Vanadium-free catalyst for selective catalytic reduction and method of its production

FIELD: process engineering.

SUBSTANCE: invention relates to vanadium-free catalyst for reduction of aluminium oxides by ammonium or compound decomposing thereto. It relates also to activation of homogeneous mixed cerium and zirconium oxides for nitrogen oxide reduction. Proposed catalyst comprises catalytically active coat applied on inner carries body. Note here that said coat consists, partially or completely, of homogeneous mixed cerium and zirconium oxides with cerium amount varying from 10 wt % to 90 wt % per total weight of said mix, activated for reduction by introducing transition metal. Transition metal is selected from the group including chromium, molybdenum and mixes of said transition metals or combinations thereof.

EFFECT: high-activity, vanadium-free, cheap and effective reduction catalyst.

19 cl, 9 dwg, 1 tbl, 13 ex

 

The present invention relates to a new, vanadium free catalyst used for the selective catalytic reduction of nitrogen oxides by ammonia or decaying before his connection as a reducing agent and is suitable mainly for removal of nitrogen oxides from exhaust gases generated by internal combustion engines (ice), working mainly on a lean combustible mixtures and installed on the car. The invention relates also to a method of activating a homogeneous mixed oxide of cerium and zirconium for the selective catalytic reduction of nitrogen oxides.

Emissions of harmful substances by car can fundamentally be divided into two groups. Thus, in particular, the term source emissions" or "primary emissions" call of harmful gases, which are formed as a direct result of fuel combustion in the engine and are already contained in the EXHAUST gas before passing through the EXHAUST aftertreatment device. Secondary emissions are defined as those components of the EXHAUST gas, which may be formed as a by-product in the EXHAUST aftertreatment system.

The exhaust gases of vehicles with working mainly on a lean combustible mixtures of ice along with the usual primary emissions, which include carbon monoxide CO, hydrocarbons NA and xidi nitrogen NO x, also contain oxygen in relatively large quantities, which can be up to 15 vol.%. Carbon monoxide and hydrocarbons by oxidation can be easily turned into harmless substances. The recovery of nitrogen oxides to nitrogen due to the high oxygen content in the EXHAUST gas is a much more difficult task.

One of the known methods of removal of nitrogen oxides from the EXHAUST gas in the presence of oxygen is a method of selective catalytic reduction (SCR) with ammonia at a suitable catalyst, abbreviated denoted SCR-catalyst. When the reduction of nitrogen oxides in this way are removed from the EXHAUST gas nitrogen oxides is subjected to interaction with ammonia to nitrogen and water. Used as a reducing agent ammonia can be obtained by dosing decompose to ammonia compounds, such as urea, ammonium carbamate or ammonium formate, in the exhaust tract and by subsequent hydrolysis. In addition, there are also known methods of neutralization of automobile EXHAUST gas, based on the fact that the ammonia in the phase of the internal combustion engine enriched mixture is formed as a secondary emission located above in the course of flow of the EXHAUST gas catalyst, such as catalyst-drive nitrogen oxides, and intermediate accumulate in the downstream SCR catalyst until the RA is hodovaya in the phase of the internal combustion engine on a lean mixture.

For running in periodic mode, the SCR system, which is used as the reducing agent, the ammonia formed solely in the form of secondary emissions in the EXHAUST system, requires FCC catalysts whose ability to accumulate ammonia should be sufficient in order to cover the entire demand of the reductant to diazotoluene EXHAUST gas in the phase of the internal combustion engine on a lean mixture. This is primarily suitable SCR-catalysts based on zeolites, known from numerous publications and patent applications. For example, in US 4961917 described by way of reduction of nitrogen oxides by ammonia using a catalyst, which, along with the zeolite with certain properties, also contains iron and/or copper as a promoter. Other SLE-based catalysts substituted transition metal zeolites and methods for selective catalytic reduction using SCR-catalysts are described, for example, in EP 1495804 A1, US 6914026 B2 or EP 1147801 B1.

For use in EXHAUST aftertreatment systems with dosing of urea or other decaying to ammonia compounds that provide the possibility of continuous supply system, the reducing agent from the FCC catalyst does not require the presence of a high accumulating ammonia capacity. In accordance with this the m in such systems seek to avoid the application of SCR-catalysts based on zeolites, since such catalysts because of the high cost of obtaining zeolite compounds are very expensive.

For use in such systems suitable SCR-catalysts, which along with titanium dioxide or tungsten oxide, or their mixtures also contain vanadium oxide. For example, in EP 0385164 B1 describes such a catalyst, which, along with the titanium dioxide contains at least one oxide of tungsten, silicon, boron, aluminum, phosphorus, zirconium, barium, yttrium, lanthanum or cerium, and at least one oxide of vanadium, niobium, molybdenum, iron or copper, and which are produced in the form of molded articles by pressing, respectively, the extrusion components, if necessary, after adding thereto acceptable auxiliary substances. In EP 1153648 A1 describes a structured SCR catalyst which catalyzes the hydrolysis coating contains restorative coating, the composition of which corresponds to that known from EP 0385164 B1. In EP 0246859 described SCR catalyst, which contains vanadium deposited on a mixture of cerium oxide and aluminum oxide.

A significant problem faced when using vanadium-containing FCC catalysts for neutralization of automobile EXHAUST gas, is the possible release of volatile toxic vanadium compounds at elevated temperatures of the EXHAUST gas, the light is and what it is necessary to consider the damage these compounds the harm to human health and the environment. Therefore, the interest in the market such vanadium-containing catalysts for neutralization of automobile EXHAUST gas is reduced.

Attempts to develop vanadium free SCR-catalysts as an inexpensive alternative to the high cost of systems based on zeolites have been made for a long time.

For example, in US 4798817 described SCR catalyst, which mainly contains iron sulfate in an amount of from 0.5 to 50%, applied to the mixture of 2-60% of cerium oxide and aluminum oxide. In the US 4780445 described SCR catalyst from 0.1-25% Nickel sulfate or manganese sulfate or a mixture thereof in printed on a mixture of 2-60% of cerium oxide and aluminum oxide.

In JP 2005-238195, respectively, in EP 1736232 described catalytic system for removal of oxides of nitrogen, which has a first reaction part for diazotoluene by the reaction of nitrogen oxides with ammonia and the second reaction part to excessive oxidation of ammonia and in which the first reaction part includes the first catalyst, which contains as an active ingredient at least one complex oxide containing two or more oxides selected from the group comprising silicon oxide, aluminum oxide, titanium oxide, Zirconia, and tungsten oxide, and rare earth element or a transition metal, except Cu, Co, Ni, Mn, Cr and V.

The Apostolescu, etc. in Appl. Catal. In: Environmental 62, 2006 s, presents research results of powder SCR-catalysts of Fe2O3/ZrO2with alloying impurity WO3in the artificial environment of a model EXHAUST gas.

Known vanadium free and bestiality FCC catalysts partly have a complex structure, difficult to prepare and/or do not meet the increased demand for activity and aging resistance for the possibility of their application in vehicles.

Based on the foregoing, the present invention was used to develop vanadium free having smaller compared to systems based on zeolites cost and prepared using simple tools SCR catalyst, which in comparison to currently known systems would have high catalytic activity and high resistance to aging and which would be primarily suitable for removal of nitrogen oxides from the EXHAUST gas produced by the internal combustion engine, operating mainly in the lean combustible mixtures and installed on vehicles with SLE is a continuously operating system, equipped with a dispenser of ammonia or other decaying to his connections.

