Method of preparing catalytic system for hydrofining of hydrocarbon feedstock

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

 

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

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, consisting mainly in a significant reduction in the final product sulfur content and polycyclic aromatic hydrocarbons [Kaminski ET, Khavkin, VA, Osipov LN. and other Refining and petrochemicals, 2002, No. 6, p.17-18].

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.

One of the ways to meet these requirements is the development of new catalysts with high activity in reactions of hydrog is Nolita organic sulfur compounds and hydrogenation of polycyclic aromatic hydrocarbons.

Very important for catalysts used in large Hydrotreating processes are indicators of their strength properties.

Known aluminumalloy catalyst for Hydrotreating gasoline [Autospid. The USSR №701700], obtained by mixing powders of aluminum oxide with a particle size of 10-40 and 40-200 μm, taken in a certain ratio, Nickel nitrate, nitric acid and paramolybdate ammonium, followed by molding, drying and calcination. In industry, this catalyst produced under the brand name TH-30-7, it contains molybdenum oxide - 18,0-22,0% wt., Nickel oxide - 3.0-5.0% wt.

The use of powders of aluminum oxide greatly simplifies the catalyst production technology and eliminates the waste water.

A significant disadvantage of this catalyst is the low strength properties. The index of the strength of the catalyst according to this invention does not exceed 1.6 kg/mm, which complicates its use in large-capacity processing.

A method of obtaining alumnirelations catalyst Hydrotreating of petroleum distillates by mixing the powder made from aluminum oxide hot and cold deposition in a ratio of from 3:1 to 7; 1, with a particle size of 5-40 μm, 40-150 μm and 150-400 ám Nickel nitrate, nitric acid and paramolybdate ammonium PEFC is blowing molding, drying and calcination [Autospid. The USSR №914081]. In industry, this catalyst produced under the brand KGO-5. The content of oxides of the active metals is NiO - 3,0-5,0% wt., NGO - 10,0-12,0% wt.

The method of producing catalysts TH-30-7 and KGO-5 based on the use of powders of aluminum oxide. The technology used in the production of the catalyst KGO-5, allows to improve the strength properties of the catalyst (index strength is 1.8 kg/mm), but its activity in the hydrogenolysis reactions of organic sulfur compounds, in comparison with the catalyst of TH-30-7, is reduced. As a result, the catalyst KGO-5 cannot provide diesel fractions with residual sulfur content below 350 ppm, as well as raw material for catalytic cracking with residual sulfur is not more than 0.3 wt.%. in the processing of high-sulphur crude oil in existing process units (at low pressure of 30-40 bar, high flow rate).

Known methods for producing aluminoborosilicate catalyst Hydrotreating of petroleum products, including the processing of aluminium hydroxide with nitric acid, mixed with a suspension of cobalt molybdate in solution of hydrogen peroxide, forming, drying and calcination [Autospid. The USSR №986000 and No. 1559499]. The catalysts produced in industry under the brand names ST-70 and ST-86, respectively. The content of the W oxides of active metals in these supported catalysts is Soo - 3,0-5,0% wt., NGO - 12,0-15,0% wt.

The method of obtaining these catalysts is based on the use of "bread" aluminium hydroxide, which significantly complicates the production process and increases the flow of water. The catalysts produced in accordance with the specified method, have good activity in the hydrogenolysis reactions of organic sulfur compounds, but low activity in hydrogenation reactions of polycyclic aromatic hydrocarbons and not high enough strength to operate them in large processes.

Known methods of preparation of catalysts for Hydrotreating heavy oil feedstock by obtaining granular media "tortillas" aluminium hydroxide with subsequent impregnation with a solution of Nickel nitrate and paramolybdate ammonium [autospid. The USSR №1626492, autospid. The USSR №1635374]. These catalysts are produced in industry under the brands GP-526, SE-534. The content of oxides of the active metals in the catalyst is NiO - 3,0-5,0% wt., NGO - 12,0-15,0% wt.

The disadvantage of these catalysts is relatively low activity in the hydrogenolysis reactions of organic sulfur compounds in the processing of high-sulphur crude oil.

Known preparation method of catalyst for hydrofining vacuum gas oil, by depositing alumina carrier active gererously pore-forming components, photobrush promoters [U.S. Pat. Of the Russian Federation No. 2124400]. The catalyst is produced under the brand names of Kazakhstan-a and RK-442Ni. The content of oxides of the active metals in the catalyst is NiO (Soo) - 3,0-5,0% wt., NGO - 12,0-15,0% wt.

