Method and materials for storing hydrogen

FIELD: chemical engineering.

SUBSTANCE: catalytic composition material comprises a mixture composed of acetylene hydrocarbon with aromatic substituent or potential oligomer that represent a hydrogen source and carrier and metal of VIII group that represents a heterogeneous catalyzer. The mass ratio of the hydrogen source and catalyzer ranges from 5:1 to 1000:1. The method comprises filling the system with hydrogen in the course of the contacting of acetylene hydrocarbon with the heterogeneous catalyzer in heated tank at a temperature of 50-200°C and hydrogen pressure of 5-1 atm and extracting hydrogen from the system when completely hydrated hydrocarbon in the first stage is in a contact with the same catalyzer at a temperature 200-350°C and pressure 0.5-5 atm.

EFFECT: increased rate of extracting.

10 cl, 2 dwg, 2 tbl, 8 ex

 

The invention relates to the field of catalysis and organic chemistry, in particular to develop ways to store hydrogen in catalytic systems operating on the basis of cyclic reactions of hydrogenation-dehydrogenation of organic compounds that can be used in hydrogen generators for industrial plants, in fuel cells used in vehicles, as well as other devices and vehicles equipped with hydrogen engines or power plants.

The present invention is the creation of new technologies and systems for hydrogen storage with high capacity for hydrogen compared to existing systems for hydrogen storage-based hydrides of metals, intermetallic compounds, and carbon nanomaterials (fullerenes, nanotubes), and developed in recent years, systems based on reversible catalytic hydrogenations of aromatic compounds, including condensed with heterocyclic aromatic compounds and polymers(oligomers), for example Polyphenylene. An important task is the creation of systems with multiple refills hydrogen.

Catalytic composites that are used as materials for hydrogen storage according to the present invention are mixtures consisting of (1) source : who and hydrogen - organic compounds (aromatic acetylene hydrocarbons, including phenylacetylene and diphenylacetylene and acetylene oligomers and polymers capable of reversibly and repeatedly gidrirovaniya to degidrirovaniya), (2) catalytic hydrogenation-dehydrogenation capable of reversibly and repeatedly gidrirovanii to degidrirovanii the above-mentioned organic compound or oligomer. The composite may also contain structural modifier or matrix, in which the dispersed source of hydrogen and a catalyst or promoter of the catalytic system. The catalysts are prepared by deposition of noble metals (Pt, Pd, etc. or Nickel on carbon or oxide media (e.g Sibunit, activated carbon or silica gel, alumina, aluminosilicates, other oxides and mixed oxide systems) with high specific surface from aqueous solutions of metal complexes followed by air drying and restoration in a stream of hydrogen at 200 to 300°C. In some cases, the need for preliminary reduction (activation) catalysts disappears, as the first stage of the proposed technology (charging of the system with hydrogen) involves carrying out the reaction of hydrogenation of acetylene hydrocarbons under pressure hydrogen at elevated temperatures (80-150°). The catalysts can the be obtained by applying the active component from the gas phase with the use of volatile compounds, for example carbonyl complexes.

During the preparation and activation of catalysts on the surface of the supports are formed of highly dispersed form of the reduced metal, which is highly active catalytic centers reactions hydrogenation of acetylene, such as phenylacetylene and diphenylacetylene, and dehydrogenation of the corresponding saturated with hydrogen hydrocarbons, such as cyclohexylamine and 1,2-dicyclohexylmethane. Such highly dispersed form of precious metals or Nickel is resistant to high temperatures.

As the material (substrate) or the reversible source of hydrogen for hydrogenation reactions and dehydrogenation, which is a reversible reaction, it is possible to use certain chemical compounds containing fragments of C≡C (triple bond), preferably locked stable organic fragments (for example, phenyl radical).

Hydrogen is widely used in chemical, metallurgical and other industries. He is one of the main energy sources of the future. Problems of the technological plan and the cost along with the availability and low cost of natural gas, gasoline and other raw materials of natural origin limit the commercial use of hydrogen power in the world market. Vodor the d is able to become an alternative fuel, if the problem will be solved functioning systems reversible storage (accumulation). The technical solution of these tasks intensively engaged in the largest automotive companies. The limiting factor in the use of hydrogen as a motor fuel is the establishment of systems of storage. The use of liquid hydrogen due to high production cost and temperature requirements for storage. Compressed hydrogen is much cheaper, but it requires a tank of large dimensions for storing and dangerous to use.

The discovery of materials that are able to accumulate a large amount of hydrogen per unit volume or weight, is currently the subject of research of a number of laboratories and research centers.

In recent years, a large number of works, in which as adsorbents of hydrogen are considered carbon carriers. Theoretical calculation showed that carbon nanomaterials (nanotubes) are able to accumulate up to 4.1% hydrogen. It was experimentally confirmed in a number of works (for example, J.Dillon, Storage of hydrogen in single wall carbon nanotubes, Nature, 1997, v.386, p.377-379). However, research suggests that for maximum capacity hydrogen temperature cooling systems based on carbon nanomaterials must be from Catalinas, not above -120°C. Cryogenic conditions of use are a significant drawback of such systems.

Some progress has been achieved with the use of hydrides of some metals. There are a number of patents, for example U.S. Pat. USA N 5199972 stating the advantages of using such compounds as systems for hydrogen storage and even with respect to technical transport solutions (U.S. Pat. USA N 6182717).

Research National laboratory in Los Alamos (Schwarz, 1998) showed that one of the most promising materials is magnesium hydride. It is of interest because it can store and 7.7% hydrogen, however, the kinetics of adsorption/desorption of hydrogen for him significantly slower than for other hydrides, and hydrogen require very high temperature (about 300°).

