Way catalytic sweetening products of thermal processes

 

(57) Abstract:

Usage: oil refining industry. Essence: gasoline delayed coking unit, heated to a temperature of 350-400oC, enter in the different zones of the reactor catalytic cracking of vacuum gas oil in the amount of 1-10% vol. for raw materials, in contact with 50-100% of the volume of the catalyst, followed by separation of high-octane gasoline or blended with straight-run diesel fuel in an amount of from 1 to 20 vol.%, subjected to Hydrotreating in contact with a catalyst containing the oxides of molybdenum, Nickel, aluminium and credneformatny complex [SiO212WO3] number of 1.02-4,08 wt.%, with the subsequent isolation of a stable low-sulfur diesel fuel and refined gasoline fraction of the component materials of the catalytic reforming process and the gas delayed coking unit is blended with straight-run diesel fuel in an amount of from 1 to 30 vol.%, subjected to Hydrotreating in contact with a catalyst containing the oxides of molybdenum, Nickel, aluminium and credneformatny complex [SiO212WO3] the amount of 1.02-4,08 wt. %, followed by separation of stable malosernistogo cracking of vacuum gas oil in the amount of about 1-40% by for raw materials, contact with 70-100% vol. catalyst, followed by separation of high-octane gasoline. Technical result - producing high-octane gasoline and low-sulfur diesel fuel. 2 S. p. f-crystals, 2 tab.

The invention relates to a method of catalytic refining of the products of thermal processes and can be used in the oil industry.

The prior art is the following: there is a method of processing low-octane gasoline thermal origin by catalytic cracking pre-cooked mix it with the vacuum gas oil in the presence of hydrocarbon gas diluent (U.S. Pat. The Russian Federation for invention N 2086604. Kairbekov T. M., Takaiwa M. I., Hadjiev S. N. A method of processing low-octane gasoline. - Grozny petroleum research Institute. - Appl. 10.06.93; Publ. 10.08.97. - BI N 22. - MCI46 C 10 G 11/05).

The disadvantage of this method is the excessive length of the probe light reactive gasoline thermal origin with the cracking catalyst, which inevitably leads to its kikirowy to gaseous products and the reduction of the yield of high octane gasoline.

On, the publ. 03.05.96 year).

The disadvantage of this method is that in this way catalytic sweetening products installation coking is not used, the possibility of obtaining a high-octane gasoline and low-sulfur (sulfur content less than 0.05 wt.%) of diesel fuel.

The invention is directed to solving the problem of producing high-octane gasoline and low-sulfur diesel fuel products from the delayed Coker gasoline and gasoil.

The technical result allows us to solve the problem. This technical result is achieved by way catalytic sweetening products of thermal processes (options). The first option is that gasoline delayed coking unit, heated to a temperature of 350-400oC, enter in the different zones of the reaction section of the reactor catalytic cracking of vacuum gas oil in the amount of 1-10% vol. for raw materials, in contact with 50-100% of the volume of the catalyst, followed by separation of high-octane gasoline or blended with straight-run diesel fuel in an amount of from 1 to 20 vol.%, subjected to Hydrotreating in contact with the catalyst, coderay.%, with the subsequent isolation of a stable low-sulfur diesel fuel and refined gasoline fraction of the component materials of the catalytic reforming unit. The second option is that the refinery delayed coking unit is blended with straight-run diesel fuel in an amount of from 1 to 30 vol.%, subjected to Hydrotreating in contact with a catalyst containing the oxides of molybdenum, Nickel, aluminium and credneformatny complex [SiO212WO3] number of 1.02-4,08 wt.% with the subsequent isolation of a stable low-sulfur diesel fuel, or heated to a temperature of 350-450oC enter in different zones of the reaction section of the reactor catalytic cracking of vacuum gas oil in the amount of about 1-40% by for raw materials, in contact with 70-100% vol. catalyst, followed by separation of high-octane gasoline.