The catalyst RK-442Ni appropriate to apply to facilities operating at a pressure above 50 atmospheres. Under these conditions, the catalyst has good activity in hydrogenation reactions of polycyclic aromatic hydrocarbons and hydrogenolysis of organic sulfur compounds. When the pressure of 30-40 bar, which operated most of the existing domestic installations, the activity of the catalyst in the hydrogenolysis reactions of organic sulfur compounds is significantly reduced. The catalyst RK-so has high activity in hydrogenation reactions of organic sulfur compounds and at low pressures (30 to 40 ATM), but its activity in the hydrogenation reactions of polycyclic aromatic hydrocarbons low.

It is known that the hydrogenolysis of organic sulfur compounds from different classes (mercaptans, sulfides, disulfides, benzothiophene) occurs when different technological parameters depending on the use allocable or alumonickelsilicate catalysts [Kneesaa, Ellaline, Vccmin. Chemistry and technology of fuels and oils, p.21-24, No. 1-2, 2003].

In St. the zi arises a problem of increasing the efficiency of the Hydrotreating process using catalytic systems, consisting of allocability and alumonickelsilicate catalysts. The use of catalytic systems extends the range of technological parameters of operation of the catalyst.

Known methods of Hydrotreating of petroleum distillates in the medium of hydrogen in the presence of alumina system (Ecumenical and aluminoborosilicate) catalysts, pre-activated sulfur-containing agent (elemental sulfur, disulfides) [U.S. Pat. RF№№2005765, 2140963, 2140964].

The disadvantages of these methods include relatively low strength properties of the catalyst included in the catalytic systems that does not allow you to use them in large Hydrotreating processes, and insufficient for processing high-sulfur petroleum fractions with a high content of aromatic hydrocarbons gidroobesserivaniya and hydrogenating activity.

Closest to the proposed technical solution to the technical essence and the achieved result is a method for the catalytic system hydrofining hydrocarbon layer by layer load oxide and presulfiding catalysts [U.S. Pat. Of the Russian Federation No. 2229934].

The disadvantage of this method is the relatively low efficiency in the processing of oil and gas condensate fractions with a high content of sulfur and politics the ical aromatic hydrocarbons.

The aim of the invention is the development of catalysts and catalytic systems for large scale processes hydrofining sour hydrocarbon raw materials to produce products with the desired residual content of sulfur and polycyclic aromatic hydrocarbons.

This goal is achieved by applying the method for the catalytic system hydrofining of hydrocarbon raw materials by sequential loading into the reactor almocabar and alumonickelsilicate catalysts containing molybdenum oxide 12,0-25,0% wt., the cobalt oxide of 3.0 to 6.0 wt.%, Nickel oxide is 3.0 to 6.0 wt.%, characterized in that Ecumenical and aluminoborosilicate catalysts loaded in the ratio of from 1.0:0.1 to 0.1:1.0 to preparation of these catalysts, a mixture of powders of hydroxide and/or aluminum oxide with the addition of acid to a pH of 1-5, as a mixture of powders of aluminum hydroxide use powders product thermochemical activation of gibbsite and pseudoboehmite AlOOH and content in the mixture of pseudoboehmite AlOOH is not less than 70 wt.%, and as a mixture of powders of aluminum oxide powders γ-Al2About3with a particle size of 50 microns and 50-200 microns, taken in the ratio of from 5:1 to 2:5, or powders γ-Al2About3with a particle size up to 50 microns, 50-200 μm and 200 to 400 microns,taken in the ratio of 1:8:1 to 3:6:1.

A distinctive feature of the proposed technical solution is that Ecumenical and aluminoborosilicate catalysts loaded in the ratio of from 1.0:0.1 to 0.1:1.0 to preparation of these catalysts, a mixture of powders of hydroxide and/or aluminum oxide with the addition of acid to pH 1÷5, as a mixture of powders of aluminum hydroxide use powders product thermochemical activation of gibbsite and pseudoboehmite AlOOH and content in the mixture of pseudoboehmite AlOOH is not less than 70 wt.%, and as a mixture of powders of aluminum oxide powders γ-Al2About3with a particle size of 50 microns and 50-mm taken in a ratio of from 5:1 to 2:5, or powders γ-Al2About3with a particle size up to 50 microns, 50-200 μm and 200 to 400 microns, taken in the ratio of 1:8:1 to 3:6:1.

The proposed method for the catalytic system hydrofining hydrocarbon is as follows.

In the reactor load Ecumenical and aluminoborosilicate catalysts, taken in the ratio of from 1.0:0.1 to 0,1:1,0 obtained in the following way:

Take the mixture of powders γ-Al2About3with particle sizes of 50 μm and 50-200 μm, or 50 μm, 50-200 μm and 200 to 400 μm), in a ratio of from 5:1 to 2:5 (or in a ratio of 1:8:1 to 3:6:1) and/or powder pseudoboehmite or a mixture powder of pseudoboehmite with product thermoinactivation gibbsite.

