Method of hydrogenisation catalyst reduction

FIELD: chemistry.

SUBSTANCE: invention refers to the method of the reduction of hydrogenisation catalyst by the way of serial operations of 1) hydrocarbon desorption from the surface of the spent catalyst located in the stationary layer in the media of hydrogen-containing gas at temperature 200-400°C; 2) passivation of the catalyst surface by its treatment with oxygen-containing gas (oxygen content is 0.02-0.5 vol. %) in the stationary layer at temperature 100-120°C; 3) burn-off of the hydrocarbon condensation products in the oxygen-containing gas flow at temperature 400-550°C; 4) catalyst conversion from oxide to presulphide form by their contacting with elemental sulphur in the air or inert gas flow. The burn-off of the hydrocarbon condensation products and catalyst transforming are implemented in the moving-bed catalyst with burn-off temperature being regulated with the oxygen-containing gas temperature and volume ratio oxygen-containing gas :catalyst in the range (15-30):1.

EFFECT: reduction of the hydrogenisation catalyst with minimal destruction losses of the catalyst.

3 cl, 5 tbl, 2 ex, 2 dwg

 

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

Toughening of requirements to the quality of the petroleum product produced on the basis of high-sulphur crude oil, imposes new requirements on processes hydrofining bright and residual oil fractions.

The effectiveness of these processes depends on the activity and stability of the used catalysts. Activity characterizes the velocity and depth of flow catalytic reactions, stability - resistance activity during the lifetime of the catalyst.

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

For modern catalytic processes of oil refining and petrochemistry is the most common cause of poor performance of the catalysts is the deposition of coke on the surface.

The duration of the period during which the potential of the catalyst is used with maximum efficiency (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 is s [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 be called oxidative regeneration, i.e. controlled burning products seals hydrocarbon compounds, oxygen-containing compounds at temperatures of catalysis and above [Makhutov P.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 and stability of catalysts after oxidative regeneration depends not only on the operating conditions, and method of recovery of their activity, including the preparation of the catalyst to regeneration, including desorption of hydrocarbons from the surface; the actual process of oxidative regeneration, which consists in a controlled Vigie products seal hydrocarbons, and subsequent transfer of the active components of the oxide in presulfiding form.

All hydrogenation processes are on the catalysts containing active metals as sulphides. Thus, prior to the processing of raw materials spend the activation of the catalysts by sulfatirovnie.

For example, the catalyst in the oxide form, is loaded into the reactor, first contact and the comfort at an elevated temperature with hydrogen-rich recycle gas, mixed with a sulfiding agent such as hydrogen sulfide, or easily degradable organic sulfur compounds, or raw materials, or mixtures thereof [Oil@Gas Journal, Dec.20, 1982, pp. 69-74].

In all cases, the process of sulfatirovnie catalyst in an industrial installation target process hydrofining technologically difficult and involves additional cost of time, energy, chemicals.

The most effective method of application of sulfur on the catalyst is the way sulfatirovnie outside the reactor hydrobromide hydrocarbons. For this use of sulfur-containing compounds and/or elemental sulfur.

For example, for the deposition of sulfur on the catalyst is proposed to use organic sulfur compounds with a boiling point above 100°C [Europatent No. 0460300 A1, op. 11.12.91, B. I. No. 50]. Examples of such compounds can serve as 2,2-thiodiethanol, thiodiglycolic acid, 3.3-childproperty, 1.6-dihydroxy-2.5-ditegakkan, 3.6-mitigatedby acid. Sulfur containing compounds are dissolved in water or an organic solvent, the catalyst is treated with the resulting solution, followed by drying to remove solvent. The disadvantage of this method is the high cost and scarcity of individual sulfur compounds, as well as the necessity of removing the solvent from the catalyst, which is always a CR which leads to a decrease in strength of the catalyst.

A known method of applying a catalyst to elemental sulfur by contacting the catalyst with molten sulfur at temperatures of 100-150°C until the liquid sulfur is absorbed into the pores of the catalyst particles. The catalyst is cooled so that the sulfur cures in the pores of the particles, the process of heating and cooling of the catalyst with sulfur is carried out in a stream of nitrogen [U.S. patent No. 4.177.136 from 04.12.79]. The resulting product is used as the top layer of catalytic package. The disadvantage of this method is its complexity, lack of throttling applied sulfur, including the necessity of using molten sulfur, and limitation of the process only in an environment of inert gas. All this complicates the technology and significantly increases the cost of the final product.

Most technologically advanced method of transfer catalysts of the oxide in presulfiding form is a method of obtaining catalysts in presulfiding form by mixing the granules of catalyst containing a carrier and one or more catalytically active metals in oxide form, with elemental sulfur, taken in an amount of not more than 50 wt.% from the mass of catalyst at a temperature below the melting point of sulfur, heating the mixture of the catalyst with sulfur at a temperature above the melting point of sulfur, provided telemetry sulfur used in the form of particles with a size not exceeding the size of the catalyst particles, the heated mixture of the catalyst with sulfur is carried out in a current of air or inert gas under continuous stirring [RF patent № 2229934].