The ESSENTIAL features of the invention are methods of catalytic sweetening products of thermal processes by Hydrotreating in the presence of hydrogen-containing gas and a catalyst containing the oxides of molybdenum, Nickel and aluminum at elevated temperature and pressure and by catalytic cracking celithemis of the invention is that, that in the first embodiment with the aim of producing high-octane gasoline and low-sulfur diesel fuel gasoline delayed coking unit, heated to a temperature of 350-400oC, enter in the different zones of the reaction section of the reactor catalytic cracking of vacuum gas oil in the amount of 1-10% vol. for raw materials, in contact with 50-100% of the volume of the catalyst, followed by separation of high-octane gasoline or blended with straight-run diesel fuel in an amount of from 1 to 20 vol.%, subjected to Hydrotreating in contact with a catalyst containing the oxides of molybdenum, Nickel, aluminium and credneformatny complex [SiO212WO3] number of 1.02-4,08 wt.%, with the subsequent isolation of a stable low-sulfur diesel fuel and refined gasoline fraction of the component materials of the catalytic reforming unit, and the second option gasoil delayed coking unit is blended with straight-run diesel fuel in an amount of from 1 to 30 vol.%, subjected to Hydrotreating in contact with a catalyst containing the oxides of molybdenum, Nickel, aluminium and credneformatny complex [SiO212WO3] number of 1.02-4,08 wt.% followed by separation of the stable the bulk of the reactor catalytic cracking of vacuum gas oil in the amount of about 1-40% by for raw materials, contact with 70-100% vol. catalyst, followed by separation of high-octane gasoline.

The NOVELTY of the invention lies in the fact that in the presence of gasoline delayed coking unit, enriched reactive molecules, hydrodesulphurization unit straight-run diesel fuel on catalyst containing oxides of molybdenum, Nickel, aluminium and credneformatny complex [SiO212WO3] flows with greater depth, the presence of this complex, which increases hydrogenating activity alumnirelations catalyst, reduces negative cokayne effects of unsaturated hydrocarbons contained in the composition of gasoline coking, Giriraja them. In these conditions, the degree of desulfurization of diesel fuel and gasoline coking reaches 95-96% of obtaining high-quality low-sulfur diesel fuel and a full-fledged component of the raw material of the catalytic reforming unit.

The introduction of gasoline and light gas oil of a delayed coking unit in different zones of the reaction section of the reactor of a catalytic cracking unit, bypassing the stage it is heated in a tubular furnace in a mixture of vacuum gas oil, prevents tyelnol furnace, as well as allowing contact of gasoline coking with 50-100% of the volume of catalyst, and light gas oil coking with 70-100% of the volume of the catalyst, thereby reducing the contact time of gasoline and light gas oil delayed coking unit with a catalyst that reduces the degree of kikirevenge them to gaseous products and allows you to increase the selection of high-octane gasoline.

To test the effectiveness of the proposed method catalytic sweetening of gasoline and light gas oil delayed coking unit conducted experiments on the Hydrotreating of various mixtures and catalytic cracking of vacuum gas oil with the addition of in different parts of the reaction zone of gasoline and light gas oil coking, the results of which are presented with examples and tables 1 and 2.

For comparison, experiments Hydrotreating straight-run diesel fuel at a basic catalyst ST-70 and catalytic cracking of vacuum gas oil on the catalyst ZOCOR-10. Conditions and results of experiments are presented in the same tables 1 and 2.

The invention is illustrated by the following examples:

EXAMPLE 1. 49,5 ml vacuum gas oil, heated to a temperature of 475oC, enters the upper cha is ZOCOR-10, loaded in the amount of 100 cm3and goes all the catalyst bed from the top down within 30 minutes at the same time 0.5 ml of gasoline delayed coking unit, heated to 350oC, the dosing unit is in the upper part of the reactor and passes 100% of the volume of the catalyst (100 cm3top down in the mixture coming from the top of the reactor and vacuum gasoil. The temperature in the reaction zone 475oC. the gaseous products is fixed in a gas-meter, and the liquid products collected in the receiver, where it is condensed with the subsequent separation of the gasoline fraction, light and heavy gas oils. At the end of the experience is determined by the content of the coke on the catalyst chromatographic method.