In the development of these works have been proposed fine materials of Mg2Ni obtained by mechanical mixing and grinding in ball mills, which catalyze the dissociation of hydrogen, thus significantly increasing the rate of absorption of hydrogen in such a way that it becomes comparable to the speed of adsorption for FeTi and LaNi5(Patscha N 6165663). However, the limiting hydrogen capacity for such system does not exceed 5 wt.%, and the temperature interval desorption quite narrow and also shifted into high is emperature region.

Some hydrides during their decomposition can allocate more of hydrogen, for example LiH to 12.7% or LiAlH4to 10.6% (U.S. Pat. USA N 5702491). Using the quick reaction of hydrolytic decomposition of metal hydrides with water makes the process of accumulation of hydrogen irreversible. Thus, these non-regenerating system, too expensive and could not compete with reversible systems.

In the use of metal hydrides in the automotive industry because of the low capacity of most such systems for hydrogen it is necessary to use a larger device for the filling, otherwise the resource mileage engines is very small. In addition, for the reversible extraction of bound hydrogen hydrides must be heated to temperatures above 300°C. this restricts the use of such systems for hydrogen storage.

Closest to the present invention is a method of storing hydrogen as described in U.S. patent N 6074447. The method of storage and excretion of hydrogen fuel is to use a mixture of hydrogenated hydrocarbon and a homogeneous catalyst, which when heated to 190°emit hydrogen. As the catalyst claimed iridium complex composition: IrH4{2,6-C6H3(CH2P ((CH3)3)2)2}. The concentration of catalyst extending t is from 0.01 to 0.1%. As the material (substrate), which is subjected to dehydrogenation, declared hydrocarbons class cycloalkanes: methylcyclohexane, decalin, DICYCLOHEXYL, cyclohexane, or a combination of them. The patent States that the opposite process is possible regeneration hydrogenated material at temperatures above 100°C and pressures above 10 ATM.

The disadvantage of this method is the use of tradepolicies, expensive iridium complex and the need to use filters or special shut-off devices for the separation of hydrogen from the reaction mixture as the temperature of the boiling range of the inventive substrates (for example, methylcyclohexane or cyclohexane) is significantly lower than the process temperature. The disadvantage of this method is the impossibility of separating homogeneous catalyst from the substrate, if necessary, for example for regeneration. In the application described the kinetic data (rate of hydrogen from unit volume), testifying to the efficiency of the method, as well as data on the number of cycles of hydrogenation-dehydrogenation when used for hydrogen storage. Obviously, the capacity of such a system for hydrogen continuously decreases from cycle to cycle and the use of such homogeneous systems and low-boiling substrates inefficient in the material is x for hydrogen storage. In addition, although the capacity of this system, even in a single cycle is around 6-7%, yet it is not high enough indicator for the industrial implementation of such systems.

For the hydrogenation of aromatic hydrocarbons are widely used catalysts based on platinum group metals (Pt, Pd)supported on different carriers - Al2About3, aluminosilicates and other So-known method of preparing a catalyst for hydrogenation of aromatic hydrocarbons, which consists in the introduction of Pt or Pd in the matrix of silicates, type ZSM-5 (U.S. Pat. USA N 5874622) or the method of preparation of catalysts for hydrogenation best choice copolymers (U.S. Pat. USA N 5948869). The dehydrogenation of paraffin and cycloparaffin hydrocarbons carried out using the same catalysts containing noble metals, see, for example, U.S. Pat. USA N 5672801. The majority of patents are devoted to the hydrogenation and dehydrogenation simplest such hydrocarbons as benzene, cyclohexane or their derivatives. The reaction is conducted mainly in the gas-vapor phase. Examples of carrying out reactions in the liquid phase with the use of polycyclic hydrocarbons is limited. There are several known examples of dehydrogenation of various compounds to acetylene hydrocarbons, however, as a rule, this process occurs at very high temperatures (more than 450-500° (C) and provoditsya formation of a dense carbon deposits on the catalyst surface, leading to its deactivation. At the same time widely known catalysts for the processes of hydrogenation of acetylene and its derivatives (mainly stock With3-C4) on palladium catalysts. However, the main problem being solved in these developments was the solution to the problem of removal of acetylene from ethylene by selective hydrogenation to ethylene, but not to ethane, which is an undesirable side product. However, when the hydrogenation of acetylene to ethylene there is a serious problem of the formation of the so-called "green oil", i.e. products of oligomerization of acetylene. Thus, even in the case of hydrogenation of the simplest acetylene hydrocarbons (acetylene) there are a number of problems and the overall selectivity of the process is significantly below 100%.

The technical problem to be solved in the present invention, is the creation of an effective composite catalytic system and method, and storage of hydrogen on the basis of reversible cycles of hydrogenation-dehydrogenation of acetylene hydrocarbons or polymers/oligomers containing acetylene fragments) with a protected acetylene communication by introducing a blocking terminal, for example phenyl, groups under the action of heterogeneous catalysts based on platinum group metals. This catalytic composite is a system and method of storing hydrogen using it are repeated charging and hydrogen at high speed.

The problem is solved in that in the proposed method the stage of filling the system with hydrogen in the hydrogenation of acetylene aromatic compounds (or other substrates) and the extraction of hydrogen in the dehydrogenation of the corresponding saturated formed by hydrogen (for example, politicalparties) compounds is carried out in the presence of heterogeneous catalysts containing platinum, palladium or Nickel deposited on various media with high specific surface area, under the following technological parameters.

