Catalytic system and method of nox reduction

FIELD: chemistry.

SUBSTANCE: present invention refers to catalytic system and to the method of reduction of nitrogen oxides emissions using the said system. The described catalytic system for NOx reduction contains: the catalyst containing the metal oxide substrate, catalytic metal oxide which is gallium oxide or silver oxide or both of them and initiating metal chosen from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth and their mixtures, gas flow containing the organic reducing agent and sulfur-containing substance. The described catalytic system for NOx reduction contains: the catalyst consisting of (i) the metal oxide substrate, containing aluminium oxide, (ii) catalytic metal oxide which is gallium oxide or silver oxide or both of them in quantity 1-31 mole %; and (iii) initiating metal or their combination selected from the group consisting of silver, cobalt, molybdenum, wolfram, indium, bismuth, indium and wolfram, silver and cobalt, indium and molybdenum, indium and silver, bismuth and silver, bismuth and indium and molybdenum and indium in quantity 1-31 mole %, gas flow containing (A) water in quantity 1-15 mole %; (B) gaseous oxygen in quantity 1-15 mole %; and (C) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations; and sulfur oxide; where at the specified organic reducing agent and NOx are present in approximate molar ratio carbon to NOx from 0.5:1 to 24:1. The described method of NOx reducing includes the stages of gaseous mixture containing NOx, organic reducing agent and sulfur-containing substance inflow and of said gaseous mixture contact with specified catalyst. The described method of NOx reduction includes: inflow of gaseous mixture containing (A) NOx, (B) water in quantity 1-15 mole %; (C) oxygen in approximate quantity 1-15 mole %; (D) organic reducing agent selected from the group consisting of alcanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates and their combinations and (E) sulfur oxide; and contact of said gaseous mixture with catalyst described above and containing the specified components in the defined molar ratio.

EFFECT: improved action of the catalyst.

35 cl, 10 tbl, 84 ex

 

The level of technology

This invention mainly relates to a catalytic system and method of recovery of nitrous oxide and, more specifically, to a catalyst system which consists of a multi-component catalyst, the reducing agent and compounds containing sulphur.

For a long time people have been searching for ways to reduce the harmful effects of air pollution caused by-products resulting from imperfections of the high-temperature combustion processes of organic substances. During high-temperature combustion process in the presence of large amounts of air are harmful by-products such as nitrogen oxides, commonly known as NOx. It is believed that NOxand derived compounds play a major role in the formation of ground level ozone, which causes asthma and other respiratory diseases. NOxalso promotes the formation of soot, which is associated with a number of serious impacts on health, acid rain, and pollution of coastal areas. Thus, emissions of NOxare subject to many regulatory regulations that restrict the amount of NOxthat may be present in the emitted gases emitted into the environment.

There is a method relating to NOxthat kluchevaluda selective catalytic reduction (SCR), to restore the NOxto gaseous nitrogen (N2), using ammonia (NH3) as a reductant. However, the possible dangerous consequences of the ammonia is well known, the use of NH3in the system of SLE poses additional environmental problems and other tasks that also need to be addressed. While regulators continue to impose restrictions on the reduction of emissions of NOxother regulatory requirements also reduce the allowable level of NH3that can be emitted to the atmosphere. Due to regulatory restrictions on the release of ammonia, the use of hydrocarbons and their oxygen derivatives for recovery of NOxin the course of SLE is very attractive. For these purposes has been proposed a number of catalysts including zeolites, perovskites and metals in the metal oxide substrate of the catalyst. However, existing catalytic systems or have low activity, or a small range of operating temperatures, or slightly resistant to water, which negatively affects the practical application. Moreover, the catalysts active for recovery of NOxvery sensitive to sulfur and lose their activity, if sulfur is present in the system. For example, US patent 6703343 describes the use of catalytic systems for the restoration NO x. However, these catalytic systems require specially synthesized metal oxide substrate of the catalyst with a very low level of impurities. Besides, this catalytic system is particularly sensitive to sulfur poisoning. Therefore, an effective catalytic system for the recovery of emissions of NOxthat is stable, works in a wide temperature range and works effectively in the presence of sulfur.

Brief description of the invention

The present invention describes a catalytic system, which show surprisingly improved efficiency in the presence of sulfur-containing compounds. The data of the catalytic system can be manufactured using commercially available metal oxide substrate catalysts with the usual impurities. Thus, one of the embodiments of the present invention is a catalytic system for recovery of NOxin which the catalytic system consists of a catalyst containing metal oxide substrate of the catalyst, the catalytic metal oxide containing at least one of gallium oxide or silver oxide, and initiating a metal selected from the group consisting of silver, cobalt, molybdenum, tungsten, indium, bismuth, and mixtures thereof. Also catalytic the system consists of a gas flow, containing organic reducing agent, and compounds containing sulphur.

Another embodiment of the present invention is a catalytic system for recovery of NOxin which the catalytic system consists of a catalyst containing (i) a metal oxide substrate catalyst containing alumina, (ii) a catalytic metal oxide containing at least one of gallium oxide or silver oxide in the range of from about 1 to 31 mol %, and (iii) initiating a metal, or a combination of initiating metals selected from the group consisting of silver, cobalt, molybdenum, tungsten, indium, bismuth, indium and tungsten, silver and cobalt, indium and molybdenum, indium and silver, bismuth and silver, bismuth and indium, and molybdenum and silver in the range of from about 1 to 31 mol %. The catalytic system consists of a gas stream containing (A) water in the range of from about 1 to 15 mole %; (B) gaseous oxygen in the range of from about 1 to 15 mole %; and (C) an organic reducing agent selected from the group consisting of alkanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates, and combinations thereof; and sulfur oxide. Organic reducing agent and NOxare present in a molar ratio of carbon:NOxfrom about 0.5:1 to 24:1.

Another embodiment of the present invention is a method of restoring the NOxincluding the stage of providing a gas mixture containing NOxorganic reducing agent and a compound containing sulfur; and contacting the gas mixture with the catalyst, where the catalyst consists of a metal oxide substrate of the catalyst, the catalytic metal oxide containing gallium oxide or silver oxide, and at least one of the initiator of the metals selected from the group consisting of silver, cobalt, molybdenum, tungsten, indium and bismuth.

Another embodiment of the present invention is a method of restoring the NOxcomprising: providing a gas mixture containing (A) NOx; (B) water in the range of from about 1 to 15 mole %; and (C) oxygen in the range of from about 1 to 15 mole %; (D) and the organic reducing agent selected from the group consisting of alkanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates, and combinations thereof; and (E) the sulfur oxide; and the contact specified gas mixture with a catalyst containing (i) a metal oxide substrate catalyst containing at least one of aluminum oxide, titanium dioxide, zirconium dioxide, silicon carbide or oxide of cerium; (ii) a catalytic metal oxide, present the th in number, in the range of from about 1 to 31 mol %, and containing at least one of gallium oxide or silver oxide; and (iii) initiating a metal, or a combination of initiating metals present in a quantity in the range of from about 1 to 31 mol %, and selected from the group consisting of silver, cobalt, molybdenum, tungsten, indium, bismuth, indium and tungsten, silver and cobalt, indium and molybdenum, indium and silver, bismuth and silver, bismuth and indium, and molybdenum and silver; where specified organic reducing agent and specified NOxare present in a molar ratio of carbon:NOxfrom about 0.5:1 to 24:1; and where the specified contact occurs at a temperature in the range of from about 100°C to 600°C and flow rate in the range of from about 5000 h-1up to 100,000 h-1.

Various other features, aspects and advantages of the present invention will be clearer from the following description and the accompanying claims.

A detailed description of the invention

In the following description and the claims will be given a number of terms whose definitions will be given below. The terms in the singular include the form in the plural, unless the context expressly assumes the opposite.