Then:

or in the mixture with constant stirring consistently give the nitrate of Nickel and/or cobalt) based 3.0-6.0 wt.%. (NiO and/or COO) on the catalyst, an aqueous solution of acid to obtain a pulp with a pH value of from 1 to 5, paramolybdate ammonium based 12,0-25,0% wt. Moo3on the catalyst. The resulting mass is stirred and molded by extrusion, followed by drying and calcining the obtained extrudates,

or in the mixture with constant stirring consistently give a solution of salts of active ingredients, prepared based content in the catalyst 3.0-6.0 wt.%. NiO and/or COO, 12,0-25,0% wt. Moo3,

or in the mixture add a solution of acid to obtain a pulp with a pH value of from 1 to 5. The resulting mass is formed by extrusion with subsequent drying and calcining the obtained extrudates. The calcined extrudates are impregnated with a solution of salts of active ingredients, prepared based content in the catalyst 3.0-6.0 wt.%. NiO and/or COO, 12,0-25,0% wt. Moo3.

The catalyst included in the catalytic system, after loading in the reactor is dried and activated by a translation of the oxides of molybdenum, Nickel and cobalt sulfides. As the carrier sulfiding agent use or presulfiding catalysts, or easily degradable behold organicheskoi connection for example diallyldisulfide. After activation of the catalytic system are served raw materials at a temperature of 180-300°depending on the fractional composition of the processed material at flow rate 0.2-CAS-1depending on the performance of the installation. The feedstock flow rate is gradually increased until the worker, then the temperature at the inlet of the reactor was raised to the working speeds of no more than 20°C/hour.

Use for hydrofining hydrocarbon catalytic system obtained by the present method, can significantly extend the range of process parameters and process raw materials without reducing the quality of the products.

The introduction of the catalytic system almocabar and alumonickelsilicate catalysts obtained in accordance with the invention, in a predetermined ratio allows to increase the activity of the catalytic system in the hydrogenolysis reactions of organic sulfur compounds and hydrogenation of polycyclic aromatic hydrocarbons.

The realization of the whole complex of technological operations specified in the formula of the present invention can improve reliability of the operation of the catalytic system in the processing of a wide range of petroleum fractions.

In the famous the x ways of producing catalytic systems, the above methods for producing catalysts and catalytic systems is unknown.

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

The following are specific examples of implementation of the proposed method, which he illustrated by, but not limited to.

Examples.

When testing the proposed technical solutions as catalysts used samples obtained in accordance with the formula of the invention (see table 1), which synthesis was carried out according to the following scheme.

Sample # 1

Preparing a mixture of powders γ-Al2About3, which consists of powders with particle sizes of 50 μm and 50-200 microns, taken in the ratio of 5:1.

Preparing a mixture of powders of aluminum hydroxide, consisting of powder pseudoboehmite in the amount of 70 wt.%. and product thermochemical activation of gibbsite in the amount of 30% wt.

The obtained powders are mixed in a ratio of: 70% powder γ-Al2O3and 30% of a powder of aluminum hydroxide.

In the mixture with constant stirring add nitrate of Nickel based content of NiO in the catalyst 3.0% wt., an aqueous solution of nitric acid to pH 1, paramolybdate ammonium based NGO312,0% wt. on the catalyst. The resulting mass is stirred and molded by extrusion is followed by drying and calcining.

The resulting catalyst contains NiO 3,10% wt., Moo312,09% wt.

Sample # 2

Preparing a mixture of powders γ-Al2About3, which consists of powders with particle sizes of 50 μm and 50-200 microns, taken in the ratio 2:5.

Preparing a mixture of powders of aluminum hydroxide, consisting of powder pseudoboehmite in the amount of 70 wt.%. and product thermochemical activation of gibbsite in the amount of 30% wt.

The obtained powders are mixed in the following ratio: 60% powder γ-Al2About3and 40% of a powder of aluminum hydroxide.

In the mixture with constant stirring add nitric acid to pH 5.

The resulting mass is stirred and molded by extrusion, followed by drying and calcining. Receive the media.

Prepare a solution of salts of active metals (cobalt nitrate and paramolybdate ammonium) based content in the finished catalyst is molybdenum oxide 18,0% wt., the cobalt oxide to 5.0% wt. The solution is prepared in quantity by 15-20% higher than required by the absorption of the received media.

This solution is impregnated with the resulting carrier.

The product is dried at a temperature of 100-150°C, calcined at a temperature of 450-500°C.

The resulting catalyst contains Soo 4,90% wt., Moo318,20% wt.

Sample 3

Preparing a mixture of powders γ-Al2About3in composition to the th are powders with a particle size up to 50 microns, 50-200 μm, 200-400 μm, taken in the ratio 1:8:1.