As a result of cracking receive in wt.%: gas - 19,0; gasoline - 29,0; light gasoil - 42,8; heavy gasoil - 4,3; Cox - 4,9. The quality of the gasoline was estimated by the content of aromatic hydrocarbons, which for this example is 30.7 wt.%

The influence of quantity and temperature of the added gasoline delayed coking unit at the output of gasoline are presented in table. 1.

Feedstock straight-run diesel fuel, wikipaedia within 180-360oC and containing about 0.90 wt.% serpia and 1% vol. light gas oil coking. Mixed raw material was subjected to Hydrotreating in the laboratory running the installation under hydrogen pressure on aluminumaluminium catalyst, optionally containing 1,02 wt.% kremnipolymer complex [SiO212WO3] , under the following conditions: a temperature of 390oC; pressure of 3.5 MPa; the volumetric feed rate of 2.5 h-1the ratio of hydrogen to the raw material 450:1 nl/L. In the Hydrotreating process of the obtained diesel fuel containing 0,042 wt.% sulfur (table.2).

EXAMPLE 2. and 47.5 ml vacuum gas oil, heated to a temperature of 475oC, enters the upper part of the reactor laboratory flow-through catalytic cracking unit with a stationary catalyst bed of ZOCOR-10 loaded in the number of 100 cm3and goes all the catalyst bed from the top down within 30 minutes at the same time 2.5 ml of gasoline delayed coking unit, heated to 375oC, the dosing unit is in the middle part of the reactor and passes 75% of the volume of the catalyst (75 cm3top down in the mixture coming from the top of the reactor and vacuum gasoil.

The temperature in the reaction zone 475oC.

Selection and evaluation of the quality of the products is carried out analogously to example 1.

The content of aromatic hydrocarbons in gasoline to 31.2 wt.% (PL. 1).

Feedstock straight-run diesel fuel, wikipaedia within 180-360oC and containing about 0.90 wt.% sulphur, mixed with a light oil delayed coking unit in the following ratio: 85% diesel fuel and 15 vol.% light gas oil coking. Mixed raw material was subjected to Hydrotreating in the laboratory running the installation under hydrogen pressure on aluminumaluminium catalyst, optionally containing 2.55 wt.% kremnipolymer complex [SiO212WO3]. Conditions for the Hydrotreating process analogous to example 1.

In the Hydrotreating process of the obtained diesel fuel containing 0.047 wt.% sulfur (table.2).

EXAMPLE 3. 45,0 ml vacuum gas oil, heated to a temperature of 475oC, enters the upper part of the reactor laboratory flow-through catalytic cracking unit with a stationary catalyst bed of ZOCOR-10 loaded in the number of 100 cm3and goes all the catalyst bed from the top down within 30 minutes Simultaneously 5.0 ml of gasoline delayed coking unit, heated to a temperature of 400oC, the dosing unit is in the middle of CRA vacuum gasoil.

The temperature in the reaction zone 475oC.

Selection and evaluation of the quality of the products is carried out analogously to example 1.

As a result of get cracking, wt.%: gas - 18,1; gasoline - 32,9; light gasoil - 40,5; heavy gasoil - 5,0; Cox - 3,5.

The content of aromatic hydrocarbons in gasoline is 31.3 wt.% (PL. 1).

Feedstock straight-run diesel fuel, wikipaedia within 180-360oC and containing about 0.90 wt.% sulphur, mixed with a light oil delayed coking unit in the following ratio: 70% vol. diesel fuel and 30% vol. light gas oil coking. Mixed raw material was subjected to Hydrotreating in the laboratory running the installation under hydrogen pressure on aluminumaluminium catalyst, optionally containing 4,08 wt.% kremnipolymer complex [SiO212WO3]. Conditions for the Hydrotreating process analogous to example 1.

In the Hydrotreating process of the obtained diesel fuel containing 0,050 wt.% sulfur (table.2).

