Method of activating catalytic system of hydrocarbon feedstock hydrofining

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.

EFFECT: enabled prevention and/or suppression of overheating in catalyst bed.

5 cl, 6 tbl, 12 ex

 

The invention relates to the refining, in particular to methods of activation and operation of the hydrofining catalysts of hydrocarbons.

Growth in motor fuel consumption by reducing demand for residual oil requires increasing the depth of oil refining [the state of the Russian and world markets of oil, oil products, petrochemicals and chemicals. Moscow, Tsniiteneftehim, Express information, 2002, No. 3, p.6-9]. At the same time stricter requirements to operational and environmental performance of fuels.

The tightening of requirements for residual sulfur content in the petroleum products on the basis of the domestic sulfur crudes imposes new requirements on processes hydrofining bright and residual oil fractions, associated primarily with increased activity of the catalysts in the hydrogenolysis reactions of organic sulfur compounds and hydrogenation of polycyclic aromatic hydrocarbons under the same process parameters.

Maximizing the potential of catalysts and catalytic systems is only possible when optimizing all stages of their operation, including preparation for use.

In the hydrogenation refining processes use catalysts, the production of which the media caused one or the more catalytically active metals in the form of oxide (molybdenum, Nickel, cobalt, tungsten).

Actually hydrogenolysis reactions of organic sulfur compounds, hydrogenation of unsaturated and aromatic hydrocarbons occur on the catalysts containing active metals as sulphides. Thus, prior to the processing of raw materials spend the activation of the catalysts by sulfatirovnie.

As a sulfiding agent use hydrogen sulfide [U.S. Patent No. 3239451], elemental sulfur [RF Patent №2005765], high-sulfur distillate oil and gas condensate fraction [USSR Author's certificate No. 1469639], liquid, easily decomposing organic sulfur compounds [U.S. Pat. RF 2140963] or the catalyst in presulfiding form [U.S. Pat. Of the Russian Federation No. 2229934].

All of the above methods are carried out at elevated temperature and pressure.

For example, sulfatirovnie Hydrotreating catalysts gaseous hydrogen sulfide [U.S. Patent No. 3239451] is carried out at a temperature of 200-250aboutWith the pressure of 10-150 MPa, the hydrogen sulfide concentration in the circulating gas 5-100%. The disadvantage of this method is the danger of overheating of the catalyst exothermic reactions sulfatirovnie and the lack of opportunity for prevention and/or suppression, highly corrosive gaseous hydrogen sulfide, the difficulty of obtaining and storing large quantities conc is one of gaseous hydrogen sulfide.

The implementation of how sulfatirovnie catalysts for Hydrotreating petroleum fractions using as the sulfiding agent is elemental sulfur [RF Patent №2005765] also accompanied by a significant ecoeffect. In addition, the catalyst loading in the mixture with elemental sulfur leads to the reduction of the volume of the loaded catalyst and the irregularity of his boot.

Use as a sulfiding agent of oil and gas condensate fractions [USSR Author's certificate No. 1469639] does not provide a catalytic system activity, sufficient to obtain products that meet international standards.

Use as a sulfiding agent liquid easily decomposing cerorhinca compounds allows to obtain a catalytic system with high activity during hydrofining petroleum fractions [U.S. Pat. RF 2140963]. But all these substances belong to the class of highly toxic and corrosive compounds. Therefore, the process of sulfatirovnie their use is possible only in the presence of technological Playground equipment for the filing of these compounds in the reactor process unit, which significantly limits their use.

Closest to the proposed to the technical nature and to thememo effect is the method for the catalytic system hydrofining of hydrocarbon raw materials [U.S. Pat. Of the Russian Federation No. 2229934], according to which as the sulfiding agent is used catalyst in presulfiding form. The method consists in circulating the hydrogen-containing gas through layers loaded presulfiding and oxide catalysts at specific values of temperature and pressure.

When implementing this method are observed unregulated overheating in the catalyst layer, which affects the results of the catalytic system.

The aim of the invention is to develop a method of activation of the catalytic system, which enables to prevent and/or suppress overheating in the catalyst bed.

