the resistance of the potassium carbonate against the temperature.

FIG. 14 is a graphical representation obtained by plotting the weight percentage of coke, liquid hydrocarbons and gas against different sources of hydrogen prepared in embodiments of contacting the crude feed with the inorganic salt catalyst.

FIG. 15 is a graphical representation obtained by plotting the weight percentage against the number of carbon atoms of crude products prepared in embodiments of contacting the crude feed with the inorganic salt catalyst.

FIG. 16 is a table of components prepared by embodiments of contacting the crude feed with inorganic salt catalysts, a metal salt or silicon carbide.

1027775 "- 50 -

While various modifications and other forms of the invention are possible, certain forms thereof are shown by way of example in the drawings and will be described in detail in this patent specification. The drawings do not have to be to scale. It is to be understood that the drawings and the detailed description thereof are not intended to limit the invention to. in the particular form disclosed, but on the contrary, it is intended to cover all modifications corresponding forms and other possibilities that are within the spirit and scope of the present invention.

DETAILED DESCRIPTION OF THE INVENTION In this patent, certain embodiments of the invention are described in more detail.

The terms used in this patent have the following meaning.

"Alkali metal or alkali metals" means one or more metals from group 1 of the Periodic Table, one or more compounds of one or more metals from group 1 of the Periodic Table, or a mixture thereof.

"Alkaline earth metal or alkaline earth metal" means one or more metals from group 2 of the Periodic Table, one or more compounds of one or more metals from group 2 of the Periodic Table, or a mixture thereof.

"AMU" stands for atomic mass unit.

"ASTM" stands for American Standard Testing and 30 Materials.

"C5 asphaltenes stands for asphaltenes that are insoluble in pentane. The content of C5 asphaltenes is determined according to the ASTM method D2007.

1027775 - 51 -

The percentage of hydrogen atoms and the percentage of carbon atoms of the crude feed, the crude product, the naphtha, the petroleum, the diesel and the VGO are determined according to the ASTM method D5291.

"API density" stands for the API density at 15.5 ° C. The API density is determined according to the ASTM method D6822.

"Bitumen" stands for one type of crude, prepared and / or distilled from a hydrocarbon formation.

Unless otherwise stated, boiling ranges of the crude feed and / or the total product are determined according to the -ASTM method D5307. The content of hydrocarbon components, for example paraffins, isoparaffins, olefins, naphthenes and aromatics, of naphtha is determined according to the ASTM method D6730. The aromatics content of diesel and VGO is determined according to the IP method 368/90. The aromatics content of petroleum is determined according to the ASTM method D5186.

"Bronsted-Lowry acid" stands for a molecular unit that can deliver a proton to another molecular unit.

"Brnsted-Lowry-ba.se" stands for a molecular unit that can incorporate a proton from another molecular unit. Examples of Bronsted-Lowry bases include hydroxide (0H "), water (H 2 O), carboxylate (RCO 2"), halide (Br-, Cl ", F", I "), bisulfate (HS04") and sulfate (SO42-).

"Number of carbon atoms" stands for the total number of carbon atoms in a molecule.

"Coke" means solids containing carbon-containing solids that do not evaporate under process conditions. The coke content is determined on the basis of the mass balance. The weight 1027775 "- 52 - of the coke is the total weight of the solid minus the total weight of the catalysts added.

"Content" means the weight of a component 5 in a substrate (e.g., a crude feed, a total product, or a crude product) expressed as the weight fraction or percentage by weight based on the total weight of the substrate. "Wtppm" stands for parts per million based on weight.

"Diesel" means hydrocarbons with a boiling range at 0.101 MPa between 260 ° C and 343 ° C (500-650 ° F). The diesel content is determined according to the ASTM method D2887.

"Distillate" means hydrocarbons with a boiling range at 0.101 MPa between 204 ° C and 343 ° C (4 00-650 ° F). The distillate content is determined according to the ASTM method D2887. The distillate can contain petroleum and diesel.

"DSC" stands for differential scanning calorimetry.

"Freezing point" stands for the temperature at which crystalline particles start to form in a liquid. The freezing point is determined according to ASTM D2386.

"GC / MS" stands for gas chromatography combined with mass spectrometry.

"Hard base" stands for anions as described by Pearson in the Journal of American Chemical Society, 1963, 85, p. 3533.

"H / C" stands for the weight ratio of the 30 hydrogen atoms to the carbon atoms. H / C

is determined on the basis of the values measured when determining the weight percentage 1027775 * - 53 - hydrogen and the weight percentage of carbon according to the ASTM method D5291.

"Heteroatoms" stand for oxygen, nitrogen and / or sulfur, included in the molecular structure of a hydrocarbon. The content of heteroatoms is determined according to ASTM methods E385 for oxygen, D5762 for nitrogen and D4294 for sulfur.

"Source of hydrogen" means hydrogen and / or a compound and / or compounds that react in the presence of a crude feed and the catalyst and thereby provide hydrogen for one or more of the compounds of the crude feed. A source of hydrogen may include, but is not limited to, hydrocarbons (e.g., C 1 to C 6 hydrocarbons such as methane, ethane, propane, butane, pentane, naphtha), water, or a mixture thereof. To determine the net amount of hydrogen that is delivered to one or more compounds of the crude feed, a mass balance is made.

"Inorganic salt" means a compound consisting of a metal cation and an anion.

"IP" stands for the Institute of Petroleum, nowadays the Institute of London, United Kingdom.

"Isoparaffins" stands for saturated hydrocarbons with a branched chain.

"Petroleum" means hydrocarbons with a boiling range at 0.101 MPa between 204 ° C and 260 ° C (400 - 500 ° F). The petroleum content is measured according to the ASTM method D2887.

"Lewis acid" means a compound or substance that can take up one or more electrons from another compound.

110277 75 "- 54 -" Lewis base "stands for a compound and / or a substance that can release one or more electrons to another compound.

"Light hydrocarbons" means hydrocarbons with a number of carbon atoms in the range of 1 to 6.

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

"Micro-carbon residue (" MCR ") stands for the amount of the carbon residue that remains after evaporation and after pyrolysis of a substance. The MCR content is determined according to the ASTM method D4530.

"Naphtha" stands for hydrocarbon constituents with a boiling range at 0.101 MPa between 38 ° C and 204 ° C (100-20 400 ° F). The naphtha content is determined according to the ASTM method D2887.

"Ni / V / Fe" stands for nickel, vanadium, iron or a combination thereof.

"Ni / V / Fe content" stands for the Ni / V / Fe content of a substrate. The Ni / V / Fe content is determined according to the ASTM method D5863.

"Nm3 / m3" stands for normal cubic meters of gas per cubic meter of raw feed.

"Non-acid" stands for properties of a Lewis-30 base and / or Bronsted-Lowry base.

"Non-condensable gas" means constituents and / or a mixture of constituents that are gaseous at 1027775- 55 - standard temperature and pressure (25 ° C, 0.101 MPa, hereinafter referred to as "STP").

"n-Paraffins" stands for normal saturated hydrocarbons (with a straight chain).

5 "Octane number" stands for a calculated numerical representation of the knock resistance properties of a motor fuel, compared to a standard reference fuel. The calculated octane number of naphtha is determined according to the ASTM method D6730.

"Olefins" means compounds with non-aromatic carbon-carbon double bonds. The types of olefins include, but are not limited to, cis-olefins, trans-olefins, terminal olefins, internal olefins, branched olefins, and linear olefins.

"Periodic Table" stands for the Periodic Table as described by the International Union of Pure and Applied Chemistry (IUPAC), November 2003.

"Polyaromatic compounds" means compounds with two or more aromatic rings. Examples of the polyaromatic compounds include, but this is not a limiting list, indene, naphthalene, anthracene, phenanthrene, benzothiophene and dibenzothiophene.

"Residue" means components with a boiling range 25 at 0.101 MPa, determined according to ASTM method D5307, higher than 538 ° C (1000 ° F).

"Semi-liquid" means a phase of a substance that has properties of the liquid phase of the substance and properties of the solid phase of the substance. Examples of semi-liquid inorganic salt catalysts include suspensions and / or phases that have the consistency of, for example, fudge, dough or toothpaste.

1027775 “- 56 -" SCFB "stands for standard cubic feet of gas per barrel of raw food.

"Superbase" stands for a substance that can remove protons from hydrocarbons such as paraffins and olefins under reaction conditions.

"TAN" stands for a total acid number expressed as the number of milligrams ("mg") KOH per gram ("g") of sample.

The TAN is determined according to the ASTM method D664.

"TAP" stands for temporal analysis of products.

"TMS" stands for transition metal sulfide.

"VGO" stands for ingredients with a boiling range at 0.101 MPa between 343 ° C and 538 ° C (650-1000 ° F). The VGO content is determined according to the ASTM method D2887.

It should be understood in connection with this application that if a value obtained for a property of the tested composition is outside the limits of the test method, the test method can be recalibrated to determine such a property. It should be understood that other standardized test methods may be used that are believed to correspond to the test methods referred to.

Crude oils can be produced and / or distilled from hydrocarbon-containing formations and then stabilized. Crude oils are generally solid, semi-solid and / or liquid.

Crude oils may include crude oil. The stabilization may include, but is not limited to, the removal of non-condensable gases, water, salts or combinations thereof from the crude oil to form a stabilized crude oil. Such stabilization can often take place at, or near, the place of production and / or distillation.

Stabilized crude oils are generally not distilled and / or fractionally distilled in a treatment plant for the preparation of multiple components with a specific boiling range (e.g. naphtha, distillates, VGO and / or lubricating oils). Distillation includes, but is not a limiting list, atmospheric pressure distillation methods and / or vacuum distillation methods. The non-distilled and / or non-fractionated stabilized crude oils may include quantities of at least 0.5 grams per gram of crude oils of components having a number of carbon atoms greater than 4. Examples of stabilized crude oils include whole crude oils , crude-depleted crude oils, saline-depleted crude oils, salt and volatile-depleted crude oils or a combination thereof "Volatile constituents removed" 20 means a crude oil that has been treated such that at least some of the components having a boiling point at 0.101 MPa of less than 35 ° C are removed. In general, crude-depleted crude oils contain a content of at most 0.1 grams, at most 0.05 grams or at most 0.02 grams of such components per gram of the crude-oil stripped components.

Some stabilized crude oils have properties that make it possible for the stabilized crude oil to be transported to conventional treatment installations by means of transport means (for example, pipelines, trucks or ships). Other crude oils have one or more properties that are less suitable for use. Less usable crude oils can be unacceptable for a particular means of transport and / or for a treatment installation, as a result of which the less useful crude oil acquires a lower economic value. The economic value can be such that a reservoir containing the less useful crude oil is considered too expensive to produce, transport and / or treat.

10 The properties of less useful crude oils may include, but this is not a limiting list: a) a TAN of at least 0.5; b) a viscosity of at least 0.2 PA-s; c) an API density of at most 19; d) a total Ni / V / Fe content of at least 0.00005 grams or of at least 0.0001 grams of Ni / V / Fe per gram of crude oil; e) a total heteroatom content of at least 0.005 grams of heteroatoms per gram of crude oil; f) a residue content of at least 0.01 grams of residue per gram of crude oil; g) an asphaltenes content of at least 0.04 grams of asphaltenes per gram of crude oil; h) an MCR content of at least 0.02 grams MCR per gram of crude oil; or i) a combination thereof. In some embodiments, less useful crude oils may contain at least 0.2 grams of residue, at least 0.3 grams of residue, at least 0.5 grams of residue or at least 0.9 grams of residue per gram of less useful crude oil. In certain embodiments, the less useful crude oil contains 0.2-0.99 grams, 0.3-0.9 grams, or 0.4-0.7 grams of residue per gram of less useful crude oil. In certain embodiments, less usable crude oils, per gram less usable crude oil, can have a sulfur content of at least 0.001 gram, at least 272775-59 - at least 0.005 gram, at least 0.01 gram or at least 0.02 gram.

Less useful crude oils can contain a mixture of hydrocarbons with a range of 5 boiling points. Less useful crude oils can contain per gram of less useful crude oil: at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range at 0.101 MPa between 200 ° C and 300 ° C; contain at least 0.001 grams, at least 0.005 grams or at least 0.01 grams of hydrocarbons with a boiling range at 0.101 MPa between 300 ° C and 400 ° C; and contain at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range at 0.101 MPa between 400 ° C and 700 ° C, or a combination thereof.

In some embodiments, less usable crude oils may contain, in addition to the higher boiling components, per gram of less useful crude oil, at least 0.001 gram, at least 0.005 gram or at least 0.01 gram of hydrocarbons with a boiling range of 0.01 MPa to at most 200 ° C. In general, the less usable crude oil contains per gram of less usable crude oil a content of such hydrocarbons of at most 0.2 grams or at most 25.0 grams.

In certain embodiments, less useful crude oils per gram of less useful crude oil may contain up to 0.9 grams, or up to 0.99 grams, hydrocarbons with a boiling range of at least 300 ° C. In certain embodiments, less useful crude oils per gram of less useful crude oil can also contain at least 0.001 gram of hydrocarbons with a boiling range of at least 650 ° C. In certain embodiments, less usable crude oils, per gram less usable crude oil, up to 0.9 grams or up to 0.99 grams, may contain hydrocarbons with a boiling range between 300 ° C and 1000 ° C.

Examples of less useful crude oils that can be treated according to the methods described in this patent include, but are not limited to, crude oils from the following countries 10 and regions of those countries: Alberta, Canada

Venezuelan Orinoco, the American Southern California and the American northern slope of Alaska, the Bay of Mexico of Campeche, the Argentinian San Jorge basin, the Brazilian Santos and Campos basins, the Chinese Bohai 15 wave, the Chinese Karamay, the Iraqi Zagros, the

The Kazakh Caspian Sea, the offshore area of Nigeria, the North Sea of the United Kingdom, northwestern Madagascar, Oman and the Dutch Schoonebeek.

By treating the less useful crude oils, the properties of the less useful crude oils can be improved such that the crude oils are acceptable for transport and / or handling. A crude oil and / or a less useful crude oil to be treated can be referred to as a "crude feed." The crude feed can be stripped of volatile components in the manner described in this patent specification. The crude product obtained by treating the crude feed according to the method described in this patent specification is suitable for being transported and / or refined. The properties of the crude product are closer to the corresponding properties of the typical West Texas crude oil than the properties of the crude feed, or are closer to the corresponding properties of Brent crude oil than the properties of the crude feed, and therefore have an economic value that is greater than the economic value of the raw feed. Such a crude product does not need to be pre-treated as much, or does not need to be pre-treated, so that the efficiency of refining is increased. The pretreatment may consist of, inter alia, sulfur-stripping, metal-stripping and / or distillation at atmospheric pressure, whereby impurities are removed from the crude product.

This patent describes methods for contacting a crude feed according to the invention. In addition, embodiments are described for preparing products with different concentrations of naphtha, petroleum, diesel and / or VGO, which products are generally not prepared by conventional methods.

The crude feed can be contacted with a source of hydrogen in the presence of one or more of the catalysts in a contact zone and / or in a combination of two or more contact zones.

In some embodiments, the source of hydrogen is formed in situ. Forming the source of hydrogen in situ may include reacting at least a portion of the crude feed with inorganic salt at temperatures in the range of 200-500 ° C or 300-400 ° C Catalyst, so that hydrogen and / or light hydrocarbons are formed. The in situ generation may involve the reaction of at least a portion of the inorganic salt 1027775 "- 62 - catalyst, which includes, for example, alkali metal formate.

The total product generally contains gas, vapor, liquids or a mixture thereof formed during contacting. The total product consists of, among other things, the crude product that is a liquid mixture at STP, and, in some cases, hydrocarbons that cannot be condensed at STP. In some embodiments, the total product and / or the crude product may contain solids (such as inorganic solids and / or coke). In certain embodiments, the solids may be entrained with the liquid and / or vapor during contact.

A contact zone generally consists of, among other things, a reactor, a part of a reactor, several parts of a reactor or several reactors. Examples of reactors that can be used to bring a crude feed into contact with a source of hydrogen in the presence of a catalyst include stacked bed reactors, fixed bed reactors, continuous stirred tank reactors (CSTR reactors) , spray reactors, plug flow reactors and liquid / liquid contact devices. Examples of CSTR-25 reactors include reactors with a fluidized bed and reactors with a bubble bed.

The contact conditions generally include the temperature, the pressure, the flow of the crude feed, the flow of the total product, the residence time, the flow of the source of hydrogen and combinations thereof. The contact conditions can be controlled in such a way that a crude product with certain properties is obtained.