This task is solved by the FCC catalyst containing deposited on inert housing-media catalytically active coating, which completely or partially consists of homogenes the mixed oxide of cerium and zirconium, containing cerium oxide in an amount of from 10 to 90 wt.% in terms of the total weight of this homogeneous mixed oxide of cerium and zirconium and activated for the SCR reaction by introducing sulfur or transition metal selected from the group comprising chromium, molybdenum, tungsten and mixtures thereof, or combinations thereof.

Under homogeneous mixed oxide of cerium and zirconium (briefly called mixed oxide of cerium and zirconium) in the context of the present description refers to an oxide solid powder material, which consists of at least two components of cerium oxide and zirconium dioxide. These components constitute the mixture at the atomic level. This concept does not cover physical mixture containing cerium oxide powders containing Zirconia powder. Such mixed oxides are taking into account the achievable accuracy of measurement is constant, i.e. homogeneous, the composition of the cross-section of the powder particles. Materials of this type in the literature sometimes also called "solid solutions".

In its raw state such mixed oxides of cerium and zirconium do not exhibit significant catalytic activity in the SCR reaction, as evidenced by represented in figure 1 graphical data on the activity of two selected as example, the raw mixed oxides of cerium and zirconium with the content is of cerium oxide 86 wt.% (comparative catalyst VK1 from comparative example 1), accordingly, 48 wt.% (comparative catalyst VK2 from comparative example 2), in each case calculated on the total weight of the homogeneous mixed oxide of cerium and zirconium. By results of the spent researches it has been unexpectedly found that a homogeneous mixed oxide of cerium and zirconium manifests when it is appropriate preprocessing higher SCR activity compared to conventional FCC catalysts known from the prior art. When referred to in the present description activated for the SCR reaction of a mixed oxide of cerium and zirconium refers to a homogeneous mixed oxides of cerium and zirconium, processed by one of the following methods.

Mixed oxides of cerium and zirconium trigger for the SCR reaction by the introduction of sulfur or transition metal selected from the group comprising chromium, molybdenum, and tungsten, or mixtures thereof. With trigger action components integrate into the oxide skeleton of a mixed oxide of cerium and zirconium. The combination between both activating components (sulfur and transition metal) allows to obtain a catalyst with a particularly preferred properties. Sulfur and the transition metal is injected while separately performed sequentially on stage.

To introduce sulfur can, treating the activated hydroxy mixed the cerium and zirconium mixed gas, which, along with oxygen contains sulfur dioxide (SO2. The processing of such a mixture is carried out at a temperature in the range between 150 and 800°C, preferably from 250 to 650°C, particularly preferably from 300 to 400°C. One suitable for such processing gas mixtures along with oxygen in an amount of from 0.15 to 15% vol. contains sulphur dioxide in an amount of from 5 to 50,000 ppm million, preferably from 5 to 500 ppm million, particularly preferably from 10 to 100 ppm million in Addition, this gas mixture may also contain water in an amount up to 20%vol.

To introduce sulfur can also treating mixed oxide of cerium and zirconium diluted sulfuric acid at room temperature or at slightly elevated temperatures up to 80°C, followed by drying. Drying can be conducted in air at a temperature in the range from 80 to 150°C.

The amount of sulfur introduced into the activated mixed oxide of cerium and zirconium, depends on the type of treatment and its duration. In one embodiment, activated for the SCR reaction mixed oxide of cerium and zirconium contains sulfur in an amount of from 0.01 to 5 wt.%, preferably from 0.02 to 3 wt.%, in terms of the total weight of this activated mixed oxide of cerium and zirconium.

A mixed oxide of cerium and zirconium can also be activated for the SCR reaction by the introduction of a transition metal selected from the group, including the non chrome, molybdenum and tungsten, or mixtures thereof. For this purpose, a mixed oxide of cerium and zirconium impregnated with an aqueous solution of compounds of chromium, molybdenum, tungsten or mixtures thereof, selecting the amount of solution so that the powder mixed oxide of cerium and zirconium were moist with the pores are filled, but retained its flowability. Then the powder is dried in air at a temperature in the range from 300 to 700°C for 0.5-5 h, during which the transition metal is thermally fixed in a mixed oxide of cerium and zirconium. A similar process if necessary, repeat until until after drying, the content of chromium, molybdenum, tungsten or mixtures thereof in the thus obtained mixed oxide of cerium and zirconium will not be from 2 to 20 wt.%, preferably from 5 to 15 wt.%, in terms of the total weight of the activated mixed oxide of cerium and zirconium. The approach provides the distribution of the transition metal mixed oxide of cerium and zirconium in fine form. This factor is a necessary prerequisite for effective activation of a mixed oxide of cerium and zirconium.

With especially high activity in SLE-response and high resistance to aging mixed oxides of cerium and zirconium get in the case when in addition, the promoter used is a transition metal selected from the group, what with manganese, iron, cobalt, Nickel, copper, ruthenium, rhodium, palladium, silver, iridium, platinum and gold, or mixtures thereof. This additional transition metal can be entered in the same process, in which a mixed oxide of cerium and zirconium activate chromium, molybdenum or tungsten. Used as promoters transition metals can primarily add to containing chromium, molybdenum, tungsten or a mixture of the solution and process them mixed oxide of cerium and zirconium together with the activating action of the transition metal on the same stage. The content of manganese, iron, cobalt, Nickel, copper, ruthenium, rhodium, palladium, silver, iridium, platinum, gold or mixtures thereof in the resulting activated mixed oxide of cerium and zirconium should preferably be from 0.1 to 10 wt.%, more preferably from 0.5 to 5 wt.%, in each case, calculated on the total weight of the activated mixed oxide of cerium and zirconium.

In particularly preferred embodiments, the activated mixed oxide of cerium and zirconium contains in each case in terms of its total weight sulfur in an amount of from 0.02 to 3 wt.% and/or molybdenum or tungsten in an amount of 5 to 15 wt.% and iron or copper in an amount of from 0.5 to 3 wt.%.

The above-described method is particularly suitable for activating a homogeneous mixed oxide of cerium and erchonia for SLE-reaction in the case when they calculated on its total weight, contain cerium oxide (IV) in an amount of from 10 to 90 wt.%. It is preferable to use a homogeneous mixed oxides of cerium and zirconium with a specific surface area determined by the method of Brunauer-Emmett-teller by nitrogen adsorption (BET surface), more than 50 m2/g and a content of cerium oxide (IV) in the range of 40 to 90 wt.%, particularly preferably from 45 to 55 wt.%. Used mixed oxides of cerium and zirconium can be doped with rare earth elements and may contain oxide of rare earth element in an amount of from 1 to 9 wt.% in terms of the total weight of the homogeneous mixed oxide of cerium and zirconium. Particularly preferred oxides of rare earth elements include the oxides of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium or gadolinium, or a mixture thereof.