This goal is achieved by the application of the method of activation of the catalytic system hydrofining of hydrocarbon material by circulating the hydrogen-containing gas or a mixture of hydrogen-containing gas with the starting raw material through layers loaded catalysts in presulfiding or presulfiding and oxide forms at elevated temperature and pressure, characterized in that the hydrogen in the circulating hydrogen gas or a mixture of hydrogen-containing gas with the starting raw material is introduced in portions consumption of starting materials and process temperature change speed; the ratio of circulation In Which G is 200-600 nm 3/m3catalyst, the initial hydrogen concentration in the circulating hydrogen-containing gas is 30-50 vol.%, the introduction of each portion of the hydrogen is carried out after reducing the hydrogen concentration in the circulating hydrogen-containing gas to the level 2-10 vol.%, the circulation of the hydrogen-containing gas through the layers loaded in the reactor catalysts begin when the temperature of the environment then stepped up to 80-120aboutWith speeds of 10-30aboutS/h, from 80-120aboutWith 150-200aboutWith from 5 to 10aboutS/h, from 150-200aboutTo 300-340aboutWith speeds of 10-20aboutC/h, the flow of the starting raw materials, represents a straight-run gasoline or sredneetazhnye faction, the catalytic system is carried out at a temperature of 80-120aboutWith consumption amounting to not more than 40% of the work until after a complete wetting of the catalytic system with a subsequent increase of the consumption of raw materials to the set speeds of 15-20% of the work in an hour.

A distinctive feature of the proposed technical solution is that the hydrogen in the circulating hydrogen gas or a mixture of hydrogen-containing gas with the starting raw material is introduced in portions consumption of starting materials and process temperature change speed; the ratio of circulating SIV is 200-600 nm3/m3the catalyst is, the initial hydrogen concentration in the circulating hydrogen-containing gas is 30-50 vol.%, the introduction of each portion of the hydrogen is carried out after reducing the hydrogen concentration in the circulating hydrogen-containing gas to the level 2-10 vol.%, the circulation of the hydrogen-containing gas through the layers loaded in the reactor catalysts begin when the temperature of the environment then stepped up to 80-120aboutWith speeds of 10-30aboutS/h, from 80-120aboutWith 150-200aboutWith from 5 to 10aboutS/h, from 150-200aboutTo 300-340aboutWith speeds of 10-20aboutC/h, the flow of the starting raw material, which consists of straight-run gasoline or sredneetazhnye faction, the catalytic system is carried out at a temperature of 80-120aboutWith consumption amounting to not more than 40% of working up to full wetting of the catalytic system with a subsequent increase of the consumption of raw materials to the set speeds of 15-20% of the work in an hour.

The described method is as follows.

Charged to the reactor catalysts in presulfiding form or in presulfiding and oxide form.

The obtained catalytic system is heated to a temperature of 80-120aboutWhen the circulation of the hydrogen-containing gas (hereinafter SIVs) 200-600 nm3/m3of the catalyst. The concentration of hydrogen in the circulating SIV stood the focus of 30-50 vol.%. Temperature rise carried out with a speed of 10-30aboutS/h At the same temperature are drying the catalytic system (if the composition of the catalyst system includes a catalyst in the oxide form). With this purpose, the catalytic system is maintained at the specified temperature until the termination of moisture.

If the activation process is done only in the current circulating the hydrogen-containing gas, then spend a temperature rise from 80-120aboutWith 150-200aboutWith from 5 to 10aboutC/h, then from 150-200aboutTo 300-340aboutWith speeds of 10-20aboutS/h

If the activation process is carried out in the current mix everything and starting materials, at a temperature of 80-120aboutTo begin feeding on the catalytic system of the starting raw material consumption does not exceed 40% of the work. As starting raw materials use of straight-run gasoline or sredneetazhnye faction. Increased consumption of starting material (speeds of 15-20% of worker hour) and a further rise of the temperature (in accordance with the above scheme) is carried out after complete wetting loaded in the reactor catalyst, which is determined by the appearance of the product in the separator.

During the rise of temperature or the simultaneous increase of the consumption of the starting raw materials and temperature are constantly monitoring the concentration of hydrogen in everything. If the concentration is odorata in everything will fall to 2-10 vol.% in the system impose additional portion of hydrogen to achieve a concentration of the latter in everything 30-50%vol.