Preparing a mixture of powders of aluminum hydroxide, consisting of powder pseudoboehmite in the amount of 80% by weight. and product thermochemical activation of gibbsite in the amount of 20% wt.

The obtained powders are mixed in a ratio of: 50% powder γ-Al2O3and 50% of a powder of aluminum hydroxide.

In the mixture with constant stirring successively added a solution of salts of active metals (Nickel nitrate and paramolybdate ammonium) based content in the finished catalyst is molybdenum oxide 18,0% wt., Nickel oxide - 5.0 wt%, nitric and acetic acid to pH 2.

The resulting mass is stirred and after maturation formed by extrusion, followed by drying and calcining.

The resulting catalyst contains NiO 4.82 wt.%, Moo317.90% wt.

Sample 4

Preparing a mixture of powders γ-Al2About3, which consists of powders with particle sizes of 50 μm, 50-200 μm, 200-400 μm, taken in the ratio 3:6:1.

The resulting powder γ-Al2About3mixed with powder pseudoboehmite ratio: γ-Al2About3- 90% wt., pseudoboehmite - 10% wt.

In the mixture with constant stirring add nitric acid to pH 3.

The resulting mass is stirred and after maturation formed by extrusion with subsequent what uskoi and calcining. Receive the media.

Prepare a solution of salts of active metals (cobalt nitrate and paramolybdate ammonium) based content in the finished catalyst of molybdenum oxide to 12.0 wt.%, oxide of cobalt - 3.0% wt. The solution is prepared in quantity by 15-20% higher than required by the water absorption of the obtained semi-product.

This solution is impregnated with the resulting carrier. The product is dried at a temperature of 100-150°C, calcined at a temperature of 450-500°C.

The resulting catalyst contains Soo 2,95% wt., Moo312,21% wt.

Sample 5

Preparing a mixture of powders of pseudoboehmite (70% wt.) and product thermochemical activation of gibbsite (30% wt.).

In the mixture with constant stirring, a solution of salts of active metals (Nickel nitrate and paramolybdate ammonium) based content in the finished catalyst is molybdenum oxide 16,0% wt., Nickel oxide - 4.0 wt.%, at pH=4.

The resulting mass is stirred and after maturation formed by extrusion, followed by drying and calcining.

The resulting catalyst contains NiO 4,08% wt., Moo315,85% wt.

Sample 6

Preparing a mixture of powders γ-Al2About3, which consists of powders with particle sizes of 50 μm and 50-200 microns, taken in the ratio 2:5.

In the mixture with constant stirring add nitrate of cobalt from the calculations of the TA content in the catalyst 4.0 wt.%, an aqueous solution of phosphoric acid to pH 4, paramolybdate ammonium based 16,0% wt. on the catalyst. The resulting mass is stirred and after maturation formed by extrusion, followed by drying and calcining.

The resulting catalyst contains Soo 3,96% wt., Moo316,12% wt.

Sample 7

Preparing a mixture of powders γ-Al2About3, which consists of powders with particle sizes of 50 μm and 50-200 microns, taken in the ratio of 5:1.

Preparing a mixture of powders of aluminum hydroxide, consisting of powder pseudoboehmite in the amount of 70 wt.%. and product thermochemical activation of gibbsite in the amount of 30% wt.

The obtained powders are mixed in a ratio of: 70% powder γ-Al2About3and 30% of a powder of aluminum hydroxide.

In the mixture with constant stirring add nitrate of Nickel calculated as the NiO content in the resulting intermediate to 3.0 wt.%, an aqueous solution of nitric acid to pH 2, paramolybdate ammonium based NGO312,0% wt. the resulting intermediate. The resulting mass is stirred and after maturation formed by extrusion, followed by drying and calcining.

Prepare a solution of salts of active metals (cobalt nitrate and paramolybdate ammonium) based content in the finished catalyst is molybdenum oxide 25,0% wt., the cobalt oxide to 3.0% wt. The solution was prepared in the amount of the and 15-20% higher than is required by the water absorption of the obtained semi-product.

This solution is impregnated with the obtained semi-product. The product is dried at a temperature of 100-150°C, calcined at a temperature of 450-500°C.

The resulting catalyst contains Soo 3,10% wt., NiO 2,90% wt., Moo324,86% wt.

Sample 8

Preparing a mixture of powders γ-Al2About3, which consists of powders with particle sizes of 50 μm and 50-200 microns, taken in the ratio of 5:1.

Preparing a mixture of powders of aluminum hydroxide, consisting of powder pseudoboehmite in the amount of 70 wt.%. and product thermochemical activation of gibbsite in the amount of 30% wt.