1027775 * 5 - 63 -

The contact temperatures can vary in the range of 200-800 ° C, 300-700 ° C or 400-600 ° C. In embodiments where the source of hydrogen is supplied as a gas (e.g., hydrogen gas, methane or ethane), the ratio of the gas to the crude feed is generally in the range of 1-16,100 Nm 3 / m3, 2 -8000 Nm3 / m3, 3-4000 Nm3 / m3 or 5-300 Nm3 / m3. The contacting generally takes place at a pressure in the range of 0.1-20 MPa, 1-16 MPa, 2-10 MPa or 4-8 MPa. In some embodiments where steam is added, the ratio of steam to raw feed is in the range of 0.01-3 kilograms, 0.03-2.5 kilograms or 0.1-1 kilograms of steam per kilogram of raw feed . The flow rate of the raw feed may be sufficient to keep the volume of the raw feed in the contact zone at least 10%, at least 50% or at least 90% of the total volume of the contact zone. In general, the volume of the raw feed in the contact zone is 40%, 60% or 80% of the total volume of the contact zone. In some embodiments, the contacting can take place in the presence of additional gas, for example, argon, nitrogen, methane, ethane, propanes, butanes, propenes, butenes or a combination thereof.

FIG. 1 is a schematic representation of an embodiment of the contact system 100 used to prepare the total product as a vapor.

The raw feed leaves the raw feed feed 101 and enters the contact zone 102 via line 104. The amount of catalyst used in the contact zone can vary from 1-100 grams, 2-80 grams, 3-70 grams or 4-60 grams, per 100 grams of crude feed in the contact zone. In certain embodiments, a 1027775 - 64 - diluent may be added to the crude feed to lower the viscosity of the crude feed. In some embodiments, the raw feed enters a bottom portion of the contact zone 102 via line 104. In certain embodiments, the crude feed can be heated to a temperature of at least 100 ° C or at least 300 ° C before and / or during introduction of the crude feed into the contact zone 102. In general, the crude feed can be heated to a temperature in the range of 100-500 ° C or 200-400. ° C.

In some embodiments, the catalyst is brought together with the crude feed and transferred to the contact zone 102. The crude feed / catalyst mixture can be heated to a temperature of at least 100 ° C or at least 300 ° C. before it is introduced into the contact zone 102 C. In general, the crude feed can be heated to a temperature in the range of 200-500 ° C or 300-400 ° C. In some embodiments, the crude feed / catalyst mixture is a suspension. In certain embodiments, the TAN of the raw feed can be lowered before the raw feed is supplied to the contact zone. For example, if the crude feed / catalyst mixture is heated to a temperature in the range of 100-400 ° C or 200-300 ° C, alkali salts of acidic components can be formed in the crude feed. By forming these alkali salts, some acid components can be removed from the crude feed so that the TAN of the crude feed is lowered.

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

In some embodiments, the crude feed and / or a mixture of the crude feed and the inorganic salt catalyst is introduced into the contact zone as an emulsion. The emulsion can be prepared by combining a mixture of an inorganic salt catalyst and water, and a mixture of crude feed and surfactant. In some embodiments, a stabilizer is added to the emulsion. The emulsion can remain stable for at least 2 days, at least 4 days or at least 7 days. In general, the emulsion can remain stable for 30 days, for 10 days, for 5 days or for 3 days. Surfactants include, but are not limited to, organic polycarboxylic acids (Tenax 2010; 25 MeadWestvaco Specialty Product Group; Charleston, South

Carolina, USA), C20 dicarboxylic acid fatty acid (DIACID 1550; MeadWestvaco Specialty Product Group), petroleum sulfonates (Hostapur SAS 30; Clarient Corporation, Charlotte, North Carolina, USA), Tergital NP-40 30 Surfactant (Union Carbide; Danbury, Connecticut , USA) or mixtures thereof. The stabilizers include, but are not limited to, diethylene amine (Aldrich Chemical Co .; Milwaukee, Wisconsin, U.S.A.) and / or monoethanolamine (J. T. Baker; Phillipsburg, New Jersey, U.S.A.).

The return line 106 can provide a coupling between the line 108 and the line 104. In some embodiments, the return line 106 can end up directly in the contact zone 102 and / or directly out of the contact zone 102. The return line 106 may include a flow control valve 110. The flow control valve 110 may allow at least a portion of the substance in line 108 to be returned to line 104 and / or to the contact zone 102. In some embodiments, a condensing unit may be provided in line 108 so that at least one portion of the substance can be condensed and returned to the contact zone 102. In certain embodiments, the return line 106 can be a return line for gas. The flow control valves 110 and 110 'can be used to control the flow to and from the contact zone 102 such that a constant volume of liquid is maintained in the contact zone. In some embodiments, a substantially selected range of the volume of the fluid can be maintained in the contact zone 102.

The volume of the power supply in the contact zone 102 can be monitored with the aid of standard measuring instruments. The gas inlet port 112 can be used to add the source of hydrogen and / or additional gases to the raw feed as the raw feed enters contact zone 102. In some embodiments, the steam inlet port 114 can be used to introduce steam into the contact zone 102. In certain embodiments, an aqueous stream is introduced into the contact zone 112 through the steam inlet port 11427775.

In some embodiments, at least a portion of the total product is prepared as steam coming from the contact zone 102. In certain embodiments, the total product is prepared as a vapor and / or as a vapor containing small amounts of liquids and solids from the top of the contact zone 102. The vapor is transported via line 108 to the separation zone 116. The ratio of the source of hydrogen to the crude feed in the contact zone 102 and / or the pressure in the contact zone can be changed by controlling the amount of vapor phase and / or liquid phase produced from the top of the contact zone 102. In some embodiments, the vapor produced from the top of the contact zone 102 contains at least 0.5 grams, at least 0.8 grams, at least 0.9 grams, or at least 0.97 grams of crude product per gram. raw food. In certain embodiments, the vapor produced from the top of the contact zone 102 contains 0.8-0.99 grams or 0.9-0.98 grams of crude product per gram of crude feed.

Used catalyst and / or solids may remain in the contact zone 102 as by-products of the contact process. The solids and / or the catalyst used may contain residual crude feed and / or coke.

In the separation unit 116, the vapor is cooled and separated using standard separation techniques 30, so that the crude product and gases are formed. The crude product leaves the separation unit 116 and enters the crude product receiver via line 118. The resulting crude product may be suitable for 11027775 "68 transport and / or handling. The crude product receiver 119 may contain one or more pipelines, one or more storage units, one or more transport vessels or a combination thereof. In some embodiments 5 the separated gas (e.g. hydrogen, carbon monoxide, carbon dioxide, hydrogen sulphide or methane) is transported to other processing units (e.g. for use in a fuel cell or in a sulfur recovery plant) and / or returned to the contact zone 102 via line 10 120. In certain embodiments, entrained solids and / or liquids contained in the crude product can be removed using standard physical separation methods (e.g., filtration, centrifugation, or membrane separation).

FIG. 2 shows the contact system 122 for treating raw feed with one or more catalysts, so that a total product can be obtained that can be a liquid or one that can be a liquid mixed with gas or solid. The raw feed may enter the contact zone 102 via line 104. In some embodiments, the raw feed comes from the raw feed of the raw feed feed. Conduit 104 may include a gas inlet port 112. In some embodiments, the gas inlet port 112 can exit directly into the contact zone 102. In certain embodiments, the steam inlet port 114 can be used to allow steam to be introduced into the contact zone 102. The crude feed can be contacted with the catalyst in the contact zone 102, so that a total product is obtained. In some embodiments, the conduit 106 allows at least a portion of the total product to be returned to the contact zone 102. A mixture containing the total product and / or solid and / or unreacted crude feed leaves the contact zone 102 and enters the separation zone 106 through line 108. In some embodiments, a condensing unit may be provided (e.g., in conduit 106) that allows at least a portion of the mixture to be condensed in the conduit and returned to the contact zone 102 for further processing. In certain embodiments, the recycle line 106 may be a gas return line. In some embodiments, the conduit 108 may include a filter for removing particles from the total product.

In the separation zone 124, at least a portion of the crude product can be separated from the total product and / or from the catalyst. In embodiments where the total product contains solid, the solid can be separated from the total product using standard solids separation techniques (e.g., centrifugation, filtering, decanting, membrane separation). The solid includes, for example, a combination of catalyst, spent catalyst and / or coke. In some embodiments, a portion of the gases is separated from the total product. In some embodiments, at least a portion of the total product and / or of the solids can be recycled back to line 104 and / or, in some embodiments, returned through line 126 to the contact zone 102.

For example, the recycled portion may be combined with the raw feed and fed to the contact zone 102 for further processing. The crude 1027775 product can leave the separation zone 124 via line 128. In certain embodiments, the raw product can be transported to the raw product receiving device.

In some embodiments, the total product and / or the crude product may contain at least a portion of the catalyst. Gases entrained with the total product, and / or with the crude product, can be separated using standard gas / liquid separation techniques, for example spraying, membrane separation and pressure reduction. In some embodiments, the separated gas is transported to other processing units (for example for use in a fuel cell, a sulfur recovery plant, other processing units or a combination thereof) and / or returned to the contact zone.

In some embodiments, the separation of at least a portion of the raw feed takes place before the raw feed enters the contact zone. FIG. 3 is a schematic representation of an embodiment of a separation zone combined with a contact system. The contact system 130 may be the contact system 100 and / or the contact system 122 (shown in FIGS. 1 and 2). The raw feed enters the separation zone 132 via line 104. In the separation zone 132, at least a portion of the crude feed is separated using standard separation techniques, so that a separated crude feed and hydrocarbons are obtained. The separated crude feed contains in some embodiments a mixture of components with a boiling range from 100 ° C, from 120 ° C or, in some embodiments, a boiling range from 200 ° C. In general, the separated crude feed contains a mixture of components with a boiling range between 100-1000 ° C, 120-900 ° C or 200-800 ° C. The hydrocarbons separated from the crude feed leave the separation zone 132 via line 134 to be transported to other processing units, treatment plants, storage devices or a combination thereof.

At least a portion of the separated crude feed leaves the separation zone 132 and enters the contact system 130 via line 136, wherein the crude feed is further processed into the crude product leaving the contact system 130 via line 138.

In some embodiments, the crude product prepared from a crude feed according to a process described in this patent specification is mixed with a crude oil that is the same or different from the crude feed. The crude product can, for example, be combined with a crude oil with a different viscosity, whereby a mixed product is obtained with a viscosity that lies between the viscosity of the crude product and the viscosity of the crude oil. The resulting mixed product can be suitable for transport and / or handling.

FIG. 4 is a schematic representation of an embodiment with a combination of a mixing zone 140 and a contact system 130. In certain embodiments, at least a portion of the crude product leaves the contact system 130 via line 138 and enters the mixing zone 140. In the mixing zone 140, at least a portion of the crude product is brought together with one or more process streams (e.g., a hydrocarbon stream prepared when separating one or more crude feeds, or naphtha), a crude oil, a crude 1027775 * - 72 - food or a mixture thereof, so that a mixed product is obtained. The process streams, the crude feed, the crude oil or a mixture thereof are introduced directly into the mixing zone 140 or are supplied via line 142 upstream of the mixing zone. A mixing system may be provided in or near the mixing zone 140. The mixed product can meet certain product specifications. Certain product specifications include, but this is not a limiting list, an area or a limit of the API density, of the TAN, of the viscosity or a combination thereof. It. mixed product leaves the mixing zone 140 via line 144, after which it is transported and / or processed.

In some embodiments, methanol is formed during the contacting process using the catalyst. For example, hydrogen and carbon monoxide can react to form methanol. The methanol recovered may contain dissolved salts, for example potassium hydroxide. The methanol recovered can be combined with an additional crude feed, thereby obtaining a crude feed / methanol mixture. Combining methanol with the crude feed often results in a reduction in the viscosity of the crude feed. Heating the crude feed / methanol-25 mixture to a maximum of 500 ° C can result in a reduction of the TAN of the crude feed to less than 1.

FIG. 5 is a schematic representation of an embodiment of a separation zone combined with a contact system combined with a mixing zone.

The raw feed enters the separation zone 132 through line 104. The crude feed is separated in the manner described above, thereby obtaining a separated crude feed. The separated raw feed enters contact system 130 through line 136. The crude product leaves the contact system 130 and enters the mixing zone 140 through line 138. In the mixing zone 140, other process streams and / or other crude oils introduced through line 142 are combined with the crude product to form a mixed product. The mixed product leaves the mixing zone 140 via line 144.

FIG. 6 is a schematic representation of a multiple contact system 146. The contact system .100 (shown in FIG. 1} may be arranged in front of the contact system 148. In another embodiment, the locations of the contact systems may be reversed. The contact system 100 includes one of inorganic salt catalyst The contact system 148 may contain one or more catalysts The catalyst contained in contact system 148 may be an additional inorganic salt catalyst, may be the transition metal sulfide-containing catalyst, may be a commercially available catalyst or may be a mixture thereof The crude feed enters contact system 100 via line 104 and is contacted with a source of hydrogen in the presence of the inorganic salt catalyst so that the total product is obtained. hydrogen and, in some embodiments, a crude product CT can leave contact system 100 via line 108. The hydrogen that is formed by contacting the inorganic salt catalyst with the crude feed can be used as a source of hydrogen for the contact system 148. At least a portion of the hydrogen 1027775 * - 74 - is released via line 150 from the contact system 100 transferred to a contact system 148.

In another embodiment, such hydrogen formed is separated and / or treated and then transferred via line 150 to contact system 148. In certain embodiments, the contact system 148 may form part of the contact system 100 so that the hydrogen formed directly from the contact system 100 to the contact system 148 10 flows. In some embodiments, a stream of vapor produced by the contact system 100 is directly mixed with the crude feed entering the contact system 148.

A second raw feed enters contact system 148 via line 152. In the contact system 148, the contact of the crude feed with at least a portion of the hydrogen formed and the catalyst produces a product. In some embodiments, the product is the total product. The product leaves contact systems 148 20 through line 154.

In certain embodiments, there may be at the site, or near the site, at which less useful raw food is produced; a · system · is provided which consists, among other things, of contact systems, contact zones, separation zones and / or mixing zones as shown in FIG. 1-6. After processing by means of the catalytic system, the crude feed can be considered suitable for transport and / or for use in a refinery process.

In some embodiments, the crude product and / or the mixed product are transported to a refinery and / or to a treatment plant. The crude product and / or the mixed product can be processed in such a way that commercial products are obtained such as fuel for transport vehicles, fuel for heating, lubricants or chemicals. Processing may include distilling and / or fractionally distilling the crude product and / or the mixed product, so that one or more distillate fractions are obtained. In some embodiments, the crude product, the mixed product and / or the one or more distillate fractions can be treated with hydrogen.

In some embodiments, the total product contains at most 0.05 grams, at most 0.03 grams or at most 0.01 grams of coke per gram of total product. In certain embodiments, the total product contains essentially no coke (i.e., no coke can be detected). In some embodiments, the crude product may contain at most 0.05 grams, at most 0.03 grams, at most 0.01 grams, at most 0.005 grams, or at most 0.003 grams of coke per gram of crude product. In certain embodiments, the crude product has a coke content in the range of greater than 0 to 0.05 grams, 0.00001-0.03 grams, 0.0001-0.01 grams or 0.001-0.005 grams of coke per gram of crude product, or no coke can be detected.

In certain embodiments, the crude product has an MCR content that is at most 90%, at most 80%, at most 50%, at most 30% or at most 10% of the MCR content of the crude feed. In some embodiments, the crude product has a negligible MCR content. In some embodiments, the crude product contains, per gram of crude product, at most 0.05 grams, at most 0.03 grams, at most 0.01 grams or at most 0.001 grams of MCR. In general, the 1027775 * - 76 - crude product contains 0 grams to 0.04 grams, 0.000001-0.03 grams or 0.00001-0.01 grams of MCR per gram of crude product.

In some embodiments, the total product contains non-condensable gas. The non-condensable gas generally includes, but is not a limiting list, carbon dioxide, ammonia, hydrogen sulfide, hydrogen, carbon monoxide, methane, other hydrocarbons that are not condensable in STP, or a mixture thereof.

In certain embodiments, in situ, by contact of steam and light hydrocarbons with the inorganic salt catalyst, hydrogen gas, carbon dioxide, carbon monoxide or a combination thereof can be formed. Under thermodynamic conditions, the molar ratio of carbon monoxide to carbon dioxide is generally 0.07. The molar ratio of the carbon monoxide formed to the carbon dioxide formed is, in certain embodiments, at least 0.3, at least 0.5 or at least 0.7. In some embodiments, the molar ratio of the carbon monoxide formed to the carbon dioxide formed is in the range of 0.3-1.0, 0.4-0.9, or 0.5-0.8. The ability to form carbon monoxide in situ, preferably above carbon dioxide, may be advantageous for other processes that take place in the vicinity of the process or upstream of the process. The carbon monoxide formed can be used, for example, as a reducing agent in the treatment of hydrocarbon formations, or used in other processes, for example in syngas processes.

In some embodiments, the total product as formed in this patent may contain a mixture of compounds with a boiling range between -10 ° C and 538 ° C. The mixture can contain hydrocarbons with a number of carbon atoms in the range of 1 to 4. The mixture can contain 0.001-0.8 grams, 0.003-0.1 grams or 0.005-0.01 5 grams of C4 hydrocarbons per gram of such mixture. The C4 hydrocarbons may contain 0.001-0.8 grams, 0.003-0.1 grams or 0.005-0.01 grams of butadiene per gram of C4 hydrocarbons. In some embodiments, isoparaffins and n-paraffins are produced in a weight ratio of isoparaffins to n-paraffins of at most 1.5. at most 1.4, at most 1.0, at most 0.8, at most 0.3 or at most 0.1. In certain embodiments, isoparaffins and n-paraffins are produced in a weight ratio of isoparaffins to n-paraffins in the range of 0.00001-1.5, 0.0001-1.0 or 0.001-0.1.

