RU2570649C1 - Method of obtaining bases of waxy arctic oils - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining bases of waxy arctic oils, and oil raw material is a fraction of vacuum gas oil hydrocracking, which boils away at temperature 280° C-KK, is subjected to hydroisomerisation by its contact with hydrogen at volume ratio of hydrogen to raw material 500-1000 nm³/m³ on catalyst, which contains, wt %: Pt - 0.30-0.35, WO₃ - 3.0-4.0, SiO₂ - 8.0-38.8, In₂O - 0.4-0.42, aluminosilicate - the remaining part, at temperature 240-320°C, partial pressure of hydrogen 3.5-6.0 MPa, volume speed of raw material supply 0.5-2.0 h^-1 with obtaining low-viscous base of waxy arctic oil, which has kinematic viscosity at temperature 100°C - 2.11-5.05 mm²/sec and product freezing temperature - minus 62 - minus 65°C, and to obtain medium-viscous and viscous base of waxy arctic oil hydration of obtained low-viscous base of waxy arctic oil is carried out at temperature 240-260°C, partial pressure of hydrogen 4.0-5.0 MPa, volume speed of raw material supply 0.25-0.5 h^-1, ratio of hydrogen to raw material 80-900 nm³/m³ on sulphided platinum catalyst, applied on aluminium oxide, with content of platinum counted per burnt at temperature 850°C catalyst - 0.45-0.5 wt %, the following fractioning with separation of medium-viscous base of waxy arctic oil, which has kinematic viscosity at temperature 100°C - 5.06-10.10 mm²/sec and temperature of product freezing - minus 62 - minus 65°C, and viscous base of waxy arctic oil, which has kinematic viscosity at temperature 100°C - 10.11-15.12 mm²/sec and temperature of product freezing - minus 62 - minus 65°C.

EFFECT: obtaining target products with improved characteristics.

2 tbl, 5 ex

Description

The invention relates to the field of oil refining and petrochemicals, in particular to a method for producing low-curing bases intended for the production of lubricants for various purposes (motor, hydraulic, gear oil, grease) for the operation of machinery and equipment in severe weather conditions of the Arctic and the Far North.

The decisive indicator in the development of lubricants operating in extremely harsh environmental conditions at temperatures of minus 60 ° C and below, regardless of their type and purpose, is a certain level of viscosity-temperature properties, namely a low pour point (below minus 50 ° C) and low viscosity at low temperatures, which allows the engine to start in the cold.

The most highly solidifying components of oil raw materials that determine the level of viscosity and temperature properties of the obtained base oils (bases) are normal structure paraffins, as well as naphthenic and aromatic hydrocarbons with unbranched long chain alkyl substituents. To reduce the pour point and improve low-temperature properties, it is necessary to strive to reduce the content of these components in oil raw materials to the maximum possible level. In order to reduce the pour point and improve low-temperature properties, processes such as are used: 1) low-temperature dewaxing using selective solvents (solvent dewaxing); 2) catalytic dewaxing; 3) hydroisomerization.

In solvent dewaxing, the removal of solid carbons from oil raw materials occurs under the influence of low temperatures and the difference in solubility of hydrocarbons of various structures in solvents. In practice, either a mixture of polar and non-polar solvents (methyl ethyl ketone: toluene, acetone: toluene) taken in various ratios (from 30 to 60 wt.% Ketone and from 70 to 40 wt.% Toluene) or bifunctional are used to carry out the solvent dewaxing process solvents combining the functions of both polar and non-polar solvents, such as methyl isobutyl ketone or methyl isopropyl ketone.

The multiplicity of the solvent to the feed depends on the viscosity of the dewaxed raffinate: with an increase in the viscosity of the oil fractions, the solvent consumption increases. Typically, the ratio of the solvent to the feed is (2-3): 1 for the distillate feed and (3.0-4.5): 1 for the residual feed. Such quantities as the rate of separation of the liquid part from the solid, the yield of dewaxed oil, the pour point of the target product, and the oil content in the gut or petrolatum depend on the amount of solvent taken. This process has a number of significant drawbacks: high operating costs due to the need for regeneration of a large amount of solvent, limited use of raw materials of various compositions, low quality of the resulting oils. Lynch, T.R. Process chemistry of lubricant base stocks. T.R. Lynch Canada, Mississauga: CRC Press, 2008, 369 p.

