Method of regenerating catalytic systems of hydrogenation processes

FIELD: petroleum processing.

SUBSTANCE: method is accomplished by burning out carbon-containing compounds in oxygen-containing gas medium and comprises stages: desorption of hydrocarbons from catalyst surface performed in plant reactor and burning out of hydrocarbon thickening products performed on a special installation in indirect-heating rotary kiln at 450-550°C and excessive pressure 0.4-1.0 bar. Desorption of hydrocarbons from catalyst surface is carried out in a hydrogen-containing gas medium with 60-80 vol % H2, while gradually raising temperature from 200-220°C to 380-400°C at a rate 35-30°C/h following by aging of catalysts at 380-400°C until concentration of hydrocarbons in hydrogen-containing gas is no higher than 0.5 wt %, after which temperature is lowered to 100-120°C at a rate 20-25°C/h and active catalyst components are passivated. Passivation is accomplished by treatment at 100-120°C and excessive pressure 4-10 bar with mixture of inert gas and oxygen-containing gas, in particular carbon dioxide and/or air used in amount providing oxygen concentration in gas mixture 0.02-0.5 vol %, which corresponds to consumption of gas mixture 400-600 nm3/m3 catalyst. Treatment is conducted until oxygen concentrations at inlet and outlet of reactor are leveled.

EFFECT: enabled industrially feasible maximally possible restoration of catalyst activity with minimum destruction loss of catalyst.

4 tbl, 7 ex

 

The invention relates to the refining, in particular to a method of hydrofining petroleum fractions.

The increase in the consumption of motor fuels and base oils in 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 and oils, consisting mainly in a significant reduction in product sulfur content and polycyclic aromatic hydrocarbons [Kaminski ET, Khavkin, VA, Osipov LN. and other Refining and petrochemicals, 2002, No. 6, p.17-18].

Toughening of requirements to the quality of the petroleum product produced on the basis of domestic sulfur crudes, imposes new requirements on processes hydrofining bright and residual oil fractions, related primarily to increased activity and stability of operation of the catalysts in the hydrogenolysis reactions of organic sulfur compounds, the hydrogenation of unsaturated mono -, bi - and polycyclic aromatic hydrocarbons under the same process parameters.

Existing technical solutions in the field of production of catalysts hydro is anization processes [RF Patents №2140963, 2103065, 2124400, 2198733, 2216404, 2183505] and technological methods of their operation [RF Patents №2229934, 2124042, 2140964, 2225433] allow to solve these problems when using fresh catalysts.

Operation catalysts for hydrogenation processes are always accompanied by a decrease in their activity.

The duration of the period during which the potential of the catalyst is used with the maximum possible (the first period between regenerations), depends on the composition of used catalytic system and its operational conditions (the quality of the processed material, process parameters and ranges from 4-6 months in the processing of gasoline and middle distillate fractions of secondary origin [Refining and petrochemicals, 2003, No. 1, p.17-20] up to 6 years when the Hydrotreating straight-run gasoline fractions [Refining and petrochemicals, 2004, No. 4, p.47-51].

Partially restore the activity of catalysts for hydrogenation processes can oxidative regeneration, the process of controlled burning products seals hydrocarbon compounds, oxygen-containing compounds at temperatures of catalysis and above [Makhutov R.M., Morozov B.F., Kutepov B. I. Regeneration of catalysts in the refining and petrochemical industry. - M.: Chemistry, 1978, p.3. 103-105].

The activity of the catalyst after regeneration and the dates of their further use the AI depends on the conditions and duration of operation, as well as the method and conditions of the regeneration process.

Depending on the composition used in the regeneration of oxygen-containing mixture distinguish between vapor and gas regeneration.

For example, the known method of regeneration, which consists in passing the spent adsorbent at a temperature 121-399aboutWith the flow of regeneration gas which is a mixture of inert gas with oxides of carbon, hydrogen, and water vapor [Application No. 97112457/04, publication date 10.08.1998.]. The above-described method relates to vapor recovery.

The most significant disadvantage of vapor regeneration methods applied to catalysts for hydrogenation processes is the danger of flooding of the catalyst in the initial period of the regeneration, when the catalyst is not sufficiently warmed up. With further increase in temperature there is an instant evaporation of water, which is accompanied by destruction of the granules of the catalyst.