In some embodiments, the total product and / or the crude product may contain ratios or amounts of olefins and / or paraffins that are generally not found in crude oils produced or distilled from a formation. The olefins include a mixture of olefins with a terminal double bond ("alpha-olefins") and olefins with internal double bonds.

In certain embodiments, the olefin content of the crude product is a factor of 2, 10, 50, 100 or at least 200 greater than the olefin content of the crude feed. In some embodiments, the olefin content of the crude product is at most a factor of 1000, at most a factor of 500, at most a factor of 300 or at most a factor of 250 greater than the olefins content of the crude feed.

1027775 - 78 -

In certain embodiments, the hydrocarbons with a boiling range between 20-400 ° C have an olefin content in the range of 0.00001-0.1 grams, 0.0001-0.05 grams, or 0.01-0.04 per gram. hydrocarbons with a boiling range in a range of 20-400 ° C.

In some embodiments, at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams of alpha olefins can be prepared per gram of crude product. In certain embodiments, the crude product contains 0.0001-0.5 grams, 0.001-0.2 grams, or 0.01-0.1 grams of alpha olefins per gram of crude product. In certain embodiments, the hydrocarbons with a boiling range between 20-400 ° C have a content of alpha olefins in the range of 0.0001-0.08 grams, 0.001-0.05 grams or 0.01-0.04 grams per grams of 15 hydrocarbons with a boiling range between 20-400 ° C.

In some embodiments, the hydrocarbons with a boiling range between 20-204 ° C have a weight ratio of alpha olefins to olefins with an internal double bond of at least 0.7, at least 0.8, at least 0.9 , at least 1.0, at least 1.4 or at least 1.5. In some embodiments, the hydrocarbons with a boiling range between 20-204 ° C have a weight ratio of alpha-olefins to olefins with an internal double bond, in the range of 0.7-10, 0.8-5.0, 9-3 or 1-2. The weight ratios of alpha olefins to olefins with an internal double bond of the crude oils and of commercially available products is generally at most 0.5. The ability to increase the amount of alpha olefins produced relative to the amount of olefins with an internal double bond produced, 1027775 "- 79 - can facilitate the conversion of the crude product into commercially available products.

In some embodiments, the contact of a crude feed with a source of hydrogen, in the presence of an inorganic salt catalyst, may give hydrocarbons with a boiling range between 20-204 ° C, which include linear olefins.

The linear olefins have double bonds of the cis and trans species. The weight ratio of linear olefins with double bonds of the trans species to linear olefins with double bonds of the cis type is at most 0.4, at most 1.0 or at most 1.4. In certain embodiments, the weight ratio of linear olefins with double bonds of the trans species to linear olefins with double bonds of the cis type is in the range of 0.001-1.4, 0.01-1.0 or 0.1- 0.4.

In certain embodiments, hydrocarbons with a boiling range in the range 20-20-204 ° C have an n-paraffins content of at least 0.1 gram, at least 0.15 gram, at least 0.20 gram or at least 0, 30 grams per gram of hydrocarbons with a boiling range in the range of 20-400 ° C. The content of n-paraffins per gram of hydrocarbons from such hydrocarbons may be in the range of 0.001-0.9 grams, 0.1-0.8 grams or 0.2-0.5 grams. In some embodiments, such hydrocarbons may have a weight ratio of the isoparaffins to n-paraffins of at most 1.5, at most 1.4, at most 1.0, at most 0.8 or at most 0.3 .

From the n-paraffins content of such hydrocarbons, it can be estimated that the 10277.75 "- 80 - content of n-paraffins of the crude product is in the range of 0.001-0.9 grams, 0.01-0 , 8 grams or 0.1-0.5 grams per gram of crude product.

In some embodiments, the crude product 5 has a total Ni / V / Fe content of at most 90%, at most 50%, at most 10%, at most 5% or at most 3% of the Ni / V / content Fe of the crude feed. In certain embodiments, the crude product contains at most 0.0001 grams per gram of crude product, at most 1 x 10-5 grams or at most 1 x 10 "6 grams

Ni / V / Fe. In certain embodiments, the crude product has a total Ni / V / Fe content per gram of crude product in the range of 1 x 10 7 g to 5 x 10 "5 g, 3 x 10 7 g to 2 x 10" 5 grams or 1 x 10 ~ 6 grams to 15 x 10 "5 grams.

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

In certain embodiments, the API density of the crude product is at least 10% higher, at least 50% higher, or at least 90% higher than the API density of the crude feed. In certain embodiments, the API density of the crude product may be in the range of 13-50, 15-30 or 16-20.

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 of the crude feed. In certain 1027775 "- 81 embodiments, the crude product has a total heteroatom content of at least 10%, at least 40% or at least 60% of the total heteroatoms content of the crude feed.

The crude product can have a sulfur content of at most 90%, at most 70% or at most 60% of the sulfur content of the crude feed. The sulfur content of the crude product per gram of crude product can be at most 0.02 grams, at most 0.008 grams, at most 0.005 grams, at most 0.004 grams, at most 0.003 grams or at most 0.001 grams.

In certain embodiments, the crude product has a sulfur content per gram of crude product in the range of 0.0001-0.02 grams or 0.005-0.01 grams.

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 feed. The nitrogen content of the crude product per gram of crude product can be at most 0.004 grams, at most 0.003 g or at most 0.001 grams. In some embodiments, the crude product has a nitrogen content per gram of crude product in the range of 0.0001-0.005 grams or 0.001-0.0.03 grams.

In some embodiments, the crude product contains 0.05-0.02 grams or 0.09-0.15 grams of hydrogen per gram of crude product. The H / C ratio of 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 of the crude product is 80-120% or 90-110% of the H / C ratio of the

raw food. In other embodiments, the H / C ratio of the crude product is 100-120% of the H / C ratio of the crude feed. A H / C ratio

102 7 7 75 "- - 82 - of the crude product that deviates by less than 20% from the H / C ratio of the crude feed, indicates that a minimal amount of hydrogen is absorbed and / or consumed in the process.

The crude product contains components with a range of boiling points. In some embodiments, the crude product contains: at least 0.0001 grams, or 0.001 to 0.5 grams, hydrocarbons boiling in the range of 0.111 MPa to at most 200 ° C or to at most 204 ° C; at least 0.001 gram, or 0.001 to 0.5 gram, hydrocarbons with a boiling range at 0.101 MPa between 200 ° C and 300 ° C; at least 0.001 grams, or 0.001 to 0.5 grams, hydrocarbons with a boiling range at 0.101 MPa between 300 ° C and 400 ° C and at least 0.001 grams, or 0.001 to 0.5 grams, hydrocarbons with a boiling range at 0.101 MPa between 400 ° C and 538 ° C.

In some embodiments, the crude product has a naphtha content of 0.00001-0.2 grams, 0.0001-0.1 grams, or 0.001-0.05 grams per crude product. In certain embodiments, the crude product contains 0.001-0, 2 grams or 0.01-0.05 grams of naphtha. In some embodiments, the naphtha contains at most 0.15 gram, at most 0.1 gram or at most 0.05 gram of olefins per gram of naphtha. In certain embodiments, the crude product contains 0.00001-0.15 grams, 0.0001-0.1 grams or 0.001-0.05 grams of olefins per gram of crude product. In some embodiments, the naphtha per gram of naphtha has a benzene content of at most 0.01 grams, at most 0.005 grams or at most 0.002 grams. In certain embodiments, the naphtha has a benzene content that cannot be detected or a benzene content in the range of 1 x 10 ~ 7 grams to 1 x 10-5 grams, 11027775 "- 83 - 1 x 10'6 grams up to 1 x 10 -5 grams or 5 x 10 ~ 6 grams to 1 x 10 -4 grams. Compositions containing benzene can be considered as compositions that are hazardous to handle, so that a crude product that has a relatively low benzene content often does not have to be handled in a special way.

In certain embodiments, the naphtha may contain aromatic compounds. The aromatic compounds may include compounds with a monocyclic ring and / or compounds with a polycyclic ring. Compounds with a monocyclic ring may include, but this is not a limiting list, benzene, toluene, orthoxylene, metaxylene, paraxylene, ethylbenzene, 1-ethyl-3-methylbenzene; 1-ethyl-2-15 methyl benzene; 1,2,3-trimethylbenzene; 1,3,5-trimethylbenzene; 1-methyl-3-propylbenzene; 1-methyl-2-propyl benzene; 2-ethyl-1,4-dimethylbenzene; 2-ethyl-2,4-dimethylbenzene; 1,2,3,4-tetramethylbenzene; ethyl, pentylmethylbenzene; 1,3-diethyl-2,4,5,6-tetramethyl-benzene; triisopropyl orthoxylene; substituted congeners of benzene, toluene, orthoxylene, metaxylene, paraxylene or mixtures thereof. Monocyclic aromatics are used in a wide variety of commercially available products and / or are sold as separate components. The crude product produced in the manner described in this patent specification generally has an increased content of monocyclic aromatics.

In certain embodiments, the crude product per gram of crude product has a toluene content of 0.001-0.2 grams, 0.05-0.15 grams, or 0.01-0.1 grams. The crude product has a metaxylene content of 0.001-0.1 grams, 0.005-0.09 grams or 0.05-1027775 -84-0.08 grams per gram of crude product. The crude product has an orthoxylene content of 0.001-0.2 grams, 0.005-0.01 grams or 0.01-0.05 grams per crude product. The crude product has a paraxylene content of 0.001-5 0.09 grams, 0.005-0.08 grams or 0.001-0.06 grams per crude product.

The octane number of the naphtha often increases due to the increase in the aromatics content of the naphtha. Crude oils can be assessed based on the ability to convert the crude oil into gasoline. The possibility of converting the crude oil into gasoline includes, but not only, the calculated octane number of the naphtha portion of the crude oil. Crude oils generally have a calculated octane number in the range of 35-60. If the octane number of gasoline is higher, 15 often fewer additives are required to increase the octane number of gasoline. In certain embodiments, the crude product contains naphtha with an octane number of at least 60, at least 70, at least 80, or at least 90. In general, the octane number of the naphtha is in the range of 60-99, 70-98. or 80-95.

In some embodiments, the crude product has a total content of aromatics in hydrocarbons with a boiling range between 204 ° C and 500 ° C (the total "of naphtha and petroleum") that is at least 5%, at least 10%, is at least 50% or at least 99% higher than the total aromatics content in the total naphtha and petroleum from the crude feed. In general, the total content of aromatics in the total of the naphtha and the petroleum of the crude feed is 8%, 20%, 75% or 100% greater than the total content of aromatics in the total of the naphtha and the petroleum of the raw food.

In some embodiments, the petroleum and naphtha may have a total content of polyaromatic compounds 1027775 * - 85 - in the range of 0.00001-0.5 grams, 0.0001-0.2 grams, or 0.001-0.1 grams per gram. of the total amount of petroleum and naphtha.

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

In some embodiments, the crude product contains at least 0.001 gram per gram of crude product, more than 0 to 0.7 gram, 0.001-0.5 gram or 0.01-0.1 gram of petroleum. In certain embodiments, the crude product contains 0.001-0.5 grams or 0.01-0.3 grams of petroleum. In some embodiments, the petroleum has an aromatics content of at least 0.2 grams, at least 0.3 grams, or at least 0.4 grams, per gram of petroleum. In certain embodiments, the petroleum per gram of petroleum 20 has an aromatics content in the range of 0.1-0.5 grams or 0.2-0.4 grams.

In certain embodiments, the freezing point of the petroleum may be lower than -30 ° C, lower than -40 ° C, or lower -50 ° C. Due to the increase in the content of aromatics of the petroleum portion of the crude product, the density and freezing point of the petroleum portion of the crude product often increases. A crude product with a petroleum portion with a high density and a low freezing point can be refined into a turbine fuel for aircraft with the desired properties of a high density and a low freezing point.

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

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

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

In some embodiments, the crude product may contain at least a portion of the catalyst. In some embodiments, a crude product contains more than 0 grams, but less than 0.01 grams, 0.00000-0.001 grams, or 1027775 grams of 0.00001-0,0001 grams of catalyst per gram of crude product. The catalyst can help stabilize the crude product during transport and / or during treatment in processing plants. The catalyst 5 can prevent corrosion, prevent friction and / or ensure that the crude product can more easily separate water. A crude product containing at least a portion of the catalyst can be further processed into lubricants and / or other commercial products.

The catalyst used to treat a crude feed in the presence of a source of hydrogen to obtain the total product may be a single catalyst or may consist of multiple catalysts. The catalyst used may initially be a catalyst precursor which is converted in the contact zone to the catalyst when it is contacted with hydrogen and / or with a crude feed containing sulfur.

The catalysts used in bringing the crude feed into contact with a source of hydrogen, so that the total product is obtained, can help reduce the molecular weight of the crude feed. Although we do not want to be bound by theory, it is possible that the catalyst in combination with the source of hydrogen may be able to reduce the molecular weight of components of the crude feed by the action of basic (a Lewis base or a Bronsted-Lowry base) and / or superbasic components of the catalyst. Examples of catalysts that may have the properties of a Lewis base and / or a Bronsted-Lowry base include the catalysts described in this patent.

> 10277 75-88

In some embodiments, the catalyst is a TMS catalyst. The TMS catalyst contains a compound that contains a transition metal sulfide. For the purposes of this application, the weight of the transition metal sulfide in the TMS catalyst is determined by adding the total weight of the transition metal or transition metals to the total weight of the sulfur in the catalyst. The atomic ratio of transition metal to sulfur is generally in the range of 0.2-20, 0.5-10 or 1-5. Examples of transition metal sulfides can be found in "Inorganic Sulfur Chemistry"; composed by G. Nickless; Elsevier Publishing Company; Amsterdam-London-New York; Copyright 1968; chapter 19.

In certain embodiments, the TMS catalyst may contain a total of at least 0.4 grams, at least 0.5 grams, at least 0.8 grams, or at least 0.99 grams of one or more transition metal sulfides per gram of catalyst. In certain embodiments, the TMS catalyst contains per gram of catalyst having a total content of one or more transition metal sulfides in the range of 0.4-0.999 grams, 0.5-0.9 grams, or 0.6-0.8 grams.

The TMS catalyst contains one or more transition metal sulfides. Examples of transition metal sulfides include pentlandite (Fe4.5Ni4.5S8), smythite (Fe6.75Ni2.25Sn), bravoite (Fe0.7Nio, 2Coo, iS2), mackinawite (Feo.75Nio.25So, 9), argentopentlandite (AgFe6Ni2S8), isocubanite (CuFe2S3), isocalcopyrite (CusFegSiö), sphalerite (Zno.95Feo.05S), leukhoekite (Cu9Fe9Si6), chatkalite (Cu6FeSn2S8), sternbergite (AgFe2S), CuFe2Site (FeS2), pyrrhotite (Fe aX) S (x = 0 to 0.17)), heazlewoodite (Ni3 S2) or vaesite (NiS2).

1027775 - 89 -

In some embodiments, the TMS catalyst contains one or more transition metal sulfides combined with alkali metal or alkali metals, alkaline earth metal or alkaline earth metals, zinc, zinc compounds, or a mixture thereof. The TMS catalyst is represented in some embodiments by the general formula Ac [MaSjb] d / · wherein A represents alkali metal, alkaline earth metal or zinc; M represents a transition metal from groups 6-10 of the Periodic System; and S 10 is sulfur. The atomic ratio of a to b is in the range of 0.5 to 2.5 or in the range of 1 to 2. The atomic ratio of c to a is in the range of 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 TMS catalyst may contain well-known alkali and / or alkaline earth metal / transition metal sulfides (e.g., bartonite (K3Fei0Si4), rasvumite (KFe2S3), djerfisherite 20 (K6NaFei9Cu4NiS26Cl), chlorobartone24 (K6.10) SiO2F2, Si0.10, Si0.10 and / or coyoteite (NaFe3Ss (H2 O) 2) In some embodiments, the TMS catalyst contains bartonite prepared in situ Bartonite prepared in situ may be referred to as synthetic bartonite. natural and / or synthetic bartonite described in this patent.

In some embodiments, the TMS catalyst may contain at most 25 grams, at most 15 grams, or at most 1 gram of support material per 100 grams of TMS catalyst. In general, the TMS catalyst contains 0 to 25 grams, 0.00001 to 20 or 0.0001 to 10 grams of carrier material per 100 grams of the TMS catalyst. Examples of support materials that can be used for the TMS catalyst include refractory oxides, porous carbon materials, zeolites, or mixtures thereof.

As can be seen from an X-ray diffraction assay, the TMS catalyst containing alkali metal or alkali metals, alkaline earth metal or alkaline earth metals, zinc, compounds of zinc or a mixture thereof can contain one or more transition metal sulfides, alkali metal transition metal sulfides. two metals, transition metal sulfides with a transition metal with a higher valence, transition metal oxides or a mixture thereof. A portion of the alkali metal-containing component or of the alkali-metal-containing components, of the alkaline earth-metal-containing component or of the alkaline-earth-metal-containing components, of the zinc-containing component and / or a portion of the transition metal-sulfide-containing component of the TMS catalyst may be present in some embodiments as an amorphous composition that cannot be detected by X-ray diffraction techniques.