Depending on the composition used for the oxidative regeneration of the 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 121-399°C gas flow composed of a mixture of inert gas with oxides of carbon, hydrogen, and water vapor [application No. 97112457/04, publication date 1998.08.10.]. 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 reduce the loss of activity and strength is possible when carrying out the regeneration gas.

Gas re inertia is held in the stream of the mixture of inert gas, usually nitrogen, oxygen, taken at a concentration of 0.5 to 20 vol.% [Technology catalysts. /Edited Ipomaea. - L.: Chemistry, 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 catalysts can be achieved when carrying out the oxidative regeneration of out-of-reactor process unit for specialized installation in a rotary kiln indirect heating at a temperature of 450-550°C and a pressure of 0.4 to 1.0 MPa [Makhutov P.M., Morozov B.F., Kutepov B. I. Regeneration of catalysts in the refining and petrochemical industry. - M.: Chemistry, 1978, C-110] provided the process with process parameters (temperature and amount of oxygen supplied to the furnace gas, the concentration of oxygen in it), physico-chemical characteristics of the catalyst (the nature of the medium, the composition of the active components, the content of the coke).

When carrying out the oxidative regeneration at the specialized unit must be noted that all the catalysts for hydrogenation processes during operation become pyrophoric properties. Uncontrolled combustion catalyst to bring the to the irreversible loss of its activity and loss of strength, what makes it further operation inefficient.

It is necessary to provide precautions for discharging spent 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 on the surface of the spent catalyst flammable in air connections active components in the form of finely dispersed sulphides and metal thin oxide film, after which the catalyst is almost loses pyrophoric properties.

There is a method of oxidative regeneration of catalysts by burning the products of condensation of hydrocarbons in the environment of the oxygen-containing gas at a pressure of 0.45-3.5 ATM [RF patent № 2053843]. This method applies to gas regeneration, but does not stage passivation of the catalyst, and therefore can only be carried out in a reactor of the plant.

Carrying out the oxidative 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 seals hydrocarbon h the activity of the catalyst, in the zone of low temperatures.

Closest to the proposed technical solution to the technical essence and the achieved result is a method of restoring the activity of catalysts for hydrogenation processes by burning products seal carbon-containing compounds in the environment of the oxygen-containing gas with a preliminary desorption of hydrocarbons from the catalyst surface in the environment of the hydrogen-containing gas while gradually raising the temperature of 200-220°C up to 380-400°C and the passivation compounds their active components by processing at a temperature of 100-120°C and a pressure of 4-10 MPa with a mixture of inert gas with an oxygen-containing component, 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°C and a pressure of 0.4 to 1.0 MPa [RF patent № 2282501].

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 a method of restoring the activity of catalysts for hydrogenation processes by successive is piracy desorption of hydrocarbons from the surface of the waste placed in a stationary layer of catalysts in the environment of the hydrogen-containing gas at a temperature of 200-400°C; passivation of the surface of the catalysts due to their processing in the stationary layer at a temperature of 100-120°C oxygen-containing gas with an oxygen content of 0.02 to 0.5 vol.%; the burning products of the condensation of hydrocarbons in the stream of oxygen-containing gas at a temperature of 400-550°C; transfer catalysts of the oxide in presulfiding form by contact with elemental sulfur in the current of air or inert gas, provided that the burning products of the condensation of hydrocarbons and translation of the catalysts of the oxide in presulfiding form is carried out in a moving catalyst bed, the temperature of the burning products of the condensation of hydrocarbons is regulated by the temperature of the oxygen-containing gas and the volumetric ratio of oxygen-containing gas catalyst (15-30):1; the temperature of the oxygen-containing gas as reducing the carbon content of the catalyst is directed into the burning products of the condensation of hydrocarbons, is

when the carbon content (wt.%) respectively

270-380°Cabove 10
380-420°C10-4
420-480°C4-2
480-550°Cless than 2,

the oxygen concentration in the oxygen-containing gas at Vigie products seal of hydrocarbons is 12-20%.

A distinctive feature of the proposed technical solution is the fact that burning products seal hydrocarbons and translation of the catalysts of the oxide in presulfiding form is carried out in a moving catalyst bed, the temperature of the burning products of the condensation of hydrocarbons is regulated by the temperature of the oxygen-containing gas and the volumetric ratio of oxygen-containing gas catalyst (15-30):1; the temperature of the oxygen-containing gas as reducing the carbon content of the catalyst is directed into the burning products of the condensation of hydrocarbons, is

when the carbon content (wt.%) respectively

270-380°Cabove 10
380-420°C10-4
420-480°C4-2
480-550°Cless than 2,

the oxygen concentration in the oxygen-containing gas at Vigie products seal of hydrocarbons is 12-Ob.%.