After reaching the temperature of the catalyst layers 340aboutTo make the shutter speed for 2 hours, then transferred to the operation mode.

Compliance specified in the formula of the present invention, parameters allows to use printed on presulfiding catalyst username agent and to achieve a high activity catalyst system. Violation processing mode catalysts leads to a partial loss of usernamea agent, the destruction of the catalyst and, consequently, to reduced activity of the catalytic system.

Batch adding of hydrogen in the circulating SIV allows you to maintain its concentration at a given level and to regulate the amount of heat generated during the activation process.

Manual feeding of raw materials at a temperature of 80-120aboutWith on the catalytic system during its activation leads to additional rent generated by sulfatirovaniu heat that allows you to adjust the temperature of the layers of the catalyst even when the activation of the catalytic systems of significant amounts (more than 60 m3).

In the known methods the activation of the catalytic system using the described technologies is unknown.

Thus, this solution meets the criteria of "novelty" and "significant difference".

Neither the e specific examples of implementation of the proposed method.

Examples.

When implementing the present invention used catalyst samples, the characteristics of which are summarized in table 1.

As starting raw materials used straight-run gasoline and sredneetazhnye faction, whose characteristics are given in table 2.

The composition of the catalytic systems according to examples 1-12 are shown in table 3.

Technological parameters of the proposed method the activation of the catalytic systems according to examples 1-12 are shown in table 4. This table shows the maximum temperature layers of the catalysts by the aforementioned examples.

To obtain a catalytic system that is highly active, the temperature drop across the layers of the catalyst during activation should be 20-40aboutC. If the temperature difference across the layers of the catalysts during catalytic activation of the system will be below the 20aboutWith, this means that the reaction conversion included in the catalyst composition of the oxides of the active metals in the sulfide has not been completely. The activity of this catalytic system is low. The excess of the temperature drop across the layers of the catalyst during the activation of the catalytic system 40aboutWith may lead to violation of the integrity of the granules of the catalyst. This is also a negative scared the results of the catalytic system.

The catalytic system activity resulting from activation by the proposed method was evaluated by the residual sulfur in the product obtained in the process of hydrofining gasoline, middle distillate fractions and vacuum gasoil. The characteristics of these fractions are given in table 5. Technological parameters of operation of the catalytic systems according to examples 1-12 and data on the content of residual sulfur in the resulting products are shown in table 6.

Detailed description of actions to implement the proposed technical solution is given below in the examples.

Moo3
Table 1

Characteristics of the samples of catalysts used in the implementation of the present invention
IndicatorsCatalysts
RK-231RK-231SRK-442RK-442SRK-242
Presulfiding or oxide form of the catalystoxidepResult.oxidepResult.oxide-Naya
The content of active components:
13,512,8a 12.712.2to 12.0
Soo4,84,5---
NiO--4,64,14,0
Sulfur content, % mass011,8012,10
Table 2

Characteristics of samples of starting materials used when implementing the present invention
The name of the parameterRaw material No. 1PRaw material No. 2S
The type of raw materialsStraight-run gasoline fractionStraight-run diesel fraction
Density, kg/m3754820
Fractional composition,aboutFrom:
start boiling 75181
end of boil178340
The content of total sulfur, % mass.0,51,4

Table 3

The composition of the catalytic systems used in the implementation of the present invention
Example No.The content in the composition of the catalytic system, % mass
RK-242RK-231SRK-231RK-442SRK-442
Example 1-100---
Example 2-5050--
Example 3-100---
Example 4---5050
Example 5---100-
Example 61070--20
When is EP 7 -100---
Example 8-100---
Example 9-100---
Example 10-100---
Example 11-100---
Example 12 (prototype)-100---

Table 4

Technological parameters of the proposed method the activation of the catalytic system.
Catalytic

the system obtained in example No.
The ratio of circulating SIV, nm3/m3catalystThe initial

concentration of hydrogen in CSG, %vol.
The concentration of bodoro

Yes, which introduced a new portion of the hydrogen, %vol.
Starting

raw, No.
Initial RAS

move the starting raw materials, nm3per hour (% of working)
Increased RAS
the progress of the starting raw materials, nm3per hour (% of worker hour)
The speed of temperature rise,aboutMaximum

the temperature drop across the layers of catalysts,about
From temperature-ambient to 80-120aboutFrom 80-120aboutWith 150-200aboutFrom 150-200aboutTo 300-340about
1234567891011
Example 1200302UTS.--1051030
Example 2600302UTS.--30102040
Example 33005010No. 1P30 (33)15 (16)30102025
Example 43005010No. 2S80 (40)75 (20)30102025
Example 5 300302OTC--30102035
Example 63005010No. 2S48 (40)24 (20)30102025