The use of water vapor leads to partial leaching of compounds of active metals, which when further operation affects the catalyst activity.

To minimize loss of activity and strength is possible when carrying out the regeneration gas.

There is a method of regeneration gas, the main feature of cataloguessexy the use of nitrogen as the inert and coolant [Technology catalysts. Edited Ipomaea, Leningrad: Khimiya, 1974, p.69].

Gas regeneration can be performed:

or in the reactor process plants,

- or out-of-reactor process unit on a specialized system of regeneration.

The maximum recovery with minimum loss of strength of the catalyst is achieved by carrying out the regeneration outside of the reactor process unit for specialized installation in a rotary kiln indirect heating at a temperature of 450-550aboutC and a pressure of 0.4 to 1.0 MPa [Makhutov R.M., Morozov B.F., Kutepov B. I. Regeneration of catalysts in the refining and petrochemical industry. - M.: Chemistry, 1978, p.3. 108-110].

When carrying out the regeneration at the specialized unit must be noted that all the catalysts for hydrogenation processes during operation become pyrophoric properties. Uncontrolled ignition of the catalyst leads to the irreversible loss of its activity and a decrease in strength, which makes it further operation impossible.

It is necessary to provide safety measures for the unloading of the catalyst to prevent its ignition when exposed to air. To this end it is recommended to conduct passivation of the catalyst. The essence of the operation passivation is blocked in mild conditions contained is and the surface of the spent catalyst flammable in air connections active components in the form of finely dispersed sulphides and metals, then the catalyst is almost loses pyrophoric properties.

Closest to the proposed technical solution to the technical essence and the achieved result is a method of regeneration of the catalyst by the burning products of the condensation of hydrocarbons in the environment of the oxygen-containing gas in the temperature interval 260-600aboutC, at a pressure of 0.45-3.5 ATM [RF Patent №2053843].

This method of regeneration refers to the regeneration gas, but does not stage passivation of the catalyst and, therefore, can only be carried out in a reactor of the plant. Regeneration of catalysts in the reactor process unit is always accompanied by a significant temperature drop in the reactor, which leads to the destruction of part of the catalyst in the zone of high temperatures, and incomplete Viigo products seal of hydrocarbons in the part of the catalyst in the zone of low temperatures.

The aim of the invention is to develop technical solutions, allowing to carry out in industrial conditions the maximum possible recovery of the catalysts for hydrogenation processes with minimal loss of the catalyst due to the destruction.

This goal is achieved by implementing a method of regeneration to the of talization and catalytic systems for hydrogenation processes by the burning of carbon-containing compounds in the environment of the oxygen-containing gas, includes stage desorption of hydrocarbons from the catalyst surface, carried out in the reactor process unit, and the burning products of their seals on the specialized installation in a rotary kiln indirect heating at a temperature of 450-550aboutC and a pressure of 0.4 to 1.0 MPa, provided that the desorption of the hydrocarbons from the surface of the catalysts is carried out in an environment of hydrogen containing gas with a hydrogen content of about 60-80% by with the gradual rise in temperature from 200-220aboutWith up to 380-400aboutWith speeds of 25-30aboutC/h, followed by exposure of the catalytic system at a temperature of 380-400aboutTo achieve the hydrocarbon concentration in the hydrogen-containing gas is not more than 0.5 wt.% and lowering the temperature to 100-120aboutWith speeds of 20-25aboutWith/hour, with subsequent passivation compounds active components of the catalyst by treating at a temperature of 100-120aboutC and a pressure of 4-10 MPa with a mixture of inert gas with an oxygen-containing component, which is used as the carbon dioxide and/or air in an amount to provide a concentration of oxygen in the gas mixture of 0.02-0,50%, with a flow rate of 400-600 nm3/m3catalyst to equalize the oxygen concentration at the inlet and outlet of the reactor.