Specified in the formula of the present invention the sequence and conditions comply with the Oia operations:

- desorption of hydrocarbons from the catalyst surface,

- passivation of the catalyst surface,

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 installation oxidative regeneration.

Specified in the formula of the present invention conditions the burning products of the condensation of hydrocarbons from the surface provide a high intensity of the process and eliminate the possibility of overheating of the catalyst above the maximum allowable temperature, which is determined by thermal stability of the catalyst.

For aluminoborosilicate catalysts significant deterioration of the strength characteristics and the decrease in the content of active components is observed upon heating above a temperature of 550°C, for alumonickelsilicate - 520°C for zeolite catalysts - 500°C.

Given in the formula of the present invention, the temperature dependence of oxygen-containing gas from the carbon content of the regenerated catalyst provides optimum temperature oxidative regeneration.

The process of burning product the seal of the hydrocarbons with the catalyst surface is accompanied by the following reactions:

(1)+O2=CO2+395,4 kJ/mol

(2)+1/2 O2=CO+110,4 kJ/mol

(3) CO+1/2 O2=CO2+285,0 kJ/mol

(4) S+O2=SO2+298 kJ/mol

(5) 2H2+O2=2H2O+136 kJ/mol

(6) 2MoS+5O2=Moo3+2SO2

(7) 2NiS+3O2=2NiO+2SO2

(8) 2CoS+3O2=2CoO+2SO2

Response 1-8 begin at a temperature of at least 270°C. as a result of these reactions is of considerable heat, which added to the warmth of the oxygen-containing gas. This can lead to a sharp temperature rise in the catalyst bed in the reaction zone. In order to avoid overheating of the catalyst the temperature of the oxygen-containing gas should be regulated depending on the carbon content of the catalyst in accordance with the formula of the invention.

Depth implementation of the reactions 1-8 and required withdrawal from the reaction zone allocated in this district heat is given in the formula of the present invention, the volumetric ratio of oxygen-containing gas catalyst. Exceeding the specified flow rate of oxygen-containing gas will lead to the removal of the catalyst together with the combustion gases. Low consumption, will not provide the feed in the reaction zone sufficient oxygen.

After conducting the burning of carbonaceous deposits of the active components of the catalyst of nahodatsa oxide form.

Mixing of the catalyst in the oxide form, with elemental sulfur under the conditions of formulas of the present invention enables to print on the surface of the catalyst, the amount of sulfur, sufficient to transfer the active components of the catalyst of oxides into sulfides without excessive overheating of the catalyst and the use of toxic liquid organic sulfur compounds.

The application of a previously described above technical solutions to restore the activity of catalysts for hydrogenation processes we adopted the combination and conditions of each operation performed is not known.

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

Proposed method of restoring the activity of catalysts for hydrogenation processes is as follows.

After the termination of the supply of raw materials in the digester hydrofining fixed bed catalyst carry out desorption of the hydrocarbons from the catalyst surface, which loaded in the reactor the catalyst serves the hydrogen-containing gas with a hydrogen content of about 60-80% by when the temperature in the reactor 200-220°C. Gradually speeds of 25-30°C/hour raise the temperature in the reactor up to 380-400°C. Determine the concentration of hydrocarbons in the hydrogen-containing gas. Stand Katalizator specified conditions to achieve the hydrocarbon concentration in the hydrogen-containing gas is not more than 0, > = 5%, then reduce the temperature in the reactor to 100-120°C at a rate of 20-25°C/hour.

When the temperature in the reactor 100-120°C are transferred to the operation passivation. To do this, 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 use oxygen and/or 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 40-60°C, hold unloading of the catalyst and carry unloaded catalyst for specialized installation oxidative regeneration, the composition of which includes a block oxidative regeneration block diagram is shown in figure 1) and the unit preconfigure (schematic diagram is given in figure 2).

From that came catalyst selected a representative sample, which is analyzed for carbon content. Depending on the carbon content of the received for recycling the catalyst to set the operation mode of the block oxidative regenerat and begin operation Viigo carbon-containing compounds.

What passivated catalyst is fed into the hopper B-11, whence it flows evenly on the surface of the sieve With-11. Regulation of the feed of the catalyst from the hopper B-11 sieve-11 is a gate valve installed at the bottom of the hopper B-11. Vibrating sieve-11 allows the separation of inert balls and catalyst dust from pregenerating catalyst.

Disqualified aregenerally catalyst with a vibrating sieve With a-11 through a conveyor-lift T-11 is fed into a hopper B-21.

