Catalyst for selective hydrogenation of organic compounds and method thereof

FIELD: chemistry.

SUBSTANCE: catalyst for selective hydrogenation of organic compounds contains mesoporous carbon carrier and active part - nanodispersed particles of the VIII group metals with content on the carrier in the range from 1 to 10%. The method for catalyst preparation includes the thermochemical treatment of the carrier, its impregnation with the solution containing active part, and then the metals of VIII group are reduced at first in the alkaline media at ultrasonic action with frequency 35 kHz, then with formaldehyde solution.

EFFECT: enhancing of catalyst activity.

6 cl, 5 dwg, 7 ex

 

The invention relates to the chemical industry, namely the production of heterogeneous catalysts selective processes of liquid-phase hydrogenation, alkylation and arilirovaniya organic compounds, as well as the development of methods for their production, and can be successfully implemented in the chemical and pharmaceutical industry for conducting hydrogenation reactions of polyunsaturated ketones, organic synthesis and the production of biologically active drugs.

Known hydrogenation catalyst (RU # 2304464, CL B01J 23/44, B01J 31/24, B01J 37/18, 2005.12.28)containing the compound of palladium and modifying additive, at the same time as the source of palladium compounds using bis-acetylacetonate, palladium, as well as modifying additives - phosphine (PH3), with the following molar ratio of the components: bis-acetylacetonate palladium/phosphine = 1:0.1 to 1:1.

The main disadvantages of this catalyst is not sufficiently strong bond palladium compounds with modifying additive and complexity of the reuse of the catalyst.

Also known catalyst for hydrogenation of unsaturated hydrocarbons (RU # 2239495, CL B01J 35/02, B01J 23/50, B01J 23/66, SS 5/02, SS 5/09, 2001.02.08)containing a catalytically active amount of palladium and, if necessary, the silver on the support, it carries the spruce is a molded product with a three-form cross-section, moreover, these lobes are provided with through-holes.

The main disadvantages of this catalyst is the complexity of the synthesis process of the catalyst, the lack of environmental friendliness, as well as the lack of strength of binding of the metal particles with the carrier.

Closest to the proposed catalyst is a catalyst for selective hydrogenation of organic compounds (RU # 2259877, B01J B01J 23/89 23/84, B01J 37/02, SS 5/09, SS 11/167, 2001.05.03), comprising a carrier and an active part. As an active part use is based on the total weight of the catalyst 1-30 wt.% copper, 0.001-5 wt.% palladium, 0.001 to 6 wt.%, at least one metal selected from Ag, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo, and the remainder, at least one carrier selected from aluminum oxide, silicon dioxide and titanium dioxide. The catalyst used for the hydrogenation of organic compounds - alkynes.

The disadvantage of this catalyst is its high cost due to high metal content, insufficient yield of the final product, as well as insufficient hydrogenating activity of the catalyst due to the large size of the particles of the medium.

A method of obtaining the hydrogenation catalyst (RU # 2304464, CL B01J 23/44, B01J 31/24, B01J 37/18, 2005.12.28), based on the recovery of palladium compounds with hydrogen in the presence of modificados the th Supplement phosphine, which is injected to the stage of recovery of the compounds of palladium (II)bis-acetylacetonate palladium at a temperature of formation of the catalytic system of 70-80°C and the optimum time of formation of the catalyst 10-15 minutes

The main disadvantage of this method is the lack of strength of binding of the metal particles with the modifier.

Closest to the proposed method is a method of producing catalyst for selective hydrogenation (RU # 2259877, CL B01J B01J 23/89 23/84, B01J 37/02, SS 5/09, SS 11/167, 2001.05.03), including thermochemical preparation of the carrier, the carrier impregnated with a solution of the active component. Thermochemical treatment is annealing the carrier 200÷900°C. After impregnation carry out the calcination of the carrier at 300÷500°C for 4÷10 h and the impregnation solution socializaton.

The disadvantage of this method is the use of high temperatures at intermediate processing catalyst, and a multi-stage process for the synthesis of the catalyst.

The problem solved by the claimed invention is a process for the synthesis catalyst under milder conditions, simplifying the process of synthesis of the catalyst, the reduction of material and economic costs and waste process, increasing the bonding strength of the active ingredient with the carrier, as well as increasing environmental processes is the use of the catalyst.

The technical result of the invention is to create a universal catalyst with high activity and selectivity in hydrogenation processes, alkylation and arilirovaniya when carrying out the processes under mild conditions, and reduction in the value of its synthesis and application in chemical reactions due to the absence of necessary use in the process of distillation solvent recycling.

