Method of hydrogenating synthetic oil and method of producing base fuel

FIELD: chemistry.

SUBSTANCE: invention relates to a method of hydrofining synthetic oil, realised by bringing synthetic oil, obtained via Fischer-Tropsch synthesis and having content of C-9-21 hydrocarbons greater than or equal to 90 wt %, into contact with a hydrofining catalyst which has a support which contains one or more solid acids selected from ultra-stable Y-(USY) zeolite, aluminosilicate, zirconia-silicate and aluminium-bromine oxide catalyst and at least one metal selected from a group comprising group VIII metals, deposited on the support, in the presence of hydrogen with regulation of the reaction temperature when the hydrofining catalyst is in contact with the synthetic oil, in order to hydrofine the synthetic oil such that content (wt %) of C8 or lower hydrocarbons in the synthetic oil after contact is 3-9 wt % higher than before contact. The invention also relates to a method of producing base fuel material.

EFFECT: obtaining base oil with excellent low-temperature rheological properties with good output of the middle fraction of the synthetic oil.

6 cl, 8 ex, 2 tbl, 1 dwg

 

The technical field

The present invention relates to a Hydrotreating process synthetic oil, and particularly to a Hydrotreating process synthetic crude oil obtained by a Fischer-Tropsch synthesis. The invention further relates to the manufacturing process of the material of the base fuel.

The prior art inventions

Environment friendly clean liquid fuels with low sulphur and aromatic hydrocarbons were aimed in recent years from the point of view of ecology. One process of manufacturing pure fuels, which were studied in the oil industry, is a Fischer-Tropsch synthesis ("hereinafter referred to as synthesis CFT"), which uses carbon monoxide and hydrogen as raw materials. As the FT synthesis makes it possible to manufacture the liquid base fuel rich in paraffins and containing no sulfur, it is seen as having great potential.

However, synthetic oil obtained by the FT synthesis (hereinafter also referred to as "synthetic oil CFT"), have a high content of normal paraffins and include oxygen-containing compounds, such as alcohols, and therefore difficult to directly use such synthetic oil as fuel. More specifically, the octane rating of such synthetic oil is insufficient cnym for use as motor gasoline, while their low-temperature rheological properties are inadequate for use as diesel fuels. In addition, oxygen-containing compounds, such as alcohols, adversely affect the stability of the fuel oxidation. Consequently, the FT synthetic oil is usually used as the material of the base fuel after Hydrotreating to convert normal paraffins in the synthetic oil into ISO and for the conversion of oxygen-containing compounds with other substances.

Specifically for manufacturing materials for the base diesel fuel, materials base kerosene, materials basic aviation fuel and the like, for example, low-temperature rheological properties of the material of the base fuel are increased by an appropriate mixture rich in ISO average fraction obtained by Hydrotreating the heavy paraffin fraction FT synthetic oil, or the average fraction with an increased degree of isomerization of paraffins obtained by hydroisomerization average fraction of synthetic oil CFT (for example, see Patent documents 1 and 2).

[Patent document 1] international Publication patent No. 00/020535.

[Patent document 2] Published French patent No. 2826971.

In this case, increasing t is bowannie reduce the manufacturing cost of diesel fuel, these requirements apply also to the production of fuels through FT synthesis. Therefore, a desirable goal is to maximize the amount of material of the base diesel fuel, which may be made of synthetic oil CFT.

As mentioned above, the sources of the material of the base diesel fuel in the FT synthetic oil, heavy paraffinic fraction (especially the fraction with a boiling point of 360°C and above) and the average fraction (especially the fraction with a boiling point of 150-360°C), but although the materials of the base fuel, obtained by Hydrotreating paraffin fractions, have excellent rheological properties, they can be produced only in limited quantities from the FT synthetic oil, and because they are often used as lubricants and the like, it is not always possible to ensure a sufficient amount of material of the base fuel. When using the technology described in patent document 2, it is difficult to achieve low-temperature rheological properties required for materials of the base diesel fuel through a simple hydroisomerization average fraction of synthetic oil CFT, and output the average fraction significantly reduced when it is combined with the removal of the heavy fraction.

The aim of the present invention, which was made in light of the circumstances, given the data above, is the provision of a method of Hydrotreating a synthetic oil that can handle the average fraction of synthetic oil obtained by the FT synthesis with adequate improving low-temperature rheological properties of the medium fraction, at the same time maintaining a satisfactory yield of the middle fraction. Another objective of the invention is the provision of a manufacturing process of the material of the base fuel, through which can be obtained from the material of the base fuel with excellent low-temperature rheological properties in good yield average fraction of synthetic oil obtained by the FT synthesis.

The result is a lot of research aimed at achieving the objectives as set out above, the inventors have found that when synthetic oil FT, contains a specific number of a certain faction, in contact with the Hydrotreating catalyst, the selection of reaction conditions, based on the specific content of hydrocarbons, results in a substantially lower point cloud obtained for the average fractions, even at considerable reduction of losses average faction.

Specifically, the Hydrotreating process of synthetic oil according to the invention is characterized by the fact that when contacting a synthetic oil obtained by Fischer-Tropsch synthesis, have her hydrocarbons C9-21 90 mass % or more, with a Hydrotreating catalyst in the presence of hydrogen content (mass %) C8 and lower hydrocarbons in synthetic oil after contact is 3-9 mass % more than before the contact.

In the Hydrotreating process of synthetic oil according to the invention may sufficiently improve the low-temperature rheological properties of the medium fractions with satisfactory maintain its exit from synthetic oil. In addition, the Hydrotreating process of synthetic oil according to the invention is able to lower the amount of oxygen-containing compounds, such as alcohols. In addition, since it is possible to modify the average fraction of synthetic oil CFT products, useful as materials for the base diesel fuel, via a simple Hydrotreating in accordance with the invention, it enables to produce green diesel fuel economical way.