The obtained powders are mixed in a ratio of: 70% powder γ-Al2O3and 30% of a powder of aluminum hydroxide.

In the mixture with constant stirring, a solution of active metal salts (nitrate of cobalt and paramolybdate ammonium) based content in the resulting semi-product of molybdenum oxide to 12.0 wt.%, oxide of cobalt - 3.0% wt., at pH 2.

The resulting mass is stirred and after maturation formed by extrusion, followed by drying and calcining.

Prepare a solution of salts of active metals (cobalt nitrate and paramolybdate ammonium) based content in the finished catalyst is molybdenum oxide 25,0% wt., the cobalt oxide to 6.0 wt.%. The solution was prepared in the share of the ve 15-20% higher than is required by the water absorption of the obtained semi-product.

This solution is impregnated with the obtained semi-product.

The product is dried at a temperature of 100-150°C, calcined at a temperature of 450-500°C.

The resulting catalyst contains Soo 5,96% wt., Moo325,10% wt.

The catalyst samples No. 9-12 are prepared in accordance with the data of table 1, the blending operation on the source powders of oxide and aluminum hydroxide, the active components are carried out by analogy with the above descriptions of the synthesis of the samples No. 1 to 8.

The main characteristics of the samples of the catalysts are given in table 2.

It is seen that under the conditions of synthesis samples of the catalyst included in the catalytic system described in the formula of the invention (sample No. 1-8), produces catalysts with high strength characteristics. The increase of the content in the powder of aluminium hydroxide product thermochemical activation of gibbsite higher values embodied in the formula of the present invention results in a catalyst with low strength (sample 9). Because of the low strength characteristics of this sample for further tests were not considered. Changing the synthesis conditions, samples of the catalysts embodied in the formula of the invention (No. 9-12), leads to considerable the mu reduce the strength of the catalysts, which will adversely affect the stability and durability of the used catalytic system.

The raw material used samples of oil fractions, whose characteristics are given in table 3.

The composition used for testing catalytic systems, process parameters and the results obtained in examples 1-10 are shown in table 4. Detailed description of the implementation of the present invention is described in examples 1-3.

Example 1

90 g of the catalyst sample No. 1 was transferred to presulfiding form outside of the reactor process unit according to the method described in the patent of Russian Federation №2229934, to obtain the catalyst in presulfiding form with a sulfur content of 13 wt.%.

In the reactor sequentially from the bottom up, load 9 g of sample No. 2 in oxide form, 102 g of sample No. 1 in presulfiding form (90 g oxide). The obtained catalyst system is dried in a current of inert gas at a temperature of 120-180°at a pressure of 10 kgf/cm2. After the termination of the moisture separator catalytic system is cooled to a temperature of 100°and begin activation.

Hold the replacement of the inert gas in the hydrogen-containing gas with a hydrogen content of not less than 80% vol. (SIVs), raise the pressure up to 30 kgf/cm2and begin to raise the temperature at the inlet of the reactor to 340°what about the speed of 15° C/hour. When the temperature at the inlet to the reactor 340°stop temperature rise and maintain the system in these conditions for 2 hours. Activation completed.

Cool catalytic system before reaching the temperature at the inlet to the reactor 180°and begin feeding raw material No. 1 (gasoline fraction) with a speed of 0.5 h-1. Over the next three hours volumetric feed rate is gradually increased up to 5.0 hours-1.

Raise the temperature at the inlet of the reactor to 300°With a speed of 20°C/hour.

Establish working process parameters: pressure of 30 ATM, the ratio of everything: raw materials 250 nm3/m3, the volumetric feed rate 5.0 h-1temperature 300°C.

When these process parameters are stable hydrogenation product with residual sulfur less than 0.2 ppm.

Example 2

In the reactor sequentially from the bottom up, load 90 g of sample No. 4 in oxide form, then 9 g of sample No. 3 in oxide form.

The obtained catalyst system is dried in a stream of hydrogen containing gas at a temperature of 120-180°at a pressure of 10 kgf/cm2. After the termination of the moisture separator catalytic system is cooled to a temperature of 150°and begin activation.

In the reactor serves disulfide (sulfur content of 50% wt.) with a speed of 6 g/hour for 4 hours. One is temporarily start the rise of the temperature at the inlet of the reactor to 340° With speeds of 15°C/hour. When the temperature at the inlet to the reactor 340°stop temperature rise and maintain the system in these conditions for 2 hours. Activation completed.

Cool catalytic system before reaching the temperature at the inlet to the reactor 250°and begin feeding raw material No. 2 (diesel fraction) with a speed of 0.5 h-1. Over the next three hours volumetric feed rate is gradually increased up to 3.0 hours-1. Raise the temperature at the inlet of the reactor to 350°With a speed of 20°C/hour.