This object is achieved in that in the catalyst for selective hydrogenation of organic compounds, including the media and the active part according to the invention as a carrier using mesoporous carbon media, as an active part of the use of nanosized particles of metals of group VIII, the content of which the carrier is 1÷10%. As mesoporous carbon media use soot.

Use as an active part of the nanosized particles of metals of group VIII allows to achieve a technical result, namely to increase the activity of the catalyst and the yield of the target product by combining the functions of heterogeneous and homogeneous catalysts. The content of the metal nanoparticles is from 1 to 10% is chosen because when the content decreases below this interval significantly reduced the activity of the catalyst, while increasing bol is e 10% significantly increases its cost. Use as a carrier mesoporous carbon particles is caused primarily by the need to increase available for the deposition of metal nanoparticles the surface of the carrier. The use of soot particles useful because they represent aggregates of more or less firmly bonded together by small grains (about 25÷35 nm), containing mainly mesopores.

In the method of producing catalyst for selective hydrogenation of organic compounds, including thermochemical processing of the carrier, the carrier impregnated with a solution of the active part, according to the invention after impregnation of the carrier additionally carry out the restoration of metals of group VIII first in an alkaline environment when exposed to ultrasound with a frequency of 35 KHz, then formaldehyde. Thermochemical preparation of media spend by thermooxidation in a quartz furnace at a temperature of 600÷900°C or oxidation of the surface with nitric acid in a strongly acidic medium at a temperature of 85÷95°C. After recovery of the catalyst may be subjected to additional processing activator (dibutylamine, tributylamine etc) when heated in the ionic liquid for 5÷10 h at the reaction temperature.

Thermochemical processing of media spend to increase mesoporosity and specific surface area of carbon media due to oxide the value of carbon on the surface, as well as to improve the hydrophilic properties of the medium and the formation of the oxide groups on the surface. The carrier impregnated with a solution of the active part is required for uniform distribution of the nanosized metal particles. Recovery Paladiy on the surface of the carrier was performed with the aim of obtaining a catalytically active metal nanoparticles. The use of ultrasound and formaldehyde relates to the synthesis of particles with high hydrophilicity. Heating of the catalyst within 5÷10 hours at a reaction temperature in a solution of ionic liquid and an activator for activating the catalyst for catalytic reaction.

The invention is illustrated by drawings, where figure 1 shows the dependence of the conversion of bromine benzol (curve 1) and styrene (curve 2), and outputs stilbene (curve 3) and biphenyl (curve 4) on reaction time in the presence of catalyst (Pd/C (5% Pd); figure 2 - in the presence of catalyst (Pd/C (5% Pd); 3 - in the presence of Pd/C catalyst (20% Pd); 4 - in the presence of Pd/C catalyst (5% Pd); 5 - in the presence the Pd/C catalyst (5% Pd).

The catalyst is a multi-component system, consisting of the recovered metal particles deposited on a matrix of mesoporous carbon media - soot.

The proposed method for the preparation of the catalyst for selective hydrogenation of organic the ski compounds is as follows. Mesoporous particles of soot are pre thermochemical processing: thermal-oxidative or chemical modification. Oxidative modification of carbon black is carried out at a temperature of 600-900°C in a flow quartz furnace. A weighted sample of soot in a quartz boat is loaded into a quartz furnace, heated to a predetermined temperature in the air and off the heating. Chemical modification of carbon black is carried on surface oxidation with nitric acid in a strongly acidic medium at a temperature of 85-95°C. the Application of active component on a carrier is the carrier impregnated with a solution of palladium hydroxide required to obtain relevant content on media concentration (1-10%). Recovery of metal nanoparticles is carried out in aqueous alkaline medium with ultrasound. Next hydroxide metal restore solution of formaldehyde according to the scheme:

Thus obtained catalyst allows the reaction of selective hydrogenation, and alkylation and arilirovaniya organic compounds with a high yield of the target products in cooled reactors, including in ionic liquids. Ionic liquids for carrying out the process of hydrogenation, alkylation and arilirovaniya can be a Quaternary salt of nitrogen or phosphorus melting temperature below 100°C. As cations in the process can be used: diethyl-propyl-butyl-ammonium and dipropyl-dibutil-ammonium. The most effective are ionic liquids C4Clim[BF4], C4lim[F6]that will provide the process in more mild conditions: pressure 5÷10 bar. and the temperature is 30÷40°C.

The research results on the effectiveness of the proposed catalyst in the Heck reaction illustrated by examples.