To obtain high-quality low-hardening bases, it is necessary to use modern hydrocatalytic processes. British Petroleum has developed a method for producing low-curing substrates, which is carried out in a hydrogen atmosphere on a Pt-containing catalyst supported on mordenite. A significant drawback of this process is its applicability only to light oil raw materials. US 3,668,113 A, 06/06/1972.

A known method of producing raw materials of any viscosity after selective purification or hydrocracking using zeolite-containing catalysts that are highly selective with respect to normal ZSM-5 paraffins, developed by Mobile Oil Corporation (Mobile Lube Dewaxing - MLDW). In the process of catalytic dewaxing, a two-stage processing of oil raw materials is carried out:

1) the stage of catalytic dewaxing on zeolite-containing catalysts, in which there is a decrease in pour point due to selective cracking of normal paraffins;

2) the stage of hydrofinishing, in which there is a decrease in the content of nitrogen and sulfur-containing compounds in the target product, as well as partial hydrogenation of unsaturated hydrocarbons, which helps to improve the viscosity index (VI), color and stability of the target product. US 4,229,282 A, 05/09/1989

The main disadvantage of the catalytic dewaxing process is the low yield of dewaxed oil, which is due to the selective cracking of normal paraffins to light hydrocarbons that are not part of the target product (dewaxed oil).

A known method for producing base oils with a low pour point by hydroisomerization of paraffinic oil raw materials, developed simultaneously by Chevron - Isodewaxing Wilson M.W., Mueller T.A., Kraft G.W. "Commercialization of Isodewaxing - A New Technology for Dewaxing to Manufacture High Quality Lube Base Stocks", FL-94-112, NPRA, November 1994 and Mobile Oil Corporation - Mobile Selective Dewaxing (MSDW) [Helton T.E., Degnan TF, Mazzone dn et al. Catalytic hydroprocessing a good alternative to solvent processing. Oil and Gas Journal. 1998, 96, No. 29, p. 58-67. These processes are based on the selective isomerization of normal chain long-chain paraffin hydrocarbons, which leads to a change in the properties of the target product due to a change in the structure of the components while preserving these components in the oil feedstock and, as a result, increasing the yield of dewaxed oil. These processes use Pt-containing catalysts supported on zeolites of a specific structure (SAPO, MTT). As in the case of catalytic dewaxing, the production of low-hardening oils during hydroisomerization is carried out in two stages: 1) the stage of hydroisomerization (improvement of low-temperature parameters due to a change in the structure of long-chain paraffins); 2) the stage of hydrofinishing (improving color, stability, VI due to the hydrogenation of unsaturated hydrocarbons).

Since catalysts, processes of catalytic dewaxing and hydroisomerization contain a noble metal deposited on a zeolite-containing carrier, these processes are more suitable for processing low-sulfur oil raw materials, in particular, residues of hydrocracking of vacuum gas oil (WG), pump and petrolatums.

These processes are carried out in a hydrogen atmosphere in flow-type reactors with a stationary catalyst bed. Table 1 below presents the main technological parameters of the catalytic dewaxing and hydroisomerization:

The main component of the catalysts for hydrogenation processes are crystalline aluminosilicates - zeolites of the ZSM family (ExxonMobil processes) and SAPO silicoaluminophosphates (Chevron processes), Group VI and VIII metals (including noble metals) as the active component. The choice of carriers is due to the presence of numerous strong acid centers in their structure, on the developed and accessible surface of which a finely dispersed distribution of metals is possible, as well as molecular sieve properties.

Known for an improved method for the catalytic dewaxing of hydrocarbon oils described in US 4,229,282 A, 10.21.1980. In this process, oils with a high content of paraffin hydrocarbons in the presence of hydrogen are contacted with a zeolite dewaxing catalyst containing an active hydrogenating component (nickel, tungsten). Dewaxed oil has good stability, has a low bromine number compared to products of previous technologies. The process can be used for dewaxing both crude oils, fuel fractions, and for lubricating oils. The process of dewaxing raw materials boiling at a temperature above 177 ° C is carried out in the presence of hydrogen at a temperature of 232-510 ° C; pressure 0.34-20.7 MPa; a space velocity of 0.1-20 h ^-1 ; the multiplicity of hydrogen circulation 89-3563 m ³ / m ³ . The process catalyst contains a hydrogenating component (nickel) in an amount of 0.87-7% wt., Tungsten in an amount of 2.1-21% wt. and crystalline zeolite ZSM-5 with a pore size of more than 5 Å. The matrix of the catalyst is alumina. Raw materials may be partially subjected to solvent dewaxing. The resulting product has a kinematic viscosity at a temperature of 100 ° C of 10.29-10.71 mm ² / s, a viscosity index of -92.2, pour point - minus 17 ° C.