In some embodiments, crystalline particles of the TMS catalyst and / or mixtures of the crystalline particles of the TMS catalyst have a particle size of at most 108 A, at most 103 A, at most 100 A or at most 40 A. In normal practice, the particle size of the crystalline particles of the TMS catalyst is generally at least 10 A.

The TMS catalyst containing alkali metal or alkali metals, alkaline earth metal or alkaline earth metals, zinc, compounds of zinc or a mixture thereof can be prepared by mixing a sufficiently large amount of deionized water, a desired 1027775 "- 91 - amount of transition metal oxide and a desired amount of a carbonate or of carbonates of a metal from groups 1-2, of an oxalate or of oxalates of a metal of groups 1-2, of an acetate or of acetates of a metal from the group groups 1-2, of zinc carbonate, of zinc acetate, of zinc oxalate or of a mixture thereof, so that a wet paste is formed. The wet paste can be dried at a temperature of 100-300 ° C or 150-250 ° C, so that a transition metal oxide / salt mixture is formed. The transition metal oxide / salt mixture can be calcined at a temperature in the range of 300-1000 ° C, 500-800 ° C or 600-700 ° C, so that a transition metal oxide / metal salt mixture is formed. The transition metal-oxide / metal salt mixture can be reacted with hydrogen to give a reduced solid intermediate. The addition of hydrogen can take place at a flow rate large enough to provide an excess of hydrogen relative to the transition metal oxide / metal salt mixture.

Hydrogen can be added to the transition metal oxide / metal salt mixture for 10-50 hours or for 20-40 hours, so that a reduced solid intermediate is obtained which is elemental transition. Contains metal. Hydrogen can be added 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 understood that the duration of the reduction, the reaction temperature, the choice of gas, the pressure of the reducing gas and / or the flow rate of the reducing gas used to prepare the solid intermediate, often 1027775 ' - 92 - depend on the relative mass of the chosen transition metal oxide. In some embodiments, the reduced intermediate may pass through a 40 mesh screen with minimal force.

The reduced solid intermediate can be added stepwise to a warm (e.g. 100 ° C) diluent / elemental sulfur mixture, and / or one or more compounds of sulfur at a rate at which heat development and gas development are controlled. The diluent may contain any suitable diluent that causes sulfurization heat to be dispersed. The diluent may contain solvents with a boiling range from at least 100 ° C, at least 150 ° C, at least 200 ° C, or at least 300 ° C. In general, the diluent has a boiling range between 100-500 ° C, 150-400 ° C or 200-300 ° C. In some embodiments, the diluent consists of VGO and / or xylenes. Sulfur compounds include, but this is not a limiting list, hydrogen sulfide and / or thiols. The amount of sulfur and / or sulfur compounds can vary from 1-100 mol%, 2-80 mol%, 5-50 mol%, 10-30 mol%, based on the number of mol of the metal from groups 1-2 or of zinc in the salt of the metal from groups 1-2 or in the zinc salt. After adding the reduced solid intermediate to the diluent / elemental sulfur mixture, the resulting mixture can be heated stepwise to a final temperature of 200-500 ° C, 250-450 ° C or 300-400 ° C, and 30 it is held at the final temperature for at least 1 hour, for at least 2 hours or for at least 10 hours. Generally, the 1027775 * - 93 - end temperature is maintained for 15 hours, for 10 hours, for 5 hours, or for 1.5 hours. After heating to the elevated temperature of the sulfurization reaction, the diluent / catalyst mixture can be cooled to a temperature in the range of 0-100 ° C, 30-90 ° C, or 50-80 ° C, so that the catalyst is easily removed from the mixture can be recovered. The sulfurized catalyst can be separated from the diluent in an oxygen-free atmosphere using standard techniques and washed with at least a portion of a low-boiling solvent (e.g. pentane, heptane or hexane) to obtain the TMS catalyst. The TMS catalyst can be brought into powder form using standard techniques.

In some embodiments, the catalyst is an inorganic salt catalyst. The anion of the inorganic salt catalyst may contain an inorganic compound, an organic compound or a mixture thereof. The 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, alkali metal 25 metaalpyruvaten, alkaline earth metal carbonates, earth alkali metal hydroxides, alkaline earth metal hydrides, aardalkalimetaalamiden, alkaline earth metal sulfides, alkaline earth metal acetates, aardalkalimetaaloxalaten, aardalkalimetaalformiaten, or aardalkalimetaalpyruvaten 30 a mixture thereof.

Catalysts consisting of inorganic salt include, but are not limited to, mixtures of: NaOH / RbOH / CsOH; KOH / RbOH / CsOH; NaOH / KOH / RbOH; 1027775 "- 94 -

NaOH / KOH / CsOH; K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3; Na 2 O / K 2 O / K 2 CO 3; NaHCO 3 / KHCO 3 / Rb 2 CO 3; LiHCO 3 / KHCO 3 / Rb 2 CO 3; KOH / RbOH / CsOH mixed with a mixture of K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3; K 2 CO 3 / CaCO 3; K 2 CO 3 / yig CO 3; Cs 2 CO 3 / CaCO 3; Cs 2 CO 3 / CaO; 5 Na 2 CO 3 / Ca (0 H) 2; KH / CsCO 3; KOCHO / CaO; Cs0CH0 / CaCO3?

CsOCHO / Ca (OCHO) 2; NaNH 2 / K 2 CO 3 / Rb 2 O; K 2 CO 3 / CaCO 3 / Rb 2 CO 3; K 2 CO 3 / CaCO 3 / Cs 2 CO 3; K 2 CO 3 / MgCO 3 / Rb 2 CO 3; K 2 CO 3 / MgCO 3 / Cs 2 CO 3; or Ca (OH) 2 mixed with a mixture of K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3.

In some embodiments, the inorganic salt catalyst contains at most 0.00001 grams, at most 0.001 grams or at most 0.01 grams of lithium, calculated as the weight of the lithium per gram of inorganic salt catalyst. In some embodiments, the inorganic salt catalyst contains from 0 grams but less than 0.01 grams, 0.0000001-0.001 grams or 0.00001-00001 grams of lithium, calculated as the weight of the lithium, per gram of the inorganic salt catalyst.

In certain embodiments, an inorganic salt catalyst contains one or more alkali metal salts containing an alkali metal having an atomic number of at least 11. The atomic ratio of alkali metal having an atomic number of at least 11, relative to alkali metal having an atomic number greater than 11 In some embodiments, if the inorganic salt catalyst contains two or more alkali metals, it is in the range of 0.1 to 10, 0.2 to 6 or 0.3 to 4. The inorganic salt catalyst may, for example, contain salts of sodium, potassium and rubidium, the ratio of sodium to potassium being in the range of 0.1-6; the ratio of sodium to rubidium is in the range of from 0.1 to 675; and the ratio of potassium to rubidium is in the range of 0.1-6. In another example, the inorganic catalyst contains a sodium salt and a potassium salt, the atomic ratio of sodium to potassium being in the range of 0.1 to 4.

In some embodiments, the inorganic salt catalyst also contains metals from groups 8-10 of the Periodic Table, compounds of 10 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 .System or a mixture thereof. The metals from groups 8-10 include, but this is not a limiting list, iron, ruthenium, cobalt or nickel. Group 6 metals include, but this is not a limiting list, chromium, molybdenum or tungsten. In some embodiments, the inorganic catalyst contains 0.1-0.5 grams or 0.2-0.4 grams of Raney nickel per gram of the inorganic salt catalyst.

In some embodiments, the inorganic salt catalyst also contains metal oxides from groups 1-2 and / or from group 13 of the Periodic System. The metals from group 13 belong, but this is not a limiting list, boron or aluminum. Non-limiting examples of metal oxides include lithium oxide (Li 2 O), potassium oxide (K 2 O), calcium oxide (CaO), or aluminum oxide (Al 2 O 3).

In certain embodiments, the inorganic catalyst contains substantially no Lewis acids (e.g., BCI3, AICI3 and SO3), Bronsted-Lowry acids (e.g., H30 +, H2SO4, HCl, and HNO3), substantially no glass-forming compositions (e.g., 1027775¾ - 96 - borates and silicates) and essentially no halides.

The inorganic salt catalyst may contain, per gram of an inorganic catalyst, 0.1 gram, 0.000001-0.01 gram, or 0.00001-0.005 gram of: a) halides; b) compositions which form glass at temperatures of at least 350 ° C or at most 1000 ° C; c) Lewis acids; d) Bronsted-Lowry acids; or e) a mixture thereof.

The from inorganic. saline catalyst can be prepared using standard techniques. For example, a standard amount of each component of the catalyst can be combined using standard mixing techniques (e.g., grinding and / or pulverizing). In other embodiments, inorganic composition is dissolved in a solvent (e.g., water or a suitable organic solvent), so that an inorganic composition / solvent mixture is obtained. The solvent can be removed using standard separation techniques to prepare the inorganic salt catalyst.

In some embodiments, inorganic salts of the inorganic salt catalyst can be incorporated into a support, so that a supported inorganic salt catalyst is obtained.

Examples of carriers include, but are not limited to, zirconium oxide, calcium oxide, magnesium oxide, titanium oxide, hydrotalcite, alumina, germanium oxide, iron oxide, nickel oxide, zinc oxide, cadmium oxide, antimony oxide, and mixtures thereof. In some embodiments, an inorganic salt, a metal from groups 6-10 and / or a compound of a metal from groups 6-10 can be introduced into the support 1027775 -91 by impregnation. Alternatively, inorganic salts can be melted or softened by heating and pushed into a support of metal or metal oxide and / or applied to a support of metal or metal oxide so that a supported inorganic salt catalyst is obtained.

At a predetermined temperature or in a temperature range where the structure of the catalyst loses its regularity, the structure of the inorganic salt catalyst generally becomes non-homogeneous, permeable and / or mobile. The inorganic salt catalyst can lose its regularity without substantially changing its composition (e.g. without the salt falling apart). Without wishing to be bound by theory, it is believed that the inorganic catalyst loses its regularity (becomes mobile) as the distances between the ions in the lattice of the inorganic salt catalyst increase. As the distances between the ions increase, the crude feed and / or the source of hydrogen can penetrate into the inorganic salt catalyst instead of remaining on the surface of the inorganic salt catalyst. The penetration of the crude feed and / or of the source of hydrogen into the inorganic salt often results in an increase in the contact area between the inorganic salt catalyst and the crude feed and / or the source of hydrogen. As a result of the increase in the contact area and / or the reactivity area of the inorganic salt catalyst, the yield of crude product often increases, the formation of residue and / or coke is often limited and / or it often becomes 1027775- 98 easier to change the properties of the raw product compared to the same properties of the raw food. The non-regularity of the inorganic salt catalyst (e.g. non-homogeneity, permeability and / or mobility) can be determined by using DSC methods, methods for measuring the ionic conductivity, TAP methods, eye evaluation, X-ray diffraction methods or a combination thereof.

The use of TAP for determining the properties of catalysts is described in U.S. Patent Nos. 4,626,412 to Ebner et al .; 5,039,489 to Gleaves et al .; and 5,264,183 to Ebner et al. A TAP system can be obtained from Mithra Technologies (Foley, Missouri, U.S.A.). The TAP analysis can take place at a temperature in the range of 25-850 ° C, 50-500 ° C or 60-400 ° C, at a heating speed in the range of 10-50 ° C or 20-40 ° C and at a vacuum in the range of 1 x 10 "13 to 20 lx 10" 8 torr. The temperature can remain constant and / or increase as a function of time. As the temperature of the inorganic salt catalyst increases, the discharge is of gas measured by the inorganic salt catalyst Examples of gases developed by the inorganic salt catalyst include carbon monoxide, carbon dioxide, hydrogen, water or mixtures thereof The temperature at which there is an inflection (sharp increase) of the gas evolution of the inorganic salt catalyst is considered to be the temperature at which the inorganic salt catalyst loses its structure.

1027775 - 99 -

In some embodiments, the inflection of the gas released by the inorganic salt catalyst can be observed in a temperature range determined by using TAP. The temperature or temperature range is called the "TAP temperature". The initial temperature of the temperature range determined by using TAP is called the "minimum TAP temperature."

The inflection of released gas observed with inorganic salt catalysts suitable for contact with a crude feed is in a TAP temperature range of 100-600 ° C, 200-500 ° C or 300-400 ° C . In general, the TAP temperature range is the range of 300-500 ° C. In some embodiments, different compositions of suitable inorganic salt catalysts also exhibit gas reflections, but at different TAP temperatures.

The magnitude of the ionization inflection associated with released gas may be an indication of the regularity of the particles in a crystal structure. With a very regular crystal structure, the ions are generally strongly interconnected and it takes more energy (ie, more heat) to release ions, molecules, gases or a combination from the structure. With an irregular crystal structure, the ions are not as strongly connected to each other as with a very regular crystal structure. Because the ions are less connected to each other, less energy is generally required to release ions, molecules and / or gases from an irregular crystal structure, and therefore the amount of ions is 1027775-s - 100 - and / or amount of gas released from an irregular crystal structure at a selected temperature, generally greater than the amount of ions and / or the amount of gas released from a very regular crystal structure.

In some embodiments, when a differential scanning calorimeter is used, at a heating rate or a cooling rate of 10 ° C, a dissociation heat of the inorganic salt catalyst can be observed in the range of 50 ° C

up to 500 ° C. In a DSC method, a sample can first be heated to a first temperature, cooled to room temperature, and then heated a second time. The transitions observed during the first heating are generally characteristic of entrained water and / or entrained solvent and need not be characteristic of the dissociation heat. The easily observable drying of a moist or hydrated sample can, for example, generally take place below 250 ° C, generally between 100 and 150 ° C. The transitions observed during the cooling cycle and during the second heating correspond to the dissociation heat of the sample.

By "heating transition" is meant the process that occurs when regularly arranged molecules and / or atoms in a structure lose their regular arrangement as the temperature increases during DSC analysis. By "cooling transition" is meant the process that occurs when molecules and / or atoms in a structure become more homogeneous as the temperature decreases during DSC analysis. In some embodiments 1027775 - 101 - the heating / cooling transition of the inorganic salt catalyst occurs in a temperature range that can be determined by DSC. The temperature or temperature range at which the heating transition of the inorganic salt catalyst occurs during a second heating cycle is called the "DSC temperature." The lowest DSC temperature of the temperature range during a second heating cycle is called the "minimum DSC-10 temperature". The inorganic salt catalyst can exhibit a heat transition in the range of 200-500 ° C, 250-450 ° C or 300-400 ° C.

With an inorganic salt containing inorganic salt particles that form a relatively homogeneous mixture, the shape of the peak associated with the heat absorbed during a second heating cycle can be relatively narrow. With an inorganic salt catalyst containing inorganic salt particles whose mixture is poorly homogeneous, the shape of the peak associated with the heat absorbed during a second heating cycle can be relatively broad. Absence of peaks in the DSC spectrum indicates that the salt in the temperature range that is traversed does not absorb or release heat. The non-occurrence of a heating transition generally indicates that the structure of the sample does not change during heating.

As the homogeneity of the particles of a mixture consisting of an inorganic salt increases, the capacity of the salt decreases to remain solid and / or semi-liquid during heating. The homogeneity of an inorganic mixture may be related to the ion beam 1027775 "- 102 - of the cations in the mixtures. With cations with smaller ion rays, the ability of the cations to share electron density with corresponding anions increases, and the acidity of the corresponding anions increases.

If the anion is a hard base, with a series of ions with a corresponding charge, a smaller ion beam results in stronger attracting forces between the cation and the anion. The stronger attracting forces between the ions often result in the heat transition temperatures of the salt and of one or more homogeneous mixtures of particles of the salt increasing. (a sharper peak and a larger area under the DSC curve). Mixtures containing cations with a smaller ion beam are often more acidic than cations with a larger ion beam, and therefore the acid strength of the inorganic salt mixture increases as the cation radius decreases. For example, the contact of a crude feed with a source of hydrogen in the presence of an inorganic mixture containing lithium cations often gives a greater amount of gas and / or coke than the contact of the crude feed with a source of hydrogen in the presence of a inorganic salt-containing catalyst containing cations with a larger ion beam than lithium. The ability to inhibit the formation of gas and / or coke increases the total liquid product yield of the process.

In certain embodiments, the inorganic salt catalyst may contain two or more inorganic salts. The minimum DSC temperature can be determined for each of the inorganic salts. The minimum DSC temperature of the inorganic salt catalyst may be below the minimum DSC temperature of at least one of the inorganic metal salts of the inorganic salt catalyst. The inorganic salt catalyst may, for example, be potassium carbonate and cesium carbonate Potassium carbonate and cesium-5 carbonate exhibit a DSC temperature higher than 500 ° C. A K2CO3 / Rb2CO3 / Cs2CO3 catalyst exhibits a DSC temperature in the range of 290-300 ° C.