As mentioned above, the introduction of sulfur in combination with the introduction of the transition metal allows you to get activated mixed oxide of cerium and zirconium are particularly preferred properties. For this purpose, on the one hand, containing the transition metal homogeneous mixed oxide of cerium and zirconium can be entered sulfur by treating the SO2-and oxygen-containing gas mixture or by treatment with dilute sulfuric acid followed by drying. Transitional IU is all, contained in the mixed oxide of cerium and zirconium, can represent one selected from the group comprising chromium, molybdenum, tungsten, manganese, iron, cobalt, Nickel, copper, ruthenium, rhodium, palladium, silver, iridium, platinum and gold, or combinations thereof. On the other hand, in the sulfur-containing homogeneous mixed oxide of cerium and zirconium is possible as described above to enter the transition metal. Execution stages for the introduction of sulfur and the introduction of the transition metal in one or another sequence results in a catalyst with different chemical composition. What exactly is the sequence of execution of these stages provides in General a more efficient activation of the mixed oxide of cerium and zirconium, depends on the quality of the source material homogeneous mixed oxide of cerium and zirconium and used to activate the transition metal oxide. This is the task of optimizing prepared eventually activated mixed oxide of cerium and zirconium catalysts tailored to their specific destination.

Application of activated described above for the SCR reaction of a mixed oxide of cerium and zirconium in an inert casing-carrier receive the catalyst (catalytic Converter for selective catalytic vosstanovleniya nitrogen ammonia or decaying connection to him. Such case the carrier may be made of ceramics or metal. When using a ceramic flow-through cell element or a ceramic substrate in the form of a filter with permeable walls of the channels receive the SCR catalyst, which is particularly suitable for the removal of nitrogen oxides from the EXHAUST gas produced by the internal combustion engine, operating mainly in the lean combustible mixtures and installed on the car. Case carrier can still cover active mixed oxide of cerium and zirconium completely or only partially. Case-the media cover the active mixed oxide of cerium and zirconium is always the case, when the EXHAUST system, which is equipped with a vehicle for use which is intended SCR catalyst, a sufficient mounting space for additional hydrolysis catalyst to the input side of the SCR-catalyst and additional catalyst for the oxidation of ammonia (check the ammonia catalyst) with the output side of the SCR-catalyst. In such a system, the hydrolysis catalyst is designed to decompose decompose to ammonia compounds dosed into the exhaust tract, with release of ammonia. The appointment of a catalyst for the oxidation of ammonia is to oxidize exploding in certain operating modes is through the SCR catalyst, the excess ammonia to nitrogen and to prevent in this way the emission of ammonia into the environment. When there is insufficient as the mounting space of the hydrolysis catalyst can be applied on the coating with active mixed oxide of cerium and zirconium, which you can use the full length of the body of the carrier. Similarly the coverage proposed in the invention is a mixed oxide of cerium and zirconium can be applied only on part of the body of the carrier, while in other parts in this zoned location coverage in the course of flow of the EXHAUST gas before it is possible to apply the coating of the catalyst of the hydrolysis and/or in the course of flow of the EXHAUST gas, after it is possible to apply a coating of catalyst for the oxidation of ammonia and/or another coating of the SCR-catalyst.

FCC catalysts obtained by complete or partial coating of the inert body of the carrier proposed in the invention is activated for the SCR reaction mixed oxide of cerium and zirconium, which represents a homogeneous mixed oxide of cerium and zirconium-containing cerium oxide is from 10 to 90 wt.%, preferably from 40 to 90 wt.%, particularly preferably from 45 to 55 wt.%, in each case, calculated on the total weight of this homogeneous mixed oxide of cerium and zirconium, and also which is the object of the present invention, in preferred embodiments contain the oxide of rare earth element in an amount of from 1 to 9 wt.% in terms of the total weight of the homogeneous mixed oaks is Yes cerium and zirconium. The oxide of rare earth element represents thus the oxide of an element selected from the group comprising scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium and gadolinium, or a mixture of their oxides.

Contained in the proposed invention the catalyst is a mixed oxide of cerium and zirconium, activated by the introduction of sulfur and/or transition metal, contains sulfur in an amount of from 0.01 to 5 wt.%, preferably from 0.02 to 3 wt.%, and/or chromium, molybdenum, tungsten or mixtures thereof, particularly preferably molybdenum and/or tungsten, in an amount of from 2 to 20 wt.%, preferably from 5 to 15 wt.%. Data on the quantitative content of components in each case are specified in terms of the total weight of the activated mixed oxide of cerium and zirconium. In a particularly preferred options proposed in the invention, the catalyst contains, in addition, as the promoter is a transition metal selected from the group comprising manganese, iron, cobalt, Nickel, copper, ruthenium, rhodium, palladium, silver, iridium, platinum and gold, or mixtures thereof in an amount of from 0.1 to 10 wt.%, preferably from 0.5 to 5 wt.%, most preferably contains iron or copper in an amount of from 0.3 to 3 wt.%.

Similar to the proposed invention the catalysts are inexpensive and vanadium free alternative to SCR-catalysts based on zeolites and distinguish what I exceptionally high SCR activity at a corresponding desired resistance to aging under hydrothermal conditions.

Below the invention is described in more detail by examples and comparative examples with reference to accompanying the description of graphic materials showing:

in figure 1 is presented in graphical form data on the degree of conversion of nitrogen oxides in the raw, not activated homogeneous mixed oxides of cerium and zirconium-containing cerium oxide 86 wt.% (comparative catalyst VK1), respectively, 48 wt.% (comparative catalyst VK2), calculated on the total weight of the homogeneous mixed oxide of cerium and zirconium,

figure 2 is presented in graphical form data on the degree of conversion of nitrogen oxides on offer in the invention catalyst (K1)containing activated for the SCR reaction by introducing sulfur mixed oxide of cerium and zirconium with a high content of cerium (containing cerium oxide 86 wt.% in terms of the total weight of the homogeneous mixed oxide of cerium and zirconium), in comparison with SLE activity of traditional SCR-catalyst (comparative catalyst VK3-based zeolite, a comparative catalyst VK4 on the basis of vanadium, a comparative catalyst VK5 based on Fe/W/ZrO2),

figure 3 is presented in graphical form data on the degree of conversion of nitrogen oxides on offer in the invention catalyst (K2)containing activated for the SCR reaction way of the introduction of sulfur mixed oxide of cerium and zirconium (containing cerium oxide 48 wt.% in terms of the total weight of the homogeneous mixed oxide of cerium and zirconium), in comparison with SLE activity of traditional SCR-catalyst (comparative catalyst VK3-based zeolite, a comparative catalyst VK4 on the basis of vanadium, a comparative catalyst VK5 based on Fe/W/ZrO2),

figure 4 is presented in graphical form data on the degree of conversion of nitrogen oxides on offer in the invention catalyst (K3)containing activated for the SCR reaction by introducing tungsten homogeneous mixed oxide of cerium and zirconium, in comparison with SLE activity of traditional SCR-catalyst (comparative catalyst VK3-based zeolite, a comparative catalyst VK4 on the basis of vanadium, a comparative catalyst VK5 based on Fe/W/ZrO2),

figure 5 is presented in graphical form data on the degree of conversion of nitrogen oxides on offer in the invention catalyst (K4)containing activated for the SCR reaction by the introduction of iron and tungsten homogeneous mixed oxide of cerium and zirconium, in comparison with SLE activity of traditional SCR-catalyst (comparative catalyst VK3-based zeolite, a comparative catalyst VK4 on the basis of vanadium, a comparative catalyst VK5 based on Fe/W/ZrO2),

figure 6 is presented in graphical form data on the degree of conversion of nitrogen oxides on offer in the invention catalyst containing activerow the tion for the SCR reaction by the introduction of iron and tungsten homogeneous mixed oxide of cerium and zirconium, in the freshly prepared state (catalyst K5) and after hydrothermal artificial aging (catalyst K5') in comparison with SLE activity of conventional FCC catalysts after hydrothermal aging (comparative catalyst VK3' based on zeolite, a comparative catalyst VK4' on the basis of vanadium, a comparative catalyst VK5' based on Fe/W/ZrO2),