From the hopper B-21 catalyst by vibrating feeder In to 11 enters the reactor regeneration R-11, where at a temperature of 400-550°C is burning carbonaceous deposits from the catalyst surface (oxidative regeneration). The specified temperature provided by the temperature in the reactor oxygen-containing gas coming from the furnace heating P-11 with the temperature 270-550°C depending on the carbon content on the catalyst, and the concentration of oxygen in it (12-20%), as well as the volumetric ratio of oxygen-containing gas catalyst (15-30):1.

At the exit of the reactor oxidative regeneration R-11 catalyst falls into a hopper B-31, where the selection of flue gases and partial cooling of the catalyst. From the hopper B-31 catalyst through the gate flows to vibrac the district feeder-21 and falls onto the conveyor-lift T-21, which provides its submission on the surface of the sieve S-21, where the separation of regenerated catalyst from the resulting regeneration of dust and crumbs.

If regeneration is exposed to a mixture of catalysts with different diameter, the catalyst sieved on a sieve With a-21, is directed to the sieve C-31, which establish the respective lattice, allowing the separation of different particle size of the catalyst.

The monitoring process of burning carbon deposits lead content in the regenerated catalyst carbon residue content of not more than 0.8 wt.%) and sulfur (residual content of not more than 0.4 wt.%). The sample is collected with a sieve S-21 or S-31 through every hour.

The catalyst obtained after the operation of burning carbon deposits, refer to the block preconfigurable where conduct the transfer operation of the catalysts of the oxide in presulfiding form.

For this catalyst with baskets-31 (or S-21) regeneration unit (see figure 1) is fed into the hopper B-12 unit preconfigure (see figure 2), where through the gate by gravity to the conveyor-lift T-12. On the same conveyor through the dispenser D-12 serves solid elemental sulphur, crushed to a size of no more than average size of the catalyst particles, in the estimated amount. For the of utilizatorul Hydrotreating, having extrudates diameter of 2-5 mm and a length of 3-7 mm, the particle size of sulfur does not exceed 5 mm

With conveyor T-12 mixture of the catalyst with elemental sulfur powder is fed into a hopper B-22, where the vibratory feeder b-12 is fed into the reactor preconfigurable R-12, where it is heated to a temperature of 120-160°C for 60 minutes with continuous stirring. Heating a mixture of sulfur from the catalyst occurs by the flow of heated in a furnace heated P-12 to a temperature of 140-200°C air or inert gas at a flow rate of the last 2,0-4,5 nm3/m3catalytic Converter.

At the exit of the reactor preconfigurable R-12 catalyst falls into a hopper B-32, where there is a partial cooling of the catalyst. From the hopper B-32 catalyst through the gate onto the vibrating feeder-22 falls onto the conveyor-lift T-22, and presented with the installation.

The catalyst is directed to the installation of hydrogenation processes.

Proposed method of restoring the activity of catalysts for hydrogenation processes is illustrated by, but is not limited to the examples below.

Information about the catalysts used to illustrate the proposed method of restoring the activity of catalysts for hydrogenation processes are given in table 1. This table summarizes the characteristics of the catalysts of the s after passivation. Physico-chemical properties of fresh catalysts are characterized by their content of active compounds of components and collective crushing strength.

Conditions of carrying out the stages of desorption of hydrocarbons from the catalyst surface, passivation compounds active components of the catalysts, the burning products of the condensation of hydrocarbons and obtain catalysts in presulfiding the form given in tables 2, 3, 4, 5, respectively.

In table 4 also gives the physico-chemical characteristics of the catalysts obtained after performing the operation, the burning products of the condensation of carbon in table 5 - physical and chemical characteristics of the catalysts after the operation of transferring them from the oxide in presulfiding form.

Physico-chemical properties of the catalysts after passivation are characterized by carbon and sulfur, after burning products seal - carbon, oxides of active metals and durability, presulfiding - strength and sulphur.

Data on the content of sulfur and carbon in peseverance catalysts are used to select the mode of operation of burning the carbonaceous deposits from the catalyst surface.

Data on the carbon content on the catalyst after burning sediments indicate full is the removal from the surface of 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. The latter is characterized as the presence or absence of change of content of the oxides of the active metals and collective strength crush strength.

An important indicator of the proposed method is to minimize the loss of the catalyst due to the destruction due to the reduction of mechanical strength at the stage of the burning products of the condensation of hydrocarbons. These indicators are summarized in table 4.

The sulfur content in the composition presulfiding catalyst is determined by the composition of the catalyst and ranges from 9-15 wt.%.

Presulfiding the catalyst should have a tensile splitting strength, allowing to load the catalytic system with use of special devices, and to withstand the loads occurring during operation and regeneration. The latter are determined by rates of collective strength crush strength. For catalysts for hydrogenation processes the tensile splitting strength shall be not less than 1.8 kg/mm, crush strength is not less than 0.8 MPa.