In some embodiments, the TAP temperature 10 may be between the DSC temperature of at least one of the inorganic salts and the DSC temperature of the inorganic salt catalyst. The TAP temperature of the inorganic salt catalyst can be in the range of 350-1500 ° C. The DSC temperature of the same inorganic salt catalyst can be in the range of 200-300 ° C and the DSC temperature of individual salts can be at least 500 ° C or at most 1000 ° C.

A catalyst consisting of inorganic salt which has a TAP temperature and / or a DSC temperature of 150-500 ° C, 200-450 ° C or 300-400 ° C, and which does not decompose at these temperatures, can at many embodiments can be used to convert high molecular weight and / or high viscosity compositions (e.g., a crude feed) into liquid products.

In certain embodiments, the inorganic salt catalyst may exhibit a higher conductivity than the individual inorganic salts during heating in a temperature range of 200-600 ° C, 300-500 ° C or 350-450 ° C. An increased conductivity of the inorganic salt catalyst is generally attributed to the fact that the particles of 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 a single component of the inorganic salt. existing catalyst.

The ionic conductivity of inorganic salts can be determined by using Ohm's law: V = IR, where V is the voltage, I is the current and R is the resistance. To measure the ionic conductivity, the inorganic salt catalyst can be introduced into a quartz vessel containing two wires (e.g., copper wires or platinum wires) that are separate from each other but are contained in the inorganic salt catalyst .

FIG. 7 is a schematic representation of a system that can be used to measure the ionic conductivity. The quartz vessel 156 containing the sample 158 can be introduced into a heating device and can be heated stepwise to a desired temperature. During the heating, wire 162 is brought under a voltage from the voltage source 160. The current obtained through the wires 162 and 164 is measured with a meter 166. The meter 166 can be a multimeter or a Wheatstone bridge, but 30 is not limited to that. If the sample 158 becomes less homogeneous (becomes more mobile) without decomposition occurring, the resistance of the sample will decrease and the current determined with meter 166 will increase.

1027775 "- 105 -

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

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

The catalyst consisting of inorganic salt can soften if it is heated to temperatures higher than 50 ° C and lower than 500 ° C. When the inorganic salt catalyst becomes soft, liquid and solid catalyst particles can occur together in the matrix of the inorganic salt catalyst. In some embodiments, the catalyst particles, upon heating to a temperature of at least 300 ° C, or at most 800 ° C, can deform themselves under the influence of gravity, or deform under a pressure of at least 0.007 MPa, or at most 0.101 MPa so that the inorganic salt catalyst is converted from a first to a second form. After cooling the inorganic salt catalyst to 20 ° C, the second form of the inorganic salt catalyst can no longer return to the first form of the inorganic salt catalyst. The temperature at which the inorganic salt is converted from the first form to the second form is called the "deformation temperature".

The distortion temperature can embrace a temperature range or can be a single temperature. In certain embodiments, the particles of the inorganic salt catalyst themselves deform under the influence of gravity or under the influence of a pressure upon heating to a deformation temperature lower than the deformation temperature of each of the individual inorganic metal salts. In some embodiments, the inorganic salt catalyst contains two or more inorganic salts with a different deformation temperature. The deformation temperature of the inorganic salt catalyst differs in some embodiments from the deformation temperature of the individual inorganic metal salts.

In certain embodiments, the inorganic salt catalyst is liquid and / or semi-liquid at or above the TAP temperature and / or the DSC temperature. In some embodiments, the inorganic salt catalyst mixed with the crude feed may form a phase other than the crude feed at or above the minimum TAP temperature and / or DSC temperature. In some embodiments, the liquid or semi-liquid inorganic salt catalyst has low solubility in the crude feed at the minimum TAP temperature (e.g., 0 to 0.5 grams, 0.0000001-0.2 grams, or 0.0001-0) 1 gram of inorganic catalyst consisting of inorganic 1027775 salt per gram of crude feed or is it insoluble in the crude feed (e.g. 0 g to 0.05 g, 0.000001-0.01 g or 0.00001-0.001 gram of inorganic salt per gram of crude feed).

In some embodiments, powder X-ray diffraction methods are used to determine the distance between the atoms in the inorganic salt catalyst. The shape of the D010 peak of the X-ray spectrum can be viewed and the location of the inorganic salt particles relative to each other can be estimated. Peaks in the X-ray diffraction spectrum represent various compounds of the inorganic salt catalyst. With powder X-ray diffraction, the Thaw peak can be viewed and the distance between the atoms can be estimated. With a catalyst consisting of an inorganic catalyst containing very regularly ordered inorganic salt atoms, the Thaw peak has a relatively narrow shape. With an inorganic salt catalyst (e.g., a K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst) containing randomly arranged inorganic salt atoms, the shape of the Thaw peak may be relatively broad or the Thaw peak may not be present. To determine if the regularity of the arrangement of the inorganic salt atoms changes during heating, an X-ray diffraction spectrum of the inorganic salt catalyst may be included prior to heating and compared to an X-ray diffraction spectrum recorded after heating. . The Thaw peak (corresponding to the inorganic salt atoms) in the X-ray diffraction spectrum taken at temperatures higher than 50 ° C may be absent, or may be wider than the Thaw peaks in 1027775 - the X-ray diffraction spectrum that is recorded at temperatures below 50 ° C. In addition, the X-ray diffraction pattern of the individual inorganic salt can exhibit relatively narrow Thaw peaks at the same temperatures.

The contact conditions can be controlled such that in addition to limiting and / or preventing the formation of by-product, the total composition of the product (and therefore of the crude product) for a given crude feed can be varied. The total composition of the product includes, but is not a limiting list, paraffins, olefins, aromatics or mixtures thereof. These compounds form the compositions of the crude product, and the non-condensable hydrocarbon gases.

Controlling the contact conditions in combination with the catalyst described in this patent can give a total product with a coke content lower than predicted. Comparison of the MCR content of different crude oils can make it possible to rank crude oils based on their tendency to form coke. A crude oil with an MCR content of 0.1 grams MCR per gram of crude oil is expected to form more coke than a crude oil with a 25. MCR content of 0.001 grams MCR per gram of crude oil. Less useful crude oils generally have an MCR content of at least 0.05 grams of MCR per gram of less useful crude oil.

In some embodiments, the residue and / or coke content deposited on the catalyst during the reaction period may be at most 0.1 grams, at most 0.05 grams or at most 0.03 grams of residue and / or coke per grams of catalyst. In certain embodiments, the weight of the residue and / or the coke deposited on the catalyst is in the range of 0.0001-0.1 grams, 0.001-0.05 grams, or 0.01. -0.03 grams. In some embodiments, the catalyst used contains substantially no residue and / or coke. In certain embodiments, the contact conditions are controlled such that no more than 0.015 grams, no more than 0.01 grams, no more than 0.005 grams, or no more than 0.003 grams of coke are formed per gram of crude product. Contacting a crude feed with the catalyst under controlled contact conditions gives a smaller amount of coke and / or residue than the amount of coke and / or residue obtained by heating the same under the same contact conditions. crude feed in the presence of a refining catalyst, or in the absence of a catalyst.

In some embodiments, the contact conditions can be controlled such that at least 0.5 grams, at least 0.7 grams, at least 0.8 grams, or at least 0.9 grams of crude feed are converted to the crude feed per gram of raw feed. product. In general, 0.5-0.99 grams, 0.6-0.9 or 0.7-0.8 grams of crude product per gram of crude feed is prepared during contacting. The conversion of the crude feed into a crude product with a minimum amount of residue and / or coke, if present, in the crude product allows the crude product to be converted into commercial products in a refinery with minimal pretreatment. In certain embodiments, per gram of crude feed 30 at most 0.2 gram, at most 0.1 gram, at most 0.05 gram, at most 0.03 gram or at most 0.01 gram of the crude feed is converted into non-condensable hydrocarbons. In some embodiments, 0 1027775 - 110 - to 0.2 grams, 0.0001-0.1 grams, 0.001-0.05 grams or 0.01-0.03 grams of non-condensable hydrocarbons are produced per gram of crude feed .

To maintain the desired reaction temperatures, the temperature of the contact zone can be controlled, the flow rate of the raw feed can be controlled, the speed of the flow of the total product can be controlled, the speed and / or the amount of the catalyst feed or a combination thereof can be arranged. In some embodiments, the temperature of the contact zone can be controlled by changing the flow of a gaseous source of hydrogen and / or an inert gas through the contact zone so that the amount of hydrogen is diluted and / or excess heat from the contact zone is disposed of.

In some embodiments, the temperature of the contact zone can be controlled such that the temperature of the contact zone is below or above the desired temperature "Ti". In some embodiments, the contact temperature is controlled such that the temperature of the contact zone is below the minimum TAP temperature and / or below the minimum DSC temperature. In certain embodiments, the Ti may be 30 ° C lower than, 20 ° C lower than or 10 ° C lower than the minimum TAP temperature and / or the minimum DSC temperature. In one embodiment, the contact temperature can be controlled such that it is 370 ° C, 380 ° C or 390 ° C during the reaction period, the minimum TAP temperature and / or the minimum DSC temperature being 400 ° C.

1027775 - Ill -

In other embodiments, the contact temperature is controlled such that the temperature is equal to or higher than the TAP temperature of the catalyst and / or the DSC temperature of the catalyst. For example, if the minimum TAP temperature and / or the minimum DSC temperature is 450 ° C, the contact temperature can be controlled such that it is 450 ° C, 500 ° C or 550 ° C during the reaction period. Controlling the contact temperature based on the TAP-10 temperatures of the catalyst and / or the DSC temperatures of the catalyst can provide improved properties of the crude product. By controlling this, for example, the formation of coke can be reduced, the formation of non-condensable gases can be reduced, or a combination thereof.

In certain embodiments, the inorganic salt catalyst can be conditioned before adding the crude feed. In some embodiments, the conditioning can take place in the presence of the crude feed. Conditioning of 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, and then cooling the inorganic salt catalyst to a second temperature of 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 of 150-700 ° C.

600 ° C or 300-500 ° C, and then cooled to a second temperature in the range of 25-240 ° C, 30-200 ° C

1027775 - 112 - or 50-90 ° C. The temperatures of the conditioning can be determined by determining the ionic conductivity at different temperatures. In some embodiments, the temperatures of the conditioning can be determined on the basis of DSC temperatures obtained at heating / cooling transitions, obtained by heating and cooling the inorganic salt catalyst multiple times in a DSC device. The conditioning of the inorganic salt catalyst can allow the contact of a crude feed to take place at lower reaction temperatures than the temperatures used with conventional catalysts for treating with hydrogen.

In some embodiments, the content of the total product of naphtha, distillate, VGO or a mixture thereof can be changed by varying the rate at which the total product is removed from a contact zone. For example, reducing the rate of removal of the total product often causes the total contact time of the crude feed with the catalyst to increase. Alternatively, increasing the pressure relative to the initial pressure may cause an increase in contact time, an increase in the yield of crude product, at a given rate of mass flow from the raw feed or from the source of hydrogen cause an increase in the uptake of hydrogen from the gases in a crude product, or cause a change in a combination of these effects. Increasing the contact time of the crude feed with the catalyst can lead to an increased amount of diesel, petroleum or naphtha and a decreased amount of VGO, compared to the amounts of diesel, petroleum, naphtha and VGO that are prepared with shorter contact times. The increase in the contact time of the total product in the contact zone can also change the average number of carbon atoms of the crude product.

An increased contact time can lead to a higher weight percentage of compounds with a small number. carbon atoms (and therefore for a higher API density).

In some embodiments, the contact conditions may vary over time. For example, the contact pressure and / or contact temperature can be increased to increase the amount of hydrogen that the crude feed absorbs when producing the crude product. The ability to change the amount of hydrogen absorbed by the crude feed while improving other crude feed properties provides an increase in the types of crude products that can be prepared from a single crude feed. The possibility of preparing several raw products from a single crude feed can make it possible to meet different requirements in the field of transport and / or handling.

The uptake of hydrogen can be determined by comparing the H / C ratio of the crude feed with the H / C ratio of the crude product. An increase in the H / C ratio of the crude feed relative to the H / C ratio of the crude product indicates the incorporation of hydrogen into the crude product from the source of hydrogen. A relatively small increase in the H / C ratio of the crude product (an increase of 20% over the crude feed) indicates a relatively low use of hydrogen gas during the 1027775- 114 process. It is desirable that with a minimal consumption of hydrogen a substantial improvement in the properties of the crude product compared to the properties of the crude feed is achieved.

To change the properties of the crude product, the ratio of the source of hydrogen to the crude feed can also be changed. Due to the ratio of the source of hydrogen to. To increase the crude feed, for example, a crude product can be obtained that has an increased VGO content per gram of crude product.

In certain embodiments, contact of the crude feed with the inorganic salt catalyst in the presence of light hydrocarbons and / or steam gives more liquid hydrocarbons and less coke in a crude product than contact of a crude feed with an inorganic salt catalyst in the presence of hydrogen and steam. In embodiments involving contact of the crude feed with methane in the presence of the inorganic salt catalyst, at least a portion of the components of the crude feed may contain carbon atoms and hydrogen atoms (derived from the methane) contained in the molecular structure of the components.

In certain embodiments, the volume of the crude product formed with the source of hydrogen in the presence of an inorganic salt catalyst is at least 5% greater, at least 10% greater, or at least 15% greater, or at most 100% larger than the volume of a crude product that is formed in a thermal process at STP. The total volume of the crude product that is formed by contacting the crude feed with the inorganic salt catalyst can be at least 110% of the volume of the crude feed at STP. It is believed that the increase in volume is caused by a decrease in density. The lower density can generally be at least partially caused by hydrogenation of the crude feed.

In certain embodiments, a crude feed with per gram of raw feed is at least 0.02 grams, at least 0.05 grams, or at least 0.1 grams, sulfur and / or at least 0.001 grams of Ni / V / Fe. presence of an inorganic salt catalyst contacted with a source of hydrogen without reducing the activity of the catalyst.

In some embodiments, the inorganic salt catalyst can be regenerated at least partially by removing one or more components that contaminate the catalyst. The contaminating components include, but this is not a limiting list, metals, sulfides, nitrogen, coke, or a mixture thereof. Sulphide-containing contaminants can be removed from the used inorganic salt catalyst by contacting the used catalyst with steam and carbon dioxide to obtain hydrogen sulfide.

Nitrogen-containing contaminants can be removed by contacting the used inorganic salt catalyst with steam to form ammonia. Coke-containing impurities can be removed from the used inorganic salt catalyst by contacting the used inorganic salt catalyst with steam and / or methane, so that hydrogen and carbon oxide are obtained. In some embodiments, one or more gases is formed from a mixture of used inorganic salt catalyst and residual crude feed.

In certain embodiments, a mixture of used inorganic salts (e.g. coke, in the presence of steam, hydrogen, carbon dioxide and / or light hydrocarbons, are heated to a temperature in the range of 7 00-1000 ° C or 800-900 ° C, until a minimum amount of gas and / or liquids is obtained. The gas can contain a greater amount of hydrogen and / or carbon dioxide than the reacting gas. The gas may contain, for example, 0.1-99 mol or 0.2-8 mol of hydrogen and / or carbon dioxide per mol of reacting gas. The gas can contain a relatively small amount of light hydrocarbons and / or carbon monoxide. For example, less than 0.05 grams of light hydrocarbons per gram of gas and less than 0.01 grams of carbon monoxide per gram of gas. The liquid phase may contain water, for example more than 0.5-0.99 grams or more than 0.9-0.9 grams of water per gram of liquid. In some embodiments, the catalyst and / or solids used may the contact zone is treated to recover metals (e.g. vanadium and / or nickel) from the catalyst and / or solid used. The catalyst and / or solid used can be treated by using well-known separation techniques, for example heating, treatment with chemicals and / or gasification.

1027775 - 117 -

EXAMPLES

The following are non-limiting examples of catalyst preparations, catalyst testing, and systems with controlled contact conditions.

Example 1. Preparation of a K-Fe sulfide catalyst

A K-Fe sulfide catalyst was prepared by combining 1000 grams of iron oxide (Fe2 O3) and 580 g of potassium carbonate with 412 g of deionized water to form a wet paste. The wet paste was washed at 200 ° C

dried to form a zeroxide / potassium carbonate mixture. The iron oxide / potassium carbonate mixture was calcined at 500 ° C to form an iron oxide / potassium carbonate mixture. The iron oxide / potassium carbonate mixture was reacted with hydrogen to form a reduced intermediate containing iron metal. Hydrogen was added for 48 hours at 450 ° C and 11.5-12.2 MPa (1665-1765 psi). The solid intermediate was pushed through a sieve under the influence of a very low force.

The solid intermediate was added stepwise to a VGO / m-xylene / elemental sulfur mixture at 100 ° C at a rate such that gas evolution was controlled. After adding the solid intermediate, the resulting mixture was heated stepwise to 300 ° C and held at 300 ° C for 1 hour. The solvent / catalyst mixture was cooled to a temperature below 100 ° C and the sulphurized catalyst was separated from the mixture. The sulfurized catalyst was isolated by placing it in an glove box under an atmosphere of argon

1027775J

118 'filtration, and was washed with m-xylene to yield 544.7 grams of the K-Fe sulfide catalyst. The K-Fe sulfide catalyst was powdered by passing the catalyst through a 40 mesh screen.