Example 1

The Pd/C catalyst (0.5% of Pd), oxidative modification. Reaction conditions: 21.2 mg of the catalyst, and 0.98 g of sodium acetate and 10 ml of ionic liquid was placed in the reactor and sequentially added reagents - Brabanthal (10 mmol), styrene (15 mmol) and sodium acetate (12 mmol) or alkylamine (20 mmol) for binding formed Nug, as well as the catalyst. Then after the mixture was passed for 15 min current of dry argon. Later in the argon atmosphere of the reactor was collected and 1 ml of the original reaction mixture, was added 10 ml of cyclohexane containing a fixed number of n-decane as a standard, and with vigorous stirring carried out the extraction of the unreacted starting compounds and the resulting reaction products. Then the reactor was closed and under intensive stirring of the reaction mixture was placed in an oil bath, preheated to the reaction temperature of 140°C. the Degree of conversion of the original brough the benzene and styrene were determined by their mass content in the sample initial mixture of reagents and samples, taken during the catalytic reaction; the outputs are the products of the reaction of stilbene and diphenyl expected reacted bramasol. Control was also analyzed compounds that are extracted by cyclohexane of two-component mixtures of ionic liquid + Pd/C, the ionic liquid + dibutylamine and dibutylamine + Pd/C after passing through them at 25°With a current of dry argon for 15 minutes the results of the experiments shown in figure 1, which shows the dependence of the conversion of bromine benzol (curve 1) and styrene (curve 2), and outputs stilbene (curve 3) and biphenyl (curve 4) on reaction time.

Example 2

The catalyst is Pd/C (5% Pd), oxidative modification. Reaction conditions: 21.2 mg of the catalyst, 2.58 g of dibutylamine. Preparation and analysis as in example 1. The results of the experiments are shown in figure 2, which shows the dependence of the conversion of bromine benzol (curve 1) and styrene (curve 2), and outputs stilbene (curve 3) and biphenyl (curve 4) on reaction time.

Example 3

The Pd/C catalyst (20% Pd), oxidative modification. Reaction conditions: 21.2 mg of the catalyst, 3,36 g dibutylamine. Preparation and analysis as in example 1. The results of the experiments shown in figure 3, which shows the dependence of the conversion of bromine benzol (curve 1) and styrene (curve 2), and outputs stilbene (curve 3) and biphenyl (Criva) on reaction time.

Example 4

The Pd/C catalyst (5% Pd), oxidative modification. Reaction conditions: 21.2 mg of the catalyst, 3,63 g tributylamine. Preparation and analysis as in example 1. The results of the experiments shown in figure 4, which shows the dependence of the conversion of bromine benzol (curve 1) and styrene (curve 2), and outputs stilbene (curve 3) and biphenyl (curve 4) on reaction time.

Example 5

The Pd/C catalyst (5% Pd), oxidative modification. Reaction conditions: 21.2 mg of the catalyst, 2,53 g dibutylamine. Before the reaction was carried out preliminary activation of catalyst. In a reactor were placed 10 ml of ionic liquid was injected 20 mmol of dibutylamine and catalyst. Then, through the mixture for 15 min passed a current of dry argon in argon atmosphere, a sample was taken for analysis. Then the reactor was closed and under vigorous stirring a mixture of the catalyst, the amine and the ionic liquid is pre-heated for 5-10 hours at 140°C. after preheating the reactor at 140°C was injected reagents - Brabanthal and styrene (10 and 15 mmol, respectively). Preliminary activation was long enough heated at the reaction temperature (140°C) source of catalyst, ionic liquid and dibutylamine. The results of the experiments shown in figure 5, which shows the dependence of the conversion of bromine benzol (crooked is 1) and styrene (curve 2), and outputs stilbene (curve 3) and biphenyl (curve 4) on reaction time.

As can be seen from the experimental results, a higher percentage of active metal in the reaction system is not accompanied by an increase in the output of stilbene and conversion of the starting materials. During the process without pre-activation (examples 1-4) used most effectively as coreagent dibutylamine. However, the more efficient the process is performed after pre-activation (example 5). In the pre-activation of the catalytic system, first, dramatically increases the initial rate of consumption of reagents and accumulation of the desired product and, secondly, about 12 hours to achieve complete conversion of bromine benzol and stoichiometric conversion of the styrene, the yield of stilbene is not less than 80%. It is therefore evident that in order to ensure almost complete conversion of the starting reagents and the high selectivity of the process required an excess of activator - dibutylamine.