According to the invention the catalytic composite material for hydrogen storage contains as a source of hydrogen organic substance capable of reversible reactions hydrogenation-dehydrogenation, and the heterogeneous catalyst, and the organic substance use acetylene hydrocarbons with aromatic assistant at triple bond or polyacetylenes oligomer, and as a catalyst material comprising carbon or oxide media with high specific surface and coated with at least one metal of group VIII in the mass ratio of organic matter and catalyst from 5:1 to 1000:1.

The material may additionally contain structural modifier (matrix), in which dispergirovany the s source of hydrogen and a catalyst.

In addition, it may further comprise a promoter and a catalyst. The material of acetylene hydrocarbons with aromatic Deputy at the triple bond is preferably diphenylacetylene or phenylacetylene.

As the carbon carrier material contains activated carbon or graphitized activated carbon, and as the oxide carrier contains silicon oxide or aluminum oxide.

As the metal of group VIII material contains platinum, or palladium, or Nickel, or an alloy of platinum with palladium in an amount of from 0.05 to 50% by weight of a heterogeneous catalyst, preferably from 0.5 to 5.0%).

Catalysts containing platinum, palladium or Nickel or other platinum metals or their mixture, prepared by impregnation (water capacity) of various carbon or oxide media with high surface area activated carbon; graphitized carbons type of Sibunit, oxides of silicon or aluminium) with aqueous solutions of salts or complexes of the active metals, such as Ni(NO3)2N2PtCl6or H2PdCl4, followed by drying in air at 100 to 150°and a recovery current of hydrogen at 100-400°C, preferably at 200 to 300°C. Already at the stage of preparation of the catalysts on their surface are formed finely dispersed particles of a noble is yellow or Nickel, which is highly active in the reactions of hydrogenation and dehydrogenation. Used as smaller carriers (particle size - 5-100 μm) to provide a stable suspension of the catalyst in the substance of the substrate, which is necessary to maintain a high reaction rates of hydrogenation/dehydrogenation even without stirring. It is preferable to use platinum or alloys of platinum with palladium as active component due to their increased stability to caking when exposed to the reaction medium at elevated (up to 300-350°C) temperatures. When applying an active metal at the same time can be applied to the promoter catalyst (copper, iron, chromium).

The catalyst and the hydrogen source can be dispersed in a structural modifier, for example in the form of a block of foam ceramics or ceramic monolith.

According to the invention as carriers you can use other neutral or weak acid media such as silicon oxide or aluminum oxide. Use as carriers acidic media type aluminosilicates (zeolites) limited, as in the conditions of the reactions of hydrogenation/dehydrogenation may flow side reactions of polymerization of acetylene hydrocarbons, cracking and opening of a cycle, leading to irreversible stages.

According to the SNO invention as object hydrogenation (substrate) at the stage of filling the catalytic system hydrogen used organic compounds - acetylene hydrocarbons containing aromatic substituents at triple bond to prevent polymerization by a triple bond, and polyunsaturated (acetylene oligomers and polymers)capable of reversibly and repeatedly gidrirovaniya to degidrirovaniya. Preferably using diphenylacetylene and phenylacetylene, you can use disaffiliation and naphthylacetate and aromatic acetylene compounds more complex structure.

The choice of substrate molecules such hydrocarbons due to the fact that in the conditions of the hydrogenation reactions of these compounds and dehydrogenation their saturated derivatives of these substances are in liquid state and are characterized by low volatility (low vapor pressure), which contributes to the formation of stable suspensions of particles of the catalyst in the catalytic system and favors the occurrence of catalytic reactions at high speeds.

It is obvious that in terms of the proposed method, the reaction mixture is, for example, diphenylacetylene and hydrogenated product will be in the liquid state and its entrainment with the gas stream (hydrogen) can be reduced to zero.

The task is also solved by a method of storing hydrogen by refuelling with hydrogen at high pressure using catalytics the CSO composite material, containing as a source of hydrogen organic substance capable of reversible reactions hydrogenation-dehydrogenation and catalytic hydrogenation-dehydrogenation and hydrogen from catalytic composite material when it is heated under reduced pressure, characterized in that the catalytic composite material using the above-described material, the filling is carried out with the participation of organic matter and heterogeneous catalyst comprising a catalytic composite at a temperature of from 50 to 200°and a hydrogen pressure of 5 to 100 atmospheres, and a hydrogen gas is carried out at the contacting hydrogenated at refueling of organic substances with the same catalyst at a temperature of from 200 to 350°and a pressure of from 0.5 to 5.0 ATM.

Moreover, the filling and release of hydrogen carried out without stirring the reaction mixture catalytic composite material comprising a catalyst and an organic substance.

The proposed method of storing hydrogen in the catalytic system consists of two stages:

1) the stage of filling the system with hydrogen during the contacting of the original organic matter (substrate) (e.g., diphenylacetylene) and heterogeneous catalyst containing highly dispersed metal, for example platinum, metal is eskay heated vessel (autoclave), preferably but not necessarily provided with a device for mixing substances catalytic system with speed up to 500 rpm (mechanical stirrer with water seal), at temperatures in the range of 50-200°S, preferably 100 to 150°C, hydrogen pressure of 5-100 bar, preferably 5 to 20 MPa, and the ratio of substrate: catalyst = 5:1 to 1,000:1, preferably from 100:1 to 20:1.

2) the stage of evolution of hydrogen from the system when getting in touch already providerone in the first stage of the substrate, for example 1,2-dicyclohexylmethane, with the same catalyst at temperatures of 200-350°C, preferably 270-320°and at a pressure of 0.5 to 5.0 atmospheres, preferably at atmospheric pressure.