Although the cause of this effect Hydrotreating process synthetic oil according to the invention is not precisely understood, the authors of the present invention proposed the following. It has been suggested that the above-mentioned effect, because under conditions in which the FT synthetic oil having the composition described above is subjected to Hydrotreating in such a way that the increase of the content of C8 or lower uglevodorov the RH is within the range, above, obtaining the cracking of naphtha, which can cause a low yield of the middle fraction, significantly slowed down, while the n-paraffins with a high number of carbon atoms, which are the cause of poor rheological properties at low temperatures, respectively decompose and isomerized.

In the Hydrotreating process of synthetic oil according to the invention of synthetic oil is preferably subjected to Hydrotreating with the regulation of the reaction temperature during the contacting of the catalyst Hydrotreating with synthetic oil in such a way that the content (mass %) C8 and lower hydrocarbons in synthetic oil after contact is 3-9 mass % more than before the contact.

In the Hydrotreating process of synthetic oil according to the invention of synthetic oil is preferably oil containing hydrocarbons C9-14 is not more than 70 mass%, and synthetic oil is preferably subjected to Hydrotreating in such a way that the content of hydrocarbons C9-14 (mass %) in synthetic oil after contact is at least 2 mass % more than before contact, and the content of hydrocarbons C15-21 (mass %) in synthetic oil after contact is at least 2 mass % less than before contact.

This can further improve the performance of rheological properties at low temperatures, when a satisfactory yield of the middle fraction. Perhaps the reason for this effect is that the Hydrotreating of synthetic oil in the conditions described above, stimulates the hydroisomerization middle fraction and decomposes C15 or large normal paraffins to kerosene fractions C9-14, resulting in significantly improved rheological properties average fraction at low temperature.

In the Hydrotreating process of synthetic oil according to the invention, the Hydrotreating catalyst is preferably a catalyst containing a medium containing an ultra-stable Y-zeolite and one or more catalyst selected from aluminosilicate, alumbrera oxide and zirconiasilicate catalysts, and at least one metal selected from the group consisting of metals belonging to Group VIII of the Periodic Table deposited on a specified device.

Also for contact between synthetic oil and a Hydrotreating catalyst in a Hydrotreating process synthetic oil according to the invention preferably the reaction temperature is 200-370°C, the partial pressure of hydrogen is 1.0-5.0 MPa and space velocity of the liquid is 0.3-3.5 h-1.

The manufacturing process of the material of the base fuel in accordance with the invention is characterized by the presence of stage Hydrotreating, to the ora synthetic oil, obtained by Fischer-Tropsch synthesis and having a content of hydrocarbons C9-21 90 mass % or more, comes in contact with a Hydrotreating catalyst for hydrotreatment of synthetic oil in the presence of hydrogen so that the content (mass %) C8 and lower hydrocarbons in synthetic oil after contact is 3-9 mass % more than before contact, and the stage at which the average fraction obtained from the synthetic crude oil obtained from stage hydrotreatment.

In accordance with the invention, it is possible to provide a Hydrotreating process synthetic oil, which can adequately improve the low-temperature rheological properties of the medium fraction, at the same time maintaining a satisfactory yield of the middle fraction, even when processing the average fraction of synthetic oil obtained by the FT synthesis. Also the invention provides a method of manufacturing a material of the base fuel, whereby the material of the base fuel with excellent low-temperature rheological properties can be obtained in good yield average fraction of synthetic oil obtained by the FT synthesis.

Brief description of drawing

The drawing is a block diagram showing an example of a preferred device for the manufacture of ecologically the ACLs fuel.

10 - the Reaction column 12: the catalyst bed Hydrotreating, 20 - distillation column 100: a device for the manufacture of the material of the base fuel.

The Hydrotreating process of synthetic oil according to the invention is distinguished by contacting a synthetic oil obtained by a Fischer-Tropsch synthesis and having a content of hydrocarbons C9-21 90 mass % or more, with a Hydrotreating catalyst for hydrotreatment of synthetic oil in the presence of hydrogen so that the content (mass %) C8 and lower hydrocarbons in synthetic oil after contact is 3-9 mass % more than before the contact.

Synthetic oil is supplied to the Hydrotreating process of synthetic oil according to the invention, can be the average fraction (for example, the fraction with a boiling point of 150-360°C), obtained by fractional distillation of crude oil from the Fischer-Tropsch synthesis with hydrocarbons C9-21 90 mass % or more. In accordance with the invention is preferred to use the average fraction obtained by fractional distillation in such a way that the content of hydrocarbons C9-14 is not more than 70 mass %.

As examples of catalysts for Hydrotreating in this description may be mentioned catalysts produced by coating metal group is s VIII of the Periodic Table as the active metal on the carrier, containing a solid acid.

As a preferred media in this description can be referred containing one or more solid acids selected from an ultra-stable Y(USY) zeolite, aluminosilicate, zirconiasilicate and alumbrera oxide catalyst. The media is more preferably medium containing USY zeolite and at least one solid acid selected from aluminosilicate, alumbrera oxide and zirconiasilicate catalyst, and even more preferably medium containing USY zeolite and Lombardy oxide catalyst or USY zeolite and Lombardy oxide catalyst.

When USY zeolite is a Y-zeolite, which was overstability by hydrothermal treatment and/or acid treatment, and he again forms a pore size of 20-100Å in addition to the microporous structure of 20Å and less typical Y-zeolite. When USY zeolite is used as catalyst carrier Hydrotreating, there is no particular limitation on the average particle size, but they preferably have a size of not more than 1.0 μm and more preferably not more than 0.5 μm. The molar ratio of silica/alumina (molar ratio of silica with respect to the alumina, hereinafter referred to as the silica/alumina") in USY zeolite is preferably 10-200, is more preferably 15-100 and even more preferably 20-60.