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 about the restored and the activity of the catalyst.

Example 1.

Restoring the activity of the catalyst PK-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.%.

Main physical and chemical characteristics of fresh catalyst PK-442Ni shown in table 1.

After the termination of the supply of raw materials to the catalyst PK-442NI established that the concentration of hydrogen in the hydrogen-containing gas 60 vol.%, the temperature in the reactor 220°C. Gradually, at a rate of 25°C/h, increased the temperature in the reactor up to 400°C. 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 120°C at a rate of 20°C/hour. When the temperature in the reactor 120°C was replaced with hydrogen gas to nitrogen. Set the pressure in the reactor 4 ATI and started operation passivation.

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 0.50%. After aligning the oxygen concentration at the inlet to the reactor and the reactor exit temperature in the reactor was lowered to 40°C and started unloading the catalyst.

After unloading about who ate the 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 the block oxidative regeneration of specialized units (scheme shown in figure 1), the reactor R-11, which represents the rotating speed of 0.7-1.0 rpm horizontal cylindrical tank with internal longitudinal partitions.

Burning was carried out at pressure of 1.0 MPa and a temperature of 550°C, provide by filing in the reactor regeneration process air with a temperature of 270°C, the oxygen concentration of 20 vol.% when the ratio of oxygen-containing gas to the catalyst is 15:1.

Loss after dropping out of the regenerated catalyst from the resulting in operation and regeneration of dust and crumbs amounted to 3.5%.

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

The transfer of catalyst from the oxide in presulfiding form was carried out on the unit preconfigurable specialized regeneration unit (see figure 2). The sulfur content in the mixture fed to the reactor R-12, was 15 wt%. The temperature in the reactor R-12 was maintained at 120°C by feeding into the reactor of air heated in the furnace P-12 to a temperature of 160°C. the residence time of the catalyst in the heating zone was 60 min, the speed of rotation of the reactor is 0.7 rpm

Than what their characteristics fresh, after passivation, after the burning of fat and presulfiding catalyst PK-442Ni shows that changes in the chemical composition of the catalyst is practically nonexistent, the products of condensation of hydrocarbons removed almost completely. Strength characteristics and activity of the catalyst decreased slightly, catalyst losses due to the destruction to a minimum.

Example 2.

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

Main 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 to 200°C. Gradually, at a rate of 30°C/hour, raised the temperature in the reactor to 380°C. 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 100°C at 25°C/hour. When the temperature in the reactor 100°C was replaced with hydrogen gas to nitrogen. The mouth is rebuilt reactor pressure of 10 MPa and started operation passivation.

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 40°C 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 the block oxidative regeneration of specialized units (scheme shown in figure 1), the reactor R-11 which is a stationary horizontal cylindrical vessel equipped inside the moving tape to move the catalytic Converter.

Burning was carried out at a pressure of 0.4 MPa and a temperature of 450°C, provide by filing in the reactor regeneration process air with a temperature of 380°C, the oxygen concentration of 12% vol. when the ratio of oxygen-containing gas to the catalyst 30:1.

Loss after dropping out of the catalyst formed from the process of exploitation and regeneration of dust and crumbs was 3.0%.

Physico-chemical characteristics of the catalyst after burning products seals the Oia is summarized in table 4.

The transfer of catalyst from the oxide in presulfiding form was carried out on the unit preconfigurable specialized installation (see figure 2). The sulfur content in the mixture fed to the reactor R-12, was 12 wt%. The temperature in the reactor R-12 was maintained at 160°C by feeding into the reactor of air heated in the furnace P-12 to 200°C. the residence time of the catalyst in the heating zone was 60 min, the speed of rotation of the reactor to 1.0 rpm

Comparison of the characteristics of fresh, after passivation, after the burning of fat and presulfiding catalyst RK-so shows that changes in the chemical composition of the catalyst is practically nonexistent, the products of condensation of hydrocarbons removed almost completely. Strength characteristics and activity of the catalyst decreased slightly, catalyst losses due to the destruction to a minimum.

Implementation of the proposed method for the regeneration of catalytic systems for hydrogenation processes in examples 3-11 were carried out in a sequence similar to that of examples 1-2, burning foods seal of hydrocarbons was carried out in a reactor whose construction is described in example 1. When implementing the present invention according to example 11 (prototype) operation preconfigurable not performed. The transfer of metal oxides into sulfides conducted directly to the public in the Hydrotreating reactor by feeding into the reactor of disulphides at a temperature of 180-340°C.

Information used to run the examples 3-11 catalysts, the process parameters of each operation and the results obtained are given in tables 1-5.

It is seen that during the operation the burning products of the condensation of hydrocarbons from the catalyst surface in accordance with the formula of the invention (examples 1-8) and their physicochemical and performance characteristics change slightly. Loss of catalysts in the form of crumbs and dust is minimal.