Establish working process parameters: pressure of 30 ATM, the ratio of everything: the raw material 300 nm3/m3, the volumetric feed rate 3.0 h-1temperature 320°C.

When these process parameters are stable hydrogenation product with residual sulfur 350 ppm, polycyclic aromatic hydrocarbons 9.2% wt.

Example 3

50 g of the catalyst in the oxide form "sample # 3 and sample # 4" is transferred to presulfiding form outside of the reactor process unit according to the method described in the patent of Russian Federation №2229934, obtaining catalysts in presulfiding form with a sulfur content of 12 wt.%.

Catalysts in presulfiding form are mixed and loaded into the reactor. Drying and activation of the obtained catalytic systems are at the ERU 1.

Cool catalytic system before reaching the temperature at the inlet to the reactor 250°and begin feeding raw material No. 2 with a speed of 0.4 h-1. Over the next three hours volumetric feed rate is gradually increased up to 2.0 h-1. Establish the relationship everything: raw material 330 nm3/m3raise the temperature at the inlet of the reactor to 330°With a speed of 20°C/hour. When the temperature reached in the reactor 330°To carry out the replacement of raw material No. 2 for raw materials No. 3, establish the operating parameters of the process (temperature 330°C, a pressure of 40 ATM, the volumetric feed rate of 1.8 h-1the ratio of everything: raw materials 350 nm3/m3).

When these process parameters are stable hydrogenation product with residual sulfur 600 ppm, polycyclic aromatic hydrocarbons 18% wt.

It is seen that the test results for examples, made in accordance with the formula of the invention (examples 1-6), surpass the results of the tests performed under the terms of the prototype (example 10).

When the discrepancy between the composition of the catalytic system and the synthesis conditions included samples of catalysts (examples 7-9) the catalytic activity of the system during operation is significantly reduced.

Table is CA 1.

The list of samples of the catalysts used when implementing the present invention.
Sample # Powder hydroxidePowder γ-Al2About3AcidPHInput method active ingredients*
The content in the initial mixture, wt.%The content of pseudoboehmite powder hydroxide, % wt.The content in the initial mixture, wt.%The ratio of the powders with particle size, microns
Up to 50, 50-200Up to 50, 50-200, 200-40
123456789
No. 13070705:1-nitric11
No. 24070602:5-nitric52
No. 3508050-1:8:1nitric and acetic23
No. 41 10090-3:6:1nitric32
No. 510070---nitric43
No. 6--1002:5-phosphate41
No. 73070705:1-nitric21+2
No. 83070705:1-nitric23+2

Continuation of table 1
123456789
No. 95060502:5-nitric21
No. 10--1006:0,5-nitric61
No. 11--/td> 100-0,5:9:1nitric32
No. 1220100801:6-nitric33
* 1 - dry salt mixture, 2 - impregnation of extrudates with a solution of active metal salts, 3 - salt solutions of the active metals in the mixture.

Table 2.

Characteristics of samples of the catalysts used when implementing the present invention.
Sample # The content in the catalyst, % wt.Strength
MoONiOSooThe cleavage strength, kg/mmThe crushing layer, MPa
No. 112.093.10-2.10.98
No. 218.20-4.902.21.0
No. 317.904.82-2.11.1
No. 412.21-2.952.11.1
No. 5 15.854.08-2.01.0
No. 616.12-3.962.11.0
No. 7At 24.862.903.102.01.1
No. 825.10-5.962.01.1
No. 911.903.121.20.45
No. 1015.20-3.981.80.75
No. 1114.974.12-1.60.68
No. 1212.12-3.951.60.70

Table 3

The list and characteristics of samples of raw materials used in implementing the present invention.
SampleNameFractional composition of,Content % wt.
Nicholas, °K.K., °sulfurpolic. ar.
No. 1Gasoline fraction 751800.08-
No. 2Diesel fraction1803601.918
No. 3Vacuum gasoil3505202.326

/tr>
Table 4.

The composition used for testing catalytic systems, the process parameters of the tests and their results.
Example No.The samples were rolled.RatioSulfiding agent****raw materialsTechnological parametersThe content in the product
Ni-MoCo-MoNi-Mo:Co-MoTemperature, °Pressure, ATMThe ratio of everything:raw materials, nm3/m3The volumetric feed rate, h-1Residual sulfur, ppmPolycyclic aromatics, wt.%
123456789101112
When is EP 1 No. 1No. 21,0:0,1P1300302505,0>0.2-
Example 2No. 3No. 40,1:1,0D2320303003,03509.2
Example 3No. 3No. 41,0:1,0P3330403501,863018
Example 4No. 5No. 60,1:1,0P3330353501.868019
Example 5No. 1No. 81,0:1,0D2320303003.065517
Example 6No. 7*P2320303003.067217
Example 7No. 1No. 20,05:1,0P2320 303003,0250020
Example 8No. 9No. 101,0:0,05P2320303003,0300024
Example 9No. 11No. 120,05:1,0P2320303003,0380024
Example 10 (prototype)KGO-TH-1,0:1,0P2320303003,0370025
5**86***
* the ratio of the oxides of cobalt and Nickel in the catalyst is 1.0:1.0 to