The catalyst carrier can be obtained by molding a mixture containing a solid acid and a binder, and then firing. The ratio of mixing of the solid acid is preferably 1-70 mass%, and more preferably 2-60 mass % based on the total weight of the carrier. When the medium contains USY zeolite, the content of the USY zeolite is preferably 0.1 to 10 mass % and more preferably 0.5 to 5 mass % based on the total weight of the carrier. When the medium contains USY zeolite and Lombardy oxide catalyst, the mixing ratio of USY zeolite and alumbrera oxide catalyst (USY zeolite/alumbrera oxide catalyst) is preferably the weight ratio of 0.03-1. When the medium contains USY zeolite and silica-alumina catalyst, the mixing ratio of USY zeolite and silica-alumina catalyst (USY zeolite/silica-alumina catalyst) also preferably comprises a weight ratio of 0.03-1.

In this soobrattee there are no particular restrictions on the binder, but alumina, silica, silica-alumina catalyst, titanium oxide and magnesium oxide are preferred, and alumina is particularly preferred. The mixing ratio of the binder is preferably 20-98 mass % and more preferably 30-96 mass % based on the total weight of the carrier.

The temperature on the yoke mixture preferably is in the range of 400-550°C, more preferably in the range of 470-530°C and even more preferably in the range of 490-530°C.

As specific examples of the metals from Group VIII of the present invention can be mentioned cobalt, Nickel, rhodium, palladium, iridium and platinum. Among them, it is preferable to use one or a combination of two or more metals selected from Nickel, palladium and platinum.

These metals can be deposited on the above-mentioned carriers by conventional methods, such as impregnation or ion exchange. The amount of deposited material is not particularly limited, but the total weight of the metal preferably is 0.1 to 3.0 mass % with respect to the media.

In this invention there are no particular restrictions on the design of the device used for the Hydrotreating process of synthetic oil according to the invention, and it can be equipped with one of the reaction column or more than one reaction column. In accordance with the invention, a reactor with a fixed circulating layer, with a gasket catalyst, preferably used for Hydrotreating of synthetic oil.

Hydrotreating synthetic oil may be conducted under the following reaction conditions. The partial pressure of hydrogen may be 0.5 to 12 MPa, and is preferably 1.0 to 5.0 MPa. Bulk liquid velocity (LHSV) of synthetic oil can is t be 0,1-10,0 h -1and preferably is 0.3-3.5 h-1. Here there are no particular restrictions on the ratio of hydrogen/oil, and it may be 50-1000 NL/L or preferably 70-800 NL/L.

All existing technical requirements, the term "LHSV (hourly space velocity of fluid" refers to the volumetric flow rate of crude oil under normal conditions (25°C, 101,325 PA) per unit volume of the catalyst layer with a gasket catalyst, and it is expressed as h-1or the reverse clock. Unit "NL" for the amount of hydrogen in the ratio of hydrogen/oil represents the volume of hydrogen (L) under normal conditions (0°C, 101,325 PA).

The reaction temperature (the average temperature in the layer of catalyst for Hydrotreating can be 180-400°C, preferably 200-370°C, more preferably 250-350°C and even more preferably 280-350°C. If the reaction temperature for Hydrotreating exceeds 370°C, not only the output of the average fraction will be substantially reduced, but the product will be painted and its use as a material of the base fuel will be limited. If the reaction temperature is below 200°C, the components of alcohol will not be deleted and will remain.

In accordance with the invention of synthetic oil is preferably subjected to Hydrotreating with the regulation of the reaction temperature during the contacting of the catalyst Hydrotreating with a synthetic oil such clicks the zoom, the content (mass %) C8 and lower hydrocarbons in synthetic oil after contact is 3-9 mass % more than before the contact.

The content of C8 and lower hydrocarbons (mass %), the content of hydrocarbons C9-21 (mass %), the content of hydrocarbons C9-14 (mass %) and the content of hydrocarbons, C14-21 (mass %) synthetic oil before contact and after contact can be determined, for example, gas chromatography or other known methods of analysis of samples taken at the inlet or the outlet of the reaction column.

For the Hydrotreating process of synthetic oil according to the invention the reaction conditions, in which the content of C8 and lower hydrocarbons (mass %) in synthetic oil after contact is 3-9 mass % more than before contact, are specified at the same time confirming the content of hydrocarbons having different numbers of carbon atoms in synthetic oil before and after contact by the method described above, and the hydrotreatment is performed under those conditions. In addition to the conditions for the content of C8 and lower hydrocarbon Hydrotreating can also be produced under given reaction conditions, resulting hydrocarbons C9-14 (mass %) in synthetic oil after contact was at least 2 mass % of b is the more before the contact, and the content of hydrocarbons C15-21 (mass %) in synthetic oil after contact was at least 2 mass % less than before contact.

Synthetic oil (fluid) after contact, which was released from the reaction column is separated in the separator gas-liquid, for example, unreacted hydrogen gas or light hydrocarbon gases, consisting of C4 and lower hydrocarbons, and light hydrocarbon oil consisting of C5 and larger hydrocarbons.

Separated liquid hydrocarbon oil additionally fractionized for use as the material of the base fuel, as, for example, the base gasoline, the base diesel fuel, base oil, base light oil or the base material of aviation fuel.

The manufacturing process of the material of the base fuel according to the invention will be now explained. The manufacturing process of the material of the base fuel in accordance with the invention is distinguished by the content of stage Hydrotreating, in which synthetic oil obtained by a Fischer-Tropsch synthesis and having a content of hydrocarbons C9-21 90 mass % or more, in contact with the Hydrotreating catalyst for hydrotreatment of synthetic oil in the presence of hydrogen so that the content (mass %) C8 and lower corner is Ogorodov in synthetic oil after contact is 3-9 mass % more before the contact, and the stage at which the average fraction obtained from the synthetic crude oil obtained in stage hydrotreatment.