Example 6

The catalyst was prepared as follows. Mesoporous soot particles were subjected to thermal-oxidative treatment. A weighted sample of soot in a quartz boat was loaded in a quartz furnace was heated to a temperature of 700°C in air and off heating. The carrier was impregnated with a solution of hydroxide Pd at a concentration of 1.4 mg/is L. Recovery of metal nanoparticles was carried out in an aqueous alkaline medium with ultrasound at a frequency of 35 kHz. Next hydroxide of the metals recovered formaldehyde solution (13.3 M) according to the scheme:

Received the catalyst with a Pd content of 1 wt.%.

Example 7

The process of preparation of the catalyst is similar to example 6, except that conducted chemical modification of carbon black by surface oxidation catalyst with nitric acid in a strongly acidic medium at a temperature of 90°C. was Obtained a catalyst with a Pd content of 1 wt.%.

The results obtained indicate that the use as a catalyst for selective hydrogenation of nano-particles of metals of group VIII, stable in the matrix mesoporous carbon media is a highly effective way to optimize the processes of hydrogenation, and alkylation and arilirovaniya organic compounds, in particular polyunsaturated ketones.

Thus, this catalyst and its production method can be successfully used in the chemical and pharmaceutical industries for carrying out reactions in organic synthesis.

1. A catalyst for selective hydrogenation of organic compounds comprising a carrier and an active part, different those who, as media use mesoporous carbon media, as an active part of the use of nanosized particles of metals of group VIII, the contents of which are on the media is 1-10%.

2. The catalyst according to claim 1, characterized in that as mesoporous carbon media use soot.

3. The method of producing catalyst for selective hydrogenation of organic compounds according to claim 1, including thermochemical processing of the carrier, the carrier impregnated with a solution of the active part, wherein after impregnation of the carrier additionally carry out the restoration of metals of group VIII first in an alkaline environment when exposed to ultrasound with a frequency of 35 kHz, then a solution of formaldehyde.

4. The method according to claim 3, characterized in that thermochemical preparation of media spend by thermooxidation in a quartz furnace at a temperature of 600-900°C.

5. The method according to claim 3, characterized in that thermochemical preparation of media spend by surface oxidation with nitric acid in a strongly acidic medium at a temperature of 85-95°C.



 

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1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to field of creating luminescent nanostructural composition ceramic materials on the basis of silicon dioxide and zinc orthosilicate (willemite) and can be applied in light-emitting and blinker devices development, for instance, plasma display panels, light matrix indicators, traffic lights, etc., which irradiate definite colour tone of visible spectrum. Luminescent nanostructural composition ceramic material, which contains silicon dioxide SiO2 and doped with manganese willemite Zn2SiO4, additionally contains zinc oxide ZnO, silicon dioxide representing crystobalite, willemite is doped with manganese by formula Zn2-xMnxSiO4, where variable x takes values in range from 0.05 to 0.15, material components are taken in following ratio: crystobalite - 45÷55 wt %, zinc oxide 5÷7 wt %, willemite 38÷50 wt %, cristobalite and zinc oxide grains size being in range from 55 to 70 nm, and sizes of willemite grains being in range from 10 to 22 nm.

EFFECT: created material has radiation of increased green light intensity in band 500÷570 nm, and allows increasing efficiency of glow centre excitation and increase quantum yield.

9 ex, 1 tbl, 1 dwg

FIELD: nanotechnology.

SUBSTANCE: invention relates to nanotechnology and nanomaterials and can be used at receiving of inorganic and organic-inorganic fine-grained and nano-structured metallised materials, metal-polymers and nanocomposite. Suspension of organic-inorganic nanostructures, containing nanoparticles of noble metals, implemented in the form of poly-complex in two-phase reacting system, consisting of two volume contacting immiscible liquids. Poly-complex includes organic molecules, containing amides in amount 2 or more, and nanoparticles of noble metals. Suspension is received by means of forming of two-phase reacting system, consisting of two contacting volumetric immiscible liquids, addition in it of restorative and synthesis of nanoparticles. Additionally metallised molecules of precursors are dissolved in hydrophobic phase, reducer is added into aqueous phase, and in the capacity of ligands there are used organic molecules, into content of which there are included amides in amount 2 or more. Invention provides receiving of new nano-structured organic-inorganic polymeric complexes on the basis of polyamines, containing nanoparticles of noble metals (Pd, Au) of size up to 10 nm, which allows high specific surface area and are characterised by narrow dispersion of dimensions.

EFFECT: it is provided high density of particles packing in organic-inorganic nano-structures and high performance of transformation of initial material into nanoparticles of noble metals.