The amount of hydrogen that can accumulate catalytic system by the proposed method can reach values of 9.0-9.2 wt.% with a maximum ratio of substrate: catalyst. In this capacity value is hydrogen, introduced into the system during a complete hydrogenation of the substrate, the dissolved hydrogen and the hydrogen adsorbed on the catalytic centre (metal particles of Nickel, platinum or palladium).

The observed technical effects - high hydrogen capacity (up to 9 wt.%), multiple refills offer in the present invention the composite hydrogen systems, high speed stages of hydrogenation, degidrirovanie is due to the fact, that catalysts containing platinum, are highly active and selective in the reactions of hydrogenation/dehydrogenation and highly stable to high temperatures. The use of heterogeneous catalyst allows, if necessary (recharging system new catalyst) to separate the catalyst for regeneration. The use of high-boiling substrates avoids the need for additional devices for the separation of hydrogen from the volatile components of the catalytic system.

The invention is illustrated by the following charts.

Figure 1 shows the dependence of the hydrogen pressure in the autoclave in the course of phenylacetylene hydrogenation catalyst 5% Pt/Sibunit at 140°from the time of process:

a stirring at 300 rpm;

b - stirring at 500 rpm

Figure 2 shows the dependence of the amount of hydrogen released when the dehydrogenation dicyclohexylamine catalyst 15% Pt/C at 280°from the time of process:

a first loop;

b - re dehydrogenation.

The invention is illustrated by the following examples.

Example 1.

In the autoclave load 0.6 g of catalyst 5% Pt/C (activated carbon) and 10 g phenylacetylene and at a hydrogen pressure of 50 ATM and stirring with a speed of 500 Rev/min, heat the mixture to 160°C.

Note the R 2.

The reaction of phenylacetylene hydrogenation was carried out according to example 1, except that the stirring of the reaction mass was carried out with a frequency of 300 rpm, the Amount of hydrogen theoretically able to stratics on hydrogenation just downloaded Faciliteiten is 11 liters, i.e. organic substrate is able to store approximately 9.8 percent. Kinetic curves of hydrogen absorption in the course of phenylacetylene hydrogenation of examples 1 and 2, based on the readings of the pressure gauge shown in figure 1.

The results of the experiments of examples 1 and 2 show that the full hydrogenation of phenylacetylene in these conditions occurs in 60-80 minutes.

Example 3.

In the flow reactor (quartz tube with a diameter of 7 mm) was loaded with 2 ml (0.7 g) catalyst 15% Pt/C and was carried out by feeding to the reactor melt DFA (diphenylacetylene) in a stream of hydrogen at a pressure of 5 ATM. The molar ratio of N2/DFA was 16/1 at different volumetric flow rates DFA equal to 0.75 and 1.5 h-1. The reaction temperature was 180°C.

The results of the catalytic test are shown in table 1.

Table 1
Space velocity, h-1Conversion DFAThe product composition, wt.%
DFADiphenylethanDZHE
0,75100,0--100,0
1,5100,0-11,9at 88.1

The table shows that the bulk velocity of 0.75 h-1by complete hydrogenation of the DFA with 100% selectivity.

Example 4.

In the flow reactor (quartz tube, with a diameter of 7 mm) was loaded with 2 ml (0.7 g) catalyst 15% Pt/C and at atmospheric pressure was carried out by feeding into the reactor, DCGA (1,2-dicyclohexylmethane)obtained in the reaction according to example 3. The volumetric feed rate of dicyclohexylamine of Sastamala 2 h-1at the reaction temperature of 320°C. the results of the experiment showed that under these conditions is complete dehydrogenation of DCGA in DFA 100% selectivity.

Example 5.

In the autoclave load 0.6 g of the catalyst 15% Pt/C (activated carbon) and 11 g DCGA and under atmospheric pressure and stirring with a speed of 500 Rev/min, heat the mixture to 280°C. the Total amount of hydrogen released from the closed system (autoclave) was about 10 liters or 0.9 g (see figure 2). This means that the capacity DCGA hydrogen is about 8.2%.

The catalytic system was tested in the method of storing hydrogen in 2 cycles of dehydrogenation/hydrogenation of the resulting DFA on p is the iMER 3/re-dehydrogenation. From the graph in figure 2 shows that the system capacity of hydrogen in 2 cycles is practically not reduced.

Example 6.

In the flow reactor (quartz tube with a diameter of 7 mm) was loaded with 2 ml (0.7 g) catalyst 5% Pt-2% Pd/CKT-4. The catalyst is an alloy of platinum with palladium deposited on a graphitized coal of mark SKT-4. Next was carried out by feeding to the reactor melt DFA, in a stream of hydrogen at a pressure of 20 ATM. The molar ratio of N2/DFA was 16/1 at different volumetric flow rates DFA, 0.5, 0.75 and 1.5 h-1. The reaction temperature was 180°C.

The results of catalytic tests are shown in table 2.

Table 2
Space velocity, h-1Conversion DFAThe product composition, wt.%
DFADiphenylethanDZHE
0,5100,0--100,0
0,75100,0-4,096,0
1,5100,0-30,669,4

The table shows that the bulk velocity of 0.5 h-1by complete hydrogenation of the DFA with 100% selectivity.

the example 7.

In the autoclave load 0.6 g of catalyst 5% Pt/C (activated carbon) and 10 g of 1,4-diphenylbutadiyne representing polyacetylenic oligomer (dimer), and at a pressure of 70 ATM and stirring with a speed of 500 Rev/min, heat the mixture to 160°C and maintained for 2 hours.