Hydrotreating synthetic oil at the stage hydrotreatment is preferably carried out under conditions for the Hydrotreating process of synthetic oil according to the invention described above.

The middle fraction can be a fraction with a boiling point in the range 150°C-360°C. in order to obtain a material of the base diesel fuel fraction in the range 150°C-360°C preferably is obtained as the average fraction.

Device for the manufacture of the material of the base fuel used to produce material base fuel according to the invention will be now explained. The drawing is a block diagram showing an example of a preferred device for the manufacture of the material of the base fuel in accordance with the invention. The device 100 for the fuel fabrication shown in the drawing, consists of the reaction column 10 and distillation column 20 for the distillation of the reaction product obtained from the reaction column 10. The reaction column 10 represents a reaction column with a stationary layer comprising a layer of a Hydrotreating catalyst 12. In the reaction column 10 synthetic oil is subjected to Hydrotreating through a process of Hydrotreating synthetic oil from which retenu, as explained above. Top with the reaction column 10 is connected to the pipe L1 to supply synthetic oil in the reaction column 10, and line L2 for supplying hydrogen is connected upstream than the L1 pipeline from the reaction column 10. Also at the bottom of the reaction column 10 is connected to the pipe L3 to remove the reaction product from the reaction column 10, and the other end of the pipe L3 connected with a distillation device 20 with normal pressure.

Distillation device 20 is used for fractionation of the reaction product obtained through the reaction column 10, in the different fractions with specific ranges of boiling points. Distillation device 20 provides a fraction in the range 150°C-360°C, suitable as the material of the base diesel fuel, for example. The reaction product from the distillation device 20 can be fractionated on the gas fraction (C4 and lighter hydrocarbons), the fraction of heavy naphtha (a fraction with a boiling point 80-145°C), a kerosene fraction (a fraction with a boiling point 145-260°C), the fraction of light oil (a fraction with a boiling point of 260-360°C) and the fraction of the balance of the pickup (the fraction with a boiling point of 360°C and above), to obtain the desired material of the base fuel. Each fraction separated by distillation device 20, is transported to the PEFC is blowing stage pipeline (L4-L8), coupled with a distillation device.

EXAMPLES

The present invention will be now explained in more detail by the following examples, with the understanding that these examples are not in any way restrictive of the invention.

<Preparation of Catalyst >

<Catalyst 1>

After mixing and stirring USY zeolite with an average particle size of 0.9 μm (molar ratio of silica/alumina: 37), aluminosilicate catalyst (molar ratio of silica/alumina 14) and alumina binder in a weight ratio of 3:57:40 mixture was molded in a cylindrical shape with a diameter of about 1.6 mm and a length of about 3 mm and calcined at 500°C for 1 hour, to obtain a carrier. The carrier was impregnated with an aqueous solution of hexachloroplatinic acid to platinum plating. He was then dried at 120°C for 3 hours and calcined at 500°C for 1 hour to obtain a catalyst 1. The weight of the deposited platinum was 0.8 mass % with respect to the media.

<Catalyst 2>

Catalyst 2 was prepared by forming media and annealing, deposition of the metal, drying and firing in the same manner as catalyst 1, except that Lombardy oxide catalyst was used instead of the aluminosilicate catalyst for catalyst 1.

<Catalyst 3>/p>

Catalyst 3 was prepared by molding media and annealing, deposition of the metal, drying and calcination in the same manner as catalyst 1, except that the carrier was impregnated with an aqueous solution of hexachloroplatinic acid and an aqueous solution of palladium chloride instead of an aqueous solution of hexachloroplatinic acid for catalyst 1, and the weight of the deposited platinum and palladium
was 0.7 mass % and 0.1 mass%, respectively, in relation to the media.

<Hydrotreating synthetic oil CFT>

(Example 1)

After stuffing catalyst 1 (150 ml) in a reactor with a stationary layer of synthetic oil obtained by fractional distillation of crude oil, synthesized through the synthesis of CFT and having a content of hydrocarbons C9-21 (boiling point 150-360°C) 100 mass % and the content of hydrocarbons C9-14 (boiling point 150-250°C) 45 mass % (normal paraffin content of C9-21: 90 mass %, the content of alcohols: 5 mass %, the olefin content: 5 mass % (all based on the total weight of the raw material)) (hereinafter also referred to as "synthetic original oil"), served as the source material at the rate of 300 ml/h and Hydrotreating was carried out by a stream of hydrogen with the following reaction conditions.

First, hydrogen was fed to the synthetic source oil is era of the column with respect to the hydrogen/oil 340 nl/l, moreover, the check valve was adjusted to a constant pressure at the inlet to the reaction column to 3.0 MPa, and the reaction temperature (the average temperature on the layer of catalyst) was adjusted for the content of C8 and lower hydrocarbons 7 mass % synthetic oil after contact (reaction product) under these conditions. Adjusted the reaction temperature was 308°C.

Subjected to hydrofining synthetic oil (the reaction product was analyzed by gas chromatography, and the content of C8 and lower hydrocarbons in synthetic oil (mass %), the content of hydrocarbons C9-21 (mass %), the content of hydrocarbons C9-14 (mass %) and the content of hydrocarbons C15-21 (mass %), as well as the content of alcohol (mass %), were identified. Synthetic original oil was also measured by this method, and the content (mass %) of each component was determined.

A clear distillation of synthetic oil after Hydrotreating (reaction product) was produced fraction of hydrocarbons C9-21 (a fraction with a boiling point of 150-360°C), and its point of turbidity was measured. A clear distillation of synthetic source of oil is also produced fraction of hydrocarbons C9-21 (a fraction with a boiling point of 150-360°C), and its point of turbidity was measured. Cloud point were measured using avtomaticheskogo the test apparatus for determining the temperature fluidity loss/cloud point (MPC-101A, the product Tanaka Scientific, Ltd.).