23 cl, 12 dwg, 1 ex

FIELD: electrical engineering.

SUBSTANCE: invention relates to semiconductor electronics and can be used for making heavy duty and high-precision transistors. The transistor contains a first set, which includes N1>1000000 regions with the same conductivity, a second set which includes N2 >1000000 regions with the same conductivity, as well as a third set, which includes N3>1000000 regions with opposite conductivity. The regions are made with formation of a first set of separate same-type point p-n junctions between regions from the first and third sets and a second set of separate same-type point p-n junctions between regions from the second and third sets. Electrodes, adjacent regions included in at least one of the said sets, for which the condition Ni>1000000, where i∈{1, 2, 3}, is satisfied, are connected in parallel by one conductor, i.e. are connected into a single current node.

EFFECT: obtaining high-precision heavy duty transistors with stable electrical parametres.

21 cl, 9 dwg

FIELD: physics.

SUBSTANCE: invention is related to the field of nanomaterials application. It is suggested to use carbon of bulbous structure as sensitive element of detector in terahertz range of waves that absorbs electromagnet radiation (EMR) in the range of frequencies of 30 - 230 THz.

EFFECT: improved performance characteristics.

3 dwg

FIELD: chemistry.

SUBSTANCE: invention refers to the high-strength epoxide composition used for impregnation at production of high-strength glass-, carbon,- organic-, and boron plastics working in the wide temperature range and used in different industrial sectors (machinery construction, shipbuilding, aircraft and space industries, for production of the parts of complicated configuration e.g. thin- and thick-walled casings). The invention refers also to the method for preparation of the said composition including the following components (weight parts): 10-100 - diglycidyl resorcinol ether, 10-100 - product of epichlorohydrin condensation with triphenol, 6-12 - oligoether cyclocarbonates with mass ratio of cyclocarbonate groups in the range from 18 to 29, 28-50 - curing agent (primary aromatic amine), 0.5-2.5 - curing agent (tertiary amine), 0.25-1.25 - mixture of carbon and silicate nanomaterials. The mass ratio of diglycidyl resorcinol ether to product of epichlorohydrin condensation with triphenol is in the range from 1 : 9 to 9 : 1. Metaphenylen diamine or 4,4'-diaminodiphenylmethane or their eutectic mixtures in ratio from 40 : 60 to 60 : 40 are used as primary aromatic amine. Mono-, di and trimethylsubstituted pyridine or monovinylsubstituted pyridine are used as tertiary aromatic amine. The carbon nanomaterial is fullerene C2n, wherein n is no less than 30, the silicate nanomaterial is organobentonite, the fullerene : organobentonite ratio is in the range from 1 : 3 to 3 : 1. The method of composition preparation consists in stirring of nanomaterials mixture with oligoether cyclocarbonates by ultrasonic action at frequency 22-44 kHz during 30-45 min. Then the obtained suspension is mixed with beforehand prepared mixture of diglycidyl resorcinol ether and product of epichlorohydrin condensation with triphenol. After that the curing agent in the form of aromatic primary and tertiary amine mixture is added. The ready composition is cured in step mode with maximal curing temperature 155°C.

EFFECT: invention allows obtaining of the composition with high physical, mechanical and dissipative properties.

2 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention can be used for hydrogen recombination in reactor sections of nuclear power stations and other facilities. Description is given of a catalyst for recombination of hydrogen and oxygen, containing a solid porous carrier with hydrophobisated catalytic coating of a platinoid metal. This catalyst is distinguished by that, the carrier is made from a valve metal, obtained using powder metallurgical technique, with specific surface are of 0.05-1.50 m2/g; the catalyst carrier is made from porous plates of titanium or o tantalum, or niobium, or zirconium of thickness 0.3-2.0 mm. Described also, is a method of making the said catalyst, involving saturation of the carrier with a solution of platinoid compound, reduction of the said compound to a metal, as well as hydrophobisation of the catalytic coating by moistening it with a suspension of fluorine-containing polymer with an organic stabiliser and subsequent calcination. This method is distinguished by that, the carrier is kept in the suspension for 5-30 s. The carrier is held in a single position and all stages for preparation of hydrophobisated catalytic coating are carried out in that position. Translational oscillations at frequency 1-2 Hz are imparted when saturating the carrier.

EFFECT: provision for reliable functioning of the catalyst for recombination of hydrogen and oxygen in conditions of prolonged contact with wet medium, as well as cutting on preparation time.

3 cl, 1 tbl, 1 ex, 2 dwg

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