The resulting K-Fe sulfide catalyst was analyzed using X-ray diffraction techniques. From the analysis of the X-ray diffraction spectrum, it was determined that the catalyst contained 10 troilite (FeS), K-Fe sulfide (KFeS2), pyrrhotite and iron oxides (e.g. magnetite, Fe3C> 4). No peak was observed in the X-ray diffraction spectrum that could be attributed to iron sulfides (e.g., pyrite, FeS2).

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

A 600 ml continuously stirred tank reactor (made of 316 stainless steel) was provided with an inlet opening for feeding to the bottom, a single outlet for vapor, three thermocouples in the inner part of the reactor and an ash-driven six-blade Rushton turbine 'honors diameter. of 1.25 inches.

The K- prepared as described in Example 1

Fe sulfide catalyst (110.3 grams) was charged to the reactor. Hydrogen gas was introduced into the reactor in an amount of 8,000 Nm3 / m3 (50,000 SCFB) and this hydrogen gas was mixed with bitumen (from the Lloydminster area of Canada). The bitumen entered the reactor through the feed inlet port on the bottom, thereby forming a hydrogen / crude feed mixture. During the 185 hour reaction time, 1027775 g of continuous hydrogen gas and crude feed were supplied to the reactor and products were continuously removed from the reactor through the vapor outlet of the reactor. The crude feed was fed at a speed of 67.0 g / h, so that the liquid level of the crude feed was kept at 60% of the reactor volume. To measure the liquid level in the reactor, use was made of a source of 137 Cs gamma radiation of 50 millicuria and of a sodium iodide-containing scintillation detector.

The hydrogen gas / crude feed was contacted with the catalyst at an average internal reactor temperature of 430 ° C. Contacting the hydrogen / crude feed with the catalyst gave a total product in the form of vapor discharged from the reactor. The vapor discharged from the reactor left the vessel through the single upper outlet. The top of the reactor was electrically heated to 430 ° C, thereby preventing the reactor vapor from condensing on the inner portion of the top of the reactor.

After leaving the reactor, the discharge vapor from the reactor was cooled and separated into a high-pressure gas / liquid separator and a low-pressure gas / liquid separator, whereby a liquid stream and a gas stream were obtained. The gas stream was passed to a counter-current basic washing plant in which acid gases were removed, and was then quantified using standard chromatographic techniques. The total product contained 0.918 grams of crude product and 0.089 grams of non-condensable hydrocarbon gases per gram of total product. In the reactor 1027775-120, 0.027 grams of solid per gram of crude feed remained.

The properties and compositions of the crude product and of the non-condensable hydrocarbons prepared by this process are summarized in Table 5.1 of FIG. 8, Table 2 of FIG. 9 and Table 3 of FIG. 10.

This example shows a method of contacting a crude feed with hydrogen in the presence of a transition metal sulfide-containing catalyst, whereby a total product is obtained with a minimal additional formation of coke. The total product consisted, inter alia, of a crude product that was a liquid mixture at STP and that contained no more than 0.1 gram of non-condensable hydrocarbon gases per gram of total product.

By comparing the results of the MCR content of the crude feed (13.7% by weight) in Table 1 with the solids formed during the process (2.7% by weight) it can be seen that the combination of the controlled conditions and the catalyst gave a smaller amount of coke than indicated by the ASTM method D4530.

The non-condensable hydrocarbons contain C 2, C 3 and C 4 hydrocarbon. On the basis of the sum of the weight percentages of the C2 hydrocarbons (20.5 grams) shown in Table 2, the ethylene content can be calculated per gram of the total amount of C2 hydrocarbons. The C2 hydrocarbons of the hydrocarbon gases contain 0.073 grams of ethylene per gram of the total amount of the C2 hydrocarbons. On the basis of the sum of the weight percentages of the C3 hydrocarbons shown in Table 2, the propylene content per gram of the total amount of the C3 hydrocarbons can be calculated. The C3 hydrocarbons 1027775 "- 121 - of the non-condensable hydrocarbon gases contain 0.21 grams of propylene per gram of the total amount of the C3 ~ hydrocarbons. The C4 hydrocarbons of the non-condensable hydrocarbon gases had a weight ratio of isobutane to n-butane of 0.2.

This example shows a process for preparing a crude product containing at least 0.001 grams of hydrocarbons with a boiling range at 0.101 MPa 10 to at most 204 ° C (400 ° F), containing at least 0.001 grams of hydrocarbons with a boiling range at 0.101 MPa between 204 ° C and 300 ° C, contains at least 0.001 grams of hydrocarbons with a boiling range at 0.101 MPa between 300 ° C and 400 ° C, and contains at least 0.001 grams of hydrocarbons with a boiling range at 0.01 MPa between 400 ° C and 538 ° C (1000 ° F). Hydrocarbons having a boiling range below 204 ° C include isoparaffins and n-paraffins, and the ratio of such isoparaffins to n-paraffins was 1.4 at most.

The crude product contained boiling point distributions corresponding to those of naphtha, petroleum, diesel and VGO. The crude product contained at least 0.001 grams of naphtha and the naphtha portion of the crude product had an octane number of at least 70. The naphtha portion of the crude product had a benzene content of at most 0.01 grams of benzene per gram of naphtha. The naphtha portion of the crude product contained no more than 0.15 grams of olefins per gram of naphtha. The naphtha portion of the crude product contained at least 0.1 grams of aromatics with a monocyclic ring per gram of naphtha.

1027775 - 122 -

The crude product contained at least 0.001 grams of petroleum. The petroleum portion of the crude product had a freezing point of less than -30 ° C. The petroleum portion of the crude product contained aromatics, and the petroleum portion of the crude product had an aromatics content of at least 0.3 grams of aromatics per gram of petroleum. The petroleum portion of the crude product contained at least 0.2 grams of aromatics with a monocyclic ring per gram of petroleum.

The crude product contained at least 0.001 grams of diesel. The diesel fraction of the crude product contained aromatics, and the diesel fraction of the crude product had an aromatics content of at least 0.4 grams of aromatics per gram of diesel.

The crude product contained at least 0.001 grams of VGO.

The VGO portion of the crude product contained aromatics, and the VGO had an aromatics content of at least 0.5 grams of aromatics per gram of VGO.

Example 3. Preparation of a K-Fe sulfide catalyst in the absence of a hydrocarbon diluent

A K-Fe sulfide catalyst was prepared by combining 1000 g of iron oxide and 173 g of potassium carbonate with 423 g of deionized water to form a wet paste. The wet paste was processed as described in Example 1 to form the solid intermediate. The solid intermediate was pushed through a 40 mesh screen with a slight force.

In contrast to Example 2, the solid intermediate was mixed with elemental sulfur in the absence of a hydrocarbon diluent. The solid intermediate was mixed with powdered elemental sulfur under an atmosphere of argon in a glove box, placed in a sealed carbon steel cylinder, heated to 400 ° C, and maintained at 400 ° C for 1 hour. The sulfurized catalyst was removed from the carbon steel reactor as a solid. The potassium iron sulfide catalyst was ground using a mortar and pestle so that the resulting catalyst powder passed through a 40 mesh screen.

The resulting potassium iron sulfide catalyst was analyzed by X-ray diffraction techniques. It was determined from the X-ray diffraction spectrum that the catalyst contained pyrite (FeS2), iron sulfide (FeS) and pyrrhotite (Fei-xS). Using mixed X-ray diffraction techniques, no mixed potassium iron sulfide compounds or iron oxide compounds were found.

Example 4. Contact of a crude feed with a source of hydrogen in the presence of a K-Fe sulfide catalyst, with an increased ratio of hydrogen gas to crude feed

The device, the crude feed and the reaction procedure were the same as in Example 2, except that the ratio of hydrogen gas to the crude feed was 16,000 Nm 3 / m3 (100,000 SCFB). The K-Fe sulfide catalyst (75.0 grams) prepared as described in Example 3 was charged to the reactor.

The properties of the crude product obtained by this method are summarized in Table 1 of FIG. 8 and in Table 3 of FIG. 10. The weight percentage of VGO obtained in Example 4 is greater than the weight percentage of VGO obtained in Example 2. The percentage by weight of distillate obtained in Example 4 is smaller than the percentage by weight of distillate obtained in Example 2. The API density of the product obtained in Example 4 is lower than the API density of the product obtained in Example 2. A higher API density indicates that hydrocarbons with a larger number of carbon atoms were prepared.

After contact with the crude feed, the TMS catalyst in the reactor was analyzed. In this analysis, it was found that the transition metal sulfide-containing catalyst, after it had been in the presence of the crude feed and hydrogen, contained K3 Fe10 Si4. Example 5. TAP test of a K2CO3 / Rb2CO3 / Cs2CC> 3 catalyst and of the individual inorganic salts. In all TAP tests, a 300 mg sample was placed in a TAP reactor at a rate of 50 ° C per minute. system heated from room temperature (27 ° C) to 500 ° C. The water vapor and carbon dioxide gas that were released were measured with a mass spectrometer from the TAP system.

K2 CO3 / Rb2 CO3 / Cs2 CO3 catalyst supported on alumina showed a current outflow of more than 0.2 volts at 360 ° C for carbon dioxide released from the inorganic salt catalyst, and a current outflow of 0.01 volts water released by the inorganic salt catalyst. The minimum TAP temperature, as determined by the 10 log of the ion current off. to set against the temperature, was 360 ° C. FIG. 11 is a graphical representation of the 10-log graphs of the ion stream of gases emitted by the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst ("log (I)") against the 1027775 - 125 temperature (" T "). Graphs 168 and 170 are 10-log values for the ion streams for water and CO2 released by the inorganic salt catalyst. At 360 ° C there is a strong inflection of the water and the CO2 released by the inorganic salt catalyst.

On the other hand, the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst, the potassium carbonate and the cesium carbonate exhibit observable inflection of the stream at 360 ° C for neither released water nor for released carbon dioxide.

The substantial increase in the amount of gas released by the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst demonstrates that the inorganic salt catalysts consisting of two or more different inorganic salts may be arranged less regularly than the individual carbonate salts . Example 6. DSC test of an inorganic salt catalyst and of individual inorganic salts In all DSC tests, a 10 mg sample was heated to 520 ° C at a rate of 10 ° C per minute at a rate of 10 ° C per minute cooled from 520 ° C to 0.0 ° C, and then heated at a speed of 10.0 ° C per minute from 0 ° C to 600 ° C, using a differential scanning calorimeter ( DSC) Model DSC-7, manufactured by Perkin-Elmer (Norwalk, Connecticut, USA).

DSC analysis of a K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst during the second heating of the sample showed that the salt mixture exhibited a broad heat transition between 219 ° C and 260 ° C. The middle point of the temperature range was 250 ° C. The area under the 1027775 heat transition curve turned out to be -1.75 joules per gram after calculation. It was found that at the minimum DSC temperature of 219 ° C, irregularity of the crystals began to occur.

In contrast to these results, no clear heat transitions were observed with cesium carbonate.

DSC analysis of a mixture of Li 2 CO 3, Na 2 CO 3 and K 2 CO 3 during the second heating cycle showed that the Li 2 CO 3 / Na 2 CO 3 / K 2 CO 3 mixture exhibited a sharp heat transition between 390 ° C and 400 ° C. The middle point of the temperature range was 385 ° C. The area under the heat transition curve was calculated to be -182 joules per gram after calculation. It was determined that the mobility started at the minimum DSC temperature of 390 ° C. The sharp heat transition indicates a substantially homogeneous mixture of salts.

Example 7. Test of the ionic conductivity with respect to K 2 CO 3 of an inorganic salt catalyst or of an individual inorganic salt

All tests were carried out by placing 3.81 cm (1.5 inches) of the inorganic salt catalysts or of the individual inorganic salts in a 25-quartz vessel with platinum or copper wires separated but separated from each other were in the sample, the quartz vessel being in a muffle furnace. The wires were connected to a 9.55 volt dry cell and to a current limiting resistor of 220,000 ohms. The muffle furnace was heated to 600 ° C and the. current was measured using a microamp meter.

1027775 "- 127 - FIG. 12 is a graphical representation of graphs of the logarithm of the resistance of the sample to the resistance of potassium carbonate ("log (r K2 CO3)") to the temperature ("T"). Curves 172, 174, 176, 178 and 180 are graphs of the resistance of K2CO3, the resistance of CaO, the resistance of a K2CO3 / Rb2CO3 / Cs2CO3 catalyst, the resistance of a Li2CO3 / K2CO3 / Rb2CO3 / Cs2CO3- catalyst and the resistance of a Na 2 CO 3 / K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst.

CaO (curve 174) shows a relatively large stable resistance with respect to K2 CO3 (curve 172) at temperatures in the range of 380-500 ° C. A stable resistance indicates an ordered structure and / or ions that do not tend to move apart during heating. The K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst, the

Li 2 CO 3 / K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst and the Na 2 CO 3 / K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst (curves 176, 178 and 180) show a sharp decrease in resistivity with respect to temperatures in the range of 350-500 ° C with respect to See K2CO3. A decrease in the resistivity generally indicates that current delivery was observed during the tensioning of the wires contained in the inorganic salt catalyst. The data of FIG. 12 show that catalysts consisting of inorganic salt are generally more mobile at temperatures in the range of 350-600 ° C than the pure inorganic salts.

FIG. 13 is a graphical representation of graphs of the logarithm of the resistance of a Na 2 CO 3 / K 2 CO 3 / Rb 2 CO 3 /

Cs 2 CO 3 catalyst with respect to the resistance of K 2 CO 3 ("log (r K 2 CO 3)") to the temperature ("T"). Curve 182 1 027775r - 128 - is a graph of the ratio of the resistance of a Na2CO3 / K2CO3 / Rb2CO3 / Cs2CO3 ~ catalyst to the resistance of K2CO3 (curve 172) to the temperature during heating of the Na2CO3 / K2CO3 / Rb2 CO3 / Cs2 CO3-5 catalyst. After heating, the Na 2 CO 3 / K 2 CO 3 / Rb 2 CO 3 /

Cs2CC> 3 catalyst cooled to room temperature and then heated in the conductivity measurement device. Curve 184 is a graph of the logarithm of the resistance of a Na 2 CO 3 / K 2 CO 3 / Rb 2 CO 3/10 Cs 2 CO 3 catalyst against the resistance of K 2 CO 3 to the temperature during heating of the inorganic salt catalyst after it was cooled from 600 ° C up to 25 ° C. The ionic conductivity of the reheated Na 2 CO 3 / K 2 CO 3 / Rb 2 CO 3/15 Cs 2 CO 3 catalyst increased relative to the ionic conductivity of the original Na 2 CO 3 / K 2 CO 3 / Rb 2 CC 3 / Cs 2 CO 3 catalyst.

On the basis of 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 on cooling takes a different form (a second form) that is not the same as the form (a first form) before any form of heating has taken place.

Example 8. Test of the flow properties of an inorganic salt catalyst

A 1-2 cm thick layer of powdered K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst was placed in a quartz dish. The dish was placed in an oven and heated at 500 ° C for 1 hour. To determine the flow properties of the catalyst, the dish was tilted after heating in the oven. The K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst did not flow. When pressed with a spatula, the catalyst had the consistency of a toffee.

In contrast, the individual carbonate salts were free-flowing powders under the same conditions.

Under the same conditions, a Na 2 CO 3 / K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst became liquid in the dish and flowed easily (e.g., just like water). Examples 9-10: Contact of a crude feed with a source of hydrogen in the presence of a K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst and steam

Except when variations are shown in the description, in Example 9-27 the following device was used and the following general procedure was followed.

Reactor: A 250 ml Hastelloy C Parr autoclave (Parr model no. 4567) with a working pressure at 500 ° C of 35 MPa (5000 psi) was equipped with a mechanical stirrer and a 800 watt Gaumer ribbon heater. A Eurotherm control device that was able to keep the autoclave with an accuracy of ± 5 ° C at an ambient temperature of up to 625 ° C, an inlet opening for gas, an inlet opening for steam, one outlet opening and thermocouple to keep the inside temperature at 25 to take. Before heating, the top of the autoclave was insulated with a glass cloth.

Additive vessel: An additive vessel (250 ml made of 316 stainless steel) was provided with a controlled heating system, suitable valves for controlling the amount of gas, a pressure release device, thermocouples, a pressure gauge and a control valve that was able to withstand high temperatures' 1027775- 130 - (Swagelok Valve # SS-4UW) with which the flow of a warm, viscous and / or pressurized raw food could be controlled in a flow rate range of 0-500 g / min After the crude feed was introduced into the addition vessel, the outlet side of the high temperature-resistant control valve was attached to the first inlet port of the reactor.

The addition vessel was isolated before use.