figure 7 is presented in graphical form data on the degree of conversion of nitrogen oxides on offer in the invention catalyst (K6)containing activated for the SCR reaction by introducing iron, tungsten and sulfur homogeneous mixed oxide of cerium and zirconium, in comparison with SLE activity of traditional SCR-catalyst (comparative catalyst VK3-based zeolite, a comparative catalyst VK4 on the basis of vanadium, a comparative catalyst VK5 based on Fe/W/ZrO2),

on Fig - presents in graphical form the data about the degree of conversion of nitrogen oxides on offer in the invention catalyst in the freshly prepared state (K3)containing activated for the SCR reaction by introducing tungsten homogeneous mixed oxide of cerium and zirconium (containing cerium oxide 48 wt.% in terms of the total weight of the homogeneous mixed oxide of cerium and zirconium), compared to conventional FCC catalysts containing oxide wolf the AMA, the cerium oxide and zirconium dioxide (comparative catalyst VK6-based Ce{ZrO2-WO3}, comparative catalyst VK7 on the basis of W{CeO2-ZrO2}), and

figure 9 is presented in graphical form data on the degree of conversion of nitrogen oxides on offer in the invention the catalyst after artificial hydrothermal aging (K3')containing activated for the SCR reaction by introducing tungsten homogeneous mixed oxide of cerium and zirconium (containing cerium oxide 48 wt.% in terms of the total weight of the homogeneous mixed oxide of cerium and zirconium), compared to conventional FCC catalysts containing tungsten oxide, cerium oxide and zirconium dioxide (comparative catalyst VK6' on the basis of Ce{ZrO2-WO3}, comparative catalyst VK7' on the basis of W{CeO2-ZrO2}).

Study the degree of conversion of nitrogen oxides as a measure of SLE activity

Mixed oxides of cerium and zirconium from all the following examples, suspended in water, grinded and applied on a ceramic honeycomb element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm After annealing the cell element at 500°C for two hours in the air supplied from the cellular elements DL the tests in the exhaust system model of the EXHAUST gas cut a cylindrical core with a diameter of 25.4 mm and a length of 76,2 mm

The tests were carried out in the laboratory exhaust system model of the EXHAUST gas under the following conditions.

The composition model OG
NO [about. part./million]500
NH3[vol. part./million]450
O2[vol.%]5
H2O [vol.%]1,3
N2rest
General test conditions
Hourly average gas flow rate (SCSP) [h-1]30000
Temperature [°C]500, 450, 400, 350, 300, 250, 200, 175, 150
Conditioning before starting measurementsthe atmosphere model EXHAUST gas, 600°C, a few minutes

During the measurement of suitable analytical methods to determine the concentration of nitrogen oxides in the model EXHAUST gas with the catalyst. Based on known data about the contents in the model EXHAUST gas dosing in them, oxides of nitrogen, which was checked by analysis of the EXHAUST gas before the catalyst at which kondicionirovanie at the beginning of each test, and on the basis of data on the measured content of nitrogen oxides in the model of the EXHAUST gas over a catalyst used to calculate the degree of conversion of nitrogen oxides on the catalyst at each temperature using the following formula:

,

where CI/o(NOx)=CI/o(NO)+CI/o(NO2)+CI/o(N2O)...

For the assessment of SLE activity of the studied materials on the obtained data we have plotted the graphs of the degree of conversion of nitrogen oxidesfrom measured before the catalyst temperature.

Comparative example 1

Homogeneous mixed oxide of cerium and zirconium-containing cerium oxide 86 wt.% and with a content of lanthanum oxide 4 wt.% in terms of the total weight of this mixed oxide suspended in water, grinded and applied on a ceramic honeycomb element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm After annealing the cell element at 500°C for two hours by air from prepared using the comparative catalyst VK1 cut out the core for testing in the exhaust system model of the EXHAUST gas, and determined the degree of conversion of nitrogen oxides on the catalyst.

Comparative example 2

Homogeneous mixed oxide CERI and zirconium-containing cerium oxide 48 wt.% in terms of the total weight of this mixed oxide suspended in water, grinded and applied on a ceramic honeycomb element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm After annealing the cell element at 500°C for two hours by air from prepared using the comparative catalyst VK2 cut out the core for testing in the exhaust system model of the EXHAUST gas, and determined the degree of conversion of nitrogen oxides on the catalyst.

Figure 1 graphically presents the results are not activated homogeneous mixed oxides of cerium and zirconium in the form of comparative catalyst VK1 (○) and comparative catalyst VK2 (□) by passing the model EXHAUST gas. Both materials, as expected, is not characterized by any significant degree of transformation of their nitrogen oxides in the SCR reaction with ammonia. Observed for the comparative catalyst VK2 at 250°C the degree of conversion of oxides of nitrogen, equal to 3.4%, lies within a given error measurement method.

Comparative example 3

For comparison with the prior art as a comparative catalyst prepared standard FCC catalyst commercially available type based on relisozlengo zeolite deposited on cell element with a volume of 0.5 l and a density of CA is Alov 62 channels per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm. From this comparative catalyst carved denoted by VK3 a core test in the exhaust system model of the EXHAUST gas, and determined the degree of conversion of nitrogen oxides on the catalyst in its prepared state.

Another core cut from the same comparative catalyst and denoted below in VK3', were subjected to artificial aging at 650°C for 48 hours Aging was performed in a furnace under hydrothermal conditions in an air atmosphere containing 10 vol.% water vapor and 10% vol. the oxygen.

Comparative example 4

For further comparison with the prior art to prepare another standard FCC catalyst commercially available type based on the V2O5/TiO2/WO3in the form of a coating deposited on a cell element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm. From this comparative catalyst carved denoted by VK4 the core for testing in the exhaust system model of the EXHAUST gas, and determined the degree of conversion of nitrogen oxides on the catalyst in its prepared state.

From this comparative catalyst as in comparative example 3, cut out another core that within 48 h was kept at 650°C in air atmosphere is e, containing 10 vol.% water vapor and 10% vol. the oxygen. This core are outlined below through VK4'.

Comparative example 5

Based on the publication Apostolescu, etc. in Appl. Catal. In: Environmental 62, 2006 press, p.104, prepare another comparative catalyst, which coating contains iron in an amount of 1.4 wt.% and tungsten in an amount of 7 wt.% on the media Zirconia (without cerium oxide). As the hull of the carrier of such coverage as well as in other comparative examples and the examples used ceramic honeycomb element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm. From this comparative catalyst carved denoted by VK5 the core for testing in the exhaust system model of the EXHAUST gas, and determined the degree of conversion of nitrogen oxides on the catalyst in its prepared state.

From this comparative catalyst as in comparative example 4, cut another core that within 48 h was kept at 650°C in air atmosphere containing 10 vol.% water vapor and 10% vol. the oxygen. This core are outlined below through VK5'.

Comparative example 6

In EP 1736232 A1 describes two different ways of cooking FCC catalysts, the main components of which are the oxide of tungsten, about what led cerium and zirconium dioxide. In paragraph [0007] the specified publication described is particularly suitable for the selective catalytic reduction of NOx by urea catalyst obtained by adding the cerium oxide of tungsten and Zirconia.