A distinctive feature of the proposed technical solution is the I, the desorption of hydrocarbons from the surface of the catalysts is carried out in an environment of hydrogen containing gas with a hydrogen content of about 60-80% by with the gradual rise in temperature from 200-220aboutWith up to 380-400aboutWith speeds of 25-30aboutC/h, followed by exposure of the catalytic system at a temperature of 380-400aboutTo achieve the hydrocarbon concentration in the hydrogen-containing gas is not more than 0.5 wt.% and lowering the temperature to 100-120aboutWith speeds of 20-25aboutWith/hour, with subsequent passivation compounds active components of the catalyst by treating at a temperature of 100-120aboutC and a pressure of 4-10 MPa in a mixture of inert gas with an oxygen-containing component, which is used as the carbon dioxide and/or air in an amount to provide a concentration of oxygen in the gas mixture of 0.02-0,50% vol. with a flow rate of 400-600 nm3/m3catalyst to equalize the oxygen concentration at the inlet and outlet of the reactor.

The specified limits on the concentration of hydrogen in the hydrogen-containing gas and the selected temperature stage of desorption of the hydrocarbons from the surface of the catalysts described in the formula of the proposed invention, allow for almost complete removal from the surface of the catalyst of hydrocarbons to exclude the reduction reaction of compounds active components,which significantly reduces the catalyst activity.

Specified in the formula of the present invention, the process parameters of the stage passivation compounds active components of catalysts allow at relatively low temperatures to block connection of active components of the catalyst surface oxide film, which prevents the ignition of the catalyst by contact with atmospheric air at the discharge of catalyst from the reactor plant and shipping it to a specialized recovery plant.

Using as the oxygen-containing component, carbon dioxide or mixtures with air can be used for carrying out stage passivation process gases, thereby increasing the environmental friendliness of the process.

The application of a previously described above technical solutions when conducting the regeneration of catalysts for hydrogenation processes is not known.

Thus, the present invention meets the requirements of "novelty" and "significant difference".

The proposed method for the regeneration of catalysts for hydrogenation processes is as follows.

After the termination of the feed loaded in the reactor the catalyst install the concentration of hydrogen fed to the reactor the hydrogen-containing gas 60-80 vol.% and the temperature in the reactor 200-220aboutC. Gradually, with SC is the rate of 25-30 aboutWith/hour, increase the temperature in the reactor up to 380-400aboutC. Determine the concentration of hydrocarbons in the hydrogen-containing gas. Maintain the catalyst in these conditions to achieve the hydrocarbon concentration in the hydrogen-containing gas is not more than 0.5 wt.% then reduce the temperature in the reactor to 100-120aboutWith speeds of 20-25aboutC/hour. When the temperature in the reactor 100-120aboutTo replace the hydrogen-containing inert gas, for example nitrogen, and set the pressure in the reactor 4-10 MPa. After complete displacement of hydrogen from the reactor in the composition of the inert gas injected oxygen-containing component with a flow rate of 400-600 nm3/m3catalyst in an amount to provide a concentration of oxygen in the gas mixture of 0.02-0,50%. As the oxygen-containing component is used carbon dioxide and/or air.

After aligning the oxygen concentration at the inlet to the reactor and the reactor exit temperature in the reactor is reduced to 40-60aboutWith and carry out the unloading of the catalyst, carrying unloaded catalyst for specialized installation and start regeneration in a rotary kiln indirect heating at a temperature of 450-550aboutC and a pressure of 0.4 to 1.0 MPa.

The proposed method for the regeneration of catalysts is illustrated by, but is not limited to the examples below.

Information about katal is the congestion, used to illustrate the proposed method for the regeneration of catalysts and catalytic systems for hydrogenation processes are given in table 1. This table summarizes the characteristics of the catalysts after passivation. Physico-chemical properties of fresh original catalysts are characterized by a content of compounds active ingredients and strength, passivated - carbon and sulphur.

Conditions of carrying out the stages of desorption of hydrocarbons from the catalyst surface, passivation compounds active components of the catalysts and the burning products of the condensation of hydrocarbons are given in table 2, 3, 4, respectively. In table 4 are also physico-chemical and performance characteristics of the regenerated, i.e. completed all three stages of processing catalysts. As a performance indicator used in the conversion of sulphur achieved when using these catalysts in Hydrotreating processes of crude oil. This indicator gives an idea of the restoration of the activity of the catalyst after regeneration. A very important indicator of regeneration is to minimize the loss of the catalyst during regeneration due to the destruction. This indicator is also shown in the table 4. Data on the carbon content of the regenerated catalyst indicate p is lnote removal from the catalyst products of the condensation of hydrocarbons, i.e. about the efficiency of the stage of the burning products of the condensation of hydrocarbons with the catalyst surface.