EXAMPLE 4. 49,5 ml vacuum gas oil, heated to a temperature of 475oC, enters the upper part of the reactor laboratory flow-through catalytic cracking unit with the number of main telephone is a top down within 30 minutes At the same time 0.5 ml of light gas oil of a delayed coking unit, heated to a temperature of 350oC, the dosing unit is in the upper part of the reactor and passes 100% of the volume of the catalyst (100 cm3top down in the mixture coming from the top of the reactor and vacuum gasoil.

The temperature in the reaction zone 475oC.

Selection and evaluation of the quality of the products is carried out analogously to example 1.

As a result of cracking receive in wt.%: gas - 19,0; gasoline - 27,2; light gasoil - 41,0; heavy gasoil - 8,3; Cox - 4,5.

The content of aromatic hydrocarbons in gasoline - 31,0 wt.% (PL. 1).

Feedstock straight-run diesel fuel, wikipaedia within 180-360oC and containing about 0.90 wt.% sulphur, mixed with gasoline delayed coking unit in the following ratio: 99% diesel fuel and about 1. % gasoline coking. Mixed raw material was subjected to Hydrotreating analogously to example 3 at a temperature of 360oC.

In the Hydrotreating process of the obtained diesel fuel containing 0,039 wt.% sulfur and gasoline containing 0,029 wt.% sulfur (table.2).

EXAMPLE 5. 40,0 ml vacuum gas oil, heated to a temperature of 475oC, does utilizator ZOCOR-10, loaded in the amount of 100 cm3and goes all the catalyst bed from the top down within 30 minutes at the same time 10.0 ml light gas oil of a delayed coking unit, heated to a temperature of 400oC, the dosing unit is in the middle part of the reactor and passes 85% of the volume of the catalyst (85 cm3top down in the mixture coming from the top of the reactor and vacuum gasoil.

The temperature in the reaction zone 475oC.

Selection and evaluation of the quality of the products is carried out analogously to example 1.

As a result of cracking receive in wt. %: gas - 18,5; gasoline and 26.9; light gasoil - 43,3; heavy gasoil - 7,2; Cox - 4,1.

The content of aromatic hydrocarbons in gasoline is of 33.0 wt.% (PL. 1).

Feedstock straight-run diesel fuel, wikipaedia within 180-360oC and containing about 0.90 wt.% sulphur, mixed with gasoline delayed coking unit at the following ratio: 90% diesel fuel and 10% vol. gasoline coking. Mixed raw material was subjected to Hydrotreating analogously to example 2 at a temperature of 360oC.

In the Hydrotreating process of the obtained diesel fuel containing 0,038 wt.% sulfur and gasoline containing 0,027 wt.% sulfur (table.2).

3and goes all the catalyst bed from the top down within 30 minutes at the same time 20,0 ml light gasoil delayed coking unit, heated to a temperature of 450oC, the dosing unit is in the middle part of the reactor and passes 75% of the volume of the catalyst (75 cm3top down in the mixture coming from the top of the reactor and vacuum gasoil.

The temperature in the reaction zone 475oC.

Selection and evaluation of the quality of the products is carried out analogously to example 1.

As a result of cracking receive in wt. %: gas - 19,8; gasoline - 27,0; light gasoil - 43,0; heavy gasoil - 6,0; Cox - 4,2.

The content of aromatic hydrocarbons in gasoline to 33.8 wt.% (PL. 1).

Feedstock straight-run diesel fuel, wikipaedia within 180-360oC and containing about 0.90 wt.% sulphur, mixed with gasoline delayed coking unit in the following ratio: 80% vol. diesel fuel and about 20. % gasoline coking. Mixed raw material was subjected to Hydrotreating analogously to example 1 at a temperature of 360oC.

In the Hydrotreating process of the obtained diesel fuel containing 0,037 wt.% sulfur and gasoline containing 0,026 wt.% seronegative products of the delayed coking unit - gasoline and light gas oil helps to increase the depth of oil processing with the increase in the production of high-quality low-sulfur diesel fuel and high-octane gasoline.