The results of the experiments of example 7 show that complete hydrogenation of 1,4-diphenylbutadiyne to 1,4-dicyclohexylmethane in these conditions occurs within 110-120 minutes.

Example 8.

In the autoclave load of 1 g of catalyst 5% Pt/C (activated carbon) and 10 g of 1,4-dicyclohexylmethane and under atmospheric pressure and stirring with a speed of 500 Rev/min, heat the mixture to 320°C and maintained for 4 hours. The total amount of hydrogen released from the closed system (autoclave), amounted to about liters of 10.05 or 0,99, This means that the capacity of 1,4-dicyclohexylmethane hydrogen is 9.9 wt.%.

1. The catalytic composite material for hydrogen storage, containing a source of hydrogen organic substance capable of reversible reactions hydrogenation - dehydrogenation, and the heterogeneous catalyst, characterized in that the organic substance use acetylene hydrocarbons with aromatic assistant at triple bond or polyacetylenes oligomer, and as a catalyst - a material including at Narodny or oxide media with high specific surface and coated, at least one metal of group VIII in the mass ratio of the organic substance and the catalyst is from 5:1 to 1000:1.

2. The material according to claim 1, characterized in that it further comprises a structural modifier, in which dispersed the source of hydrogen and a catalyst.

3. The material according to claim 1, characterized in that it further comprises a promoter and a catalyst.

4. The material according to claim 1, characterized in that the acetylene hydrocarbons with aromatic Deputy at the triple bond is diphenylacetylene or phenylacetylene.

5. The material according to claim 1, characterized in that as the carbon carrier contains activated carbon or graphitized activated charcoal.

6. The material according to claim 1, characterized in that as the oxide carrier contains silicon oxide or aluminum oxide.

7. The material according to claim 1, characterized in that as the metal of group VIII contains platinum, or palladium, or Nickel, or an alloy of platinum with palladium in an amount of from 0.05 to 50% by weight of a heterogeneous catalyst.

8. The method of storing hydrogen by refuelling with hydrogen at high pressure using a catalytic composite material containing as a source of hydrogen organic substance capable of reversible reactions hydrogenation - dehydrogenation and catalyst guide the investments - dehydrogenation and hydrogen from catalytic composite material when it is heated under reduced pressure, characterized in that the catalytic composite material using the material according to any one of claims 1 to 7, the filling is carried out with the participation of organic matter - acetylene hydrocarbon and a heterogeneous catalyst in the catalytic composition of the composite material at a temperature of from 50 to 200°and a hydrogen pressure of 5 to 100 atmospheres, and a hydrogen gas is carried out at the contacting hydrogenated at refueling of organic substances with the same catalyst at a temperature of from 200 to 350°and the pressure from 0.5 to 5 ATM.

9. The method according to claim 8, characterized in that the filling and release of hydrogen carried out without stirring the reaction mixture catalytic composite material comprising a catalyst and an organic substance - acetylene hydrocarbons.



 

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2 cl, 1 dwg

FIELD: separation and cleaning of synthesis-gas.

SUBSTANCE: proposed section consists of device for partial condensation of synthesis-gas including the following components: heat exchanger A for cooling the synthesis-gas fed to section, separator B connected with heat exchanger A and intended for separation of synthesis-gas into gas fraction consisting mainly of hydrogen and carbon monoxide and liquid fraction consisting mainly of carbon monoxide and methane, evaporator C for further separation of gas fraction fed from separator B into gas fraction consisting mainly of hydrogen and liquid fraction consisting mainly of carbon monoxide, evaporator D where hydrogen absorbed in liquid and remaining liquid containing mainly carbon monoxide are evaporated; this liquid may be directed to distilling tower; section is also provided with one more evaporator E where hydrogen absorbed in liquid fraction of separator B is removed through evaporation; this liquid contains mainly carbon monoxide and methane; liquid may be directed to distilling tower F for separation of gaseous carbon monoxide and obtaining methane from lower part of column. Section is also provided with unit for washing with nitrogen which includes washing column G for separation of admixtures by action of nitrogen from gas fraction of evaporator C and recovery of admixtures as fuel gas. Nitrogen washing unit adjoins the partial condensation device.

EFFECT: enhanced heat exchange; low cost of process.

13 cl, 1 dwg, 1 tbl

FIELD: separation and cleaning of synthesis-gas.

SUBSTANCE: proposed section consists of device for partial condensation of synthesis-gas including the following components: heat exchanger A for cooling the synthesis-gas fed to section, separator B connected with heat exchanger A and intended for separation of synthesis-gas into gas fraction consisting mainly of hydrogen and carbon monoxide and liquid fraction consisting mainly of carbon monoxide and methane, evaporator C for further separation of gas fraction fed from separator B into gas fraction consisting mainly of hydrogen and liquid fraction consisting mainly of carbon monoxide, evaporator D where hydrogen absorbed in liquid and remaining liquid containing mainly carbon monoxide are evaporated; this liquid may be directed to distilling tower; section is also provided with one more evaporator E where hydrogen absorbed in liquid fraction of separator B is removed through evaporation; this liquid contains mainly carbon monoxide and methane; liquid may be directed to distilling tower F for separation of gaseous carbon monoxide and obtaining methane from lower part of column. Section is also provided with unit for washing with nitrogen which includes washing column G for separation of admixtures by action of nitrogen from gas fraction of evaporator C and recovery of admixtures as fuel gas. Nitrogen washing unit adjoins the partial condensation device.