Example 1.

Regeneration of the catalyst RK-442Ni. The catalyst has been in use on the installation of deep hydrofining vacuum gas oil with a sulfur content of 2.0 to 2.5 wt.% without regeneration for three years. The amount of catalyst loaded in the reactor amounted to 108 so Basic physical and chemical characteristics of fresh catalyst RK-442Ni shown in table 1.

After the termination of the supply of raw materials to the catalyst RK-442Ni established that the concentration of hydrogen in the hydrogen-containing gas 60 vol.%, the temperature in the reactor 220aboutC. Gradually, at a rate of 25aboutWith/hour, raised the temperature in the reactor 400aboutC. the Concentration of hydrocarbons in the hydrogen-containing gas was 4.2 wt.%. The catalyst was kept in these conditions to achieve the hydrocarbon concentration in the hydrogen-containing gas of 0.5 wt.%, then lowered the temperature in the reactor to 120aboutWith speeds of 20aboutC/hour. When the temperature in the reactor 120aboutWith was replaced with hydrogen gas to nitrogen. Installed a reactor pressure of 4.0 MPa.

After complete displacement of hydrogen from the reactor to the nitrogen fed to the reactor, added air in an amount to provide a concentration of oxygen in the mixture gas is at 0.50%. Set the flow rate of the gas mixture of 400 nm3/m3of the catalyst. After aligning the oxygen concentration at the inlet to the reactor and the reactor exit temperature in the reactor was lowered to 40aboutWith and started unloading the catalyst.

After unloading carried out an analysis of the catalyst on the content of sulfur and carbon. The data are given in table 1.

Burning products seal of hydrocarbons from the surface of the catalyst was carried out on specialized installation in a rotary kiln indirect heating at a temperature of 550aboutC and a pressure of 0.4 MPa. After dropping out of the regenerated catalyst from the resulting in operation and regeneration of dust and crumbs obtained 104 t of the catalyst, i.e. loss amounted to 3.5%.

Physico-chemical and performance characteristics of the regenerated catalyst is summarized in table 4.

Comparison of the characteristics of fresh, passivated and regenerated catalyst RK-442Ni shows that changes in the chemical composition of the catalyst is practically nonexistent, activity and durability of the catalyst has decreased slightly. Catalyst losses due to the destruction is minimal. The products of condensation of hydrocarbons removed almost completely.

Example 2.

Regeneration of the catalyst RK-so. The catalyst has been in use at the facility gidrolaga is arovane mixed middle distillate fractions with sulfur content of 1.6-2.0 wt.%, the content of unsaturated hydrocarbons 10-15 wt.%.

The amount of catalyst loaded in the reactor was 40 so Basic physical and chemical characteristics of fresh catalyst RK-a shown in table 1.

After the termination of the supply of raw materials to the catalyst RK-so established that the concentration of hydrogen in the hydrogen-containing gas 80% vol. and the temperature in the reactor 200aboutC. Gradually, with speed 30aboutWith/hour, raised the temperature in the reactor to 380aboutC. the Concentration of hydrocarbons in the hydrogen-containing gas was 3.5 wt%. The catalyst was kept in these conditions to achieve the hydrocarbon concentration in the hydrogen-containing gas of 0.4 wt.%, then lowered the temperature in the reactor to 100aboutWith speeds of 25aboutC/hour. When the temperature in the reactor 100aboutWith was replaced with hydrogen gas to nitrogen. Set the pressure in the reactor 10 MPa.

After complete displacement of hydrogen from the reactor to the nitrogen fed to the reactor, added air in an amount to provide a concentration of oxygen in the gas mixture of 0.02 vol.%. Set the flow rate of the gas mixture of 600 nm3/m3of the catalyst. After aligning the oxygen concentration at the inlet to the reactor and the reactor exit temperature in the reactor was lowered to 40aboutWith and started unloading the catalyst.