Hydrocracking lubricants with a low pour point and good stability are obtained by multi-stage processing: stage 1 - hydrocracking of raw materials (boiling point over 343 ° C) at a pressure of 6.9-20.7 MPa; Stage 2 - gas-liquid separation; Stage 3 - dewaxing at a pressure of 6.9-20.7 MPa, a temperature of 274-426 ° C, a space velocity of 0.2-20 h ^-1 on the dewaxing catalyst - zeolite ZSM-5, ZSM-11, mordenite associated with hydrogenation component; Stage 4 - hydrotreating at high pressures to stabilize the resulting base oil. Each stage is carried out at high pressure, due to which the circulation of hydrogen is carried out with minimal additional compression. The pressure (partial) of circulating hydrogen increases by no more than 5.2 MPa before passing into the hydrocracking zone. US 4,283,271 A, 08/11/1981.

In order to reduce the pour point of the oils, we propose a process for the catalytic dewaxing of hydrocarbons boiling at temperatures above 454 ° C, in the presence of a zeolite catalyst, followed by hydrotreating a product containing a hydrogenating component (tungsten, molybdenum, nickel, cobalt, platinum, palladium in the form of a free element, sulfide or oxide) and one or more zeolites - ZSM-5, ZSM-11, ZSM-23, ZSM-35. The hydrotreating catalyst is used in the form of an extrudate, in which the metal is in an amount of 0.05-25 wt.% In the form of oxide or in the form of sulfide; zeolite - in an amount of 5-40 wt.%. The conditions for the catalytic dewaxing process: temperature 260-357 ° C, pressure 1.4-6.9 MPa (13.6-68.05 atm), space velocity 0.5-4.0 h ^-1 hydrogen consumption 142.5 -712.7 m ³ / m ³ . The conditions of the hydrotreating process: temperature 246-287 ° C, partial pressure of hydrogen 1.03-10.34 MPa (10.2-102 atm), space velocity 0.1-4 h ^-1 , hydrogen consumption 89-890.8 m ³ / m ³ . US 4,490,242 A, 12/25/1984.

The process of dewaxing a hydrocarbon feed containing normal and weakly branched paraffins with a relatively high pour point takes place on a noble metal promoted by zeolite beta followed by dewaxing on a base metal promoted by beta zeolite. The process of dewaxing hydrocarbons with a relatively high pour point and a certain amount of paraffin hydrocarbons includes the following stages: 1) catalytic dewaxing at a temperature of 200-500 ° C, pressure from atmospheric to 25 MPa, the amount of hydrogen 20-4000 nl / l (per unit volume of liquid raw materials), space velocity of 0.1-10.0 h ^-1 , the catalyst contains zeolite beta, hydrogenating / dehydrogenating noble metal (platinum, palladium) in an amount of 0.01-10 wt.%; 2) catalytic dewaxing of the product of the first stage of dewaxing is carried out at a temperature of 200-500 ° C, pressure from atmospheric to 25 MPa, the amount of hydrogen is 20-4000 nl / l (per unit volume of liquid raw materials), the volumetric rate is 0.1-10.0 h ^-1 , the catalyst includes zeolite beta, hydrogenation / dehydrogenation base metal (group VIA, VIIIA - cobalt, Nickel, molybdenum, tungsten, or mixtures thereof) in an amount of 0.1-0.25 wt.%. Previously, the feed can be hydrotreated before the dewaxing stages in the case of a high content of aromatic hydrocarbons (up to 10-60 wt.%) And paraffins (more than 10 wt.%). US 4,554,065 A, 11/19/1985.

A method of obtaining low-setting oils through the use of the hydrocracking-dewaxing process is given in EP 0092376 B1, 04/14/1983. The process of catalytic dewaxing involves contacting the hydrocracking fraction with a catalyst containing crystalline zeolite ZSM-23 in the presence of hydrogen at a temperature of 260-482 ° C; a pressure of 1.48-20.79 MPa, a volumetric flow rate of 0.2-20.0 h ^-1 . The conditions for the hydrocracking process of raw materials boiling above 343 ° C are: temperature 260-482 ° C, pressure 7-20.79 MPa and space velocity 0.1-5.0 h ^-1 . The dewaxed hydrocracking oil is then hydrotreated at a temperature of 176-371 ° C, a pressure of 7.0-20.79 MPa and a space velocity of 0.1-10.0 h ^-1 . The catalyst of any of the processes (hydrocracking, dewaxing, hydrotreating) contains a hydrogenation element, which can be used as a metal or several metals of groups VIII, VI. The catalyst also contains a binder material - aluminum oxide.