The results are shown in table 1. The content of each component shown in table 1, represents the value based on the total weight synthetic oil.

Table 1
Syntheti. original oilExample 1Example 2Example 3Example 4Example 5
The reaction temperature (°C)-308297318308308
The partial hydrogen pressure (MPa)-3,03,03,03,03,0
The volumetric rate of fluid (h-1)-2,02,02,02,02,0
Against the s hydrogen/oil (nl/l) -340340340340340
The content ≤C8 (mass %)073977
The content of C9-C21 (mass %)1009397919393
The content of C9-C14 (mass %)455048554951
Content C15-C21 (mass %)554349364442
The content of alcohols (mass %)50000 0
Point cloud-fraction C9-C21 (°C)7-15-8-21-14-16
Lowering the cloud point relative to the synthetic source of oil (°C)-2215282123
The lower maintenance C15-C21 against synthetic source of oil (mass %)-127191113
The increase in the content of C9-C14 towards synthetic source of oil (mass %)-531046

(Example 2)

The hydrotreatment was carried out in the same manner as in Example 1 except that the reaction temperature was adjusted to the content of C8 and lower hydrocarbons 3 mass % in sintet the cooling oil after contact (reaction product). The reaction temperature (the average temperature by weight catalyst layer) was 297°C. Synthetic oil after contact (reaction product) was analyzed in the same manner as in Example 1. The results are shown in table 1.

(Example 3)

The hydrotreatment was carried out in the same manner as in Example 1 except that the reaction temperature was adjusted to the content of C8 and lower hydrocarbons 9 mass % synthetic oil after contact (reaction product). The reaction temperature (the average temperature by weight catalyst layer) was 318°C. Synthetic oil after contact (reaction product) was analyzed in the same manner as in Example 1. The results are shown in table 1.

(Example 4)

The hydrotreatment was carried out in the same manner as in Example 1 except that the catalyst 2 was used instead of catalyst 1 in Example 1. The reaction temperature (the average temperature by weight catalyst layer), adjusted for the content of C8 and lower hydrocarbons 7 mass % synthetic oil after contact (reaction product) in the same manner as in Example 1, was found equal to 308°C. Synthetic oil after contact (reaction product) was analyzed in the same manner as in Example 1. The results are shown in table 1.

(Use the 5)

The hydrotreatment was carried out in the same manner as in Example 1 except that the catalyst 3 was used instead of catalyst 1 in Example 1. The reaction temperature (the average temperature by weight catalyst layer), adjusted for the content of C8 and lower hydrocarbons 7 mass % synthetic oil after contact (reaction product)obtained in the same manner as in Example 1, was equal to 308°C. Synthetic oil after contact (reaction product) was analyzed in the same manner as in Example 1. The results are shown in table 1.

(Comparative Example 1)

The hydrotreatment was carried out in the same manner as in Example 1 except that the reaction temperature was adjusted to the content of C8 and lower hydrocarbons 1 mass % synthetic oil after contact (reaction product). The reaction temperature (the average temperature by weight catalyst layer) was 270°C. Synthetic oil after contact (reaction product) was analyzed in the same manner as in Example 1. The results are shown in table 2. The content of each component shown in table 2, is a value, based on the total weight synthetic oil.

Table 2
Syntheti. original oilCompare. example 1Compare. example 2Compare. example 3
The reaction temperature (°C)-270245324
The partial hydrogen pressure (MPa)-3,03,03,0
The volumetric rate of fluid (h-1)-2,02,02,0
The ratio of hydrogen/oil (nl/l)-340340340
The content ≤C8 (mass %)01012
The content of C9-C21 (mass %)1009910088
The content of C9-C14 (mass what the f %) 4545,54560
Content C15-C21 (mass %)5553,55528
The content of alcohols (mass %)501,50
Point cloud fractions C9-C21 (°C)733-23
Lowering the cloud point relative to the synthetic source of oil (°C)-4430
The lower maintenance C15-C21 against synthetic source of oil (mass %)-1,5027
The increase in the content of C9-C14 towards synthetic source of oil (mass %)-0,50(Comparative Example 2)

The hydrotreatment was carried out in the same manner as in Example 1 except that the reaction temperature was set to the content of C8 and lower hydrocarbons 0 mass % synthetic oil after contact (reaction product). The reaction temperature (the average temperature on the layer of catalyst) was 245°C. Synthetic oil after contact (reaction product) was analyzed in the same manner as in Example 1. The results are shown in table 2.

(Comparative Example 3)

The hydrotreatment was carried out in the same manner as in Example 1 except that the reaction temperature was adjusted to the content of C8 and lower hydrocarbons 12 mass % synthetic oil after contact (reaction product). The reaction temperature (the average temperature by weight catalyst layer) was 324°C. Synthetic oil after contact (reaction product) was analyzed in the same manner as in Example 1. The results are shown in table 2.

As shown in table 1, it was confirmed that the Hydrotreating in Examples 1-5 can lower the point of turbidity average fraction (C9-C21) of at least 15°C, at the same time maintaining a high yield of the middle fraction (C9-C21) 91 % or more. This shows that the Hydrotreating process of synthetic oil on izaberete the Oia allows performance with high yield material of the base diesel fuel with excellent low-temperature rheological property cloud point below 0°C from the FT synthetic oil.

Application in industry.

In accordance with the invention, it is possible to provide a Hydrotreating process synthetic oil, which can adequately improve the low-temperature rheological properties of the medium fraction, at the same time maintaining a satisfactory yield of the middle fraction, even when processing the average fraction of synthetic oil obtained by the FT synthesis. The invention also provides a process of manufacturing the base material of the fuel, whereby the material of the base fuel with excellent low-temperature rheological properties can be obtained in good yield average fraction of synthetic oil obtained by the FT synthesis.