After unloading conducted the analysis of the catalyst on the content of sulfur and carbon. The data are given in table 1.

Regeneration of the catalyst was carried out on specialized installation in a rotary kiln indirect heating at a temperature of 450aboutC and a pressure of 0.4 MPa. After dropping out of the regenerated catalyst from the resulting in operation and regeneration of dust and crumbs obtained 38,8 t catalyst, i.e. loss amounted to 3%.

Physico-chemical and performance characteristics of the regenerated catalyst is summarized in table 4.

Comparison of the characteristics of fresh, passivated and regenerated catalyst RK-so shows that changes in the chemical composition of the catalyst is practically nonexistent, activity and durability of the catalyst has decreased slightly. Catalyst losses due to the destruction is minimal. The products of condensation of hydrocarbons removed almost completely.

Implementation of the proposed method for the regeneration of catalytic systems for hydrogenation processes in examples 3-6 were carried out in a sequence similar to examples 1-2. Information used to run the examples 3-6 catalysts, process parameters and the results obtained are given in tables 1-4.

It is seen that when carrying out regeneration in accordance with the formula of the invention (examples 1-4) physical and chemical characteristics of the cat is of the catalysts changed slightly. Loss of catalysts in the form of crumbs and dust is minimal.

Conducting regeneration deviation of process parameters from the given in the formula of the invention (examples 5 and 6) leads to a significant decrease in the activity of the catalyst, the deterioration of its mechanical properties and large losses.

Carrying out regeneration in accordance with the technical solution described in the prototype (example 8), is carried out in a reactor of the plant. Stage desorption of hydrocarbons and passivate the catalyst surface are absent. As a result, the regenerated catalyst catalytic activity and durability is considerably lower than with fresh. Catalyst losses when the overload in the form of dust and crumbs significant. The products of condensation of hydrocarbons not removed completely (high carbon content).

From the above data it is evident that the implementation of the proposed method for the regeneration of catalysts and catalytic systems for hydrogenation processes occurs with minimal loss of activity and strength.

Brand catalyst
Table 1.

Information about the catalysts used in the illustration of the proposed method for the regeneration of catalytic systems for hydrogenation processes.
ExampleRaw materials processedPeriod between regenerations, moConversion of sulfur, %The catalyst is freshThe catalyst was passivated
Content, wt.%Strength,Content, wt.%
Moo3SooNiOMPaS
Example 1RK-442Nithe HAC. gasoil3680,015.5-4,50,9815,58,5
Example 2RK-somixed raw materials1295,514,84,6-0,9018,68,4
Example 3RC-222+ST-70*sredneetazhnye FR.4896,214,5/14,2-/4,24,3/-0,96/0,8812,3/10,88,6/8,7
Example 4RK-231Nigasoline2499,815,0-4,20,864,5 9,0
Example 5TNK-2000diz. FR-AI2496,015,04,3-0,7812,68,9
Example 6TH-70gasoline6099,614,34,0-0,808,68,4
Example 7 (prototype)RK-somixed raw materials1295,514,54,4-0,9117,88,6
* in the numerator figures RK-222, in the denominator - ST-70

60
Table 2.

Conditions for stage desorption of hydrocarbons from the catalyst surface.
ExampleThe concentration of H2in SIV,% vol.T-RA beginning,aboutThe speed of temperature rise to the maximum,aboutS/hThe maximum temperatureaboutConc. hydrocarbon gases in everything at the end of the stage, wt.%The speed reduction t-ry,aboutS/hT-RA the end of the stage,about
Example 1220254000,520120
Example 280200303800,425100
Example 375210253800,520100
Example 470200303800,325120
Example 550230204100,630130
Example 690190353700,81590
Example 7 (prototype)Stage no

Example 1
Table 3.

Conditions for stage passivation compounds active catalyst components.
ExampleTemperatureaboutPressure, MPaOxygen-containing componentThe oxygen concentration in the gas mixture, vol.%The flow of the mixture of gases, nm3/m3catalyst
1204the air0,50400
Example 210010CO20,02600
Example 31106CO2+air0,25500
Example 41005the air0,30500
Example 513012the air0,60350
Example 6903the air0,01650
Example 7 (prototype)Stage no

td align="left" namest="c0" nameend="c9"> *regeneration is carried out in reactor technology installation in a mixture of air with nitrogen oxides.
Table 4.