Carrying out this operation with the deviation of process parameters from the given in the formula of the invention (examples 9 and 10) leads to a significant decrease in the activity of the catalyst, incomplete Viigo carbon-containing compounds, the deterioration of its mechanical properties and large losses.

The technical solution described in the prototype (example 11), not provided by the control characteristics are fed into the reactor burning oxygen-containing gas, the amount, and the transfer catalysts of the oxide in presulfiding form outside of the reactor of the plant.

The lack of control over the quantity and characteristics are fed into the reactor burning oxygen-containing gas leads to sharp fluctuations of temperature in the reactor burning (regeneration) and uncontrolled temperature rise above let the s values. As a result, the durability of the catalyst and the content of active components is significantly reduced (compared to fresh). Catalyst losses when the overload in the form of dust and crumbs significant. The catalyst activity decreased significantly. Conversion of sulfur on the catalyst after regeneration was only 89,6% compared to 95.5 from fresh.

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

1. The method of restoring the activity of catalysts for hydrogenation processes by sequential desorption of hydrocarbons from the surface of the waste, while stationary layer of catalysts in the environment of the hydrogen-containing gas at a temperature of 200-400°C; passivate the surface of the catalysts due to their processing in the stationary layer at a temperature of 100-120°C oxygen-containing gas with an oxygen content of 0.02 to 0.5% vol. the burning products of the condensation of hydrocarbons in the stream of oxygen-containing gas at a temperature of 400-550°C; transfer catalysts of the oxide in presulfiding the form and by the contact with elemental sulfur in the current of air or inert gas, characterized in that the burning products of the condensation of hydrocarbons and translation of the catalysts of the oxide in presulfiding form is carried out in a moving catalyst bed, the temperature of the burning products of the condensation of hydrocarbons is regulated by the temperature of the oxygen-containing gas and the volumetric ratio of oxygen-containing gas, the catalyst is equal to (15-30): 1.

2. The method according to claim 1, characterized in that the temperature of the oxygen-containing gas as reducing the carbon content of the catalyst is directed into the burning products of the condensation of hydrocarbons, is when the carbon content (wt.%) respectively:
270-380°C above 10
380-420°C 10-4
420-480°C 4-2
480-550°C less than 2.

3. The method according to claim 1, characterized in that the concentration of oxygen in the oxygen-containing gas at Vigie products seal of hydrocarbons is 12-20%.



 

Same patents:

FIELD: oil and gas industry.

SUBSTANCE: invention refers to methods of hydrogenating processing oil stock at presence of catalytic system and hydrogen and it can be implemented in oil processing industry. The method of hydro-fining oil fractions at raised temperatures and pressure and circulation of hydrogen containing gas in two stages at presence of a package of alumina support catalyst is performed at the temperature of 330-390°C, pressure 40-50 atm, circulation of hydrogen containing gas 250-400 nm3/m3 of stock, volume rate of stock supply 0.8-1.3 n-1 at presence of catalysts package, which at the first stage includes the catalyst of a protecting layer as an upper retaining layer and ANM (alumina-nickel-molybdenum) as a lower layer at the following ratio of components, wt %: catalyst of protecting layer 3.0-10.0, alumina-nickel-molybdenum catalyst - the rest; on the second stage catalyst package includes AKM (alumina-cobalt-molybdenum catalyst or ANM as an upper layer and AKM as a lower layer at the following ratio of components, wt %: alumina-cobalt-molybdenum catalyst 20.0-30.0, alumina-nickel-molybdenum catalyst - the rest.

EFFECT: development of efficient method of hydro-fining oil fractions.

3 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: catalyst is processed with sulphiding agent, which includes sulphur-organic compound and oil fraction, in particular 1.0-2.0%-solution of dimethyldisulphide in Diesel fuel, dimethyldisulphide being introduced into Diesel fuel step-by-step; thermoprocessing of catalyst being carried out as step-by-step increase of temperature within the interval 160-340°C, after which temperature is reduced to 28-290°C, with general activation duration 20-30 hours.

EFFECT: reduction of equipment corrosion with sulphur oxides, obtaining ecologically pure, low-sulphureous Diesel fuel, polycyclic aromatic hydrocarbons in small amount, increasing degree of unlimited hydrocarbons and reduction of gumming-up of main hydropurification catalyst.

3 cl, 6 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of hydrotreating catalyst activation containing metal oxide of group VIB and metal oxide of group VIII containing contacting catalyst, acid and organic additive with boiling point within 80-500°C and water solubility, at least, 5 gram per litre (20°C, atmospheric pressure), optionally with following drying in the environment providing at least, 50% of the additive remains in the catalyst. There are disclosed hydrotreating catalyst produced by the method described above, and method of hydrotreating raw hydrocarbons there after applied.