Continuation of table 4
1234567891011
Example 7150201UTS.--53515
Example 87006020UTS.--40152580
Example 9600302No. 2S100 (50)40 (20)30102020
Example 10300302No. 2S80 (40)20 (10)3 102060
Example 11300302No. 2S80 (40)60 (30)30102020
Example 12 (prototype)Not regulated70noUTS.UTS.UTS.Not regulated10Not regulated150

Example 1.

Charged to the reactor the catalyst RK-231S (presulfiding form) and heated in a current of CSG with a hydrogen content of 30 vol.% to a temperature of 100-120aboutWith a speed of 10aboutC/h Ratio of circulating SIV is 200 nm3/m3of the catalyst. Because presulfiding the catalyst does not contain moisture, the stage of drying is eliminated. When the temperature of the catalyst 100-120aboutWith the continued rise of temperature up to 150-200aboutWith a speed of 5aboutS/h At the temperature of the catalyst 150-200aboutWith continued temperature rise to 300-340aboutWith a speed of 10aboutS/h At the time of temperature rise are constantly monitoring the concentration of hydrogen in CSG. When the concentration of hydrogen in CSG reduced to 2% vol. in the system enter the stage is niteline portion of the hydrogen to achieve the concentration of the latter in CSG 30% vol.

The maximum temperature difference over the layer of catalyst during the activation process in this example was 30aboutC.

After reaching the temperature of the catalyst layers 340aboutTo make exposure for 2 hours, then transferred to the operation mode.

In the hydrofining on the resulting catalytic system, the diesel fraction with a high content of sulfur (1.8 wt.%) the obtained product with residual sulfur or 0.035 wt.%, that is consistent with the current international standards for diesel fuel.

Example 2.

Charged to the reactor catalysts in presulfiding RK-231S and oxide RK-231 form.

The obtained catalytic system is heated in a current CSG with a hydrogen content of 30 vol.% to a temperature of 100-120aboutWith speed 30aboutC/h Ratio of circulation SIVs 600 nm3/m3of the catalyst. At the same temperature are drying catalyst system (catalyst system includes a catalyst in the oxide form). With this purpose, the catalytic system is maintained at the specified temperature until the termination of moisture. After the termination of moisture continued rise of temperature from 100 to 120aboutWith 150-200aboutWith a speed of 10aboutC/h, then from 150-200aboutTo 300-340aboutWith speeds of 20aboutS/h in EMA of temperature rise constantly monitoring the hydrogen concentration in CSG. When the concentration of hydrogen in CSG is reduced to 10% vol. in the system impose additional portion of hydrogen to achieve a concentration of the latter in CSG 30 vol.%

The maximum temperature difference over the layer of catalyst during the activation process was 40aboutC.

After reaching the temperature of the catalyst layers 340aboutTo make exposure for 2 hours, then transferred to the operation mode.

In the hydrofining on the resulting catalytic system, the diesel fraction with a sulfur content of 1.8 wt.% the obtained product with residual sulfur 0.005 wt.%

Example 3.

Charged to the reactor the catalyst RK-231S (presulfiding form) and heated in a current of CSG with a hydrogen concentration of 50 vol.% to a temperature of 80-100aboutWith speed 30aboutC/h Ratio of circulating SIV is 300 nm3/m3of the catalyst. Because presulfiding the catalyst does not contain moisture, the stage of drying is eliminated. When the temperature of the catalyst 80-100aboutTo begin feeding on the catalytic system of the starting raw material No. 1P a flow rate of 30 m3/h, which is 33% of the work. After complete wetting of the catalyst (the appearance of the raw material in the separator) begin to increase the consumption of raw materials with a speed of 15 m3/h (16% of working) and the recovery rate is the temperature is elevated up to 150-200 aboutWith a speed of 10aboutS/h At the temperature of the catalyst 150-200aboutWith continued temperature rise to 300-340aboutWith speeds of 20aboutS/h At the time of temperature rise constantly monitoring the hydrogen concentration in CSG. When the concentration of hydrogen in CSG is reduced to 10%. in the system impose additional portion of hydrogen to achieve a concentration of the latter in CSG 50%vol.