One of the embodiments of the present invention, comprising the his of the catalytic system for the selective reduction of NO xused catalytic system, which consists of a catalyst, a reducing agent and compounds containing sulfur. The catalyst consists of a metal oxide substrate of the catalyst, the catalytic metal oxide and at least one of the initiator of the metal. The reducing agent consists of organic compounds. Disclosed in this description of the catalytic system works effectively in the presence of sulfur.

Metal oxide substrate of the catalyst may contain aluminum oxide, titanium dioxide, zirconium dioxide, cerium dioxide, silicon carbide or any mixture of these substances. Typically, the metal-oxide substrate catalyst contains gamma-alumina with a strongly developed surface containing impurities, in one of the embodiments of the present invention, at least about 0.2 percent by weight, in another embodiment of the present invention, at least about 0.3 weight %. Metal oxide substrate of the catalyst may be manufactured by any method known in the art, such as a joint precipitation, spray drying and solelim way.

The catalyst also contains a catalytic metal oxide. In one of the embodiments of the present invention the catalytic metal oxide contains gallium oxide. In one of the private options, the ants implementation of the present invention, the catalyst contains from about 5 to 31 mole percent of gallium oxide. In another private embodiments of the present invention, the catalyst contains from about 12 to 31 mole percent of gallium oxide. In addition, another one of the private embodiments of the present invention, the catalyst contains from about 18 to 31 mole percent of gallium oxide, where in all cases the molar percentages are calculated by dividing the number of moles of catalyst metal on the total number of moles of the metal component of the catalyst including the catalyst substrate and every person initiating the metal. In another embodiment of the present invention the catalytic metal oxide comprises silver oxide. In another private embodiments of the present invention, the catalyst contains from about 0.5 to 31 mol % of silver oxide. In another private embodiments of the present invention, the catalyst contains about 1 to 8 mol % of silver oxide. In addition, another one of the private embodiments of the present invention, the catalyst contains about 1 to 5 mol % of silver oxide, where in all cases the molar percentages are calculated by dividing the number of moles of catalyst metal on the total number of moles of the metal component of the catalyst including the catalyst substrate and every person initiating the metal.

The catalyst consists of at least one initiator of the metal. Initiating the metal may consist of, at least, silver, cobalt, molybdenum, bismuth, tungsten or India. Besides initiating the metal can also be a combination of more than one of these metals. The catalyst typically contains from about 1 to 31 mol % initiator of metal. In some embodiments, implementation of the present invention, the catalyst contains from about 1 to 15 mol % initiator of metal. In some other embodiments, implementation of the present invention, the catalyst contains from about 1 to 9 mol % initiator of metal. In a particular embodiment of the present invention, the catalyst contains about 1 to 5 mol % initiator of metal. Note that the term "initiating metal" include elemental metals, metal oxides or salts initiating metal, such as Co2O3. In a particular embodiment of the present invention the catalytic metal oxide comprises silver oxide, in addition, the catalytic system must contain at least one of initiating metals selected from the group consisting of cobalt, molybdenum, tungsten, indium, bismuth, and mixtures thereof.

The catalyst may be manufactured by the method of pre is sustained fashion wetting, which includes the use of a homogeneous and a pre-prepared solution of the precursor catalytic metal oxide and catalytic metal in contact with the metal oxide substrate of the catalyst. Particles of metal oxide used for the substrate of the catalyst, prokalyvayutsya before applying the precursor solution. In some embodiments, implementation of the present invention the primary stage of drying is carried out at about 80°C To 120°C for about 1-2 hours, followed by the basic process of annealing. The calcination can be carried out in the temperature range from about 500°to 800°C. In some embodiments, implementation of the present invention, the calcination is carried out in the temperature range from about 650°C. to 725°C. In some embodiments, implementation of the present invention, the annealing is performed for 2 to 10 hours. In some other embodiments, implementation of the present invention, the annealing is performed for 4 to 8 hours. Particles sieved to select and use those, the diameter of which is approximately from 0.1 to 1000 micrometers. In one of the embodiments of the invention the particle size ranges from about 2 to 50 micrometers in diameter. On the basis of surface area and total pore volume of the particles of the metal oxide substrate of the catalyst, it is possible to calculate the required loading of the catalyst. Specialists in this field it is clear that due to the loading of the catalyst surface area and porosity may be about 20-30% lower in the resulting catalyst. Catalyst loading was determined based on the total volume of the pores of the substrate, which is the volume of the metal precursor, which you can download pre-wetting. Download the precursor usually selected so that the quantity of metal was less than a monolayer of active metal oxide on metaloxide substrate of the catalyst. In some embodiments, implementation of the present invention as a General, necessary to load the amount of precursor used dual pore volume, and loading of metal is taken within about 1 to 5 mmol of a mixture of catalytic metal oxide and catalytic metal per gram of metal oxide substrate of the catalyst.

At subsequent stages of manufacture of the catalyst can be prepared solutions of precursors of the catalytic metal oxide and one or more initiating metals. Solutions of precursors can be prepared in water, hydrophilic organic medium or in a mixture thereof. Hydrophilic organic medium contains carboxylic acids, alcohols and their mixtures, such as, but not limited to, acetic acid and ethanol. The solutions are usually obtained by mixing the PR is hanicheskih solvents with metal salts, such as, but not limited to, nitrates metals, citrates, oxalates, acetylacetonates, molybdates or benzoate, in the quantity necessary to prepare the solution with suitable both molarity, which is required for catalytic composition. In some embodiments, implementation of the present invention, the metal salts are molibdenium heteropolar anions or ammonium molybdate. The method used for the manufacture of catalytic systems known in the field of engineering and includes placing the substrate metal oxide catalyst on a honeycomb matrix when using wash primer or extrusion of suspension to the required shape. The degree of purity of the metal precursor for the catalytic metal oxide, and for initiating metal is in the range of from about 95 to 99.999 percent weight percent. In one of the embodiments of the present invention all metal precursors are mixed together as much as possible homogeneous before adding the metal oxide to the substrate of the catalyst. In some other embodiments, implementation of the present invention, various metal precursors are added sequentially to the metal oxide substrate of the catalyst. In one of the embodiments of the present invention the required volume of solution is recursor is added to to cover the metal oxide substrate of the catalyst and to create a catalyst with the desired final catalyst loading. After the metal salt solution or solutions were added to the metal oxide substrate of the catalyst, the catalyst may optionally be left for a period of time, in some embodiments, implementation of the present invention, about 6-10 hours. The catalyst was then dried for a period of time at the required temperature. In the private embodiment of the present invention the catalyst may be dried under vacuum optional when passing a stream of nitrogen through the mixture. Finally, the catalyst may be calcined at the required temperature for the required time, giving the final catalyst product.

The catalysts corresponding to the embodiments of the present invention can be obtained both manually and using an automated process. Usually a manual process is used for the manufacture of catalysts a large mass, such as from 1 to 20 grams (g). The automated process is typically used when the catalysts have a small mass, such as from 5 milligrams (mg) to 100 mg. mainly manual and automated processes for preparation of the catalyst is similar, except that automated PR is the process includes automatic measurement and application of the precursor solution on the metal oxide substrate of the catalyst.