1. The method of Hydrotreating synthetic oil is different:
by contacting a synthetic oil obtained by a Fischer-Tropsch synthesis and having a content of hydrocarbons C9-21 90 wt.% or more,
with a Hydrotreating catalyst, which is a catalyst, which contains a carrier containing one or more solid acids selected from an ultra-stable Y(USY) zeolite, aluminosilicate, zirconiasilicate and alumbrera oxide catalyst, and at least one metal selected from the group consisting of metals belonging to group VIII of the Periodic table, applied to the nose of the tel,
in the presence of hydrogen with the regulation of the reaction temperature during the contacting of the catalyst Hydrotreating with synthetic oil,
for Hydrotreating synthetic oil so that the content (wt.%) C8 and lower hydrocarbons in synthetic oil after contact is 3-9 wt.% more than before the contact.

2. The method of Hydrotreating synthetic oil according to claim 1, characterized in that
synthetic oil has a content of hydrocarbons C9-C14 not more than 70 wt.%, and
synthetic oil is subjected to Hydrotreating in such a way that the content of hydrocarbons C9-14 (wt.%) in synthetic oil after contact is at least 2 wt.% more than before contact, and the content of hydrocarbons C15-21 (wt.%) in synthetic oil after contact is at least 2 wt.% less than before contact.

3. The method of Hydrotreating synthetic oil according to claim 1 or 2, wherein the Hydrotreating catalyst is a catalyst containing a medium containing an ultra-stable Y-zeolite and one or more catalysts selected from aluminosilicate, alumbrera oxide and zirconiasilicate catalyst, and at least one metal selected from the group consisting of metals belonging to Group VIII of the Periodic table supported on a carrier.

4. With whom persons Hydrotreating synthetic oil according to claim 1 or 2, characterized in that the contact between synthetic oil and a Hydrotreating catalyst, the reaction temperature is 200-370°C, the partial pressure of hydrogen is 1.0-5.0 MPa and space velocity of the liquid is 0.3-3.5 h-1.

5. A method of manufacturing a material of the base fuel, characterized in that it contains a stage Hydrotreating, in which synthetic oil obtained by a Fischer-Tropsch synthesis and having a content of hydrocarbons C9-21 90 wt.% or more, comes in contact
with a Hydrotreating catalyst, which is a catalyst, which contains a carrier containing one or more solid acids selected from an ultra-stable Y(USY) zeolite, aluminosilicate, zirconiasilicate and alumbrera oxide catalyst, and at least one metal selected from the group consisting of metals belonging to group VIII of the Periodic table supported on a carrier,
in the presence of hydrogen with the regulation of the reaction temperature during the contacting of the catalyst Hydrotreating with synthetic oil,
for Hydrotreating synthetic oil so that the content (wt.%) C8 and lower hydrocarbons in synthetic oil after contact is 3-9 wt.% more than before contact, and
the stage at which the average fraction - base fuel - floor which is made of synthetic oil, obtained from stage hydrotreatment.

6. A method of manufacturing a material of the base fuel according to claim 5, wherein the Hydrotreating catalyst is a catalyst containing a medium containing an ultra-stable Y(USY) zeolite and one or more catalysts selected from aluminosilicate, zirconiasilicate and alumbrera oxide catalyst, and at least one metal selected from the group consisting of metals belonging to group VIII of the Periodic table supported on a carrier.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to promoter catalysts on a combined zeolite/aluminosilicate substrate with low content of macropores and to methods of hydrocracking/hydroconversion and hydrofining, in which said catalysts are used. The catalyst contains at least one hydrogenating-dehydrogenating element, selected from a group comprising group VIB and group VIII elements, a promoter element in a controlled amount, selected from phosphorus oxide, and a substrate based on zeolite Y, defined by constant a of the unit cell of the crystal lattice, ranging from 24.40·10-10 m to 24.15·10-10 m, and based on aluminosilicate, containing silicon dioxide (SiO2) in amount exceeding 5 wt % and less than or equal to 95 wt %. The catalyst has the following characteristics: average pore diametre, total pore volume, BET specific surface area, volume of pores of different diametre, characterised by X-ray diffraction pattern and packing degree of the catalyst.

EFFECT: catalyst provides for suitable selectivity of middle distillates, ie fractions with initial boiling point of at least 150°C and final boiling point which reaches initial boiling point of residue, for example below 340°C or 370°C.

28 cl, 4 tbl, 21 ex

FIELD: chemistry, organic, processing of hydrocarbons.

SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.

EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.

14 cl, 1 ex

FIELD: petrochemical processes.

SUBSTANCE: group of inventions relates to processing of hydrocarbon feedstock having dry point from 140 to 400°C and is intended for production of fuel fractions (gasoline, kerosene, and/or diesel) on solid catalysts. In first embodiment of invention, processing involves bringing feedstock into contact with regenerable catalyst at 250-500°C, pressure 0.1-4 MPa, and feedstock weight supply rate up to 10 h-1, said catalyst containing (i) crystalline silicate or ZSM-5 or ZSM-14-type zeolite having general empiric formula: (0.02-0.35)Na2O-E2O3-(27-300)SiO2-kH2O), where E represents at least one element from the series: Al, Ga, B, and Fe and k is coefficient corresponding to water capacity; or (ii) silicate or identically composed zeolite and at least one group I-VIII element and/or compound thereof in amount 0.001 to 10.0 % by weight. Reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-4 MPa. Hydrocarbon feedstock utilized comprises (i) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of isoparaffins and naphtenes in summary amount 54-58.1%, aromatic hydrocarbons in amount 8.4-12.7%, and n-paraffins in balancing amount; or (ii) long hydrocarbon fraction boiling away up to 400°C and composed, in particular, of following fractions, °C: 43-195, 151-267, 130-364, 168-345, 26-264, 144-272. In second embodiment, feedstock boiling away up to 400°C is processed in presence of hydrogen at H2/hydrocarbons molar ratio between 0.1 and 10 by bringing feedstock into contact with regenerable catalyst at 250-500°C, elevated pressure, and feedstock weight supply rate up to 10 h-1, said catalyst containing zeolite having structure ZSM-12, and/or beta, and/or omega, and/or zeolite L. and/or mordenite, and/or crystalline elemento-aluminophosphate and at least one group I-VIII element and/or compound thereof in amount 0.05 to 20.0 % by weight. Again, reaction product is separated after cooling through simple separation and/or rectification into fractions: hydrocarbon gas, gasoline, kerosene, and/or diesel fractions, after which catalyst is regenerated by oxygen-containing gas at 350-600°C and pressure 0.1-6 MPa.