The maximum temperature difference over the layer of catalyst during the activation process was 25aboutC.

After reaching the temperature of the catalyst layers 340aboutTo make exposure for 2 hours, then transferred to the operation mode.

In the hydrofining on the resulting catalytic system gasoline fraction with a sulfur content of 0.05 wt.% the obtained product with residual sulfur 0,00002 wt.%

Example 4.

Charged to the reactor catalysts in presulfiding, RK-442S, and oxide, RC-442 forms.

The obtained catalytic system is heated in a current CSG with a hydrogen concentration of 50 vol.% to a temperature of 100-110aboutWith speed 30aboutC/h Ratio of circulating SIV is nm3/m3of the catalyst. At the same temperature are drying catalyst system (catalyst system includes a catalyst in OK the red form). With this purpose, the catalytic system is maintained at the specified temperature until the termination of moisture. After the termination of moisture begin to flow in the catalytic system of the starting raw material No. 2S consumption 80 m3/h (40% of the work). After complete wetting of the catalyst (the appearance of the raw material in the separator) begin to increase the consumption of raw materials with a speed of 40 m3/h (20% of the work) and the rise of temperature up to 150-200aboutWith a speed of 10aboutS/h At the temperature of the catalyst 150-200aboutWith continued temperature rise to 300-340aboutWith speeds of 20aboutS/h At the time of temperature rise constantly monitoring the hydrogen concentration in CSG. When the concentration of hydrogen in CSG is reduced to 10% vol. in the system impose additional portion of hydrogen to achieve a concentration of the latter in CSG 50%vol.

The maximum temperature difference over the layer of catalyst during the activation process was 25aboutC.

After reaching the temperature of the catalyst layers 340aboutTo make exposure for 2 hours, then transferred to the operation mode.

In the hydrofining on the resulting catalytic system vacuum gas oil with a sulfur content of 2.7 wt.% the obtained product with residual sulfur to 0.15 wt.%

Consistently the th operations during the implementation of the proposed technical solutions for examples 5-12 is carried out by analogy with examples 1-4.

Table 5

Characterization of samples of raw materials used in the testing of the proposed technical solutions
IndicatorsRaw material No. 3Raw material No. 4Raw material No. 5
Raw materialGasoline fractionDiesel fractionVacuum gasoil
Fractional composition,aboutFrom:
- start of boil70175350
- end of boil180360550
The content of total sulfur, % mass0,051,82,7

You can see that the activation of the catalytic system in accordance with the formula of the present invention, the temperature drop across the layers of the catalysts does not exceed 40about(Examples 1-6). The catalytic system obtained in accordance with these examples, provides the gasoline fraction with a content of residual sulfur is not more than 0,00002 wt.% (example 3), diesel fraction with a sulphur content of residual or 0.035 wt.% (examples 1, 6) and 0.005 (example 2), which corresponds to the world standards. When hydroalcoholic the research Institute of vacuum gas oil to catalytic system, obtained according to examples 4 and 5, the result is a product with residual sulfur is not more than 0, 15 wt.%, that meets the requirements of raw material for catalytic cracking.

The implementation of the method of activation of the catalytic system with exorbitant values circulating SIV (examples 7 and 8) leads to the production of catalytic systems with low activity.

The decrease of the concentration of hydrogen in CVSG used when activating the catalytic system, compared with the targets set forth in the formula of the present invention does not cause excessive heating of the catalyst (example 7), but the catalytic activity of the resulting catalytic system does not allow to obtain a product corresponding to the applicable international standards (for different contents of residual sulfur in diesel fuel must not exceed 0,0005 -0,035% of the mass). The increase in the concentration of hydrogen in CSG (example 8) leads to unregulated heating of the layers of catalysts, which affects the activity of the resulting catalytic system.