In some embodiments, implementation of the present invention, an organic reducing agents for use in the catalytic system, in embodiments of the present invention, contain hydrocarbons, which are fluid, such as liquid or gas, so that they could flow through the catalyst when the flowing gas stream for use in a catalytic system for recovery of NOx. Usually hydrocarbons with less than 16 number of carbon atoms will be fluid, although hydrocarbons with a large number of carbon atoms can also be fluid, for example, depending on the chemical structure and temperature of the gas stream. The hydrocarbons may be hydrocarbons of any type, including, for example, alkanes and alkenes as a linear chain and branched or cyclic. Organic reducing agent may contain hydrocarbons of the same type, or it may contain a mixture of different hydrocarbons. The mixture may be a mixture of hydrocarbons having the same number of carbon atoms, such as octane, octene and 1,3-dimethylcyclohexane. Similarly, the mixture may be a mixture of hydrocarbons having different numbers of carbon atoms, such as hexane and butane. Private a suitable mixture of hydrocarbons for use as a reductant in to maliciously system in different variants of implementation of the present invention is gasoline. As is well known to specialists in this field, gasoline usually consists of a mixture of linear and branched hydrocarbons, mainly from hydrocarbons having from 5 to 12 carbon atoms. In another embodiment of the present invention, an organic reducing agent consists of hydrocarbons containing oxygen. In some particular embodiments, the implementation of the present invention the catalytic system contains an organic reducing agent selected from the group consisting of alkanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates, and combinations thereof. In some embodiments, implementation of the present invention, an organic reducing agent contains a compound with at least one functional group selected from the group comprising hydroxyl, alkoxyl, carbonyl, carbonate, and combination thereof. Some non-limiting examples of suitable organic reducing agents include hexane, propane, ethane, 2,2,4-trimethylpentane, octane, propene, Aten, methanol, ethanol, 1-butanol, 2-butanol, 1-propanol, isopropanol, dimethyl ether, dimethylcarbonate, acetaldehyde, acetone, and combinations thereof.

The catalytic system also contains sulfur. In some embodiments, implementation of the present invention, the compound containing sulfur, is a gas stream containing NO xfor example in the exhaust source of combustion. In other embodiments, implementation of the present invention, the compound containing sulfur, is added to the gas stream containing the reducing agent, before, or after, or during the combination with a gas flow of NOx. Also, in other embodiments, implementation of the present invention, the compound containing the sulfur present in the gas stream containing NOxand, also, is added to the gas stream containing the reducing agent, before, or after, or during the combination with a gas flow of NOx. The number of compounds containing sulfur present in the gas stream, in one of the embodiments of the present invention is in the range of between about 0.1 ppm to 50 ppm, and in another embodiment of the present invention, in the range between about 0.1 ppm to 20 ppm. Also, in other embodiments, implementation of the present invention, the catalyst is pretreated with compound containing sulfur. In some other embodiments, implementation of the present invention, the compound containing the sulfur present in the gas stream containing NOxor added to the gas stream containing the reducing agent, either before or after, or during the combination with a gas flow of NOxand the catalyst is also pre-treatments is an connection, containing sulfur. Pre-treatment of the catalyst is a compound containing sulfur, usually occurs when exposed to the catalyst gas mixture comprising a compound containing sulfur. In various embodiments, implementation of the present invention, the compound containing sulfur is selected from the group consisting of an oxide of sulfur, mercaptan, and combinations thereof. In one embodiment of the present invention, the compound containing sulfur, consists of sulfur dioxide.

The catalytic system can be used in conjunction with a process or system that would be required to restore the emissions of NOxsuch as gas turbine, steam turbine, boiler, locomotive; or mobile exhaust system, such as, but not limited to, a diesel exhaust system. The catalytic system can also be used with systems that include the generation of gases by burning coal, the combustion of volatile organic compounds (VOCS), or by burning plastics or silicon production, or the production of nitric acid. The catalyst is usually installed inside the exhaust system, where he was exposed to the influence of dissolved gas that contains NOx. The catalyst may be a reactor lattice, and fluidized bed, covered with a monolithic, foam is shaped, cellular or membrane structure, or located in any other way within the exhaust so that the catalyst is contacted with the evolved gas. Due to the fact that the described catalytic system work effectively in the presence of sulfur, they can be successfully used for removal of NOxof gases from engines that use as a fuel for diesel because diesel fuel has a high sulfur content. Similarly, the catalytic system can work successfully with other fuels with high sulfur content.

As is well known to specialists in this area, although catalytic reactions usually are complex and consist of a large number of stages, it is considered that the overall process reaction selective catalytic reduction recovery

NOxas follows:

NOx+ O2+ organic reducing agent → N2+ CO2+ H2O (1)

The released gas stream typically contains air, water, CO, CO2, NOxand may also contain other impurities. In addition, unburned or incompletely burned fuel may also be present in the emitted gas stream. Organic reducing agent is usually served in the emitted gas stream, forming a gas mixture, which is ATEM is fed through the catalyst. A sufficient amount of oxygen for the reduction reaction of NOxmay already be present in the emitted gas stream. If the amount of oxygen present in the gas mixture is not sufficient for the reduction reaction of NOxadditional gaseous oxygen may also be introduced in the emitted gas stream in the form of oxygen or air. In some embodiments, implementation of the present invention, the gas flow contains from about 1 to 21 mol % oxygen gas. In some other embodiments, implementation of the present invention, the gas flow contains from about 1 to 15 mol % of oxygen gas.

One advantage of this invention is that the reduction can occur under low content of reducing agent". That is, the amount of reductant added to the selected gas for recovery of NOxusually little. Reducing the quantity of reducing agent for the conversion of NOxin the nitrogen can provide greater process efficiency by reducing the cost of raw materials. The molar ratio of reductant to NOxis usually in the range of about 0.25:1 to 6:1. In other embodiments of this invention the ratio is usually such that the ratio of carbon atoms in the reducing agent is approx the RNO in the range from 0.5 to 24 moles per mole of NO x. In some other embodiments, implementation of the present invention, an organic reducing agent and NOxare in a molar ratio of carbon:NOxin the range of about 0.5:1 to 15:1. In one of the private embodiments of the present invention, an organic reducing agent and NOxare in a molar ratio of carbon:NOxin the range of about 0.5:1 to 8:1.

The reduction can take place in the interval of temperatures. Typically, the temperature may be for one of the embodiments of the present invention in the range of from about 100°C to 600°C, for other option from approximately 200°C to 500°C and for another variant implementation from about 350°C. to 450°C.

The reduction can occur under conditions in which the gas mixture has a bulk velocity in one embodiment of the present invention in the range of from about 5000 hours back (h-1) up to 100,000 h-1in another embodiment in the range from about 8000 h-1up to 50,000 h-1in another embodiment in the range from about 8000 h-1up to 40,000 h-1.

An example implementation of the catalytic system can also be successfully applied in wet conditions. In private variants of implementation of the present invention the recovery of NOxis performed with the use of examples of this izaberete the Oia, which can be effective when the water content in the released gas flows. In some embodiments, implementation of the present invention, the gas flow contains from about 1 to 15 mol % of water and, in some other embodiments, implementation of the present invention, from about 2 to 10 mole percent of water.

Without further elaboration, it is believed that the specialist using this description, will take advantage of the present invention to the full extent. The following examples are provided to give additional representation for professionals who use the claimed invention. The examples are only to present the work, which contributed to the creation of the present invention. Thus, these examples are not intended to limit in any way the invention as defined in the attached claims.

Examples

The catalyst is manufactured and used in combination with a reducing agent according to embodiments of the present invention. The conversion of NOxanalyze under different conditions of the experiment, including changing the composition of the catalyst, the reducing agent, the temperature of the reactions and attitudes of the reducing agent to

NOx.

In further examples, each of the catalyst samples are made using a commercial gamma-aluminium is a Ieva substrate of the catalyst from Saint-Gobain NorPro of Stow, Ohio. The aluminum substrate of the catalyst has a purity from 99.5% to 99.7 per cent. The aluminum substrate is first made red-hot at a temperature of 725°C for 6 hours in the presence of an oxidant. As the oxidant can be air or oxidizing gas containing from about 1% to 21% oxygen in nitrogen. Aluminum particles are then sieved to select the substrate of the catalyst having a particle size diameter from about 450 micrometers to 1000 micrometers, unless otherwise specified. Before loading the substrate of the catalyst has a surface area of about 240 square meters per gram (m2/g) and pore volume coefficient was 0.796 milliliters per gram (ml/g).