In this comparative example, a comparative catalyst prepared in accordance with the above publication information, selecting quantitative proportions between the components so that the composition prepared in comparative catalyst corresponded to the structure proposed in the invention catalyst described below in example 3. In accordance with this 420 g of a mixture of ZrO2/WO3(contained in terms of its total weight of 88 wt.% ZrO2and 12 wt.% WO3) suspended in water. Then to the suspension under stirring was added a solution of cerium nitrate containing cerium 202,

From the thus obtained slurry was coated on a honeycomb element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm After drying and calcination cell element of it cut out two of the core. One of these cores (VK6) experienced in the exhaust system model of the EXHAUST gas, determining the degree of conversion of nitrogen oxides on the catalyst it is megapistoletom condition.

The second core (VK6') were subjected to artificial aging at 650°C for 48 h in an air atmosphere containing 10 vol.% oxygen and 10% vol. water vapor, and only after such treatment was determined by the degree of conversion of nitrogen oxides on the catalyst in the exhaust system model of the EXHAUST gas.

Comparative example 7

In this example, a comparative catalyst prepared in accordance with the second described in EP 1736232 A1 a method for preparation of FCC catalyst consisting of tungsten oxide, cerium oxide and zirconium dioxide. According to example 3 of this publication first from aqueous solution was besieged by a mixed compound of cerium and zirconium, and then soaked the connection tungsten-containing solution.

For this purpose, an aqueous solution containing 500 g of nitrate Zirconia and 200 g of cerium nitrate (III) (containing crystallization water), neutralized by ammonia solution, followed by precipitation of the oxide-hydroxide of cerium and zirconium. To the resulting suspension with constant stirring solution was added 60 g of metavolume ammonium in the water.

From the thus obtained slurry was coated on a honeycomb element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm After drying and calcination of the honeycomb is the first element of it cut out two of the core. One of these cores (VK7) experienced in the exhaust system model of the EXHAUST gas, determining the degree of conversion of nitrogen oxides on the catalyst in its prepared state.

The second core (VK7') were subjected to artificial aging at 650°C for 48 h in an air atmosphere containing 10 vol.% oxygen and 10% vol. water vapor, and only after such treatment was determined by the degree of conversion of nitrogen oxides on the catalyst in the exhaust system model of the EXHAUST gas.

Example 1

Of the catalyst prepared in comparative example 1, cut out the core, which for 48 h were sulfurimonas in a furnace at a temperature of 350°C in nitrogen atmosphere containing 10 vol.% oxygen, 10 vol.% moisture and sulfur dioxide in a concentration of about 20. part./million Obtained in this manner proposed in the invention catalyst K1 then tested in the model EXHAUST gas.

Figure 2 graphically presents the results of determining the degree of conversion of nitrogen oxides on offer in the invention catalyst K1 (•) in comparison with the degree of conversion of nitrogen oxides prepared according to the prior art comparative catalysts VK3 (◊, on the basis of Fe-substituted zeolite), VK4 (□, vanadium) and VK5 (×, based on Fe/W/ZrO2). Proposed in the invention catalyst K1 in the entire temperature range is characterized by the best indicators turning on amoxidal nitrogen in the SCR reaction in comparison with do not contain zeolite and vanadium comparative catalyst VK5, known from the prior art. In addition, in the temperature range from 300 to 500°C. the degree of conversion of nitrogen oxides on offer in the invention the catalyst is unexpectedly higher than that of commercially available comparative catalyst VK3 on the basis of Fe-substituted zeolite, and approximately reaches the degree of conversion of nitrogen oxides on the comparative catalyst VK4 based on vanadium.

Example 2

Of the catalyst prepared in comparative example 2, cut out the core, which for 48 h were sulfurimonas in a furnace at a temperature of 350°C in nitrogen atmosphere containing 10 vol.% oxygen, 10 vol.% moisture and sulfur dioxide in a concentration of about 20. part./million Obtained in this manner proposed in the invention catalyst K2 then tested in the model EXHAUST gas.

Figure 3 graphically presents the results of the tests proposed in the invention catalyst in comparison with the traditional comparative SCR-catalysts VK3 (◊, on the basis of Fe-substituted zeolite), VK4 (□, vanadium) and VK5 (×, based on Fe/W/ZrO2). Proposed in the invention catalyst K2 according to the degree of turning it of nitrogen oxides is also superior to the comparative catalyst VK5 in the whole temperature range and the comparative catalyst VK3 on the basis of Fe-substituted zeolite at temperatures above 300°C. since the temperature of 350°C, the degree ol the rotation of oxides of nitrogen in the proposed invention the catalyst is fully achieves the same performance of the comparative catalyst VK4 based on vanadium.

Example 3

Homogeneous mixed oxide of cerium and zirconium-containing cerium oxide 48 wt.% in terms of the total weight of this mixed oxide activated for the SCR reaction by introducing tungsten. To do this, first determine the amount of water that can absorb a homogeneous mixed oxide of cerium and zirconium without losing its flowability. The appropriate amount of water was dissolved well soluble tungsten compound in an amount which corresponded to the content of tungsten 10 wt.% in terms of the total weight of prepared activated mixed oxide of cerium and zirconium. Homogeneous mixed oxide of cerium and zirconium impregnated with the filling of pores prepared tungsten-containing solution and then for thermal fixation of tungsten within 2 hours and was kept in a furnace at 500°C in air atmosphere.

Thus obtained activated mixed oxide of cerium and zirconium suspended in water, grinded and applied on a ceramic honeycomb element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm After annealing the cell element at 500°C for two hours by air from cooked the way proposed in the invention catalyst cut out the core K3 DL the tests in the exhaust system model of the EXHAUST gas, and determined the degree of conversion of nitrogen oxides on the catalyst.

Figure 4 graphically presents the results of the test catalyst K3 in the model EXHAUST gas in comparison with the degree of conversion of nitrogen oxides by conventional FCC catalysts VK3 (◊, on the basis of Fe-substituted zeolite), VK4 (□, vanadium) and VK5 (×, based on Fe/W/ZrO2). The catalyst K3 in the entire temperature range is characterized by the degree of transformation on it, oxides of nitrogen, which basically corresponds to the degree of conversion of nitrogen oxides on the comparative catalyst VK4 based on vanadium, which is the most productive among all selected comparative catalysts. Only at a high temperature equal to 500°C, there is some loss of activity proposed in the invention catalyst as compared with the comparative catalyst based on vanadium and comparative catalyst based on zeolite.

On Fig graphically presents data on the degree of conversion of nitrogen oxides on the freshly prepared catalyst K3 in comparison with both the comparative catalysts VK6 (∗) and VK7 (Δ), which also consisted only of cerium oxide, Zirconia, and tungsten oxide, but did not contain a specific homogeneous mixed oxide of cerium and zirconium, and in the best case, in particular in the case of the comparative catalyst VK7, contained a non-homogeneous mixture. And h the th in the invention, the catalyst exhibits a much higher SCR activity in the temperature range below 300°C.

The decisive advantages of the proposed invention catalyst prior to those known from the prior art catalysts are most clearly manifested after hydrothermal aging.

The second core (K3') for 48 h and kept at 650°C°C in air atmosphere containing 10 vol.% oxygen and 10% vol. water vapour. After this treatment was determined by the degree of conversion of nitrogen oxides on the catalyst in the exhaust system model of the EXHAUST gas and the results were compared with the degree of conversion of nitrogen oxides to also subjected to aging comparative catalysts VK6' (∗) and VK7' (Δ). From what is shown on Fig.9 data suggest that performance is known from the prior art catalysts drops sharply as a result of their hydrothermal aging. Even at temperatures above 350°C the degree of conversion of nitrogen oxides on the comparative catalysts more than 50%. In contrast, the degree of conversion of nitrogen oxides on offer in the invention catalyst K3' in the temperature range above 300°C and after aging still is about 80%.