Lubricating oils with a low pour point and high stability are obtained from paraffin feedstock in successive stages: solvent purification, catalytic dewaxing on a ZSM-5 zeolite catalyst and hydrotreating. The first stage after obtaining distillate fractions (232-593 ° C) is extraction with selective solvents (furfural, phenol) of undesirable components. Heavy residual fractions are first deasphalted with propane. Next, the obtained raffinates are subjected to catalytic dewaxing in the presence of hydrogen on an aluminosilicate zeolite (silica: alumina ratio = 12) at a temperature of 260-357 ° C. Next, the flow of dewaxing products, including hydrogen, is sent to the hydrotreatment reactor to saturate olefins and improve the color of the product. After passing through the hydrotreatment zone, the products are separated, low-boiling hydrocarbons are distilled off so that flash and ignition temperatures meet the requirements. Hydrotreating of dewaxed raffinate is carried out in the presence of a catalyst containing a hydrogenating component on a non-acidic support (cobalt molybdate on alumina or nickel molybdate on alumina) at a temperature of 218-316 ° C. US 4,181,598 A, 01/01/1980.

Low-yield high-index oils with a high yield are obtained in the process of catalytic hydrodeparaffinization of hydrocarbon feedstocks on zeolite ZSM-22. The hydrodewaxing process is carried out in the presence of hydrogen and a hydrodewaxing catalyst, which includes zeolite ZSM-22 and a metal of group VIII (preferably platinum). This provides a higher yield and viscosity index of the product compared to known technologies and catalytic systems. The activity and selectivity of the catalyst, the oil yield at a given pour point also surpass other processes. Catalytic dewaxing is carried out at a pressure of 1.4-20.7 MPa, a temperature of 260-482 ° C, a volumetric feed rate of 0.2-20.0 h ^-1 , a hydrogen flow rate of 89-3563 m ³ / m ³ . The dewaxing catalyst contains a carrier (aluminum oxide) in an amount of 20-50 wt.%, A metal of group VIII in an amount of 0.1-3 wt.%, The remainder is crystalline silicate ZSM-22. After the dewaxing step, a hydrotreating step may follow at a temperature of 176-371 ° C, a pressure of 6.9-20.7 MPa (68-204 atm), a space velocity of 0.1-10.0 h ^-1 . As a raw material of the catalytic dewaxing process, a hydrocracking product is used. The process is carried out at a pressure of 6.9-20.7 MPa (68-204 atm), a temperature of 260-482 ° C, a space velocity of 0.1-5.0 h ^-1 , a hydrogen flow rate of 178-3563 m ³ / m ³ . The hydrocracking catalyst has acidic and hydrogenating-dehydrogenating functions (silica-alumina or silica-zirconia associated with nickel-tungsten or palladium, platinum, cobalt-molybdenum, nickel-molybdenum). As a result of the process, a product is obtained with kinematic viscosity at a temperature of 100 ° C in the range of 5.1-5.98 mm ² / s, viscosity index 101.5-114.3, pour point minus 45 - minus 55 ° C. US 4,574,043 A, 03/04/1986.

The use of the hydroisomerization process in combination with the hydrocracking of petroleum paraffins makes it possible to obtain high-quality lubricating oils. When using hydrocracking catalysts, according to these materials, it is possible to obtain lubricating oils with a high yield and a viscosity index of 120 and higher. The catalyst achieves such results without the use of fluorine and other promoters. The catalyst also contains an inorganic pore crystalline support with a pore diameter of at least 13 Å and one of the metals of group VIA, VIIA or VIIIA. The process is carried out under the following conditions: temperature 288-440.6 ° C, partial pressure of hydrogen 6.9-20.7 MPa, space velocity 0.2-4.0 h ^-1 . As a result of the process, a product with a viscosity index of 120-143 is obtained. US 5,264,116 A, 11/23/1993.