Gallium or silver, is used as the metal catalytic metal oxide, is added to the aluminum. Raw aluminum substrate type metal in a soluble form, which can be made from a solution of gallium nitrate having the formula Ga(NO3)3·6H2O, and from a solution of silver nitrate. For example, a solution obtained by mixing deionized water with gallium nitrate with a purity of 99,999% (base metal), obtained from Alfa-Aesar of Ward Hill, Massachusetts. All operations used milleporidae water with an electrical resistance of 18 Megohm·cm. For the initiating of the metal to the aluminum substrate add an aqueous solution of nitrate salts of the desired m is metal(s), which also has a purity of 99,999% (base metal) and obtained from Alfa-Aesar. Before applying on an aluminum substrate metal precursors as uniform mixed together. Catalysts leave on time from 6 to 10 hours and then dried under continuous vacuum with a flow of nitrogen for 4 to 5 hours at 80°C. Finally, the dried catalyst is subjected to heat treatment. The heating profile for this treatment begins with a temperature increase from 25°C to 110°C With step of 1.4°C per minute. The catalyst is maintained at 110°C for 1.5 hours, after which the temperature increase of 5°C per minute to a value of 650°C. the Catalyst can withstand 6 hours at this temperature and then cooled over a period of time from 4 to 6 hours.

The catalyst is tested in high performance 32-pipe the microreactor for the study of catalysts, unless otherwise specified. Used reactor heated with a gas distributor with the usual air gap, which evenly distributes the flow of the reagent in the parallel tubes of the reactor through the connecting capillaries. The distributor has such heating characteristics, which allow for preheating the flow of the reagent and produce evaporation of liquid reagents prior to distribution. Fully composed heated reproduced by the amplifier is mounted on a vertical moving platform, which is raised and lowered under the action of pneumatic pressure. The tube reactor is introduced into a 10-centimeter (cm) a well-insulated gold plated copper compartment reactor (dimensions 13.5 cm by 25 cm), is able to be heated to different temperatures in the range from 200°C. to 650°C.

Chemically inert o-ring KALREZ™, obtained from DuPont of Wilmington, Delaware, is used as the viscoelastic mechanical seals on each end of the tubes of the reactor. Tube reactor made of INCONEL 600 tubes™ with an external diameter of 0,635 cm and an inner diameter of 0,457 cm, obtained from Inco Alloys/Special Metals of Saddle Brook, New Jersey. Tubes move freely inside gold plated copper heating compartment. Each tube contains a Frit made of quartz fibers, on which is placed around 0,050 g of the sample in the center of each tube, through which is passed a stream of reagent modeling emitted gas stream comprising a gas mixture containing NOxand the reducing agent. To ensure uniform flow in each of the 32 investigated tubes use a single parallel tube. The fittings are connected to a dispenser for delivering a constituent of the gas mixture. The components of a composite gas mixture are fed into the mixer using a controller mass flow and then sent to the dispenser. The pressure in the dispenser is podderjivaetsa about 275,8 kilopascals (kPa). Temperature and flow in the reactor are controlled fully automatically.

After loading in the catalyst tube is subjected to heat treatment in the air stream, as described above, and then injected into reaction with a compound of the gas mixture. The exiting product is fed into the heated distribution valves for sampling, which is equipped with a number of pipes, and a continuous flow is sent to a chemiluminescent analyzer. Any thread that is not directed to an analytical device, is served in the ventilation pipe.

Switching distribution valves for routing gases is controlled by the computer and is executed at a predetermined time sequence. Chemiluminescent analyzer connected to a computer data-logging system. Data corresponding allocated from the tubes of the reactor composition, ordered by time and save. Data parallel tubes are also saved for comparison with the composition introduced into the tube reactor. Such integration of experimental data allows to determine the activity and selectivity of each sample of the catalyst.

To study the recovery of NOxuse the flow of the reagent compound gas mixture comprising a reducing agent, about 200 ppm NOx, 12 % by volume of oxygen, 7 % by volume of water and which OS the actual amount of nitrogen and optionally sulfur containing compounds. In embodiments implementing the present invention research recovery NOxcarried out in the presence of compounds containing sulfur, for example SO2. Some examples of SO2mixed with a gas mixture containing a reducing agent, and, in some other examples, the catalyst prior to the experiment process SO2. The type and amount of reducing agent in the stream varies depending on the conducted experiments. The flow rate of a constituent of the gas mixture in each tube is 29 standard cubic centimeters per minute (SKSM) to each tube.

Table 1 presents the compositions of the prepared samples of the catalyst, expressed in molar percent of each of the initiating metal and/or the catalytic metal present in the catalyst. The rest of the composition is aluminum from the aluminum substrate of the catalyst. Molar percentages are determined for each component by dividing the number of moles of a given component by the total number of moles of the metal components in the catalyst, including metal components of the metal oxide substrate of the catalyst. The abbreviation "S. p." means comparative example.

TABLE 1
Example GaInAgCoW
Crowner 1290000
Crowner 200200
Example 1272000
Example 2270002
Example 3250004
Example 4200008
Example 521 003
Example 6223003
Example 7216001
Example 8270200
Example 9250220
Example 10270020
Example 11223030

In each experiment conducted the first of a series prepared and examined various catalyst samples with different vos is canonicalname, using the described methodology of the study, at 450°C. the Results presented in table 2 show the percentage of the converted NOxin each of the catalytic systems. Non of the examples in table 2 correspond to the catalytic compositions in the examples of table 1. Although the molar ratio of reductant to NOxvaries depending on the use of the reducing agent, the molar ratio of carbon:NOxbasically is approximately 6:1 for each of the experimental systems. The abbreviation "DME" and "IPS" means dimethyl ether and isopropyl alcohol. All of the examples listed in table 2, the gas mixture containing the reducing agent contains 5 ppm SO2.

TABLE 2
Reductants
ExampleMeOHDMEEtOHAcetaldehydeAcetoneIPS
Crowner 166334544466
Crowner 214471655986
Example 1331448383769
Example 2766827374535
Example 3421718303731
Example 4562628323737
Example 521949434769
When is EP 6 231244394070
Example 7171430313642
Example 816665756290
Example 915570716080
Example 1053826252265
Example 1120--17----48

As can be seen from table 2, example 2, which uses a combination of the sid gallium, as a catalytic metal oxide, and bismuth, as the initiator of metal, shows particularly good results when using reductants such as methanol and dimethyl ether. Example 8 containing gallium and silver, and example 9, containing gallium, cobalt and silver, both show good results with ethanol, acetaldehyde, acetone and isopropyl alcohol.

Each conducted experiment of the second series prepare and investigate various catalyst samples with different reducing agents, using the described methodology of the study, at 450°C. the Results presented in table 3 show the percentage of transformed NOxin each of the catalytic systems. Most of the catalysts are shown in table 3, contain molybdenum. The abbreviation "S. p." means comparative example. Comparative example 3 consists only of the aluminum substrate. Although the molar ratio of reductant to NOxvaries depending on the use of the reducing agent, the molar ratio of carbon:NOxbasically is approximately 6:1 for each of the experimental systems. All of the examples listed in table 3, the gas mixture containing the reducing agent contains 5 ppm SO2.

TABLE 3
The catalytic compositionThe restorer
ExampleGaInMoMeOHDMEAcetaldehydeEtOHIPSAcetone
Srvnet000281511101410
Example 122008401930344921
Example 1322332815233543 19
Example 142405792746558145
Example 152520331438486937
Example 16260053825266522
Example 172702683543477229
Example 18272 024739486545
Example 1921615----1522--

As can be seen from table 3, examples 14 and 17, which uses a combination of gallium oxide as a catalytic metal oxide, and molybdenum, as the initiator of metal, show good results when using reductants such as methanol and isopropyl alcohol.