EFFECT: higher activity of both raw hydrotreating catalyst, and utilized hydrotreating catalyst being regenerated.

20 cl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention describes method of obtaining aggregated catalyst for hydrogen treatment of oil fractions. The catalyst is a composition of components in the form of compounds of one VIII group metal and two VIB group metals. Method involves mixing and chemical interaction of components, producing active complex by mechanic and chemical activation of components, which remain in solid state during the whole process performed in aggregates of mechanic and/or hydrodynamic effect, preferably in planetary centrifugal mill, at room temperature for 5-30 minutes, with free pass distance of milling bodies equal to 4.0-5.0 cm, relative collision speed of milling bodies equal to 17-34 m/s, reaction layer thickness for component mix on the surface of milling bodies equal to (0.4-2.6)·10-2 cm, with further drying, tempering and sulfidation. Active complex is dried for 10-15 minutes.

EFFECT: high-grade purification of oil products from sulfur.

1 cl, 1 tbl, 2 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: invention refers to high metal catalyst compositions, production and application thereof in hydrotreating, specifically in hydrodesulfurisation and hydrodenitrogenating. Described is carrier-free catalyst composition containing one or more metals of VIb group, one or more metals of VIII group and refractory oxide material which contains at least 50 wt % of oxide-based titanium dioxide. Described is production method of catalyst compositions implying that one or more compounds of metal of VIb group is combined with one or more compounds of metal of VIII group and with refractory oxide material containing titanium dioxide with proton liquid and optionally alkaline compound; and catalyst composition is recovered by following precipitation. Described is application of composition described above or produced by method described above, moulded and sulphided if necessary, in hydrotreating of hydrocarbon raw materials.

EFFECT: higher activity of catalyst composition.

15 cl, 8 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.

EFFECT: increase of conversion degree of sulphur, microcarbon residue.

23 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: catalysts are intended for deep hydropurification of Diesel fractions from sulphureous compounds and can be used in oil-refining and oil-chemical industry. Catalyst for process of Diesel fraction hydrodesulphurisation has following composition, wt %: molybdenum oxide MoO3 16.0-29.0, cobalt oxide CoO and/or nickel oxide - 3-8, and phosphorus - 0.1-0.5, uranium oxide 1-15, carrier - the remaining part, atomic ratio Mo/Co(Ni) and P/Mo within 1.8-2.6 and 0.08-0.15, respectively. Method of obtaining catalyst (versions) includes successive or simultaneous impregnation of oxide carrier with solution of uranyl nitrate or acetate and complex solution of salts of metals of VIII and VI groups of periodic system with further thermal processing in flow of air or nitrogen at temperature not higher than 240°C. Process of Diesel fraction hydrodesulphurization is carried out under the following conditions: partial hydrogen pressure 3.5 MPa, temperature 300-370°C, weight liquid consumption 2 hour-1, volume ratio hydrogen/fuel 300-500 in presence of catalyst of said composition or obtained by invention methods.

EFFECT: deep purification of Diesel fractions, catalyst stability, its resistance to deactivation.

9 cl, 17 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: description is given of a catalytic composition with general formula, in consideration of oxides: (X)b(M)c(Z)d(O)e (I), in which X represents at least one group VIII base metal, M represents at least one group VIB metal, Z represents one or more elements, chosen from aluminium, silicon, magnesium, titanium, zirconium, boron and zinc, O represents oxygen, one of b and c represents an integer 1, and d, e and one of b and c represents each a number bigger than 0, such that the molar ratio b:c ranges from 0.5:1 to 5:1, molar ratio d:c ranges from 0.1:1 to 50:1, and molar ratio e:c ranges from 3.6:1 to 108:1. The method of obtaining the composition involves heating a composition with general formula (NH4)a(X)b(M)c(Z)d(O)e (II), in which a represents a number bigger than 0, and X, M, Z, O, b, c, d and e are such that, they are bigger, at temperature ranging from 100 to 600°C, where the composition with formula II is in suspension form or is extracted from a suspension, optionally after maturing at temperature ranging from 20 to 95°C for a period of not less than 10 min. The above mentioned suspension is obtained by precipitation at temperature and within a period of time, sufficient for obtaining formula II composition, of at least one compound of a group VIII base metal at least one compound of a group VIB metal at least one refractory oxide material and alkaline compound in protonic liquid. At least one of the metal compounds is partially in solid state and partially in dissolved state. Description is given of volumetric metal oxide catalytic composition, obtained using the method given above, and a composition with general formula I, which can be obtained using a precipitation method, in which a refractory oxide material in quantity ranging from 15 to 40 wt % is precipitated at least with one compound of a group VIII base metal, and at least with one compound of a group VIB metal, as well as the method of obtaining it. Description is also given of the use of compositions, moulded or sulphided when necessary, in hydro-processing.

EFFECT: increased activity of catalytic compositions.