** avts No. 914081

*** avts No. 15 59499

****P - presulfiding catalyst, D - disulfides.

The method for the catalytic system hydrofining of hydrocarbon raw materials by sequential loading into the reactor almocabar and alumonickelsilicate catalysts containing molybdenum oxide 12,0-to 25.0 wt.%, oxide of cobalt, 3.0 to 6.0 wt.%, Nickel oxide is 3.0 to 6.0 wt.%, characterized in that Ecumenical and aluminoborosilicate catalysts loaded in the ratio of from 1.0:0.1 to 0.1:1.0 to preparation of these catalysts, a mixture of powders of hydroxide and/or aluminum oxide with the addition of acid to a pH of 1-5, as a mixture of powders of aluminum hydroxide use powders product thermochemical activation of gibbsite and pseudoboehmite AlOOH and content in the mixture of pseudoboehmite AlOOH is not less than 70 wt.%, and as a mixture of powders of aluminum oxide powders γ-Al2About3with a particle size of 50 microns and 50-200 microns, taken in the ratio of from 5:1 to 2:5, or powders γ-Al2About3with a particle size up to 50 microns, 50-200 μm and 200 to 400 microns, taken in the ratio of 1:8:1 to 3:6:1.



 

Same patents:

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: petrochemical process catalysts.

SUBSTANCE: preparation of crusted metallic catalyst comprises: (i) applying suspension containing diluent, catalytically active metal selected from cobalt and ruthenium groups, and optionally first refractory element (atomic number at least 20) oxide onto surface of carrier particles to form wet coating and (ii) removing at least part of diluent from wet coating, said suspension containing at least 5% by weight of catalytically active metal based on the weight of calcination residue, which would result after drying and calcination of suspension. Crusted metallic catalyst itself and hydrocarbon production process are also described.

EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

FIELD: polymerization reaction catalysts.

SUBSTANCE: catalyst, which may be useful in production of cis-1,4-polymers and cis-1,4-copolymers in synthetic rubber industry, is prepared by mixing, in hydrocarbon solvent, rare-earth element compound, conjugated diene, alkylation agent, and halogen source, said halogen source being aryldimethyl halides or their mixtures with alkylaluminum chlorides. Process is carried out at molar ratio 1:(1-100):(10-100):(0.3-3), respectively.

EFFECT: increased catalytic activity and enabled production of low-dispersity polymers characterized by good performance properties resulting in a high level of physicochemical characteristics of rubber manufactured from these polymers.

2 cl, 1 tbl

FIELD: production of carbon carrier for catalysts.

SUBSTANCE: proposed method includes heating of moving layer of granulated furnace black used as backing, delivery of gaseous or vaporous hydrocarbons into soot layer followed by their thermal decomposition on soot surface forming layer of pyrocarbon at forming of layer of pyrocarbon and activation of material compacted by pyrocarbon at temperature of 800-900°C and unloading of finished product. Granulated furnace black at specific surface of 10-30 m2/g and adsorption rate of 95-115 ml/100 g is used as backing for compacting with pyrocarbon. Then, product is subjected to activation for obtaining total volume of pores of 0.2-1.7 cm3/g. Black is compacted by pyrocarbon at two stages: at first stage, granulated black is compacted to bulk density of 0.5-0.7 g/cm3, after which material is cooled down and screened at separation of fraction of granules of 1.6-3.5 mm; at second stage, this fraction is subjected to repeated pyrolytic compacting to bulk density of granules of 0.9-1.1 g/cm3.

EFFECT: enhanced economical efficiency; increased productivity of process.

3 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention is dealing with catalysts showing high catalytic stability in production of chloroform from carbon tetrachloride via catalytic dehydrochlorination reaction. Catalyst containing γ-alumina-supported platinum is characterized by that platinum in the form of particles 1 to 12 nm in size is distributed throughout the bulk of microspheric γ-alumina particles having median diameter 30 to 70 μm and pore volume 0.3 -0.6 cm3/g. Preparation of catalyst involves impregnation step accomplished via spraying γ-alumina with aqueous platinum compound solution used in amount equal to or less than alumina pore volume followed by platinum compound reduction step, wherein this compound is deposited onto γ-alumina with aqueous solution of formic acid or alkali metal formate.