Example 4

Homogeneous mixed oxide of cerium and zirconium-containing cerium oxide 86 wt.% and with a content of lanthanum oxide 4 wt.% in terms of the total weight of this mixed oxide activated for the SCR reaction by the introduction of iron and tungsten. For e the CSO first determined the amount of water which is able to absorb a homogeneous mixed oxide of cerium and zirconium without losing its flowability. The appropriate amount of water was dissolved well soluble compound of iron (III) in amounts that corresponded to the iron content of 1.3 wt.%, well water-soluble tungsten compound in an amount which corresponded to the content of tungsten 10 wt.%. (Content data components are specified in terms of the total weight of prepared activated mixed oxide of cerium and zirconium.) Homogeneous mixed oxide of cerium and zirconium impregnated with the filling of pores cooked - iron and tungsten-containing solution and then for thermal fixation of transition metals within 2 hours and was kept in a furnace at 500°C in air atmosphere.

Thus obtained activated mixed oxide of cerium and zirconium suspended in water, grinded and applied on a ceramic honeycomb element with a volume of 0.5 l and a density of the channel 62 channel per square centimeter of cross-sectional area in the thickness of the walls of the channels to 0.17 mm After annealing the cell element at 500°C for two hours by air from cooked the way proposed in the invention catalyst carved Kern K4 for testing in the exhaust system model of the EXHAUST gas, and determined the extent ol the rotation of nitrogen oxides on the catalyst.

Figure 5 graphically presents the results of the test catalyst K4 in the model EXHAUST gas in comparison with the degree of conversion of nitrogen oxides by conventional FCC catalysts VK3 (◊, on the basis of Fe-substituted zeolite), VK4 (□, vanadium) and VK5 (×, based on Fe/W/ZrO2). The catalyst K4 in the temperature range from 150 to 400°C is characterized by the degree of transformation on it, oxides of nitrogen, which roughly corresponds to the degree of conversion of nitrogen oxides to a commercially available comparative vanadium-containing catalyst VK4 and significantly exceeds the degree of conversion of nitrogen oxide to vanadium free comparative catalysts VK3 and VK5. The decrease in the degree of conversion of nitrogen oxides on offer in the invention the catalyst at temperatures above 450°C due to the loss of selectivity associated with what is happening at high temperatures by peroxidation of ammonia.

Example 5

Analogously to example 4 were prepared another activated mixed oxide of cerium and zirconium and another proposed in the invention catalyst, using as a base material of a homogeneous mixed oxide of cerium and zirconium-containing cerium oxide 48 wt.% in terms of the total weight of this homogeneous mixed oxide of cerium and zirconium. From the obtained catalyst cut two core diameter 25.4 mm and a length of 76,2 mm Odie is one of these cores (K5) in the freshly prepared state tested on SLE activity.

The second core (K5') was first subjected to aging at 650°C for 48 h in an air atmosphere containing 10 vol.% oxygen and 10% vol. water vapour. Then the core was tested in the exhaust system model of the EXHAUST gas to determine the degree of conversion of nitrogen oxides at such a catalyst.

Figure 6 graphically presents the results of determining the degree of conversion of nitrogen oxides on the catalyst K5 (freshly prepared) and on the catalyst K5' (after hydrothermal aging) compared with those subjected to hydrothermal aging comparative catalysts VK3' (◊, on the basis of Fe-substituted zeolite), VK4' (□, vanadium) and VK5' (x, based on Fe/W/ZrO2). From the figure 6 graphs clearly follows that proposed in the invention catalyst K5-prepared condition is characterized by an exceptionally high degree of transformation on it, oxides of nitrogen, primarily in the temperature range from 150 to 400°C. the Reduction of the degree of conversion of nitrogen oxides on offer in the invention the catalyst at temperatures above 450°C is due, as in the case of catalyst K4 occurring at these temperatures the peroxidation of ammonia.

The comparison between the data on the degree of conversion of nitrogen oxides subjected to hydrothermal aging of the catalyst K5' and subjected guide is termalna aging commercially available comparative catalysts confirms, in addition, the proposed invention catalyst exceptionally high resistance to aging.

Example 6

Cooked in example 5 catalyst carved another core that within 48 h were sulfurimonas in a furnace at a temperature of 350°C in nitrogen atmosphere containing 10 vol.% oxygen and sulfur dioxide in a concentration of about 20. part./million Obtained in this manner proposed in the invention catalyst K6 containing activated by introducing tungsten, iron, and sulfur mixed oxide of cerium and zirconium, and then tested in the model EXHAUST gas.

Figure 7 graphically presents the results of the research activity proposed in the invention catalyst in comparison with the traditional comparative SCR-catalysts VK3 (◊, on the basis of Fe-substituted zeolite), VK4 (□, vanadium) and VK5 (×, based on Fe/W/ZrO2). The catalyst K6 is characterized by a high degree of turning it of nitrogen oxides in the temperature range from 300 to 450°C. the Degree of conversion on it of nitrogen oxides in the temperature range fully comparable with the degree of conversion of nitrogen oxides on the comparative catalyst VK3-based zeolite. The catalyst K6 is another example proposed in the invention catalyst that has extremely high degree of transformation on it OK the Idov nitrogen in SLE-reactions involving ammonia.

Obtained for all catalysts of the respective invention examples of evidence suggests that thanks to the purposeful introduction of sulfur and/or transition metal in a homogeneous mixed oxide of cerium and zirconium is provided a highly efficient activation of such material for the selective catalytic reduction of nitrogen oxides by ammonia, and accordingly prepared catalysts suitable for use as an alternative to traditional, standard catalysts based on zeolites and/or vanadium.

1. Vanadium free catalyst for selective catalytic reduction (SCR) of nitrogen oxides by ammonia or decaying before his connection as a reductant containing deposited on inert housing-media catalytically active coating, wherein the catalytically active coating is completely or partially consists of a homogeneous mixed oxide of cerium and zirconium-containing cerium oxide in an amount of from 10 to 90 wt.% in terms of the total weight of this homogeneous mixed oxide of cerium and zirconium and activated for the SCR reaction by introducing a transition metal selected from the group comprising chromium, molybdenum, and mixtures of such transition metals or combinations thereof.

2. The catalyst according to claim 1, wherein g is moeny mixed oxide of cerium and zirconium doped oxide of rare earth element in an amount of from 1 to 9 wt.% in terms of the total weight of this homogeneous mixed oxide of cerium and zirconium.

3. The catalyst according to claim 2, characterized in that the rare earth element oxide is an oxide of an element selected from the group comprising scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium and gadolinium, or a mixture of their oxides.

4. The catalyst according to one of claims 1 to 3, characterized in that the activated mixed oxide of cerium and zirconium contains a transition metal selected from the group comprising chromium, molybdenum, or their mixture in an amount of from 2 to 20 wt.%.

5. The catalyst according to claim 4, characterized in that the activated mixed oxide of cerium and zirconium also contains a transition metal selected from the group comprising manganese, iron, cobalt, Nickel, copper, ruthenium, rhodium, palladium, silver, iridium, platinum and gold, or their mixture in an amount of from 0.1 to 10 wt.%.