EFFECT: enhanced heat exchange; low cost of process.

13 cl, 1 dwg, 1 tbl

Catalytic reactor // 2296003

FIELD: chemical industry; production of the catalytic reactors.

SUBSTANCE: the invention is pertaining to the chemical industry, in particular, the catalytic reactor, which contains a set of the sheets forming the channels of the streams between them. In each channel of a stream there is the wavy material foils, which surfaces are coated with the catalytic material, except for the places where they contact to the sheets. On each end of the reactor there are the gas-collecting mains for the gaseous mixtures feeding in the channels of the streams. At that the gas-collecting mains are communicating with the adjacent channels separately. The reactor realizes feeding of the various gaseous mixtures in the adjacent channels , which may be under the different pressures, and the corresponding chemical reactions in them are also different. When one of the reactions is endothermic reaction, then the other reaction is exothermal; the heat is transmitted through the sheets separating the adjacent channels from the exothermic reaction to the endothermal reaction. The reactor may be used in the compact-type installation for realization of conversion of the methane with the steam, for production of the necessary heat at the methane catalytic combustion, and also Fisher-Tropsh synthesis, so this general method includes conversion of the methane in the long-chain hydrocarbons. The technical result of the invention is realization of the gaseous phases reactions at the increased pressures and especially for realization of the highly exothermal and endothermal reactions.

EFFECT: the invention ensures realization of the gaseous phases reactions at the heightened pressures and especially for realization of the highly exothermal and endothermal reactions.

9 cl, 6 dwg

FIELD: chemical industry; aircraft industry; shipbuilding industry; space industry; fire-protection; care of public health; devices for production of oxygen.

SUBSTANCE: the invention may be used for production of the cooled oxygen for breathing of the people in the emergency situations in the airplanes, the submarines, the space stations, at fires. The chemical oxygen generator contains the charge case and located in it the porous gas-permeable mechanically strong charge. The charge is made out of the mixture emitting the oxygen at the exothermal self-supporting decomposition after its initiation and contains of no more than 3 mass % of the binding agent. The charge ensures the possibility for the oxygen to pass through without damaging the non-treated material and without its volumetric volume burning. The produced oxygen passes through the charge under action of the difference of the pressures from the front of the decomposition moving in the direction to the outlet opening. The oxygen generator also contains the device for ignition and one or more the outlet openings for the produced oxygen coming out, the filters for its cooling, for prevention of the particles of corpuscles and contaminants carry-over, and also the filter with the catalyst for conversion of the produced at decomposition of CO2 into CO.

EFFECT: the invention ensures the possibility for the oxygen to pass through the charge without damaging the non-treated material and without its volumetric volume burning.

27 cl, 2 dwg

FIELD: chemical industry; chemical reactor and the method for production of hydrogen.

SUBSTANCE: the invention is pertaining to the power equipment may be used for production of hydrogen both in the stationary plants and on the vehicles. The hydrogen is produced by the hydrolysis (decomposing of water) at its interaction with the granules of the solid reactant (aluminum, silicon, etc.) definitely located inside the chemical reactor. The chemical reactor for production of the hydrogen consists of the cylindrical body with the liquid reactant medium, in which there is the temperature sensor connected with the control unit, and in the upper part of the body there is the union for withdrawal of the gaseous product of the reaction. At that inside of the body the tubular heat exchanger is installed. The tubes of the heat exchanger are arranged at least along two concentric circumferences, spaced from each other and communicate through the collector equipped with the valves for feeding of the heating carrier. Between the tubes of the heat exchanger in the liquid reactant medium there is the annular fire grate, on which the solid reactant granules are placed. The chemical reactor has the vertical spacers inserted between the tubes located on the concentric circumferences shutting the gap between the adjacent tubes. Besides there are the vertical inserts placed between the opposite tubes of the adjacent concentric circumferences shutting the gap between the tubes. At that the indicated spacers and inserts form the zones free from the solid reactant granules, and the valves of the heat carrier feeding are connected through the control unit to the temperature sensors. The method of operation of the chemical reactor for production of hydrogen provides for the liquid reactant feeding in the chemical reactor, withdrawal of the heat and the reaction products from the reaction zone with the help of the heat carrier. Before the liquid reactant feeding into the chemical reactor this reactant is heated up to the temperature ensuring the preset duration of the operational cycle of the reaction, and the heat withdrawal from the chemical reactor with the help of the heat carrier begin at reaching the temperature equal to the temperature of the liquid reactant boiling point with the increase of the heating carrier consumption till the boiling temperature of the liquid reactant will drop to 0.9÷0.8 of the liquid reactant boiling temperature, after that the consumption of the cooling heat-carrier maintain constant till completion of the chemical reaction in the chemical reactor. The inventions allow to increase efficiency of the chemical reactor, to reduce its dimensions and the mass, to improve the fire-explosion safety, to simplify the chemical reactor operation, to reduce its operational costs.

EFFECT: the inventions ensure the increased efficiency of the chemical reactor, the reduced its dimensions and the mass, the improved the fire-explosion safety, the simplified operation of the chemical reactor, the decreased its operational costs.

2 cl, 1 dwg

Gas analyzer // 2292234

FIELD: chemical or physical processes.