EFFECT: achieved retention of high catalyst activity and selectivity over a long time period without being preliminarily activated.

9 cl, 2 tbl, 4 cl

FIELD: synthesis gas generation catalysts.

SUBSTANCE: invention provides catalyst for steam generation of synthesis gas containing 2.2-8.2% nickel oxide and 3.0-6.5% magnesium oxide deposited on heat-resistant porous metallic carrier having specific surface area 0.10-0.15 m2/g, summary pore volume 0.09-0.12 cm3/g, predominant pore radius 2-20 μm, and porosity 40-60%. Synthesis gas is obtained by steam-mediated conversion of hydrocarbons at 450-850°C.

EFFECT: increased heat conductivity of catalyst and catalytic activity.

11 cl, 1 tbl, 8 ex

FIELD: chemistry of polymers, chemical technology, catalysts.

SUBSTANCE: invention relates to a method for preparing a catalyst used in polymerization of butadiene and copolymerization of butadiene with coupled dines. Method involves interaction of components comprising the compound of rare-earth element, diisobutyl aluminum hydride, triisobutyl aluminum, alkyl aluminum halide and coupled diene. Firstly, method involves mixing rare-earth element and coupled diene solutions with diisobutyl aluminum hydride solution, and the mixture is kept for 10-30 min at stirring, and then triisobutyl aluminum and alkyl aluminum halide solutions are added. After mixing all components the mixture is kept for 10-15 h in the following mole ratio of components: rare-earth element : diisobutyl aluminum hydride : triisobutyl aluminum : alkyl aluminum halide : coupled diene = 1:(3-12):(6-12):(1.5-3):(2-20), respectively, wherein rare-earth element carboxylate or alcoholate is used as a source of rare-earth element. Invention provides preparing the high-effective catalyst allowing preparing highly stereoregular polybutadiene and butadiene copolymer with the couples diene with simultaneous reducing the range of molecular-mass disposition by 3-3.5 times.

EFFECT: improved preparing method.

5 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst preparation involves interaction of rare-earth element compound, conjugated diene, and diisobutylaluminum hydride followed by ageing of reaction mixture for 10-30 min, adding tetraisobutyl-dialumoxane and alkylaluminum hydroxide at molar ratio 1:(2-20):(3-12):(6-12):(1.5-3), respectively, and ageing resulting mixture for 10-15 h. Diene utilized is in the process is pyperilene or isoprene and rare-earth element compound is rare-earth element carboxylate or alcoholate. Catalyst can, in particular, find use in production of cis-1,4-polydienes.

EFFECT: achieved preparation of high-efficiency catalyst enabling production of highly stereospecific polybutadiene or butadiene/isoprene or butadiene/pyperilene copolymers at narrower molecular mass distribution.

4 ex

FIELD: inorganic synthesis catalysts.

SUBSTANCE: passivation of ammonia synthesis catalyst is accomplished via consecutively treating reduced iron catalyst with oxidant at elevated temperatures and process flow rates. Treatment of catalyst with oxidant is commenced with water steam or steam/nitrogen mixture at 150-300°C while further elevating temperature by 50-200°C, after which temperature is lowered to 150-300°C, at which temperature water steam or steam/nitrogen mixture is supplemented by air and treatment of catalyst is continued with resulting mixture while elevating temperature by 50-200°C followed by reduction of catalyst temperature in this mixture to 150-300°C and cooling of catalyst with nitrogen/oxygen mixture at initial ratio not higher than 1:0.1 to temperature 30°C and lower until nitrogen/oxygen mixture gradually achieves pure air composition.

EFFECT: prevented self-inflammation of ammonia synthesis catalyst when being discharged from synthesis towers due to more full oxidation.

6 cl, 1 tbl, 5 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: organic synthesis catalysts.

SUBSTANCE: method of preparing catalyst based on high-silica zeolite comprises calcination of zeolite and treating it with ammonium salt solutions at 160-200°C followed by mixing with binder, drying, and calcination. High-silica zeolite utilized is ZSM-5 zeolite, which is treated with aqueous ammonium solutions until degree of Na+ cation substitution above 99% is attained.

EFFECT: increased catalytic activity and selectivity in benzene-ethylene alkylation process.

1 tbl, 6 ex

FIELD: industrial inorganic synthesis and catalysts.

SUBSTANCE: invention provides ammonia synthesis catalyst containing VII group and group VIB metal compound nitrides. Ammonia is produced from ammonia synthesis gas by bringing the latter into contact with proposed catalyst under conditions favoring formation of ammonia.

EFFECT: increased ammonia synthesis productivity.

8 cl, 2 tbl, 19 ex

Up!