Collecting the product: Vapor exiting the reactor outlet port 10 was collected in a series of cold traps with an increasingly lower temperature (immersion tubes connected to a 150 ml stainless steel 316 series of vessels). Liquid from the vapor was condensed in the cold traps. Wherein a gas stream and a liquid condensate stream were formed. To the extent necessary, the flow rate of the vapor leaving the reactor and falling through the cold was controlled by using a back pressure regulator. The flow rate and the total gas volume of the gas stream leaving the cold traps were measured using a moisture test meter (Ritter Model # TG 05 Wet Test Meter). After leaving the moisture test meter, the gas flow became. collected in a gas bag (a gas collection bag from Tedlar) and analyzed. The gas was analyzed using GC / MS (Hewlett-Packard model 5890, nowadays Agilent model 5890; manufactured by Agilent Technologies, Zion Illinois, U.S.A.). The liquid condensate stream was removed from the cold traps and weighed. The crude product and water were separated from the liquid condensate streams. The crude product was weighed and analyzed.

1027775 "- 131 -

Procedure: Cerro Negro (137.5 grams) was added to the addition vessel. The crude feed had an API density of 6.7. The crude feed had a sulfur content of 0.042 grams per gram of raw feed, a nitrogen content of 0.011 grams and a total content of

Ni / V of 0.009 grams. The crude feed was heated to 150 ° C. The K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst (31.39 grams) was introduced into the reactor.

The K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst was prepared by combining 16.44 grams of K 2 CC> 3, 19.44 grams of Rb 2 CC 3 and 24.49 grams of CS 2 CO 3. The K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst had a minimum TAP temperature of 360 ° C. The K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst had a DSC temperature of 250 ° C. The individual salts (K 2 CO 3, Rb 2 CO 3 and Cs 2 CO 3) did not show DSC temperatures in the range of 50-500 ° C. This TAP temperature is higher than the DSC temperature of the inorganic salt catalyst and lower than the DSC temperature of the individual metal carbonates.

The catalyst was rapidly heated to 450 ° C under a stream of methane of atmospheric pressure of 250 cm 3 / min. After the desired reaction temperature was reached, steam was supplied to the reactor at a rate of 0.4 ml / min and at a rate of 250 cm3 / min. The steam and the methane were supplied continuously for 2.6 hours during the addition of the crude feed to the reactor. The crude feed was pressurized in the reactor for 16 minutes with 1.5 MPa (229 psi) CH4. After the addition of the crude feed was complete, the remaining crude feed (0.56 grams) remained in the addition vessel. During the addition of the crude feed, a decrease in temperature to 370 ° C was observed.

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

From the difference between the initial weight of the catalyst and the weight of the coke / catalyst mixture, it can be calculated that 0.046 grams of coke remained in the reactor per gram of crude feed. The total product contained 0.87 grams of crude product with an average API density of 13, and gas. The gas contained 15 unreacted CH 4, hydrogen, C 2 and C 4 -C 6 hydrocarbons and CO 2 (0.08 grams of CO2 per gram of gas).

The crude product contained 0.01 grams of sulfur per gram of crude product and a total of 0.000005 grams of Ni and V. The crude product was not further analyzed.

In Example 10, the reaction procedures, the 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 of the crude product. The crude product contained 0.14 grams of naphtha, 0.19 grams of distillate and 0.45 grams of VGO per 25 grams of crude product, and had a residue content of 0.001 grams, and contained an undetectable amount of coke.

Examples 9 and 10 show that the contact of the crude feed with a source of hydrogen in the presence of at most 3 grams of catalyst per 100 grams of crude feed gives a total product containing a crude product that is a liquid mixture at STP. The crude product had a residual content of at most 272775 * 133 - at most 30% of the residual content of the crude feed. The crude product had a sulfur content and a total Ni / V content that was at most 90% of the sulfur content and the Ni / V content of the crude feed.

The crude product contained at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa to at most 200 ° C, at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 200-10 300 ° C and at least 0.001 gram of hydrocarbons with a boiling range at 0.101 MPa between 400-538 ° C (1000 ° F). Examples 11-12: Contact of a crude feed with a source of hydrogen in the presence of the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst and steam The reaction procedures, conditions and the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst of Examples 11 and 12 were same as in Example 9, except that 130 grams of crude feed (Cerro Negro) and 60 grams of the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst were used. In Example 11, methane was used as the source of hydrogen. In Example 12, hydrogen gas was used as the source of hydrogen. In FIG. 14 is a graphical representation of the amounts of non-condensable gas, crude product and coke. Bars 186 and 188 represent the weight% of prepared coke, bars 190 and 192 represent the weight% of prepared liquid hydrocarbons, and bars 194 and 196 represent the weight% of prepared gas based on the weight of the raw food.

In Example 11, 93% by weight of the crude product (bar 192), 3% by weight of gas (bar 196) and 4% by weight of coke (bar 188) were prepared, based on the weight of the Cerro Negro.

1027775 - 134 -

In Example 12, 12.84% by weight of the crude product (rod 190), 7% by weight of gas (rod 194) and 9% by weight of coke (rod 186) were prepared, based on the weight of the Cerro Negro.

In Examples 11 and 12, the use of methane as a source of hydrogen is compared with the use of hydrogen gas as a source of hydrogen. The preparation and / or transportation of methane is generally less expensive than the preparation and / or transportation of hydrogen, so that a method using methane is desired. Methane is shown to be as effective as hydrogen when contacting a crude feed in the presence of an inorganic salt catalyst to obtain a total product.

Examples 13-14: Preparation of a crude product with a chosen API density

The device, the reaction procedure and the inorganic salt catalyst were the same as in Example 9, except that the reactor pressure was varied.

In Example 13, the reactor pressure during contacting was 0.1 MPa (14.7 psi). A crude product was obtained with an API density at 15.5 ° C of 25. The total product contained hydrocarbons with a distribution of the number of carbon atoms in the range of 5 to 32 (see curve 198 of FIG. 15).

In Example 14, the reactor pressure during contacting was 3.4 MPa (514.7 psi). A crude product was obtained with an API density at 15.5 ° C of 51.6. The total product contained hydrocarbons with a distribution of the number of carbon atoms in the range of 5 to 15 (see curve 200 of FIG. 15).

1027775 - 135 -

These examples show methods of contacting the crude feed with hydrogen at different pressures in the presence of an inorganic salt catalyst to obtain a crude product with a chosen API density. By varying the pressure, a crude product with a higher or lower API density was prepared.

Examples 15-16: Contact of a crude feed in the presence of a K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst or silicon carbide, in the absence of an external source of hydrogen

In Examples 15 and 16, the apparatus, the crude feed and the reaction products were the same as in Example 9, except that the crude feed and the catalyst (or silicon carbide) were simultaneously introduced directly into the reactor. Carbon dioxide (CO2) was used as carrier gas. In Example 15, 138 grams of Cerro Negro was combined with 60.4 grams of the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst (the same catalyst as in Example 9). In Example 16, 132 grams of Cerro Negro was combined with 83.13 grams of silicon carbide (40 mesh, Stanford Materials: Aliso Viejo, CA). It is believed that such a silicon carbide under the process conditions described in this patent specification exhibits a slight, if at all, no catalytic action.

In all examples, the mixture was heated to a reaction temperature of 500 ° C over a period of 2 hours. The CO2 was fed to the reactor at a rate of 100 cm 3 / min. Vapor 30 from the reactor was collected in cold traps and in a gas bag using a back pressure of 3.2 MPa (479.7 psi). The crude product from the cold trap was stabilized and analyzed.

1027775-5 - 136 -

In Example 15, by contacting the crude feed with the inorganic salt catalyst under the atmosphere of carbon dioxide, 36.82 grams (26.68% by weight, based on the weight of the crude feed) of a colorless hydrocarbon with prepared an API density of at least 50.

In Example 16, by contacting the crude feed with the inorganic salt catalyst under the atmosphere of carbon dioxide, 15.78 grams (11.95 wt.%, Based on the weight of the crude feed) of a colorless hydrocarbon with prepared an API density of 12.

Although the yield is, for example, low, the in situ formation of a source of hydrogen in the presence of the inorganic salt catalyst proceeds better than the in situ formation of hydrogen under non-catalytic conditions. The yield of crude product in Example 16 is half the yield of crude product in Example 15. Example 15 also shows that during contact of the crude feed in the presence of the inorganic salt, and without a source of hydrogen gas is present, hydrogen is also formed.

Examples 17-20: Contact of a crude feed with a source of hydrogen in the presence of a K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst, calcium oxide and silicon carbide at atmospheric conditions

The apparatus, the reaction procedure, the crude feed and the inorganic salt catalyst were the same as in Example 9, except that the Cerro Negro was introduced directly into the reactor instead of being added by means of the addition vessel, and hydrogen gas became used as the source of hydrogen. During contacting, the reactor pressure was 0.101 MPa (14.7 psi). The flow rate of hydrogen gas was 250 cm 3 / min. The reaction temperatures, the steam flow rates and the percentages of crude product, gas and coke are shown in Table 4 of FIG. 16.

In Examples 17 and 18, the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst was used. In Example 17, the contact temperature was 375 ° C. For example 18, the contact temperature was in the temperature range of 500-10. 600 ° C.

As shown in Table 4 (FIG. 16), in Examples 17 and 18, as the temperature was raised from 375 ° C to 500 ° C, gas formation increased from 0.02 grams to 0.05 grams per gram total product. However, at the higher temperature, coke formation decreased from 0.17 grams of coke to 0.09 grams of coke per gram of crude feed. The sulfur content of the crude product also decreased at the higher temperature from 0.01 grams to 0.008 grams of sulfur per gram of crude product. Both products had an H / C of 1.8.

In Example 19, a crude feed under conditions similar to the conditions described in Example 18 was contacted with CaCO 3. The percentages of crude product, gas and coke obtained are shown in Table 4 of FIG. 16. The formation of gas increased in example 19 compared to the formation of gas in example 18. The removal of sulfur from the crude feed was not as effective as in example 18. The crude product formed in example 19 contained per gram crude product 0.01 grams of sulfur, compared to a sulfur content of 0.008 1027775 - 138 - grams of sulfur per gram of crude product for the crude product prepared in Example 18.

Example 20 is a comparative example for Example 18. In Example 20, instead of the inorganic salt catalyst, 83.13 grams of silicon carbide were introduced into the reactor. The formation of gas and the formation of coke increased considerably for example 20 compared to the formation of gas and the formation of coke of example 18. Under these non-catalytic conditions, 0.22 grams of coke per gram of crude product, 0.25 grams of non-condensable gas and 0.5 grams of crude product formed. The crude product prepared in Example 20 contained 0.036 grams of sulfur per gram of crude product compared to 0.01 grams of sulfur per gram of crude product prepared in Example 18.

These examples demonstrate that the catalysts used in Examples 17 and 18 give improved results over non-catalytic conditions and conventional metal salts. At 500 ° C and a hydrogen flow rate of 250 cm 3 / min, the amounts of coke and non-condensable gas were considerably less than. the amounts of coke and non-condensable gas prepared under non-catalytic conditions.

In the examples where use was made of inorganic salt catalysts (see Examples 17-18 of Table 4, FIG. 16), a decrease was found in the weight percentage of prepared gas relative to the prepared gas that was formed during the 30 control experiment (e.g., Example 20 of Table 4, FIG. 16). Based on the amount of hydrocarbons in the prepared gas, it is estimated that a maximum of 20% by weight, a maximum of 15% by weight, a maximum of 10% by weight, a maximum of 1027775- 139 - a maximum of 5% by weight, or nothing at all , of the crude feedstock is thermally cracked, the weight percentages being based on the total amount of crude feedstock contacted with a source of hydrogen.

Examples 21 and 22: Contact of a crude feed with a gaseous source of hydrogen in the presence of water and a K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst or silicon carbide

The devices of Examples 21 and 22 were the same as in Example 9, except that hydrogen gas was used as the source of hydrogen. In Example 21, 130.4 grams of Cerro Negro were brought into line with 30.88 grams of the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst to form a crude mixture. In Example 22, 139.6 grams of Cerro Negro were combined with 80.14 grams of silicon carbide to form the roughage blend.

The crude feed mixture was fed directly to the reactor. During heating and while waiting, the hydrogen gas was supplied to the reactor at a rate of 250 cm 3 / min. The crude feed was heated to 300 ° C over a period of 1.5 hours and was kept at 300 ° C for 1 hour. The reaction temperature was raised to 400 ° C over a period of 1 hour and was kept at 400 ° C for 1 hour. After the reaction temperature had reached 400 ° C, water was introduced into the reactor together with the hydrogen gas at a rate of 0.4 g / minute. Water and hydrogen were supplied to the reactor during the remaining heating and waiting periods. After the reaction mixture was kept at 400 ° C., the reaction temperature was raised to .500 ° C. and kept at 500 ° C. for 2 hours. Vapor from the reactor was collected in cold traps and 1 027775 - 140 - in a gas bag. Liquid product from the cold traps was stabilized and analyzed.

In Example 21, as a vapor formed on contacting the crude feed with the K 2 CCb / IU 2 CO 3/5 C 5 2 CO 3 catalyst in the hydrogen atmosphere, 86.17 grams (66.1 wt.%) Were based on the weight of the crude feed) of a dark red-brown hydrocarbon liquid (crude product) and water (97.5 g).

In Example 22, water vapor and a small amount of gas came out of the reactor. The reactor was viewed and a dark brown viscous hydrocarbon liquid was removed from the reactor. Less than 50% by weight of the dark brown viscous liquid was prepared by contacting the crude feed with silicon carbide under the atmosphere of hydrogen. In Example 21, a 25% increase in the yield of crude product compared to the yield of crude product in Example 22 was obtained.

Example 21 showed an improvement of the 20. see properties of the crude product prepared by using methods described in this patent as compared to the properties of a crude product prepared using hot water. In particular, the crude product of Example 21 had a lower boiling point than the crude product of Example 22, as evidenced by the fact that the crude product prepared in Example 22 could not be prepared in the form of a vapor. It was determined that the crude product prepared in Example 21 had better flow properties than the crude product prepared in Example 22.

Examples 23-24: Contact of a crude feed with a source of hydrogen in the presence of a K 2 CO 3 / Rb 2 Cl 3 / Cs 2 CO 3 catalyst to obtain a crude product with a volume greater than the volume of a crude product prepared under non-catalytic conditions The apparatus, the crude feed, the inorganic catalyst and the reaction procedure were the same as described in Example 9, except that the crude feed was directly introduced into the reactor and hydrogen gas was used as the source of hydrogen. The crude feed (Cerro Negro) had an API density of 6.7 and a density of 1.02 g / ml at 15.5 ° C.

In Example 23, 102 grams of the crude feed (100 ml of crude feed) and 31 grams of K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst were introduced into the reactor. A crude product (87.6 grams) was prepared which had an API density of 50 and a density of 0.7796 g / ml (112 ml) at 15.5 ° C.

In Example 24, 102 grams of crude feed (100 ml of crude feed) and 80 grams of silicon carbide were introduced into the reactor. A crude product (70 grams) was prepared which had an API density of 12 and a density of 0.9861 g / ml (70 ml) at 15.5 ° C.

Under these conditions, the volume of the product prepared in Example 23 was about 10% greater than the volume of the crude feed. The volume of the crude product prepared in Example 24 was considerably smaller (40% smaller) than the volume of the crude product prepared in Example 23. A substantial increase in the volume of the product makes it possible for the producer to form a larger volume of crude product per volume of crude oil supplied.

1027775 - 142 -

Example 25. Contact of a crude feed with a source of hydrogen in the presence of a K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst, sulfur and coke

The apparatus and the reaction procedure were the same as in Example 9, except that the steam was introduced into the reactor at 300 cmV minute. The K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst was prepared by combining 27.2 grams of K 2 CO 3, 32.2 grams of Rb 2 CO 3 and 4 0.6 grams of CS 2 CO 3.

The crude feed (130.35 grams) and the K 2 CO 3 / Rb 2 CO 3/10 Cs 2 CO 3 catalyst (31.6 grams) were introduced into the reactor. The Cerro Negro crude oil contained per gram of crude feed a total of 0.04 grams of aromatics with a boiling range between 149-260 ° C (300-500 ° F), a total of 0.000640 grams of nickel and vanadium, 0.042 grams of sulfur and 0, 56 grams of residue. The API density of the crude feed was 6.7.

Contact of the crude feed with methane in the presence of the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst gave 0.95 grams of total product and 0.041 grams of coke per gram of crude feed.

The total product contained 0.91 grams of crude product and 0.028 grams of hydrocarbon gas per gram of total product. The total amount of gas collected contained 0.16 mole of hydrogen, 0.045 mole of carbon dioxide and 0.025 mole of C 2 and C 4 -C 6 hydrocarbons, determined by GC / MS, per mole of gas. The remainder of the gas consisted of methane, air, carbon monoxide and a trace (0.004 mol) of evaporated crude product.

The crude product was analyzed using a combination of gas chromatography and.

Mass spectrometry. The crude product contained a mixture of hydrocarbons with a boiling range between 100-538 ° C. The total liquid product mixture contained 0.006 grams of ethylbenzene (a compound with a monocyclic 1027775 "- 143 - ring, with a boiling point at 0.101 MPa of 136.2 ° C) per gram of mixture. This product could not be detected in the crude feed.