In each experiment conducted third series prepare and investigate various catalyst samples using n-octane as the reductant, using the described methodology of the study, at 400°C. the Results presented in table 4 show the percentage of transformed NOxin each of the catalytic systems. All of the catalysts shown in table 4 contain silver. Although the molar ratio of reductant to NOxvaries depending on the use of reducing agent molar ratio equal to the clan:NO xbasically is approximately 6:1 for each of the experimental systems. All of the examples listed in table 4, the gas mixture contains 600 ppm n-octane. In the last two columns of data, the catalyst was pretreated SO2. Pre-treatment of the catalyst SO2carried out by exposure to gas mixtures containing 5 ppm SO2at 400°C for 16 hours. In this set of experiments, each sample includes 3 passes in 3 different conditions. At first the conditions of the fresh catalyst is introduced into contact with a gas mixture that does not contain any amount of SO2. During the second conditions with the same catalyst pre-treated with a gas mixture containing SO2and then enter into contact with a gas mixture that does not contain any amount of SO2. In third conditions, the same catalyst is pretreated with a gas mixture containing SO2and then enter into contact with a gas mixture that contains 1 ppm SO2. Basically, each catalyst shows the best results in terms 2 and 3 compared to condition 1.

TABLE 4
ExampleThe composition of the catalyst The content of SO2in the flow
(ppm)
The condition 1The condition 2Condition 3
GaInAg001
The catalyst pre-treated
SO2
The percentage of transformed NOx
Srprised 4002779595
Example 2027029898 98
Example 212522979696
Example 222233408689
Example 232504178486
Example 24204424751
Srprised 5005188889
Example 25221602635
Example 6 200972328
Example 270029483523

Each conducted experiment the fourth series prepare and investigate various catalyst samples using isopropyl alcohol as a reducing agent, using the described methodology of the study, at 450°C. the Results presented in table 5 show the percentage of transformed NOxin each of the catalytic systems. All of the catalysts shown in table 5 contain silver. Although the molar ratio of reductant to NOxvaries depending on the use of the reducing agent, the molar ratio of carbon:NOxbasically is approximately 6:1 for each of the experimental systems. In the last two columns of data, the catalyst was pretreated SO2. Pre-processing each of the catalyst SO2is described in the preceding paragraph by the way. In this set of experiments, each sample includes 3 passes in 3 different conditions. In the first set of conditions with which II the catalyst is introduced into contact with the gas mixture, which does not contains any number of SO2. Secondly, the conditions of the same catalyst pre-treated with a gas mixture containing SO2and then enter into contact with a gas mixture that does not contain any amount of SO2. In third conditions, the same catalyst is pretreated with a gas mixture containing SO2and then enter into contact with a gas mixture that contains 1 ppm SO2. 3 line number SO2contains the index a or b. The index "a" shows that the gas mixture used for these experiments contains 150 ppm of isopropyl alcohol, and the index "b" shows that the gas mixture contains 400 ppm of isopropyl alcohol. Each catalyst shows the best results under the conditions 2 and 3 compared to condition 1.

tr>
TABLE 5
ExampleThe catalytic compositionThe content of SO2in the flow
(ppm)
The condition 1The condition 2Condition 3
GaInAg0a0b1b
The catalyst pre-treated SO2
The percentage of transformed NOx
Crowner 600271280
Example 28270242590
Example 292522518 80
Example 3022333749
Example 3125043960
Example 3220444738
Example 3322163733
Example 34200921322
Crowner 700292 1418

In each of the conducted experiment, the fifth series will explore a variety of reducing agents at a temperature of 450°C in the presence or in the absence of SO2in the gas mixture. These experiments are performed using catalyst containing 27% Ga and 2% Ag. Although the molar ratio of reductant to NOxvaries depending on the use of the reducing agent, the molar ratio of carbon:NOxbasically is approximately 6:1 for each of the experimental systems. The results presented in table 6 show the percentage of the converted NOxin each of the catalytic systems. The abbreviation "2,2,4-TMP" means 2,2,4-trimethylpentane.

TABLE 6
The restorer0 ppm SO25 ppm SO2
C3H66369
EtOH2665
D1790
2,2,4-TMP7270
Hexane2845

Each conducted experiment sixth series exploring various reducing agents at a temperature of 450°C in the presence or in the absence of SO2in the gas mixture. These experiments are performed using catalyst containing 24% Ga and 5% Mo. Although the molar ratio of reductant to NOxvaries depending on the use of the reducing agent, the molar ratio of carbon:NOxbasically is approximately 6:1 for each of the experimental systems. The results presented in table 7, show the percentage of the converted NOxin each of the catalytic systems. The abbreviation "2,2,4-TMP" means 2,2,4-trimethylpentane.

TABLE 7
The restorer0 ppm SO25 ppm SO2
MeOH778
EtOH5555
D5380
C3H645 64
2,2,4-TMP2365
Hexane3030
Octane5140

In each of the conducted experiment, the seventh series in 96-tube reactor as reducing agents investigate methanol and dimethyl ether at a temperature of 400°C in the presence of a gas mixture containing 5 ppm SO2, 1000 ppm NOx, 2% water, 13% O2and the remainder helium at a nominal flow rate 13000 h-1. Table 8 presents how the catalytic composition and the activity of the catalyst for each experiment. The remaining number of moles of catalyst includes a metal oxide substrate of the catalyst, which in these experiments has an average particle size of 20 micrometers. Although the molar ratio of reductant to NOxvaries depending on the use of the reducing agent, the molar ratio of carbon:NOxbasically is approximately 6:1 for each of the experimental systems. The catalyst activity is expressed in moles converted NOxin N2per gram of catalyst per hour. Nitrogen is directly determined by gas is chromatography.

TABLE 8
ExampleCatalystThe restorer
BiInAgGaMeOHDME
Example 350171200,00160,0017
Example 360170120,00140,0016
Example 370126120,000510,00079
Example 38066170,000360,00051
Example 39406130,000330,00047
Example 400012170,000260,00041
Example 412012120,000190,00035
Example 422121200,000150,00031
Example 43023060,000150,00030
Example 440121700,000200,00030
Example 4511000--4,1E-05
Crowner 800290--1,4E-06
Example 46012126--0,00032

In each experiment conducted eighth series in 96-tube reactor as reducing agents investigate propene and eaten at a temperature of 400°C in the presence of a gas mixture containing 5 ppm SO2, 1000 ppm NOx, 2% water, 13% O2and the remainder helium at a nominal flow rate 13000 h-1. Table 9 presents as catalytic composition and activity of the catalyst for each experiment. The remaining number of moles of catalyst includes a metal oxide substrate of the catalyst, which in these experiments has an average particle size of 20 micrometers. Although the molar ratio of reductant to NOxvaries in dependence the value from the used reducing agent, the molar ratio of carbon:NOxbasically is approximately 6:1 for each of the experimental systems. The catalyst activity is expressed in moles converted NOxin N2per gram of catalyst per hour. Nitrogen is directly determined by gas chromatography.