6. The catalyst according to claim 4, characterized in that the activated mixed oxide of cerium and zirconium contains sulfur in an amount of from 0.01 to 5 wt.%.

7. The catalyst according to claim 1, characterized in that the body is a carrier made of ceramic or metal.

8. The catalyst according to claim 7, characterized in that the housing carrier is a ceramic flow-through cell element or a ceramic substrate in the form of a filter with permeable walls of the channels.

9. The method of activating a homogeneous mixed oxide of cerium and zirconium-containing cerium oxide in an amount of from 10 to 90 mA is.% in terms of the total weight of this homogeneous mixed oxide of cerium and zirconium, for the SCR reaction by introducing sulfur, wherein the sulfur is injected by processing the mixed oxide of cerium and zirconium with a gas mixture containing sulphur dioxide and oxygen at a temperature in the range from 150 to 800°C. or by treating mixed oxide of cerium and zirconium diluted sulfuric acid at room temperature or slightly elevated temperatures up to 80°C, followed by drying.

10. The method according to claim 9, characterized in that the gas mixture contains water in an amount from 0 to 20 vol.%.

11. The method according to claim 9 or 10, characterized in that use homogeneous mixed oxide of cerium and zirconium-containing cerium oxide in an amount of from 10 to 90 wt.% and oxide of rare earth element in an amount of from 1 to 9 wt.%.

12. The method according to claim 9 or 10, characterized in that use homogeneous mixed oxide of cerium and zirconium-containing cerium oxide in an amount of from 10 to 90 wt.% in terms of the total weight of this homogeneous mixed oxide of cerium and zirconium and a transition metal selected from the group comprising chromium, molybdenum, tungsten, manganese, iron, cobalt, Nickel, copper, ruthenium, rhodium, palladium, silver, iridium, platinum and gold, or combinations thereof.

13. The method according to claim 9 or 10, characterized in that use homogeneous mixed oxide of cerium and zirconium-containing cerium oxide in an amount of from 10 to 90 wt.% and oxide of rare earth e is ment in the amount of from 1 to 9 wt.% in terms of the total weight of this homogeneous mixed oxide of cerium and zirconium, and a transition metal selected from the group comprising chromium, molybdenum, tungsten, manganese, iron, cobalt, Nickel, copper, ruthenium, rhodium, palladium, silver, iridium, platinum and gold, or combinations thereof.

14. The method of activating a homogeneous mixed oxide of cerium and zirconium-containing cerium oxide in an amount of from 10 to 90 wt.% in terms of the total weight of this homogeneous mixed oxide of cerium and zirconium, for the SCR reaction by introducing a transition metal selected from the group comprising chromium, molybdenum, and tungsten, or mixtures thereof, characterized in that the mixed oxide of cerium and zirconium impregnated with an aqueous solution of compounds of chromium, molybdenum, tungsten or mixtures thereof, selecting the amount of solution so that the powder mixed oxide of cerium and zirconium were moist with the filling of pores without losing its properties.

15. The method according to 14, characterized in that use homogeneous mixed oxide of cerium and zirconium containing the oxide of rare earth element in an amount of from 1 to 9 wt.%.

16. The method according to 14, characterized in that use homogeneous mixed oxide of cerium and zirconium, which also contains sulfur.

17. The method according to item 15, wherein the use of a homogeneous mixed oxide of cerium and zirconium, which also contains sulfur.

18. The use of the catalyst according to one of claims 1 to 8 for behold the objective catalytic reduction of nitrogen oxides by ammonia or decaying before his connection as a reductant.

19. Use p for removal of nitrogen oxides from exhaust gases generated by internal combustion engines that operate primarily on a lean combustible mixtures and installed on the car.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a hydrotreatment catalyst. Described is a method of producing a hydrotreatment catalyst which involves the following steps: a) at least one step for saturating a dried and/or annealed catalyst precursor containing at least one group VIII element and/or at least one group VIB element and an amorphous support using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with relative permittivity higher than 20; b) a step for maturation of said saturated catalyst precursor obtained at step a); wherein said maturation step is carried out at atmospheric pressure, at temperature ranging from ambient temperature to 60°C for maturation period of 12 to 340 hours; c) a step for drying without a subsequent step for annealing said catalyst precursor obtained at step b), wherein the drying step c) is carried out in a drying oven at atmospheric or low pressure and at temperature 50-200°C. Described is use of the catalyst obtained using the described method to carry out hydrofining and hydroconversion of hydrocarbon material.

EFFECT: high catalyst activity.

14 cl, 8 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts, particularly, to those intended for hydration of vegetable oil and fat and may be used in food, chemical and petrochemical industries. Proposed method comprises preparing granulated catalysts for liquid-phase hydration of vegetable oils and distilled fat acids by hydrogen that represent metallic palladium applied in amount of 0.5-2.0 wt % on carbon carrier of 0.5-6.0 mm-fraction with specific surface of 100-450 m2/g and volume of pores of 0.2-0.6 cm3/g. Hydration is conducted on catalyst stationary bed at 140-210°C, hydrogen pressure of 2 to 12 atm and raw stock consumption of 100 to 1500 g/(kgkt·h).

EFFECT: high hydration rate and stability of technical brands.

4 cl, 1 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for dehydrogenation of paraffin hydrocarbons and methods of producing said catalysts, as well as methods of producing olefin hydrocarbons via catalytic dehydrogenation of corresponding C3-C5 paraffin hydrocarbons and can be used in chemical and petrochemical industry. Described is a catalyst for dehydrogenation of C3-C5 paraffin hydrocarbons, which contains chromium and potassium oxides and optionally zirconium dioxide, deposited on a solid solution of formula ZnxAl2O(3+x) where x=0.025-0.25, with a defective spinel structure. Described is a method of producing the catalyst by hydrating a precursor of the solid solution, saturating with a mixture of solutions of chromic acid, potassium chromate and a zinc salt and optionally zirconyl nitrate, followed by drying and calcination in air, wherein hydration is carried out during the saturation process. A method of dehydrogenating paraffin hydrocarbons in the presence of said catalyst is also described.

EFFECT: high catalytic activity, selectivity and stability with low coke formation.

14 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hydrogen using catalysts. Described is a method of producing hydrogen via direct decomposition of natural or liquefied petroleum gas (LPG), where the catalyst used is based on nickel-iron-gamma-aluminium oxide, prepared through combined adsorption of aqueous solutions of nickel and iron nitrates on gamma-aluminium oxide, carried out in 2-4 steps, where the weight ratio of nickel to iron on the catalyst surface is equal to 1:1 and total weight makes up 20-40%.

EFFECT: high output of hydrogen.

2 cl, 6 ex

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0, oxides of platinum and/or palladium and/or rhenium and/or ruthenium - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium in unipolar water taken in amount that ensures aforesaid content of metal oxide in finished catalyst, drying, tabletting and calcinating.