Beyond consumption of the starting materials indicated in the formula of the invention also leads to negative results. For example, if the initial consumption of raw materials more than 40% of the work (example 9), ecoeffect exceeding 40aboutNot observed, but Akti the activity of the obtained catalyst system does not allow the processing of high-sulphur raw materials to obtain low-sulfur products. Similar results are obtained with a more rapid increase in the feed rate of the starting raw material than is provided in the formula of the invention (example 11). Reducing consumption of starting materials on the formula of the invention (example 10) does not allow to suppress overheating the catalyst that leads to the production of catalytic systems with relatively low activity.

The activation of the catalytic system in accordance with the formula prototype (example 12) is also not possible to prevent overheating by the layers of catalysts and reduced activity of the catalytic system.

320
Table 6

The results of the catalytic systems obtained by activation in accordance with the proposed technical solution
CatalyticRaw material No.Technological parameters of operationContent
the system obtained in example No.(see tab. 5)TemperatureaboutPressure, MPaAbout. SC. feed, h-1The ratio of everything:raw materials, nm3/m3residual sulfur in product, wt%
Example 1No. 4353,03500,035
Example 2No. 4340353,03500,005
Example 3No. 3300305,03000,00002
Example 4No. 5340401,24000,15
Example 5No. 5340401,24000,14
Example 6No. 4320353,03500,035
Example 7No. 4320353,03500,15
Example 8No. 4320353,03500,13
Example 9No. 4320353,03500,21
Example 10No. 4320353,03500,20
Example 11No. 4320353,03500,17
Example 12 (FR.)No. 4320353,03500,10

1. The activation of the catalytic system hydrofining of hydrocarbon material by circulating the hydrogen-containing gas or a mixture of hydrogen-containing gas with the starting raw material through layers loaded catalysts in presulfiding or presulfiding and oxide form at elevated temperature and pressure, characterized in that the hydrogen in the circulating hydrogen gas or a mixture of hydrogen-containing gas with the starting raw material is introduced in portions, while the initial concentration of hydrogen in the circulating hydrogen-containing gas is not more than 50 vol.%, consumption of the starting raw material is carried out stepwise with consumption amounting to not more than 40% of working up to full wetting of the catalytic system with a subsequent increase of the consumption of raw materials to the set speeds of 15-20% of the work in an hour and the process temperature change speed from ambient temperature to 300-340°C.

2. The method according to claim 1, characterized in that the ratio of the circulation of the hydrogen-containing gas is 200-600 nm3/m3catalyst, the initial hydrogen concentration in the circulating hydrogen-containing gas is 30-50%vol.

3. The method according to claim 1 characterized in, the introduction of each portion of the hydrogen is carried out after reducing the hydrogen concentration in the circulating hydrogen-containing gas to the level 2-10 vol.%.

4. The method according to claim 1, characterized in that the circulation of the hydrogen-containing gas through the layers loaded in the reactor catalysts begin when the temperature of the environment then stepped up to 80-120°With speeds of 10-30°C/h, from 80-120°150-200°With speeds of 5-10°C/h, from 150-200°to 300-340°With speeds of 10-20°S/h

5. The method according to claim 1, characterized in that the feed of the starting raw material, which consists of straight-run gasoline or sredneetazhnye faction, the catalytic system starts at a temperature of 80-120°C.



 

Same patents:

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system is prepared by consecutively charging into reactor alumino-cobalt and alumino-nickel-molybdenum catalysts containing 12.0-25.0% molybdenum oxide, 3,0-6.0% nickel oxide, and 3.0-6.9% cobalt oxide provided that alumino-cobalt and alumino-nickel-molybdenum catalysts are charged at ratio between 1.0:0.1 and 0.1:1.0, preparation of catalysts employs mixture of aluminum hydroxide and/or oxide powders, to which acids are added to pH 1-5. More specifically, aluminum hydroxide powder mixture utilized is a product of thermochemical activation of gibbsite and pseudoboehmite AlOOH and content of pseudoboehmite in mixture is at least 70%, and aluminum oxide powder mixture utilized comprises powders of γ-Al2O3 with particle size up to 50 μm and up to 50-200 μm taken at ratio from 5:1 to 2:5, or γ-Al2O3 powders with particle size up to 50 μm, 50-200 μm, and up to 200-400 μm taken at ratio between 1:8:1 and 3:6:1.