Conditions of carrying out the stage of the burning products of the condensation of hydrocarbons and the results of the regeneration process.
ExampleParameters burning stageCharacteristics of the regenerated catalyst
TemperatureaboutPressure, MPaLoss, wt.%Content, wt.%Strength, MPa Conversion of sulfur, %
Moo3SooNiO
Example 15501,03,515,4-4.50,20,9779,5
Example 24500,43,014,84,5-0,10,90for 95.3
Example 35000,82,814.4V/14,2-/4,14,2/-0,10,95/0,8896,0
Example 44800,71,015,04,1-0,20,8799,6
Example 55001,09,014,6a 3.9-0,20,7891
Example 65001,07,013,93,6-0,30,7189
Example 7 *(prototype)5000,5to 12.013,83,5-1,40,485

Method of regenerating catalysts for hydrogenation processes by the burning of carbon-containing compounds in the environment of the oxygen-containing gas, comprising a stage of desorption of the hydrocarbons from the catalyst surface, carried out in the reactor process unit, and the burning products of their seals on the specialized installation in a rotary kiln indirect heating at a temperature of 450-550°and a pressure of 0.4 to 1.0 MPa, characterized in that the desorption of the hydrocarbons from the surface of the catalysts is carried out in an environment of hydrogen containing gas with a hydrogen content of 60-80%, with the gradual rise in temperature from 200-220°With up to 380-400°With speeds of 25-30°C/h, followed by exposure of the catalysts at a temperature of 380-400°to achieve the hydrocarbon concentration in the hydrogen-containing gas is not more than 0.5 wt.% and lowering the temperature to 100-120°With speeds of 20-25°C/h, followed by passivation compounds active components of the catalyst by treating at a temperature of 100-120°and a pressure of 4-10 MPa with a mixture of inert gas with an oxygen-containing component, which is used as the carbon dioxide and/or air in an amount to provide to the concentrations of oxygen in the gas mixture of 0.02-0,50%, with a flow rate of 400-600 nm3/m3catalyst, to equalize the oxygen concentration at the inlet and outlet of the reactor.



 

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10 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of preparing silicoaluminophosphate (SAPO) molecular sieves, to containing them catalysts, and to methods of catalytic dehydration with application of said catalysts. Described is method of preparing SARO molecular sieve, preferably, possessing crystalline structure SAPO-34, including the following stages: mixing source P with source Al obtaining mixture, addition to said first source Si and template obtaining suspension or slime to value in the interval from 5 to 6.8, hydrothermal processing of said suspension or slime obtaining suspension of SAPO molecular sieve, isolation from suspension of said SAPO molecular sieve and its drying, and before addition of said source Si and said template said mixture of sources P and Al is boiled with stirring, said stage of boiling is carried out at temperature in the interval from 50 to 100°C, preferably at 75°C, during period of time from 10 to 30 h, preferably 24 h. Described is SAPO molecular sieve, preferably, possessing crystalline structure SAPO-34, which can be prepared in accordance with described method and is characterised by the following chemical composition: (SixAlyPZ)O2, where x, y and z stand for mole fractions of respectively Si, Al and P, and x stands for mole fraction of Si and has value in the interval from 0.001 to 0.1, y stands for mole fraction of Al and has value within the interval from 0.25 to 0.5, z stands for mole fraction of P within the interval from 0.4 to 0.8. Described is catalyst, including SAPO molecular sieve and matrix material, selected from group, including aluminium oxide, silicon dioxide, aluminium silicate, silicon dioxide- aluminium oxide and natural kaolin, preferably, activated aluminium oxide, contains at least 50 wt % of pseudoboehmite. Described are method of converting methanol into dimethyl ether (DME), method of converting methanol into olefins in presence of described above catalyst.

EFFECT: obtaining very pure highly crystalline SAPO molecular sieves, possessing exceptional activity in dehydration reactions, with very high output.

16 cl, 4 tbl, 9 ex, 7 dwg

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