14 cl, 10 tbl, 24 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep processing of hydrocarbon stock and can be employed in petroleum processing and petrochemical industries. Particularly, invention provides catalyst for diesel fraction hydrodesulfurization process, which contains, as active component, oxygen-containing molybdenum and cobalt and/or nickel complex compound at Mo/(Co+Ni) atomic ratio 1.5-2.5 and is characterized by specific surface 100-190 m2/g, pore volume 0.3-0.5 cm3/g, prevailing pore radius 80-120 Å. Catalyst support is constituted by alumina or alumina supplemented with silica or montmorillonite. Described are also catalyst preparation procedure and diesel fraction hydrodesulfurization process.

EFFECT: increased catalytic activity and resistance of catalyst against deactivation in presence of diesel fuel hydrocarbon components and sulfur compound of thiophene and its derivatives series.

8 cl, 1 tbl, 7 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for production of low-sulfur motor fuels and methods for preparing such catalysts. Hydrodesulfurization catalyst according to invention is characterized by pore volume 0.3-0.7 mL/g, specific surface 200-350 m2/g, and average pore diameter 9-13 nm and containing following components, wt %: cobalt compounds (calculated as CoO) 2.5-7.5, molybdenum compounds (as MoO3), citric acid 15-35, boron compounds (as B2O3) 0.5-3.0, aluminum oxide - the rest, cobalt, molybdenum, citric acid, and boron optionally being part of complex compound having different stoichiometry. Catalyst is prepared by impregnating catalyst support with impregnation solution obtained by dissolving, in water or aqueous solution, following compounds: citric acid, ammonium paramolybdate (NH4)6Mo7O24·4H2O, at least one cobalt compound, and at least boron compound, addition order and component dissolution conditions being such as to provide formation of complex compounds, whereas concentration of components in solution is selected such that catalyst obtained after drying would contain components in above-indicated concentrations.

EFFECT: maximized activity of desired reactions ensuring production of diesel fuels with sulfur level below 50 ppm.

9 cl, 8 ex

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 a method for regenerating catalyst tsiklitiria hydrolysis of aminonitriles order to obtain lactam

The invention relates to the regeneration of catalysts containing zeolite type pentasil, deactivated as the result of kokoulina when carrying out the reaction of dehydrocyclization aliphatic hydrocarbons

The invention relates to a method for optimizing thermal and hydrodynamic regime of the process of regeneration of the solid granular catalysts for catalytic conversion of hydrocarbons, for example, reforming, isomerization, aromatization, etc

The invention relates to methods of oxidizing regeneration superagency catalysts, sorbents and molecular sieves, i.e

FIELD: chemistry.

SUBSTANCE: invention concerns method of hydrotreating catalyst activation containing metal oxide of group VIB and metal oxide of group VIII containing contacting catalyst, acid and organic additive with boiling point within 80-500°C and water solubility, at least, 5 gram per litre (20°C, atmospheric pressure), optionally with following drying in the environment providing at least, 50% of the additive remains in the catalyst. There are disclosed hydrotreating catalyst produced by the method described above, and method of hydrotreating raw hydrocarbons there after applied.

EFFECT: higher activity of both raw hydrotreating catalyst, and utilized hydrotreating catalyst being regenerated.

20 cl, 8 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention, in particular, relates to catalysts based on nickel, cobalt, molybdenum, aluminum oxides. Regeneration of exhausted catalyst is carried out through heat treatment in air atmosphere at 550-600°C for 1-1.5 h followed by: mechanical activation at energy concentration at least 6.6 W/g on vibrational mill; grinding into powder; adding at stirring a mixture containing nitric acid solution (concentration 3,5-7%), cobalt or nickel nitrate and ammonium paramolybdate; molding; drying; and calcination.

EFFECT: simplified regeneration procedure and enabled restoration of catalyst strength.

1 tbl, 12 ex

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to manufacture of heterogeneous catalysts for the processes of liquid-phase oxidation of inorganic and/or organic compounds, including sulfur-containing ones, with air oxygen. Invention provides heterogeneous catalyst containing (i) active component (15-50%) on polymer carrier, namely polyethylene, polypropylene, polystyrene or another polymer, said active component being variable-valence metal oxides and/or hydroxides, or spinels, and additionally (ii) modifying additive (0.5-20%), namely organic bases and/or heteropolyacids, and/or carbon-containing material.

EFFECT: increased catalytic activity.

2 cl, 5 tbl, 6 ex

The invention relates to a method for dehydrogenation of ethylbenzene to styrene in a system containing a reactor with a fluidized bed and the regenerator, in the presence of a catalyst based on iron oxide and promoters selected, for example, metal oxides such as oxides of alkali metals, oxides of alkaline-earth metals and/or metal oxides of the lanthanides group, plotted on the modified alumina
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