A known method of producing lubricating oils in the process of hydrodewaxing using a catalyst containing molecular sieves with an average pore size deposited on them active rare earth metal oxide (yttrium oxide) and at least one hydrogenation metal of group VIII or VIB. As molecular sieves with an average pore size, acidic (acidic) metal silicates are used - SAPO-11, SAPO-34, SAPO-41 and zeolites - ZSM-22, ZSM-23, ZSM35, ZSM-57, ZSM-48, ferrierite. The feed contains up to 0.2 wt.% Nitrogen and up to 3 wt.% Sulfur. The conditions of the hydrodewaxing process: temperature 250-400 ° C, pressure 0.79-20.8 MPa, space velocity 0.1-10.0 h ^-1 , hydrogen flow rate 45-1780 m ³ / m ³ . As a result of the process, a product with a viscosity index of 128-146 is obtained. US 7,662,273 B2, 02.16.2010.

A comprehensive three-stage hydrocatalytic process for producing lubricating oils, including the stages of hydrotreating, hydrodewaxing and hydrotreating, is presented in US 2012/0261307 Al, 10/18/2012. This process involves the use of a stripping / separation zone between the first two zones and the separation zone after the third stage of the process. Stripping-separation zones operate at high pressures and temperatures without using a liquid pump until the second stage of the process. The operating pressure reaches its maximum value at the inlet to the first hydrotreatment zone. Also in this process, recycling of the compressed gaseous stream from the last separation zone to the stripping zone, the first hydrotreating zone, the second hydrodewaxing zone and / or the third hydrotreating zone is used.

A known method of obtaining the basic components of low-curing petroleum oils, according to which a straight-run vacuum distillate with boiling points of 280-460 ° C is subjected to low-temperature dewaxing to obtain dewaxed oil with a pour point of minus 50 - minus 55 ° C, which is subjected to distillation with the release of light fractions with the temperature of the end a boiling point of 320-340 ° C and a pour point of minus 55 - minus 60 ° C and a residual fraction of 320-340-460 ° C and then the process is carried out in a known manner. In terms of quality, the light fraction corresponds to the basis of VMGZ low-temperature hydraulic oil used in the Far North, the residual fraction is for winter and multigrade hydraulic oil. RU 2155209 C1, 08.27.2000.

However, the described methods do not allow to obtain base oils with a pour point below minus 60 ° C, which are necessary for the production of lubricants for various purposes, operated in the Arctic and the Far North.

Closest to the claimed method for producing Arctic oils is a process - a one-stage method for producing low-setting oils using a multilayer catalyst system capable of hydrodewaxing and water treatment of hydrocracking products: the first layer is a stationary layer of a dewaxing catalyst; the second layer is a stationary layer of a catalyst hydrogenating under mild conditions. The conditions for the hydrodewaxing and water treatment processes: total volumetric rate 0.25-2.0 h ^-1 (for hydrodewaxing 10-15 h ^-1 ), the partial pressure of hydrogen is 6.9-17.2 MPa, temperature 304.4-315 , 6 ° C, excess pressure of hydrogen 10.3-17.2 MPa, the multiplicity of hydrogen circulation is 890.8-1247 m ³ / m ³ . US 4,822,476 A, 04/18/1989.

The advantage of using a large space velocity and a high partial pressure of hydrogen is achieved through the use of a collector. It allows the use of dewaxing and hydrotreating catalysts in one reactor under the same conditions. These catalysts have a high deactivation rate, however, the use of an increased partial pressure of hydrogen can reduce the coking rate of the catalysts. As a result of the process, a product with a kinematic viscosity at a temperature of 100 ° C of 10.73-11.20 mm ² / s and a viscosity index of 94-100 is obtained.

The main disadvantages of the methods for producing low-setting oils are: high catalyst deactivation rate, which negatively affects the technical and economic performance of the process; a narrow range of kinematic viscosity of the product, which significantly limits the scope of use of the obtained oils; the use of a collector, which complicates the design of the reactor, makes it more metal-intensive and creates additional difficulties in the regeneration and reloading of the catalyst.

The technical task of the present invention is to develop a method for obtaining the fundamentals of low-curing arctic oils, which provides: stable catalyst operation by selecting raw materials of optimal quality and technological parameters of its hydroprocessing, using a relatively low - 3.0-6.0 MPa hydrogen partial pressure, which greatly expands the possibilities the application of this method on technological equipment, for example, a hydrotreating / hydrofinishing unit, designed for a pressure of 4.0-5.0 MPa.