SUBSTANCE: gas analyzer comprises housing (2) that receives solid-fuel charge (3), igniter (5), and filter-cooler (7) made of gas-permeable coarse-grained powder (8) whose grain size ranges from 0.13 to 0.5 mm. Filter-cooler (7) is provided with gas-permeable disks (14) arranged perpendicular to its axis. The disks are made of a material whose thermal conductivity exceeds that of dispersion powder (8) by a factor of 15. The temperature of melting, decomposition, or sublimation of dispersion powder (8) exceeds the temperature of the products of combustion of solid-fuel charge (3) by 20%. The length of filter-cooler (7) ranges from 100 to 2500 of the mean size of the particles of powder (8) of the filter-cooler.

EFFECT: reduced temperature and contamination of combustion products.

3 dwg, 1 tbl

FIELD: chemical industry; the portable devices for the fire extinguishing.

SUBSTANCE: the invention is pertaining to the field of the fire-fighting equipment, in particular, to the portable fire extinguishers (manual, pistol, pack) and may be used for fire extinction by feeding of the fire-extinguishing agent (fluid, powder) to the center of inflammation. The stated technical solution allows to improve the operational capabilities and its usage convenience due to expansion of the range of the used fire-extinguishing matters, minimization of time used for replacement of the pressure forming means, provision of the possibility to correct the volume of the gas-generating composition according to the existing need at the simultaneous increase of effectiveness of operation due to the maximum utilization of the internal volume of the container and elimination of the unproductive feeding of the gas. The represented portable fire extinguisher has the container for the fire-extinguishing matter and the gas-generating tool for creation of the operational pressure. The portable fire-extinguisher singularity consists, that it is supplied with the a control unit, the pressure sensor located in the container, at that the gas-generating tool is made in the form of at least two gas generators arranged in the airproof cassette mounted outside the container and linked with it by means of the high-speed coupling, and the control unit interacts with each gas generator with provision of their consecutive actuation.

EFFECT: the invention ensures the increased effectiveness of operation, the improved operational capabilities, convenience of usage, expansion of the used fire-extinguishing matters, minimization of the time for replacement of the pressure forming means, the possibility to correct the volume of the gas-generating composition.

3 cl, 1 dwg

Gas generator // 2286844

FIELD: mixing.

SUBSTANCE: gas generator comprises housing provided with means for gas discharging made of openings on the side of the housing and gas generating and igniting charges mounted inside the housing and made of pyrotechnical compositions. The initiating member is mounted on one of the faces, and filter is mounted on the side and faces of the gas-generating charge. The surface of the gas-generating charge is armored from the side of the gas outlet. The auxiliary charge is mounted axially symmetrical in the gas-generating charge and is provided with layers that pass from the axially symmetrical layer to the periphery and connected with them.

EFFECT: enhanced reliability and expanded functional capability.

4 cl, 1 dwg

FIELD: petrochemical industry; devices for the high-temperature reprocessing of the raw oil, oil shales, peat, paper, board, domestic and agricultural wastes.

SUBSTANCE: the invention is pertaining to the devices intended for the high-temperature reprocessing of the raw oil, and also the shales, peat, paper, board, agricultural wastes and the domestic waste. The reaction chamber of the high-temperature reactor has the water-cooled body opened from both butts. In the internal volume of the body there is the chamber of the pyrolysis (4), the hardening chamber (5) and the sparger, which has been made with the capability of the water sputtering in the hardening chamber (5). The reaction chamber is supplied with the injectors (8) and the enveloping the body first toroidal collector (12) for the gas feeding and the second toroidal collector (15) for feeding of the reprocessing stock into the injectors (8). The body consists of two parts, the first of which is made in the form of the cone. The smaller diameter conical part (1) is adjoined with the cylindrical part (2), which diameter exceeds the greater diameter of the conic part (1). The sparger is made in the form of the parallel small pipes (3) orientated in the plane, which is perpendicular to the axis of the body, and dividing its volume into the pyrolysis chamber (4) and the hardening chamber (5). The small pipes (3) in their middle have the section salient towards the conical part (1). The small pipes have the holes (7) orientated towards the hardening chamber (50. The injectors (8) are evenly distributed along the circumference. Their outlet nozzles (9) are located in the pyrolysis chamber (4), and the inlet nozzles (10) are connected to the first toroidal collector (12). In the lateral wall of each injector (8) there is the channel (14) connected to the second collector (15). The outlet nozzles (9) of the injectors (8) can be located both in the conical part (1) of the body, and in its cylindrical part (2). The invention expands the technological capabilities of the process.

EFFECT: the invention ensures expansion of the technological capabilities of the process.

3 cl, 1 dwg

FIELD: space engineering.

SUBSTANCE: device comprises housing that receives solid source of oxygen and heater, power source, cooling system, filter, and control unit. The solid source of oxygen and heater are mounted in the changeable member whose one face is provided with electric plug whose answering part is mounted in the housing. The opposite face of the changeable member is provided with the filter. The cooling system could be provided with the fan, and the member is mounted with a spaced relation to the housing. The fan could be provided with the unit for control of the speed of rotation.

EFFECT: enhanced reliability and safety.

2 cl, 1 dwg

FIELD: fire-fighting equipment, particularly used in powder fire extinguishers, adapted to suppress fire and having different areas and volumes.