0
TABLE 9
ExampleCatalystThe restorer
BiMoInAgGaPropeneEten
Example 4700121260,0016--
Example 480061760,0012--
Example 49 0401860,0011--
Example 5000171200,0011--
Example 5104121200,00098--
Example 52800070,00097--
Example 530060230,00096--
Example 5460013 00,00094--
Example 5500012170,00094--
Crowner 90000290,00093--
Example 560170600,00090--
Example 570120660,00089--
Example 580066170,00086--
When the EP 59 00126120,00085--
Example 600029000,00075--
Crowner 100002900,00068--
Example 610017120--0,0021
Example 620017012--0,0017
Example 630012 612--0,0010
Example 640012126--0,00076
Example 65006176--0,00075
Example 66006617--0,0064
Example 670001217--0,00063
Example 680012170--0,0059
Example 69002306--0,00055
Example 70400613--0,00052
Example 710012017--0,00035
Example 72400190--0,00034
Crowner 11000290--0,00012
Example 7311000--5E-05
Example 74002900--1,1E-05

In each experiment conducted ninth series as a reductant explore methanol at a temperature of 400°C in the presence of a gas mixture containing 5 ppm SO2, 200 ppm NOx, 4% water, 13% O2and the rest of the amount of nitrogen at a nominal flow rate 28000 h-1. Table 10 presents as catalytic composition and activity of the catalyst for each experiment. The remaining number of moles of catalyst includes a metal-oxide substrate of the catalyst. Although the molar ratio of reductant to NOxvaries depending on the use of the reducing agent, the molar ratio of carbon:NOxbasically is approximately 6:1 for each of the experimental systems. The catalyst activity is expressed in moles converted NOxin N2per gram of catalyst per hour. Comparative example 12 contains only aluminum substrate and gallium oxide.

TABLE 10
ExampleCatalystThe restorer
GaAgInMoMeOH
Example 75661901,1E-05
Example 76619603,E-05
Example 77602502,1E-05
Example 781361300,00014
Example 79196601,3E-05
Example 80 062500,00014
Example 810191308,3E-06
Example 82292005,1E-06
Example 835161002,E-05
Crowner 12310003,1E-07
Example 840013131,9F-05

Have been described various embodiments of the present invention for implementing the various tasks related to the invention. It should be noted that these embodiments of the invention are only illustrative of the principles of different vari is now of the present invention. Without deviating from the essence and scope of the present invention in their various modifications and adaptation will be obvious to the person skilled in the art. Thus, it is expected that this invention applies to all suitable modifications and variations in the volume in which they are presented in the attached claims and their equivalents.

1. Catalytic system for recovery of NOxcontaining:
the catalyst containing metal oxide substrate of the catalyst, the catalytic metal oxide containing at least one of gallium oxide or silver, and initiating a metal selected from the group consisting of silver, cobalt, molybdenum, tungsten, indium, bismuth, and mixtures thereof;
the gas stream containing organic reducing agent; and
compound containing sulfur.

2. The catalytic system according to claim 1, where the specified metal oxide substrate catalyst contains at least one member selected from the group comprising aluminium oxide, titanium dioxide, zirconium dioxide, cerium dioxide, silicon carbide, or mixtures thereof.

3. The catalytic system according to claim 1, where the specified catalytic metal oxide contains from about 5 to 31 mol.% gallium oxide.

4. The catalytic system according to claim 1, where the specified catalytic metal oxide contains from about 0.5 to 31 mol.% oxide ser the bra.

5. The catalytic system according to claim 1, where the specified catalyst contains the specified trigger metal about 1 to 31 mol.%.

6. The catalytic system according to claim 1 where the catalytic metal oxide includes an oxide of gallium, and the initiating metal contains silver or a combination of indium and silver.

7. The catalytic system according to claim 1 where the catalytic metal oxide includes an oxide of silver, and the initiating metal includes indium.

8. The catalytic system according to claim 1, where the specified organic reducing agent selected from the group consisting of alkanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates, and combinations thereof.

9. The catalytic system according to claim 1, where the specified organic reducing agent selected from the group consisting of hexane, propane, ethane, 2,2,4-trimethylpentane, octane, propene, Athena, methanol, ethyl alcohol, butyl alcohol, propyl alcohol, dimethyl ether, dimethylcarbonate, acetaldehyde, acetone, and combinations thereof.

10. The catalytic system according to claim 1, where the specified organic reducing agent and specified NOxare present in a molar ratio of carbon: NOxfrom about 0.5:1 to 24:1.

11. The catalytic system according to claim 1, where the specified gas stream also contains water of about from 1 to 15 mol.%.

12. The catalytic system according to claim 1, where the specified ha the new thread also contains gaseous oxygen from about 1 to 21 mol.%.

13. The catalytic system according to claim 1, where the specified compound containing sulfur is present in the specified gas stream containing NOxor in a gas stream containing a reducing agent, or in both threads.

14. The catalytic system according to claim 1, where the specified catalyst pretreated specified compound containing sulfur.

15. The catalytic system according to claim 1, where the specified compound containing sulfur selected from the group consisting of sulfur dioxide, mercaptans and combinations thereof.

16. The catalytic system according to claim 1, where the specified compound containing sulfur, contains sulphur dioxide.

17. The catalytic system according to claim 1, where NOxobtained from the fire area, including at least one of a gas turbine, boiler, locomotive, mobile exhaust, coal combustion, incineration of plastics, incineration of volatile organic compounds on silicon production or the production of nitric acid.

18. Catalytic system for recovery of NOxcomprising: a catalyst containing (i) a metal oxide substrate catalyst containing alumina, (ii) a catalytic metal oxide that contains at least one of gallium oxide or silver about 1 to 31 mol.%, and (iii) initiating a metal, or a combination of initiating metals selected from the GRU is dust, consisting of silver, cobalt, molybdenum, tungsten, indium, bismuth, indium and tungsten, silver and cobalt, indium and molybdenum, indium and silver, bismuth and silver, bismuth and indium and molybdenum and silver from about 1 to 31 mol.%;
the gas stream containing (A) water, from about 1 to 15 mol.%; (C) gaseous oxygen is about 1 to 15 mol.% and (C) an organic reducing agent selected from the group consisting of alkanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates, and combinations thereof; and sulfur oxide;
where specified organic reducing agent and specified NOxare present in a molar ratio of carbon: NOxfrom about 0.5:1 to 24:1.

19. Method of recovering NOxthat includes stage:
providing a gas mixture containing NOxorganic reducing agent and a compound containing sulfur, and
contact the specified gas mixture with the catalyst, where the specified catalyst consists of a metal oxide substrate of the catalyst, the catalytic metal oxide containing gallium oxide or silver oxide, and at least one initiator metal selected from the group consisting of silver, cobalt, molybdenum, tungsten, indium and bismuth.

20. The method according to claim 19, where the specified catalyst pretreated specified compound containing sulfur, before what ruuskanen specified gas mixture through the catalyst.

21. The method according to claim 19, where the specified contact occurs at a temperature of from about 100 to 600°C.

22. The method according to claim 19, where the specified contact is carried out at flow rate of from about 5,000 to 100,000 h-1.

23. The method according to claim 19, where the specified metal oxide substrate catalyst contains at least one of aluminum oxide, titanium dioxide, zirconium dioxide, silicon carbide or oxide of cerium.

24. The method according to claim 19, where the specified catalytic metal oxide contains gallium oxide from about 5 to 31 mol.%.

25. The method according to claim 19, where the specified catalyst contains silver oxide from about 1 to 31 mol.%.

26. The method according to claim 19, where the specified catalyst contains the specified trigger metal about 1 to 31 mol.%.

27. The method according to claim 19, where the specified organic reducing agent selected from the group consisting of alkanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates, and combinations thereof.

28. The method according to claim 19, where the specified organic reducing agent selected from the group consisting of hexane, propane, propene, ethane, Athena, 2,2,4-trimethylpentane, octane, methanol, ethyl alcohol, butyl alcohol, propyl alcohol, dimethyl ether, dimethylcarbonate, acetaldehyde, acetone, and combinations thereof.

29. The method according to claim 19, where the specified organic reducing agent and specified NO xare present in a molar ratio of carbon: NOxfrom about 0.5:1 to 24:1.