1. Way catalytic sweetening products of thermal processes, characterized in that the gasoline delayed coking unit, heated to a temperature of 350 - 400oC, enter in the different zones of the reaction section of the reactor catalytic cracking of vacuum gas oil in the amount of 1 - 10. % for raw materials, in contact with 50 - 100% of the volume of the catalyst, followed by separation of high-octane gasoline or blended with straight-run diesel fuel in an amount of from 1 to 20 vol.%, subjected to Hydrotreating in contact with a catalyst containing the oxides of molybdenum, Nickel, aluminium and credneformatny complex [SiO212WO3] number of 1.02 - 4,08 wt.%, with the subsequent isolation of a stable low-sulfur diesel fuel and refined gasoline fraction of the component materials of the catalytic reforming unit.

2. Way catalytic sweetening products of thermal processes, characterized in that the light gasoil delayed coking unit to shift the AI with a catalyst, containing oxides of molybdenum, Nickel, aluminium and credneformatny complex [SiO212WO3] number of 1.02 - 4,08 wt.%, with the subsequent isolation of a stable low-sulfur diesel fuel, or heated to a temperature of 350 - 450oC, enter in the different zones of the reaction section of the reactor catalytic cracking of vacuum gas oil in the amount of 1 - 40 vol.% for raw materials, in contact with 70 - 100% vol. catalyst, followed by separation of high-octane gasoline.

 

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FIELD: oil-refining industry; oil-processing devices.

SUBSTANCE: the invention is pertaining to the field of the oil-refining industry, in particular, to the reactors of gas-liquid mixture. The reactor includes the body (1), the grate (2) with the located on it beads (3) and the catalytic agent (4), inlet fitting pipe (5) and outlet fitting pipe (6). Inside of the body (1) there is the mounted cone (7) with the arranged above it and forming a slit (9) with it conical ring (8). Below the slit (9) there is the mounted ring (10) with the curvilinear surface in the diametrical section, in the lower part of which there are holes (11) and the fitting pipes (12) with the impurities collectors (13). Above the ring (10) there is the ring deflector (14). The invention prevents formation on the catalytic agent surface of the surface layer of the impurities.

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FIELD: chemistry; technological processes.

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40 cl, 2 tbl, 19 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises two-step impregnation of preliminarily calcined carrier with first ammonium heptamolybdate solution and then, after intermediate heat treatment at 100-200°C, with cobalt and/or nickel nitrate solution followed by final heat treatment including drying at 100-200°C and calcination at 400-650°C. Catalyst contains 3.0-25.0% MoO3, 1.0-8.0% CoO and/or NiO on carrier: alumina, silica, or titanium oxide.

EFFECT: enhanced hydrodesulfurization and hydrogenation activities allowing involvement of feedstock with high contents of sulfur and unsaturated hydrocarbons, in particular in production of environmentally acceptable motor fuels.

3 cl, 4 tbl, 13 ex

FIELD: petroleum refining industry.

SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to the methods of production of an ecologically pure diesel fuel. Substance: carry out hydraulic purification of a mixture of a virgin diesel fraction and distillate of carbonization and a catalytic cracking. The layers of the catalysts are located in the following way. The first on a course of traffic of a gas-raw material stream protective layer of wide-porous low-percentageNi-Co-Mo/Al2O3 catalyst is made in the form of the hollow cylinders. The second layer - the catalyst with a diameter of granules of 4.5-5.0 mm. The third - the basic catalyst made in the form of granules with a diameter of 2.0-2.8 mm. The basic catalyst has a surface of 250-290 m2 /g, a pore volume - 0.45-0.6 cm3 / g, in which - no less than 80 % of poremetric volume is formed by the through internal pores predominary of a cylindrical shape with a diameter of 4.0-14.0 nanometers. The last layer on a course of raw material traffic layer is organized analogously to the second layer. Loading of 2-4 layers is performed by a method of a tight packing. The technical result - production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm from the mixture of the virgin run fraction and distillates of a carbonization and a catalytic cracking containing up to 1.3 % mass of sulfur, at a low hardness of the process and a long time interrecovery cycle.

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7 cl, 2 tbl, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.

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4 tbl, 3 ex

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