SUBSTANCE: impulse or short-term fire extinguishing module has working gas source, for instance charge of condensed agent of solid-fuel gas generator. The modules are made as main executive mechanisms for automatic and autonomous fire-suppression systems. In accordance with the first embodiment module has streamlined body. Gas generator is made as replaceable cold gas source. The module has modified gas-and-powder mixture movement path, which defines gas-and-powder mixture flow due to partial arrangement of mixture flow defining member inside module bottom neck and partial above member location inside module body. The mixture flow defining member is made as hollow cylindrical nozzle having tangential orifices in upper part of side surface thereof and central through orifice made in nozzle end having lesser diameter. The module has membrane arranged so that the membrane provides additional nozzle interior protection against external unauthorized action. The module has aerator, which is installed more efficiently with respect to body bottom neck, and figured washer. Gas-and-powder mixture flow distribution is defined by relationship between side and central nozzle orifices. In accordance with the second embodiment powder is distributed in vertical direction. Space to be protected has reduced size and powder mass to be displaced is also decreased in comparison with the module formed in accordance with the first embodiment. That is why summary outlet tangential orifice area is enough to provide pulsed gas-and-powder mixture throwing during module operation. The invention eliminates the need of powder aeration gas delivering over desirable distance in horizontal direction. Downward gas flow impinges upon solid nozzle end and passes over nozzle sides to upper module body part for powder fluidization. Solid nozzle ends protects central powder part against compaction due to gas flow action. Gas-and-powder mixture jet effluxes in the same way as in the module formed in accordance first embodiment, namely in the form of highly-turbulized jet.

EFFECT: increased fire suppression efficiency without structure complication due to provision of effective gas-and-powder mixture movement, as well as increased density and uniformity of gas-and-powder mixture spray as a result of minimized module action time, prevention of powder compaction at the beginning of gas generator actuation, improved operational convenience and fire and explosion safety while using the module.

13 cl, 5 dwg

FIELD: methods of storage of hydrogen in catalytic systems functioning on basis of cyclic hydrogenation/de-hydrogenation reactions of condensed and poly-nuclear aromatic compounds; hydrogen generators; hydrogen engines or plants.

SUBSTANCE: proposed catalytic composite material contains organic substrate as hydrogen source which is liable to hydrogenation/dehydrogenation reactions. Material contains heterogeneous catalyst including carbon or oxide carrier at high specific surface and metal of VIII (platinum) group applied on this surface at mass ratio of substrate and catalyst from 10:1 to 1000:1. Organic substrate contains the following aromatic hydrocarbons: condensed, poly-cyclic, poly-unsaturated, aromatic oligomers and polymers: biphenyl or its functional derivative, or terphenyl, or naphthalene, or anthracene, or functional derivative of one or other, polystyrene or its copolymer, polyacetylene or polycumulene. Proposed method consists in charging the composite material with hydrogen at high pressure and separation of hydrogen from it at low-pressure heating. Charging is carried out at contact of organic substrate and heterogeneous catalyst at temperature of from 50 to 180°C and hydrogen pressure of from 1 to 100 atm; separation of hydrogen is carried out at contact of hydrogenated of organic substrate with the same catalyst at temperature of from 200 to 350°C at atmospheric pressure.

EFFECT: enhanced efficiency.

9 cl, 2 dwg, 2 tbl, 7 ex

FIELD: analytical instrument making industry; production of the generators of the substances vapor microflow.

SUBSTANCE: the invention is pertaining to the analytical instrumentation technologies and is intended for solution of the problem of creation of the constant in the long-time interval flow of the substances vapor and its controlled adjustment. The generator of the microflow of the substances vapor includes: the chamber having at least one hole; the located in the chamber on its working surface source of the substances vapors; the tool for variation of the temperature of the source of the substances vapors; and the block for measuring the value of the substance vapor flow. The chamber working surface is made in the form of the mass-sensitive piezoelectric transducer of the resonance type. The tool for variation of the temperature includes: the temperature adjustment unit; the heater or the cooler arranged on the working surface of the mass-sensitive piezoelectric transducer or on the surface of the chamber. The block for measuring of the value of the substance vapor flow includes the electronic generator of the alternating voltage made in the form of the noninverting amplifier and the meter of the speed of the frequency variation. At that the outlet of the noninverting amplifier is connected to its inlet through the mass-sensitive piezoelectric transducer, and the inlet of the meter of the speed of the frequency variation is connected to an outlet of the noninverting amplifier. The invention allows to provide production of the constant controlled microflow of the substances vapor, to simplify the design and to reduce the overall dimensions of the generator.

EFFECT: the invention ensures production of the constant controlled microflow of the substances vapor, simplification of the design, reduction of the overall dimensions of the generator.

7 cl, 4 dwg, 4 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to novel catalysts that can be used, in particular, for selective hydrogenation of polyunsaturated hydrocarbons, deep oxidation of carbon monoxide, organic and organohalogene compounds, sulfur dioxide oxidation, selective chlorination and oxychlorination of hydrocarbons, nitrogen oxide reduction, and reuse of gaseous and liquid wastes. Catalytic system represents geometrically structured one including microfibers of high-silica fibrous carrier 5-20 μm in diameter, which is characterized by existence in IR spectrum of hydroxyl group spectral band having wave number ν=3620-3650 cm-1 and half-width 65-75 cm-1, by having specific surface SAr=0.5-30 m2/g as measured via BET method involving thermal desorption of argon, and at least one active element. In addition, carrier has specific surface value measured by alkali titration method SNa=5-150 m2/g at SNa/SAr ratio (5-50):1. Active element is of the nature capable of forming charged metallic or bimetallic clusters with specific bands in the region of 34000-42000 cm-1 and ratio of integral intensity of band 34000-42000 cm-1 (corresponding to charged metallic or bimetallic clusters) to integral intensity of band with maximum at 48000 cm-1, corresponding, respectively, either to metallic or to bimetallic particles, at least 1.0.

EFFECT: increased catalytic activity, increased resistance of catalyst to deactivation and elevated selectivity thereof in heterogeneous reactions.

4 cl, 6 ex

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