30. The method according to claim 19, where the specified gas stream contains water of about from 1 to 15 mol.%.

31. The method according to claim 19, where the specified gas stream contains gaseous oxygen from about 1 to 21 mol.% the oxygen.

32. The method according to claim 19, where the aforementioned compound containing sulfur selected from the group consisting of sulfur dioxide, mercaptans and combinations thereof.

33. The method according to claim 19, where the aforementioned compound containing sulfur, contains sulphur dioxide.

34. The method according to claim 19, in which the NOxobtained from the fire area, including at least one of a gas turbine, boiler, locomotive, mobile exhaust, coal combustion, incineration of plastics, incineration of volatile organic compounds on silicon production or the production of nitric acid.

35. Method of recovering NOxincluding:
providing a gas mixture containing (A) NOx; (C) water, from about 1 to 15 mol.%; (C) oxygen is about 1 to 15 mol.%; (D) an organic reducing agent selected from the group consisting of alkanes, alkenes, alcohols, ethers, esters, carboxylic acids, aldehydes, ketones, carbonates, and combinations thereof; and (E) the sulfur oxide; and
contact the specified gas mixture with a catalyst containing (i) a metal oxide substrate of the catalyst, with the containing a series, at least one of aluminum oxide, titanium dioxide, zirconium dioxide, silicon carbide or oxide of cerium; (ii) a catalytic metal oxide is present in an amount of about 1 to 31 mol.% and containing at least one of gallium oxide or silver oxide; and (iii) initiating a metal, or a combination of initiating metals present in amount of about 1 to 31 mol.% and selected from the group consisting of silver, cobalt, molybdenum, tungsten, indium, bismuth, indium and tungsten, silver and cobalt, indium and molybdenum, indium and silver, bismuth, and silver;
where specified organic reducing agent and specified NOxare present in a molar ratio of carbon: NOxfrom about 0.5:1 to 24:1 and where the specified contact is carried out at a temperature of from about 100 to 600°C and a flow rate from about 5000 to 100000 h-1.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: present invention pertains to chemical industry, particularly to catalysts used for converting natural gas, and can be used in petrochemical and oil-refining industry for making catalysts and in gas synthesis process. Description is given of a catalyst, containing a nickel aluminide matrix, inside of which nickel and molybdenum are dispersed, with the following ratio of components, in wt %: Ni3Al - 80-90, Ni - 5-10, Mo -2-10. The catalyst is obtained through self-propagating high-temperature synthesis and is used in the process of carbon dioxide conversion of methane.

EFFECT: high catalytic activity and stability of the catalyst.

2 cl, 4 tbl, 3 ex

FIELD: chemistry, pharmaceutics.

SUBSTANCE: invention relates to method of obtaining catalyst of dehydrating 4,5,6,7-tetrahydroindole into indole. Described is catalyst of dehydrating 4,5,6,7-tetrahydroindole into indole containing nickel sulphide applied on aluminium oxide, catalyst being dopated with sodium and chlorine ions and contains 0.30-2.00% of nickel, 0.20-1.50% of sulphur, 0.10-0.20% of sodium, 0.20-1.00% of chlorine. Also described is method of obtaining catalyst which lies in impregnation of aluminium oxide with nickel salt with further processing with metal sulphide at room temperature in water medium in presence of hydrochloric acid and surface-active substance. Catalyst is isolated by filtration without further washing, dopating of catalyst takes place, and dopants are fixed by means of thermal processing.

EFFECT: increase of mechanical strength and activity of catalyst, as well as increase of its service life.

4 cl, 1 dwg, 10 ex

FIELD: chemistry.

SUBSTANCE: nickel-copper oxide catalysts on metal carrier can be used in conversion of CO into CO2 in high-temperature processes of technological and exhaust gas purification, in particular, in energy and automobile industry. Catalysts on carrier, made from aluminium or its alloy are obtained by plasma-electrochemical method by means of carrier processing in alkali electrolyte, containing nickel acetate and copper acetate and additionally including trisodium phosphate, sodium tetraborate and tungstate with following ratio of components, g/l: nickel acetate Ni(CH3COO)2·4H2O-5-20; copper acetate Cu(CH3COO)2·H2O-1.3-5.0; trisodium phosphate Na3PO4·12H2O-20-30; sodium tetraborate Na2B4O7·10H2O-10-20; sodium tungstate Na2WO4·2H2O-1-3. Plasma-electrochemical processing is carried out in galvano-static mode by pulse current, alternating or alternating unidirectional, with impulse duration 0.0033-0.04 sec, voltage 240-400 V, efficient current density 5-20 A/dm2 and electricity amount consumption 1500-6000 C/dm2 of formed catalytically active layer. Obtained catalyst is stable in temperature range 300-500° and ensures degree of CO into CO2 conversion in wide limits (from 37 to 97%).

EFFECT: increased catalyst stability.

2 dwg, 1 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of production of catalysts, containing porous carrier (active aluminium oxide) and deposited on it catalytically active metal (palladium) for low-temperature oxidation of carbon oxide and can be used in means of individual and collective protection of respiratory organs of people. Described is method of obtaining palladium catalyst on active aluminium oxide for low-temperature oxidation of carbon oxide, including preliminary modification of aluminium oxide with nickel oxide in amount (0.03-0.50) % wt, impregnation with acidified with hydrochloric acid solution of palladium (II) chloride, in amount (0.1-1.5) % wt in terms of metal, reduction with sodium formiate solution with rate of solution feeding (0.1-0.4) cm/s with further washing and drying of catalyst first at room temperature during (1-2) h, then at temperature (30-40)°C during (1-2) h and then to temperature (105-115)°C with rate of its increase (10-15)°C/h.

EFFECT: obtaining more efficient catalyst for carbon oxide oxidation in wide range of its concentrations at room temperature of use.

2 tbl, 13 ex

FIELD: technological processes; chemistry.

SUBSTANCE: method of composition preparation is described, which includes: (a) adulteration of the following: 1) liquid, 2) zinc-containing compound, 3) silica-containing material, 4) alumina and 5) promoter for preparation of its mixture; where specified liquid is selected from the group that consists of water, ethanol, acetone and combination of any two and more specified compounds, and where specified promoter contains metal selected from the group that contains nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chrome, palladium, titanium, zirconium, rhodium, rhenium, and also combination of any two or more of them; (b) drying of specified mixture for preparation of dried mixture; (c) baking of specified dried mixture for preparation of baked mixture; (d) reduction of specified baked mixture with suitable reducing agent under suitable conditions for preparation of composition that contains promoter with lower valency; and (e) regeneration of specified composition. Method of composition preparation (version) is also described, which includes introduction of two promoters, as well as compositions prepared by specified methods. Method of sulfur removal from carbohydrate flow is described, which includes the following: (a) contact of specified carbohydrate flow with composition that has been prepared by the method according to any of previous points, in desulfurisation zone under conditions, under which at least partially desulfurised carbohydrate flow and sulfurised composition are formed; (b) isolation of specified at least partially desulfurised carbohydrate flow from specified sulfurised composition with preparation of isolated desulfurised carbohydrate flow and isolated sulfurised composition; (c) regeneration of at least part of specified isolated sulfurised composition in zone of regeneration to remove at least part of sulfur contained in it and/or on it with preparation of regenerated composition; (d) reduction of specified regenerated composition in reduction zone to prepare reduced composition, which contains such amount of promoter with lower valency that influences sulfur removal from sulfur-containing carbohydrate flow during contact with it; (e) return of at least part of reduced composition to desulfurisation zone. Cracked gasoline or diesel fuel prepared as a result of above mentioned method application is described.

EFFECT: preparation of compositions with sufficient abrasion resistance.