EFFECT: method of preparing catalytic systems for large-scale high-sulfur hydrocarbon feedstock hydrofining processes is provided allowing production of products with desired levels of residual sulfur and polycyclic aromatic hydrocarbons.

4 tbl, 3 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.

EFFECT: improved performance characteristics of catalyst.

2 cl, 3 tbl, 10 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.

EFFECT: the invention ensures production of the diesel fuel with improved ecological performances and with a share of sulfur less than 350 ppm.

7 cl, 2 tbl, 2 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 processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

The invention relates to the refining and can be used when cleaning the cracking of gasoline from sulfur and unsaturated compounds

The invention relates to catalysts containing on the surface of the carrier compounds of molybdenum and/or tungsten, with or without additives compounds of one or more transition metals, processes for their preparation and may find wide application in the processes of hydroperiod hydrocarbons of petroleum or coal origin
The invention relates to the refining industry, specifically to a method for diesel fuel

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic reforming carried out at temperature in the reforming zone entry not higher than 485°C is supplemented by sulfidizing accomplished by introducing sulfur-containing compounds by doses each constituting 0.001-0.02% sulfur of the weight of catalyst, intervals between doses being not less than 1/2 one dose introduction time and at summary amounts of added sulfur 0.02-0.2% sulfur of the weight of catalyst during additional sulfidizing period. Additional sulfidizing is performed one or several times over the service cycle lasting hundreds or thousands hours. One sulfur dose addition time ranges from 0.5 to 1.5 h.

EFFECT: increased yield of reforming catalysate.

3 cl, 1 tbl, 7 ex

FIELD: catalyst preparation methods.

SUBSTANCE: hydrodesulfurization catalyst is sulfidized in reflux-type reaction-distillation column in following consecutive stages: drying catalyst with inert gas; filling reaction-distillation column with sulfur-containing sulfidizing solvent; establishing hydrocarbon feedstock and hydrogen consumptions; starting recycling of sulfidizing solvent; heating reaction-distillation column to first temperature within a range of 300 to 500°F, which is higher than sulfidizing agent decomposition temperature; introducing sulfidizing agent; revealing by-product in top run, namely water azeotrope, and taking away water; monitoring breakthrough of sulfidizing agent into top run; raising temperature to second temperature within a range of 500 to 700°C and; maintaining said second temperature over a required period of time.

EFFECT: enhanced process efficiency.

14 cl, 2 dwg

FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

The invention relates to the production of liquid catalysts on the basis of aromatic sulfonic acids for the hydrolysis of fats

The invention relates to the field of petrochemical, refining, or rather to the catalysts used in the refining

The invention relates to the field of chemistry, and in particular to methods of obtaining aromatic hydrocarbons from light hydrocarbons, including petroleum gas terminal stages of separation

FIELD: petrochemical processes.

SUBSTANCE: feedstock is brought into contact with preliminarily activated zeolite-containing catalyst, namely mordenite-supported Pt, at 250-300°C, pressure 1.5-3.5 MPa, hydrogen-containing gas-to-feedstock ratio 300-1000 nm3/m3, and feed flow rate 1.0-4.0 h-1. Preliminary activation of zeolite-containing isomerization catalyst is conducted in two successive steps: drying catalyst in inert gas flow; reducing catalyst in hydrogen-containing gas flow; and supplying feedstock and setting steady-state isomerization process. Drying of zeolite-containing catalyst in inert gas flow is effected under conditions of gradually raised temperature from 120°C at temperature raise rate 10-15°C/h and ageing for 2-5 h at 120°C to 350°C followed by ageing at this temperature, whereupon temperature is lowered to 130°C. Reduction of zeolite-containing catalyst in hydrogen-containing gas flow is effected at gradually raised temperature to 220-350°C at temperature rise rate 15-25°C/h and ageing for 2-6 h at 220-350°C, whereupon temperature is lowered to 180°C. Initial feedstock is supplied at 180°C in circulating hydrogen-containing gas flow, aged for 4 h at 180°C and then gradually heated to 250°C at heating rate 5°C/h, after which further heated at heating rate 5°C a day to achieve process characteristics meeting product quality requirements.

EFFECT: increased catalyst activity, selectivity, and working stability.

2 cl, 2 tbl, 17 ex

Up!