The technical result from the implementation of the claimed invention is to obtain the target products with a wider range of kinematic viscosity at a temperature of 100 ° C from 2.11-15.12 mm ² / s and the pour point of the product is minus 62 - minus 65 ° C.

The technical problem is solved in that the petroleum feedstock - the fraction of vacuum gas oil hydrocracking, boiling off at a temperature of 280 ° C-KK, is subjected to hydroisomerization by contacting it with hydrogen at a volume ratio of hydrogen to feedstock of 500-1000 nm ³ / m on a catalyst containing, by weight. %: Pt - 0.30-0.35, WO ₃ - 3.0-4.0, SiO ₂ - 8.0-38.8, In ₂ O - 0.4-0.42, aluminosilicate - the rest, at a temperature of 240-320 ° C, a partial pressure of hydrogen of 3.5-6.0 MPa, a volumetric feed rate of 0.5-2.0 h ^-1 , a hydrogen circulation rate of 500-1000 m ³ / m ³ to obtain a low-viscosity base low hardening about Arctic oil having a kinematic viscosity at a temperature of 100 ° C - 2.11-4.75 mm ² / s and the pour point of the product - minus 62 - minus 65 ° C, and to obtain a medium-viscous and viscous base of low-curing Arctic oil, hydrogenation of the obtained low-viscosity base of low-curing arctic oil at a temperature of 240-260 ° C, a partial pressure of hydrogen of 4.0-5.0 MPa, a volumetric feed rate of 0.25-0.5 h ^-1 , the ratio of hydrogen to feed 800-900 nm ³ / m ³ on sulfided platinum catalyst supported on alumina with soda by burning platinum in terms of the catalyst calcined at a temperature of 850 ° C - 0.45-0.5 wt.%, subsequent fractionation with the release of a viscous base of low-curing Arctic oil having a kinematic viscosity at a temperature of 100 ° C - 6.33-8.14 mm ² / s and the pour point of the product is minus 62 - minus 65 ° C, and a viscous base of low-curing Arctic oil having a kinematic viscosity at a temperature of 100 ° C is 10.11-15.12 mm ² / s and the pour point of the product is minus 62 - minus 65 ° C.

In the process of hydroisomerization, reactions of selective isomerization of long-chain paraffin hydrocarbons of normal structure occur, leading to a change in the properties of the target product due to a change in the structure of the components. Hydroisomerization reactions of n-alkanes proceed in the presence of hydrogen on bifunctional catalysts having a hydrogenation-dehydrogenation function. The active component of bifunctional hydroisomerization catalysts are Group VI and VIII metals (including noble metals) supported on crystalline aluminosilicate. The choice of carriers is due to the presence of numerous strong acid centers in their structure, on the developed and accessible surface of which a finely dispersed distribution of metals is possible, as well as molecular sieve properties. The best characteristics of the target products were obtained using a catalyst containing, wt.%: Pt - 0.30-0.35, WO ₃ - 3.0-4.0, SiO ₂ - 8.0-38.8, In ₂ O ₃ - 0.4-0.42, aluminosilicate - the rest. The preparation and composition of the catalyst for the isodeparaffinization of petroleum fractions intended for the production of Arctic diesel fuel is described in patent RU 2320407 C1, 03/27/2008.

Medium-viscous and viscous low-hardening substrates according to the described method are obtained by hydrogenation of the obtained low-viscosity base of low-hardening arctic oil (hydroisomerizate) at a temperature of 240-260 ° C, a partial pressure of hydrogen of 4.0-5.0 MPa, a bulk feed rate of 0.25-0 5 h ^-1 , the ratio of hydrogen to feed 800-900 nm ³ / m ³ on a sulfidized platinum catalyst supported on alumina with a platinum content in terms of the catalyst calcined at a temperature of 850 ° C - 0.45-0.5 wt. % Then, the obtained hydrogenation is fractionated with the release of a viscous base of low-curing Arctic oil having a kinematic viscosity at a temperature of 100 ° C of 6.33-8.14 mm ² / s and the pour point of the product is minus 62 to minus 65 ° C, and a viscous base of low curing Arctic oil having a kinematic viscosity at a temperature of 100 ° C - 10.11-15.12 mm ² / s and the pour point of the product - minus 62 - minus 65 ° C.