EFFECT: improved flexibility of process and enlarged assortment of raw materials and target products.

12 cl, 3 tbl, 22 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of purifying lower alkanes from methanol through contact between the raw material and a catalyst which contains aluminium oxide at high temperature and pressure. The method is characterised by that the catalyst used is an aluminiuim-platinum catalyst and contact takes place at temperature of 180-400°C, pressure of 1.5-4.0 MPa, volume rate of supply of material of 0.4-4 h-1 and volume ratio of material : hydrogen equal to 1:(5-900).

EFFECT: invention increases degree of purity of lower alkanes from methanol.

3 cl, 9 ex

FIELD: chemistry, organic, processing of hydrocarbons.

SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.

EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.

14 cl, 1 ex

FIELD: petroleum processing and catalysts.

SUBSTANCE: field of invention is production of catalysts for catalytic hydrotreatment (desulfurization) of gasoline fractions, e.g. straight-run gasoline. Herein disclosed is block-type high-porosity cellular catalyst for hydrotreatment of straight-run gasoline having porosity at least 90-93% and microporosity up to 30%, average pore size being ranging from 0.5 to 2.0 μm. Catalyst consists of α-alumina-based carrier and active catalyst portion containing sulfated zirconium dioxide and metallic palladium in concentration 0.5-0.9 wt %. Catalyst preparation method is also claimed and is as follows. Carrier is prepared from reticular polyurethane foam and impregnated with slurry containing more than 30 wt % α-alumina, after which calcined at 1300-1500°C, impregnated with water-soluble zirconium salts, dried at 100-200°C, calcined at 450-950°C, treated with 5-10% sulfuric acid, dried, calcined at 500-550°C, treated with palladium nitrate, dried, and calcined at 400-450°C, whereupon palladium oxide is reduced to metallic palladium.

EFFECT: lowered pressure and temperature of hydrotreatment process, considerably reduced process duration, lowered sulfur level in straight-run gasoline due to developed surface of catalyst, and prevented crumbling and loss of catalyst due to cellular structure and high strength.

FIELD: oil refining industry and petrochemistry; hydrorefining of petroleum distillates.

SUBSTANCE: hydrorefining of petroleum distillates is carried out at elevated temperature and increased pressure in presence of catalyst containing carrier - highly porous cellular material on base of aluminum α-oxide modified by aluminum γ-oxide or sulfated zirconium dioxide; used as active component is palladium or palladium modified by palladium nano-particles or palladium in mixture with zinc oxide in the amount of 0.35-20.0 mass-%. The process is carried out at temperature of 150-200°C and pressure of 0.1-1.0 Mpa.

EFFECT: enhanced efficiency; facilitated procedure; possibility of hydrorefining of gasoline and diesel distillates.

2 cl, 1 tbl

FIELD: desulfurization and hydrogenation catalysts.

SUBSTANCE: invention relates to preparing hydrodesulfurization and dearomatization catalysts useful in processes of deep purification of motor fuels from sulfur-containing compounds and aromatics. A sulfur-resistant catalyst is provided including active component deposited on porous inorganic support including montmorillonite or alumina and characterized by that support is composed of zeolite H-ZSM-5 with Si/Al atomic ratio 17-45 (80-65%) and montmorillonite or alumina (20-35%), while active component is platinum or palladium, platinum and palladium in quantities, respectively, 0.2-2.0, 0.2-1,5. and 0.4-0.2% based on the total weight of catalyst. Described is also catalyst comprising platinum (0.2-2.0%) or palladium (0.2-1.5%), or platinum and palladium (0.4-2.0%) supported by Ca or Na form of montmorillonite, and also catalyst with the same active components supported by zeolite H-ZSM-5 with Si/Al atomic ratio 17-45.

EFFECT: increased sulfur-caused deactivation resistance of catalyst at moderate temperatures and under conditions efficiency in hydrodesulfurization and aromatics hydrogenation processes.

8 cl, 4 tbl, 30 ex

The invention relates to the petrochemical industry, particularly to a method of liquid-phase hydrogenation of unsaturated hydrocarbons in the part of the light fraction of pyrolysis tar
The invention relates to the field of petrochemicals, and particularly to a method of Hydrotreating a liquid hydrocarbon fractions

The invention relates to a catalyst used in the methods of hydroconversion hydrocarbons, which contain small amounts of metals

The invention relates to the refining and can be used in the process of cleaning catalytic reforming products from olefin hydrocarbons

The invention relates to the field of oil and can be used in the process of cleaning catalytic reforming products from olefin hydrocarbons

FIELD: desulfurization and hydrogenation catalysts.

SUBSTANCE: invention relates to preparing hydrodesulfurization and dearomatization catalysts useful in processes of deep purification of motor fuels from sulfur-containing compounds and aromatics. A sulfur-resistant catalyst is provided including active component deposited on porous inorganic support including montmorillonite or alumina and characterized by that support is composed of zeolite H-ZSM-5 with Si/Al atomic ratio 17-45 (80-65%) and montmorillonite or alumina (20-35%), while active component is platinum or palladium, platinum and palladium in quantities, respectively, 0.2-2.0, 0.2-1,5. and 0.4-0.2% based on the total weight of catalyst. Described is also catalyst comprising platinum (0.2-2.0%) or palladium (0.2-1.5%), or platinum and palladium (0.4-2.0%) supported by Ca or Na form of montmorillonite, and also catalyst with the same active components supported by zeolite H-ZSM-5 with Si/Al atomic ratio 17-45.