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14 cl, 10 ex, 2 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to petrochemistry, particularly, to production of zeolite-based catalyst for alkylation of isobutane by olefins and may be used in oil processing. Invention covers catalyst of alkylation of isobutane by zeolite-based olefins that contains aluminium oxide and silicon dioxide at silicon dioxide-to-aluminium oxide molar ratio equal to 2.8-7.0, sodium oxide, rare-earth element, oxides of active metals, which contains oxides of platinum and/or palladium and/or rhenium and/or ruthenium at the following ratio of components, in wt %: sodium oxide - 0.26-0.8, calcium oxide - 0.8-4.2, rare earth element oxide - 12.0-20.0,oxides of platinum and/or or palladium and/or molybdenum and/or nickel and/or cobalt - 0.02-2.0, zeolite with SiO2/Al2O3 equal to 2.8-7.0, making the rest. It covers also two versions of the method of catalyst production comprising zeolite treatment by water solutions of salts of calcium, rare earth element and ammonium at increased temperature and pressure of saturated vapors for time period required for conversion of zeolite into rare-earth calcium zeolite, its washing, drying and calcinating. In compliance with this method, first, rare-earth calcium zeolite is impregnated with unipolar water unless air escapes from zeolite pores and, then, processing is performed by impregnation with water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/ or cobalt taken in amount that ensures said content of metal oxide in finished catalyst. It comprises also drying, calcinating, or applying on rare-earth metal calcium zeolite of water solutions of salts of oxides of active metals, which contains oxides of platinum and/or palladium and/or molybdenum and/or nickel and/or cobalt. The process includes two stages: first, cold impregnation at not over 30°C, and, second, at, at least, 70°C, and finally drying, tabletting and calcinating.

EFFECT: increase in catalyst activity approximating to 100 wt %, isotope selectivity approximating to 73.5 wt %, yield of target alkyl benzene by 10-15 wt %.

16 cl, 10 ex, 2 tbl

FIELD: petrochemistry.

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3 cl, 9 tbl, 2 ex

FIELD: chemistry.

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EFFECT: precipitation and facilitation of the catalysts preparation technology.

1 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemical and chemical industry, particularly a method of preparing moulded catalysts for conversion of methane into aromatic hydrocarbons and hydrogen in nonoxidative conditions. The invention describes a catalyst for a nonoxidative methane conversion process, containing high-silica zeolite H-ZSM-5, a binding additive - calcium form of montmorillonite, modifying elements - molybdenum and cobalt, where content of the binding additive in the catalyst is not more than 40.0 wt %, while content of molybdenum and cobalt is not more than 3.0 wt % and 1.0 wt %, respectively. Described is a method of preparing a catalyst, involving modification of zeolite with promoting elements through successive wetness impregnation of zeolite H-ZSM-5 with molybdenum and cobalt salt solutions, followed by calcination, and then mixing the zeolite modified with metals with a binding additive suspension in a given proportion to obtain a moulding mass and moulding said mass into granules in a moulding device. The invention also describes a method for nonoxidative conversion of methane in the presence of the catalyst described above.

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4 cl, 7 ex, 1 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to catalytic filters for cleaning diesel engine exhaust gases. Proposed filter comprises inlet and outlet and axial length coated by first catalyst comprising platinum group metals on carrier materials and differs from known designs in that said carrier materials are selected from the group including aluminium oxide, silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide and mixes thereof, or mixed oxides. Note here that first catalyst additionally comprises at least one zeolite to accumulate hydrocarbons starting from filter inlet. Note also that section of said filter length is coated by second catalyst that contains no zeolite. Invention covers the method of fabricating said filter wherein both catalyst are applied on said filter as suspension coat. Besides it covers application of said filter for decreasing the content of carbon, hydrocarbon and ash particles in diesel engine exhaust gases.

EFFECT: improved conversion of hydrocarbons into carbon oxide.

10 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing acetylene through oxidative pyrolysis of methane in the presence of oxygen and a catalyst, characterised by that the catalyst is heated to 700-1200°C by passing electrical current through it. The catalyst used is a fechral alloy which is thermally treated on air at temperature 900-1100°C. The ratio of methane to oxygen is varied in the range of 5:1-15:1.

EFFECT: high output and selectivity of the process.

2 cl, 17 ex, 1 tbl, 1 dwg

FIELD: oxidation catalysts.

SUBSTANCE: invention relates to carbon monoxide oxidation catalysts suitable to remove it from emission gases. Use of cadmium telluride as carbon monoxide oxidation catalyst is described.

EFFECT: interaction activity and selectivity of catalyst.

1 tbl

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention provides catalyst for oxidation of ethylene into ethylene oxide, which catalyst contains no rhenium and no transition metals and comprises up to 30% silver on solid support and promoter combination mainly consisted of (i) component containing alkali metal on amount from 700 to 3000 ppm of the mass of catalyst and (ii) component containing sulfur in amount from 40 to 100% by weight of amount required to form alkali metal sulfate and, optionally, a fluorine-containing component in amount from 10 to 300 ppm of the mass of catalyst. Ethylene oxide is produced via reaction of ethylene with molecular oxygen in presence of above-defined catalyst.

EFFECT: increased selectivity of catalyst.

9 cl, 3 tbl

The invention relates to the composition of the oligomeric acid catalyst as component of liquid compositions to obtain fenolformaldegidnyh (FF) foams, does not cause corrosion of metal or having a very weak corrosive effect on their surface

The invention relates to a solid molded the catalysts are easily separated from the reactants and re-used in the reactions of alkylation, esterification and isomerization

The invention relates to the production of catalysts, namely the production of a catalyst for selective hydrogenation of unsaturated hydrocarbons

FIELD: process engineering.

SUBSTANCE: invention relates to activation of metal oxide catalysts. Proposed method uses oxides of VIII-group metals as catalysts and consists in that salts of VIII-group metals and magnesium nitrate are used as initial material and decomposed by thermal decomposition of precursor water solution. Prior to calcination, the latter is subjected to effects of super high frequency fields with circular polarisation at 2.45 GHz fir 5-40 s. Thereafter, said solution is calcinated at 600-650°C for 30 min.

EFFECT: higher yield of nanotubes.

4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a carbonylation method in which at least one compound olefinically unsaturated compound reacts with carbon monoxide in the presence of a complex catalyst of a metal of subgroup VIII of the periodic table of elements, containing an organophosphorus compound as a ligand, where the additional reagent used is at least hydrogen and hydroformylation is carried out. Carbonylation is carried out in the presence of at least one sterically hindered secondary amine with 2,2,6,6-tetramethylpiperidine , units. The invention also relates to a mixture for use in the disclosed carbonylation method.

EFFECT: invention enables to obtain desired products with high selectivity using a stable catalyst system.

18 cl, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts. Described is a method of activating metal oxide catalysts for synthesis of carbon nanomaterials, involving use of magnesium nitrate and group VIII metal salts as starting material which is treated via thermal decomposition, which involves calcination of an aqueous solution of precursors which, before calcination, is exposed to ultrasound at frequency 22 kHz and intensity 50-100 W/cm2 for 5-60 s, after which the solution is heated to temperature 600°C for 30 minutes.

EFFECT: activation method increases output of carbon nanomaterials.

2 cl, 1 tbl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: composition is based on zirconium oxide, silicon oxide and one oxide of another element M, selected from titanium, aluminium, tungsten, molybdenum, cerium, iron, tin, zinc and manganese, with the following weight ratio of these different elements: silicon oxide: 5-30%; oxide of element M: 1-20%, and up to 100% zirconium oxide, wherein the composition has acidity defined in experiments using methylbutanol equal to at least 90%. Said composition can be obtained using a method in which a liquid medium is mixed with a zirconium compound, a silicon compound, a compound of element M and a basic compound, as a result of which a precipitate forms; the precipitate then matures in the liquid medium, separated and then calcined.

EFFECT: composition is effective in treating exhaust gases of diesel engines.

23 cl, 11 tbl, 16 ex

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