The hydrogenation catalyst must have a high hydrogenating ability and may be a composition based on metals of groups VI and VIII-X and / or their combinations dispersed on a support. Metals Ni, Mo, W, Pt, Pd can be used as active components of the hydrogenation catalyst, amorphous oxides, preferably alumina, silica and / or combinations thereof can be used as a support; carbon carriers. It was found that the best characteristics of the target products were obtained using a catalyst containing, wt.%: Pt - 0.4-0.45, aluminum oxide - the rest.

The invention is further illustrated by examples of the specific implementation of the method, not limiting its scope.

Example 1

The hydrocracking fraction of vacuum gas oil, boiling off at a temperature of 280 ° C-KK, having the characteristics shown in table 2, is subjected to hydroisomerization.

The hydroisomerization of the vacuum gas oil hydrocracking fraction boiling off at a temperature of 280 ° C-KK is carried out at a temperature of 240 ° C, a partial pressure of hydrogen of 3.5 MPa, a volume ratio of hydrogen to raw material of 1000 nm ³ / m ³ and a volumetric feed rate of 0.5 h ^-1 in the presence of a catalyst supported on a modified carrier, with the content of active components in terms of the catalyst calcined at a temperature of 850 ° C, wt.%:

platinum (Pt); 0.30 tungsten oxide (WO ₃ ); 3.0 silica (SiO ₂ ); 38.8 indium oxide (In ₂ O ₃ ) 0.4 aluminosilicate rest

The low-viscosity base of low-curing Arctic oil obtained as a result of the process had a kinematic viscosity at a temperature of 100 ° C - 2.11 mm ² / s, pour point - minus 65 ° C.

Example 2

The hydrocracking fraction of vacuum gas oil boiling at a temperature of 280 ° C-KK, with the characteristics presented in table 2, is subjected to hydroisomerization at a temperature of 260 ° C, a partial pressure of hydrogen of 6.0 MPa, a volume ratio of hydrogen to feed 700 nm ³ / m ³ and the volumetric feed rate of 1.5 h ^-1 in the presence of a Pt-containing catalyst with the content of active components in terms of the catalyst calcined at a temperature of 850 ° C, wt.%:

platinum (Pt); 0.35 tungsten oxide (WO ₃ ); 4.0 silica (SiO ₂ ); 8.0 indium oxide (In ₂ O ₃ ) 0.42 aluminum silicate rest

The low-viscosity base of low-curing arctic oil obtained as a result of the process had a kinematic viscosity at a temperature of 100 ° C of 4.95 mm ² / s, and a pour point of minus 65 ° C.

Example 3

The fraction of vacuum gas oil hydrocracking, boiling off at a temperature of 280 ° C-KK, with the characteristics presented in table 2, is subjected to hydroisomerization at a temperature of 320 ° C, a partial pressure of hydrogen of 5.0 MPa, a volume ratio of hydrogen to feed 800 nm ³ / m ³ and a feed volumetric feed rate of 1.5 h ⁻¹ in the presence of the Pt-containing catalyst described in Example 1. As a result of the process, a low-viscosity base of low-curing arctic oil was obtained having a kinematic viscosity at a temperature of 100 ° C of 4.95 mm ² / s and a temperature solidification product - minus 63 ° C.

Hydrogenation of the obtained low-viscosity base of low-curing arctic oil (hydroisomerizate) is carried out at a temperature of 240 ° C, a partial pressure of hydrogen of 5.0 MPa, a volumetric feed rate of 0.25 h ^-1 , a hydrogen to feed ratio of 900 nm ³ / m ³ . As a hydrogenation catalyst, a sulfidized platinum catalyst supported on alumina with a platinum content in terms of the catalyst calcined at 850 ° C. is used, 0.5 wt.%.

The obtained hydrogenate is subjected to fractionation with the release of a viscous base of low-curing Arctic oil with a kinematic viscosity at a temperature of 100 ° C - 15.12 mm ² / s, pour point - minus 64 ° C.

Example 4

The fraction of vacuum gas oil hydrocracking, boiling off at a temperature of 280 ° C-KK, with the characteristics presented in table 2, is subjected to hydroisomerization at a temperature of 300 ° C, a partial pressure of hydrogen of 6.0 MPa, a volume ratio of hydrogen to feed 900 nm ³ / m ³ and a feed volumetric feed rate of 2.0 h ⁻¹ in the presence of the Pt-containing catalyst described in Example 1. As a result of the process, a low-viscosity base of low-curing Arctic oil was obtained having a kinematic viscosity at a temperature of 100 ° C of 5.0 mm ² / s and a temperature solidification product - minus 63 ° C.