EFFECT: increased sulfur-caused deactivation resistance of catalyst at moderate temperatures and under conditions efficiency in hydrodesulfurization and aromatics hydrogenation processes.

8 cl, 4 tbl, 30 ex

FIELD: oil refining industry and petrochemistry; hydrorefining of petroleum distillates.

SUBSTANCE: hydrorefining of petroleum distillates is carried out at elevated temperature and increased pressure in presence of catalyst containing carrier - highly porous cellular material on base of aluminum α-oxide modified by aluminum γ-oxide or sulfated zirconium dioxide; used as active component is palladium or palladium modified by palladium nano-particles or palladium in mixture with zinc oxide in the amount of 0.35-20.0 mass-%. The process is carried out at temperature of 150-200°C and pressure of 0.1-1.0 Mpa.

EFFECT: enhanced efficiency; facilitated procedure; possibility of hydrorefining of gasoline and diesel distillates.

2 cl, 1 tbl

FIELD: petroleum processing and catalysts.

SUBSTANCE: field of invention is production of catalysts for catalytic hydrotreatment (desulfurization) of gasoline fractions, e.g. straight-run gasoline. Herein disclosed is block-type high-porosity cellular catalyst for hydrotreatment of straight-run gasoline having porosity at least 90-93% and microporosity up to 30%, average pore size being ranging from 0.5 to 2.0 μm. Catalyst consists of α-alumina-based carrier and active catalyst portion containing sulfated zirconium dioxide and metallic palladium in concentration 0.5-0.9 wt %. Catalyst preparation method is also claimed and is as follows. Carrier is prepared from reticular polyurethane foam and impregnated with slurry containing more than 30 wt % α-alumina, after which calcined at 1300-1500°C, impregnated with water-soluble zirconium salts, dried at 100-200°C, calcined at 450-950°C, treated with 5-10% sulfuric acid, dried, calcined at 500-550°C, treated with palladium nitrate, dried, and calcined at 400-450°C, whereupon palladium oxide is reduced to metallic palladium.

EFFECT: lowered pressure and temperature of hydrotreatment process, considerably reduced process duration, lowered sulfur level in straight-run gasoline due to developed surface of catalyst, and prevented crumbling and loss of catalyst due to cellular structure and high strength.

FIELD: chemistry, organic, processing of hydrocarbons.

SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.

EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.

14 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of purifying lower alkanes from methanol through contact between the raw material and a catalyst which contains aluminium oxide at high temperature and pressure. The method is characterised by that the catalyst used is an aluminiuim-platinum catalyst and contact takes place at temperature of 180-400°C, pressure of 1.5-4.0 MPa, volume rate of supply of material of 0.4-4 h-1 and volume ratio of material : hydrogen equal to 1:(5-900).

EFFECT: invention increases degree of purity of lower alkanes from methanol.

3 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of hydrofining synthetic oil, realised by bringing synthetic oil, obtained via Fischer-Tropsch synthesis and having content of C-9-21 hydrocarbons greater than or equal to 90 wt %, into contact with a hydrofining catalyst which has a support which contains one or more solid acids selected from ultra-stable Y-(USY) zeolite, aluminosilicate, zirconia-silicate and aluminium-bromine oxide catalyst and at least one metal selected from a group comprising group VIII metals, deposited on the support, in the presence of hydrogen with regulation of the reaction temperature when the hydrofining catalyst is in contact with the synthetic oil, in order to hydrofine the synthetic oil such that content (wt %) of C8 or lower hydrocarbons in the synthetic oil after contact is 3-9 wt % higher than before contact. The invention also relates to a method of producing base fuel material.

EFFECT: obtaining base oil with excellent low-temperature rheological properties with good output of the middle fraction of the synthetic oil.

6 cl, 8 ex, 2 tbl, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: paraffin hydrotreating method involves the first stage at which paraffin with content C21 or higher of normal paraffins 70% wt or higher is used as basic material, and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking, catalyst consisting of metal of group VIII of the Periodic Table, which is put on carrier containing amorphous solid acid; the second stage at which raw material from paraffin is replaced for some time with light paraffin with content C9-20 of paraffins 60% wt or higher, and light paraffin contacts with catalyst at reaction temperature of 120-335 °C in presence of hydrogen for hydrocracking; and the third stage at which raw material of light paraffin is replaced with paraffin and paraffin contacts with catalyst at reaction temperature of 270-360 °C in presence of hydrogen for hydrocracking. Also, invention refers to method for obtaining material of fuel system, which involves the above method.

EFFECT: use of this invention allows improving activity of hydrocracking catalyst, which deteriorates with time.

6 cl, 1 tbl, 4 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for realising a method of hydrogenating olefins and oxygen-containing compounds in synthetic liquid hydrocarbons obtained via a Fischer-Tropsch method, containing a porous support made from γ-aluminium oxide on which a catalytically active palladium component is deposited, characterised by that pores in the support have effective radius of 4.0-10.0 nm, wherein content of foreign-metal impurities in the support is not more than 1500 ppm, and content of palladium in the catalyst is equal to 0.2-2.5 wt %. The invention also relates to a hydrogenation method using said catalyst.

EFFECT: invention enables to obtain saturated hydrocarbons from liquid Fischer-Tropsch synthesis products, which are a complex mixture of paraffin hydrocarbons with 5-32 carbon atoms, with ratio of normal paraffin hydrocarbons to isoparaffin hydrocarbons ranging from 1:1 to 7:1, containing up to 50% olefins and up to 5% oxygen-containing compounds.

2 cl, 1 tbl, 7 ex

Up!