18 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention is referred to the area of hydrocarbons preparation by catalytical hydrodeoxygenation of products of fast pyrolysis of a biomass and working out of the catalyst for this process. The catalyst of oxygen-organic products hydrodeoxygenation of fast pyrolysis of lignocellulose biomasses, containing either precious metal in amount of no more 5.0 wt % or containing nickel, or copper; either iron, or their combination in a non-sulphide restored shape in amount of not more than 40 wt % and transitive metals in a non-sulphide shape in amount of not more than 40 wt %, carrying agent - the rest, is described. Three variants of the catalyst preparation method, providing application of transition metals on the carrying agent by a method of impregnation of the carrying agent solutions of metal compounds are described, or simultaneous sedimentation of hydroxides or carbonates of transition metals in the presence of the stabilising carrier, or the catalyst is formed by joint alloying/decomposition of crystalline hydrate nitrates of transition metals together with stabilising components of zirconium nitrate type. The process of oxygen-organic products hydrodeoxygenation of a biomass fast pyrolysis is performed using the above described catalyst in one stage at pressure of hydrogen less than 3.0 MPa, temperature 250-320°C.

EFFECT: increase stability in processing processes of oxygen-containing organic raw materials with the low content of sulphur, and also soft conditions of process realisation.

10 cl, 12 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalysts of hydration, method of their production and use for hydration such as selective hydration of acetylene admixtures in non-purified olefinic and diolefiniuc flows. Described is a selective catalyst of hydration for selective hydration of acetylene admixtures in non-purified olefinic and diolefinic flows, containing only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, applied on carrier, which is alumunium oxide with the following physical characteristics: BET surface area from 30 to approximately 100 m2/g, total volume of pores on nitrogen from 0.4 to approximately 0.9 cm3/g and the average pore diameter from approximately 110 to 450 Å , where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Described are the method of catalyst production, which includes impregnation of carrier represented by aluminium oxide and having the aforesaid physical characteristics, with soluble salts of only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, from one or more solutions, obtaining impregnated carrier, where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Also described is the method of selective hydration of acetylene compounds, which includes contact of original raw material containing acetylene compounds and other unsaturated compounds, with the described above catalyst.

EFFECT: increased degree of 1,3-butadien extraction with full or nearly full conversion of C4-acetylenes.

25 cl, 1 dwg, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to the method of obtaining porous substances on a substrate for catalytic applications, to the method of obtaining porous catalysts for decomposition of N2O and their use in decomposing N2O, oxidising ammonia and reforming methane with water vapour. Description is given of the method of obtaining porous substances on a substrate for catalytic applications, in which one or more soluble precursor(s) metal of the active phase is added to a suspension, consisting of an insoluble phase of a substrate in water or an organic solvent. The suspension undergoes wet grinding so as to reduce the size of the particles of the substrate phase to less than 50 mcm. The additive is added, which promotes treatment before or after grinding. A pore-forming substance is added and the suspension, viscosity of which is maintained at 100-5000 cP, undergoes spray drying, is pressed and undergoes thermal treatment so as to remove the pore-forming substance, and is then baked. Description is also given of the method of obtaining porous catalysts on a substrate for decomposing N2O, in which a soluble cobalt precursor is added to a suspension of cerium oxide and an additive, promoting treatment, in water. The suspension is ground to particle size of less than 10 mcm. A pore-forming substance, viscosity of which is regulated to approximately 1000 cP, is added before the suspension undergoes spray drying with subsequent pressing. The pore-forming substance is removed and the product is baked. Description is given of the use of the substances obtained above as catalysts for decomposition of N2O, oxidation of ammonia and reforming of methane with water vapour.

EFFECT: obtaining catalysts with homogenous distribution of active phases and uniform and regulated porosity for optimisation of characteristics in catalytic applications.

FIELD: catalytic gas treatment.

SUBSTANCE: invention proposes catalyst for treating hydrogen-rich gas mixtures to remove carbon monoxide via methanation of carbon monoxide, said catalyst containing nickel-cerium oxide system. Catalyst is prepared by reaction of nickel compounds with cerium compound. Methanation of carbon monoxide is conducted at temperature not below 20°C and pressure not below 0.1 atm in presence of above-indicated catalyst.

EFFECT: enhanced removal of carbon monoxide to level below 10 ppm.

8 cl, 5 tbl, 9 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to catalysts and process of steam conversion of hydrocarbons to produce synthesis gas. Proposed catalyst for steam conversion of hydrocarbons contains nickel oxide (4.0-9.2%) and magnesium oxide (4.0-6.5%) supported by porous metallic nickel (balancing amount). Carrier has specific surface area 0.10-0.20 m2/g, total pore volume 0.07-0.12 cm3/g, predominant pore radius 1-30 μm, and porosity at least 40%. Described are also catalyst preparation method and generation of synthesis gas via steam conversion of hydrocarbons.

EFFECT: increased heat conductivity of catalyst resulting in stable activity in synthesis gas generation process.

8 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: description is given of a method of obtaining olefins. The method involves passing a mixture of a hydrocarbon and oxygen containing gas through a catalyst zone, which is capable of maintaining burning over the upper limit the inflammability of the fuel, with obtaining of the above mentioned olefin. The catalyst zone consists of at least, a first layer of catalyst and a second layer of catalyst, where the second catalyst layer is put in the process line after the first catalyst layer, has different content from the first layer and has general formula: M1aM2bM3cOz, where M1 is chosen from IIA, IIB, IIIB, IVB, VB, VIB, VIIB groups of lanthanides and actinoides, M2 is chosen from IIA, IB, IIB, IIIB, IVB, VB, VIB groups, and M3 is chosen from IIA, IB, IIB, IIIB, IVB, VB, VIB and VIIIB groups, a, b, c and z represent atomic ratios of the M1, M2, M3 and O components respectively. The value of a lies in the interval from 0.1 to 1.0, the value of b lies in the interval from 0.1 to 2.0, the value of c lies in the interval from 0.1 to 3.0, and the value of z lies in the interval from 0.1 to 9.0. The catalyst zone has a perovskite type structure.

EFFECT: perfection of the method of obtaining olefins.

9 cl, 4 tbl, 1 dwg, 4 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.

EFFECT: increased yield of isoparaffin hydrocarbons.

7 cl, 2 tbl, 7 ex

The invention relates to the refining and petrochemical industries

The invention relates to the field of catalysis selective hydrogenation

The invention relates to the refining sector, namely the catalytic reforming of the original naphtha

The invention relates to a catalyst for purification of gases from nitrogen oxides mainly in the presence of methane and oxygen, the conversion of natural gas and the method of its production

The invention relates to a catalyst obtain isobutene by dehydroisomerization n-butane, the method of its production and method of use of this catalyst

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalyst of olefin monomers trimerisation. Described is catalytic composition for olefin monomers trimerisation, which contains a) source of chrome, molybdenum or tungsten; b) ligand if general formula (I), in which X stands for bivalent organic group, selected from substituted or non-substituted alkylene groups, in case of substituted groups, substituents represent hydrocarbon groups; R1 and R3 represent cycloaromatic groups, which do not contain polar substituents in none of orto-positions; R2 and R4 are independently selected from obligatory substituted cycloaromatic groups, each of R2 and R4 having polar substituent in at least one orto-position; and c) cocatalyst. Also described is method of olefin monomers trimerisation, including interaction of at least one olefin monomer in conditions of trimerisation reaction with said above catalytic composition.

EFFECT: selective obtaining 1-hexagen from ethylene, reducing level of formation of by-products, especially C10.

10 cl, 2 tbl, 12 ex

The invention relates to the production of odorants for natural gas, in particular waste-free way to obtain mercaptan, as well as to a method for producing a catalyst, providing a higher degree of interaction between methyl alcohol and hydrogen sulfide and the use of such a method of producing hydrogen sulfide, which provides waste reduction production in General
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