Hydrogenation of the obtained low-viscosity base of low-curing arctic oil (hydroisomerizate) is carried out at a temperature of 260 ° C, a partial pressure of hydrogen of 4.0 MPa, a volumetric feed rate of 0.5 h ^-1 , a ratio of hydrogen to feed 800 nm ³ / m ³ . As a hydrogenation catalyst, a sulfidized platinum catalyst supported on alumina with a platinum content in terms of the catalyst calcined at a temperature of 850 ° C. is used — 0.45 wt.%.

The obtained hydrogenate is subjected to fractionation with the release of a viscous base of low-curing arctic oil with kinematic viscosity at a temperature of 100 ° C - 8.14 mm ² / s, pour point - minus 64 ° C.

Example 5

The hydrocracking fraction of vacuum gas oil boiling off at a temperature of 280 ° C-KK, with the characteristics presented in table 2, is subjected to hydroisomerization at a temperature of 290 ° C, a partial pressure of hydrogen of 3.0 MPa, a volume ratio of hydrogen to feed 500 nm ³ / m ³ and a feed volumetric feed rate of 2.0 h ⁻¹ in the presence of the Pt-containing catalyst described in Example 1. As a result of the process, a low-viscosity base of low-curing arctic oil was obtained having a kinematic viscosity at a temperature of 100 ° C of 4.50 mm ² / s and a temperature solidification product - minus 63 ° C.

Hydrogenation of the obtained low-viscosity base of low-curing arctic oil (hydroisomerizate) is carried out at a temperature of 250 ° C, a partial pressure of hydrogen of 4.0 MPa, a volumetric feed rate of 0.35 h ^-1 , a ratio of hydrogen to feed 850 nm ³ / m ³ . As a hydrogenation catalyst, a sulfidized platinum catalyst supported on alumina with a platinum content in terms of the catalyst calcined at 850 ° C. is used — 0.42 wt.%.

The obtained hydrogenate is subjected to fractionation with the release of a low-hardening viscous base of arctic oil with kinematic viscosity at a temperature of 100 ° C - 10.11 mm ² / s, pour point - minus 64 ° C.

This method allows to obtain low-viscosity, medium-viscous and viscous bases of low-curing arctic oils with kinematic viscosity at a temperature of 100 ° C in the range of 2.11-15.12 mm ² / s and the pour point of the product is minus 62-minus 65 ° C.

Claims (1)

A method of obtaining the fundamentals of low-curing Arctic oils, characterized in that the crude oil is a fraction of the vacuum gas oil hydrocracking boiling off at a temperature of 280 ° C-KK, is subjected to hydroisomerization by contacting it with hydrogen at a volume ratio of hydrogen to feed 500-1000 nm ³ / m ³ on the catalyst containing, wt.%: Pt - 0.30-0.35, WO ₃ - 3.0-4.0, SiO ₂ - 8.0-38.8, In ₂ O - 0.4-0, 42 aluminosilicate - the rest, at a temperature of 240-320 ° C, a hydrogen partial pressure of 3.5-6.0 MPa, a volumetric hourly space velocity of 0.5-2.0 hr ^-1 to obtain a low viscosity waxy bases its Arctic oil having a kinematic viscosity at 100 ° C - 2,11-5,05 mm ² / s and a pour point of the product - 62 minus - minus 65 ° C, and for a viscous medium viscosity and Arctic bases waxy oils obtained by hydrogenation was carried out low-viscosity base of low-curing arctic oil at a temperature of 240-260 ° C, a partial pressure of hydrogen of 4.0-5.0 MPa, a volumetric feed rate of 0.25-0.5 h ^-1 , the ratio of hydrogen to feed 800-900 nm ³ / m ³ on a sulfidized platinum catalyst supported on alumina, with holding platinum in terms of the catalyst calcined at a temperature of 850 ° C - 0.45-0.5 wt.%, subsequent fractionation with the release of a medium viscosity base of low-curing Arctic oil having a kinematic viscosity at a temperature of 100 ° C - 5.06-10.10 mm ² / s and the pour point of the product is minus 62 - minus 65 ° C, and a viscous base of low-curing Arctic oil having a kinematic viscosity at a temperature of 100 ° C is 10.11-15.12 mm ² / s and the pour point of the product is minus 62 - minus 65 ° C.