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

Additional crude feed (152.71 grams) was contacted with the first catalyst used (36.63 grams), with 150 grams of the total product recovered after losses. The total product contained 0.92 grams of liquid crude product, 0.058 grams of extra coke and 0.017 grams of gas per gram of total product. The gas contained 0.18 moles of hydrogen, 0.07 grams of carbon dioxide and 0.035 moles of C 2 -C 6 hydrocarbons per mole of gas. The remainder of the gas consisted of methane, nitrogen, a little air and traces of evaporated oil product (<1 mol%).

The crude product contained a mixture of hydrocarbons with a boiling range between 100-538 ° C. The part of the mixture with a boiling range below 149 ° C contained per mol of the total amount of liquid hydrocarbons 0.018 mol% of ethylbenzene, 0.04 mol% of toluene, 0.03 mol% of metaxylene and 0.060 mol% of paraxylene (compounds with a monocyclic ring with a boiling point at 0.101 MPa of less than 149 ° C). These 1027775 - 144 - products could not be detected in the raw food.

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

Additional crude feed (104 grams) was contacted with the second catalyst used (44.84 grams), whereby 104 grams of total product and 0.114 grams of coke were collected per gram of crude feed. Since 104.1 grams of the 133 grams of crude feed that was transferred were crude feed, a portion of the coke was attributed to coke formation in the addition vessel due to overheating of the. addition vessel.

The total product contained 0.86 grams of crude product and 0.025 grams of hydrocarbon gas per gram of total product. The total amount of gas contained 0.18 mole of hydrogen, 0.052 mole of carbon dioxide and 0.03 mole of C2 -C5 hydrocarbons per mole of gas. The remainder of the gas consisted of methane, air, carbon monoxide, hydrogen, and a trace of evaporated oil.

The crude product contained a mixture of hydrocarbons with a boiling range between 100-538 ° C. The portion of the boiling range below 149 ° C contained per gram of hydrocarbon mixture 0.021 grams of ethylbenzene, 0.027 grams of toluene, 0.042 grams of metaxylene, 1027775 * 145, and 0.020 grams of paraxylene, as determined above by GC / MS.

The used catalyst ("the third used catalyst") was removed from the reactor, weighed, and then analyzed. The weight of the third catalyst used was increased from 44.84 grams to a total of 56.59 grams (an increase of 79% by weight, based on the weight of the original K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst). A detailed elemental analysis of the third catalyst used was performed. The third catalyst used contained 0.90 grams of carbon, 0.028 grams of hydrogen, 0.0025 grams of oxygen, 0.046 grams of sulfur, 0.017 grams of nitrogen, 0.0018 grams of vanadium, 0.0007 grams of nickel, 0.0015 grams iron and 0.00025 grams of chloride, the remainder consisting of other transition metals such as chromium,. titanium and zirconium.

As shown by this example, coke, sulfur and / or metals deposited on and / or in the inorganic salt catalyst have no effect on the total crude product yield (at least 80% with each run) prepared by contacting a crude feed with a source of hydrogen in the presence of the inorganic salt catalyst. The crude product had a monocyclic aromatics content in the boiling range below 149 ° C that was at least 100 times the monocyclic aromatics content of the crude feed.

In the three runs, the average crude product yield (based on the weight of the crude feed) was 89.7 wt%, with a standard deviation of 2.6%; the average yield of coke was 7.5% by weight (based on the weight of the crude feed), with an average deviation of 2.7%, and the average weight of the gaseous cracked hydrocarbons was 2.3 % by weight (based on the weight of the crude feed), with a standard deviation of 0.46%. The relatively large standard deviation with both the liquid product and the coke was caused by the third test in which the temperature regulator of the feed vessel did not work properly, causing the raw feed in the feed vessel to overheat. Nevertheless, even of the large amounts of coke present in the test, no apparent adverse effect on the activity of the catalyst system can be observed.

The ratio of the amount of C2 olefins to the total amount of C2 hydrocarbons was 0.19. The ratio of the amount of C3 olefins to the total amount of C3 hydrocarbons was 0.4. The ratio of the amount of alpha olefins to the amount of internal olefins of the C4 hydrocarbons was 0.61. The 20 cis / trans ratio of the C 4 olefins was 6.34. This ratio was considerably higher than thermodynamically predicted cis / trans ratio of C4 olefins of 0.68. The ratio of alpha olefins to internal olefins of the Cs hydrocarbons was 0.92.

This ratio was greater than the thermodynamically predicted ratio of C 1 alpha olefins to internal C 5 olefins of 0.144. The cis / trans ratio of the Cj olefins was 1.25. This ratio was greater than thermodynamically predicted cis / trans-30 ratio of Cs olefins of 0.9.

Example 26: Contact of a crude feed with a relatively high content of sulfur, with a source of hydrogen in the presence of the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst

The apparatus and the reaction procedure were the same as described in Example 9, except that the crude feed, methane and steam were continuously supplied to the reactor. The feed content in the reactor was monitored by using the change in the weight of the reactor. Methane gas was continuously supplied to the reactor at a rate of 500 cm 3 / min. Steam was continuously supplied to the reactor at a rate of 6 g / min.

The inorganic salt catalyst was prepared by combining 27.2 grams of K 2 CO 3, 32.2 grams of Rb 2 CC 3 and 4 0.6 grams of CS 2 CO 3. The K 2 CO 3 / Rb 2 CO 3/15 C 5 2 CO 3 catalyst (59.88 grams) was introduced into the reactor.

In the addition vessel, a crude feed (Lloydminster bitumen, Canada) with an API density of 9.4, a sulfur content of 0.02 grams of sulfur and a residue content of 0.40 grams per gram of crude feed was added. , heated to 150 ° C. In an attempt to keep the liquid crude feed content at 50% of the volume of the reactor, the warm bitumen was continuously supplied from the addition vessel to the reactor at a rate of 10.5 g / min, but the speed was insufficient to maintain that level.

The methane / steam / crude feed mixture was contacted with the catalyst at an internal temperature of the reactor of 456 ° C. The contact of the methane / steam / crude feed mixture with the catalyst gave a total product (in this example in the form of vapor discharged from the reactor).

1027775- 148

A total of 1640 grams of raw food was processed over a period of more than 6 hours. From the difference in the initial weight of the catalyst and the weight of the residue / catalyst mixture, it could be determined that 0.085 grams of coke remained in the reactor per gram of crude feed. Upon contact of the crude feed with methane, in the presence of the K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst, 0.93 grams of total product per gram of crude feed was formed. The total product contained 0.03 grams of gas and 0.97 grams of crude product per gram of 10 total product, excluding the amount of methane and water used in the reaction.

The gas contained 0.014 grams of hydrogen, 0.018 grams of carbon monoxide, 0.08 grams of carbon dioxide, 0.13 grams of hydrogen sulfide and 0.68 grams of non-condensable hydrocarbons per gram of gas. Based on the amount of hydrogen sulfide formed, it can be estimated that the sulfur content of the crude feed was reduced by 18% by weight. As can be seen in this example, hydrogen, carbon monoxide and carbon dioxide were prepared.

The molar ratio of carbon monoxide to carbon dioxide was 0.4. .

The C 2 -C 5 hydrocarbons contain 0.30 grams of C 2 compounds, 0.32 grams of C 3-25 compounds, 0.26 grams of C 4 compounds and 0.10 grams of C 5 compounds per gram of hydrocarbons. The weight ratio of isopentane to n-pentane of the non-condensable hydrocarbons was 0.3. The weight ratio of isobutane to n-butane of the non-condensable hydrocarbons was 0.199. The C4 compounds, per gram of C4 compounds, had a butadiene content of 0.003 grams. The weight ratio of C4 alpha olefins to C4 internal olefins was 0.75. The weight ratio of C 8 alpha olefins to internal C 5 olefins was 1.08.

The data from example 25 shows that the continuous processing of a crude feed with a relatively high content of sulfur with the same catalyst in the presence of coke did not decrease the activity of the inorganic salt catalyst and an rgw product that is suitable for transport.

Example 27: Contact of a crude feed with a source of hydrogen in the presence of a K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst and coke

The apparatus and the reaction procedure were used using the same conditions as described in Example 26. The K 2 CO 3 / Rb 2 CO 3 / Cs 2 CO 3 catalyst (56.5 grams) was introduced into the reactor. A total of 2550 grams of crude feed was processed over a 6 hour period. On the basis of the difference between the initial weight of the catalyst and the weight of the residue / catalyst mixture, it was determined that, based on the weight of the crude feed, 0.114 grams of coke per gram of crude feed remained in the reactor. A total of 0.89 grams of total product per gram of crude feed was formed. The total product contained 25 grams of gas and 0.96 grams of crude per gram of total product. feed, excluding the amount of methane and water used in the reaction.

The gas contained 0.021 grams of hydrogen, 0.018 grams of carbon monoxide, 0.052 grams of carbon dioxide, 0.18 grams of hydrogen sulfide and 0.65 grams of non-condensable hydrocarbons per gram of gas. On the basis of the amount of hydrogen sulphide prepared, it can be estimated that the sulfur content of the crude feed was reduced by 14% by weight of 1027775, based on the weight of the crude feed. As shown in this example, hydrogen, carbon monoxide and carbon dioxide were prepared.

The molar ratio of carbon monoxide to carbon dioxide was 0.6.

The C 2 -C 6 hydrocarbons contain 0.44 grams of C 2 compounds, 0.31 grams of C 3 compounds, 0.19 grams of C 4 compounds and 0.068 grams of C 5 compounds per gram of C 2 -C 6 hydrocarbons. The weight ratio of isopentane to n-pentane of the non-condensable hydrocarbons was 0.25. The weight ratio of isobutane to n-butane of the non-condensable hydrocarbons was 0.15. The C4 compounds had, per gram of C4 compounds, a butadiene content of 0.003 grams.

It is demonstrated by this example that, with the same catalyst (56.5 grams), repeatedly processing a crude feed with a relatively high content of sulfur (2550 grams crude feed) in the presence of coke, the activity of the inorganic salt. did not decrease existing catalyst, and gave a crude product suitable for transport.

On the basis of this description, the person skilled in the art will understand further modifications and other embodiments of various aspects of the invention. Therefore, this description is to be considered merely as illustrative, and the purpose of this description is to make clear to those skilled in the art how the invention can be carried out in general. It is to be understood that the forms of the invention represented and described in this patent specification are to be interpreted as examples of embodiments. As will be apparent to those skilled in the art from the description of the invention, the elements and substances illustrated and described in this patent specification may be replaced by other elements and substances, portions and methods may be reversed and certain features of the invention may be separately be applied. The elements described in this patent can be changed without departing from the spirit and scope of the invention as described in the following claims.

10277753

Claims (26)

Method for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts comprising a transition metal sulfide-containing catalyst, so that a total product is obtained that the crude product wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, wherein the transition metal sulfide-containing catalyst contains a total of at least 0.4 grams of one or more transition metal sulfides per gram of the total transition metal sulfide-containing catalyst, the raw food has a residue content, determined according to the ASTM method D5307, of at least 0.2 grams of residue per 15 grams of raw food; and controlling the contact conditions such that the crude product contains at most 0.05 grams of coke per gram of crude product, and that the crude product has a residue content, determined according to the ASTM method D5307, of 20 at most 30% of the residue content of the crude feed. The method of claim 1, wherein the crude product contains 0.00001-0.03 grams or 0.0001-0.01 grams of coke per gram of crude product. A process for preparing a crude product, comprising: contacting a crude feed with a source of hydrogen in the presence of one or more catalysts comprising a transition metal sulfide-containing catalyst, so that a total product is obtained that contains crude product, the crude product being a liquid mixture at 25 ° C and 0.101 MPa, wherein the transition metal sulfide-containing catalyst contains a total of at least 0.4 grams of one or more transition metal sulfides per gram of the transition metal-sulfide-containing catalyst, wherein the crude feed has a nitrogen content of at least 0.001 grams of nitrogen per. grams of crude feed, and wherein the crude feed has a residue content of at least 0.2 grams of residue per gram of crude feed; and controlling the contact conditions such that the crude product has a content of. nitrogen has at most 90% of the nitrogen content of the crude feed, and that the crude product has a residue content of at most. 30% of the residual content of the crude feed, whereby the nitrogen content is determined according to the ASTM method D5672 and the content of residues is determined according to the ASTM method D5307. The method of claim 3, wherein the nitrogen content of the crude product is at most 80% of the nitrogen content of the crude feed. 5. A method according to any one of claims 3 or 4, wherein the crude product contains at most 0.004 grams, at most 0.003 grams or at most 0.001 grams of nitrogen per gram of crude product. 6. A process for preparing a crude product, comprising: contacting a crude feed with a "source of hydrogen" in the presence of one or more catalysts comprising a transition metal sulfide catalyst so that a total product is obtained that the crude product product, the crude 1027775 '' 154 product being a liquid mixture at 25 ° C and 0.101 MPa, wherein the transition metal sulfide-containing catalyst comprises a total of at least 0.4 grams of one or more transition metal sulfides per gram of the total transition metal sulfide 5 contains a sulphide-containing catalyst, wherein the raw feed has a sulfur content of at least 0.001 grams of sulfur per gram of raw feed, and wherein the raw feed has a content of residue of at least 0.2 grams of residue per gram of raw feed and controlling the contact conditions such that the crude product has a sulfur content that is at most 70% of the sulfur content of the crude feed, and that the crude product has a residual content of at most 30% of the residual content of the raw feed, the content of sulfur being determined according to the ASTM method D4294 and the content of residue is determined according to the ASTM method • D5307. 7. Process according to claim 6, wherein the sulfur content of the crude product is at most 6% of the sulfur content of the crude feed. 8. A method according to any one of claims 1-7, wherein the crude product, per gram of crude product, is at most 0.02 grams, at most 0.008 grams, at most 0.005 grams, at most 0.004 grams or at most 0.003 grams contains sulfur; or an amount of sulfur in the range of 0.0001-0.02 grams or in the range of 0.005-0.01 grams. 9. Process according to any of claims 1-8, wherein the residual content of the crude product is at most 10% of the residual content of the crude feed. 1027775- 155 - The method of any one of claims 1-9, wherein the crude product contains 0.00001-0.05 grams or 0.001-0.03 grams of residue per gram of crude product. A method according to any one of claims 1-10, wherein the crude product, per gram of crude product, is also 0.001-0.3 grams of vacuum gas oil, 0.001-0.5 grams or 0.01-0.1 grams of petroleum, Contains 0.4-0.9 grams or 0.6-0.8 grams of VGO, or a mixture thereof. The method of any one of claims 1 to 11, wherein the crude feed also has a Ni / V / Fe content of a total of at least 0.001 grams of Ni / V / Fe per gram of crude feed, and wherein the contact conditions are such. it can be arranged that the crude product has a total Ni / V / Fe content that is at most 90%, at most 50% or at most 10% of the total Ni / V / Fe content of the crude feed. A method according to any one of claims 1-12, wherein the crude product also comprises 1 x 10 "gram to 5 x 10-5 gram, 3 x 10-7 gram to 2 x 10" ^ gram or 20 lx 10 " 6 grams to 1 x 10- gram grams of Ni / V / Fe per gram of crude product. 14. Method as claimed in any of the claims 1-13, wherein the contact conditions are also controlled such that during contacting, determined on the basis of the mass balance, per gram of raw feed no more than 0.2 gram, no more than 0 , 15 grams or at most 0.1 grams is formed from hydrocarbons that cannot be condensed at 25 ° C and 0.101 MPa. 15. A method according to any one of claims 1-14, wherein the crude feed contains 0.2-0.99 grams or 0.3-0.8 grams of residue per gram of raw feed. A method according to any of claims 1-15, wherein at least one transition metal of the transition metal sulfides comprises one or more transition metals from groups 6-10 of the Periodic Table, one or more compounds of one or more transition metals from groups 6-10 of the Periodic System, or a mixture thereof. The method of claim 16, wherein at least one transition metal of the transition metal sulfides is iron. The method of any one of claims 1-17, wherein in at least one of the transition metal sulfides the atomic ratio of transition metal to sulfur is in the range of 0.5-10. 19. Process according to any of claims 1-18, wherein the transition metal sulfide-containing catalyst furthermore comprises one or more alkali metals, one or more compounds of one or more alkali metals, one or more alkaline earth metals, one or more compounds of one or more alkaline earth metals, zinc , one or more compounds of zinc, or a mixture thereof. The method of claim 19, wherein the atomic ratio of the alkali metal, alkaline earth metal or zinc to the transition metal is in the range of greater than 0 to 1. The method of any one of claims 1-20, 25. wherein at least a portion of the total product is prepared as a vapor, and the process further comprises condensing at least a portion of the vapor at 25 ° C and 0.101 MPa so that the crude product is formed. The method of any one of claims 1-21, wherein the method further comprises combining the crude product with a crude oil that is equal to or different from 10277733 - 157 - from the crude feed to form a mixture. 23. Crude product or raw food as can be obtained according to a method according to one of the claims 1-22. A method for preparing a fuel for transport vehicles, heating fuel, lubricants or chemicals, comprising a crude product or a mixture according to claim 23. The method of claim 24, wherein the processing comprises distilling the crude product or mixture into one or more distillate fractions. The method of any one of claims 25 or 26, wherein the processing comprises treating with hydrogen. 1027775!