Catalytic composite material for storage of hydrogen and method of storage of hydrogen in catalytic systems on basis of hydrogenation/dehydrogenation reactions of organic compounds

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

 

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 condensed and polynuclear aromatic 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.

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. Although the cost of hydrogen at the moment is three times higher than the cost of gasoline, taking into account the environmental aspect of its use for transport purposes, the use of hydrogen as fuel in the near future will come to the fore. Hydrogen can become an alternative fuel if the problem will be solved functioning systems reversible storage (NAC is the accumulation and use. 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 should be no higher than -120°C. Cryogenic conditions of use are a significant drawback of such systems.

Neko is that progress has been made in 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 for hydrogen evolution requires a fairly high temperature.

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, so that it becomes comparable to the speed of adsorption for FeTi and LaNi5(U.S. Pat. USA 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 in the high temperature 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). The use of quick response hydrolite the definition of decomposition of metal hydrides with water makes the process of accumulation of hydrogen irreversible. Thus, these systems are not regenerated, 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 is between 0.01 and 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 of Hydra is one of the 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 ineffective in materials for hydrogen storage.

For the hydrogenation of aromatic hydrocarbons are widely used catalysts based on platinum group metals (Pt, Pd)supported on different carriers - Al2About3, silicates, etc. So, there is a method of preparation of the catalyst of hydrogenation of the aromatic at the of leogardo, which consists in webaii 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 of butadiene-styrene copolymers (U.S. Pat. USA N 5948869). The dehydrogenation of paraffin and cycloparaffin hydrocarbons carried out using the same catalysts containing precious 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.

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 organic compounds under the action of heterogeneous catalysts based on platinum group metals. The technical result of the catalytic composite system and method of storing hydrogen using it is to ensure the possibility of multiple refills and hydrogen at high speed.

This technical result is achieved in that the catalytic composite material for storing odor is Yes, containing as a source of hydrogen with organic substrate capable of reversible reactions of hydrogenation and dehydrogenation, and the catalyst for the hydrogenation-dehydrogenation according to the invention, as the organic substrate contains an aromatic hydrocarbon selected from the group: condensed matter, polycyclic, polyunsaturated, aromatic oligomers and polymers, and as catalyst contains a heterogeneous catalyst comprising carbon or oxide media with high specific surface coated with the surface of at least one metal VIII (platinum) group when the mass ratio of the substrate and catalyst is from 10:1 to 1000:1.

At the same time as polycyclic aromatic hydrocarbons it may contain a biphenyl or its functional derivative, or terphenyl, and as a condensed aromatic hydrocarbon is naphthalene or anthracene, or a functional derivative of the other.

As the aromatic polymer material may also contain polystyrene or copolymer with an average molecular weight of 1000 or polyacetylene, or policemen.

As the carbon carrier material may contain activated carbon, and as the oxide carrier is silica or alumina.

As the metal of group VIII m is a material predetermined contains platinum or palladium, or Nickel, or an alloy of platinum with palladium in an amount of from 0.1 to 15% by weight of a heterogeneous catalyst.

The technical result is also achieved by the fact that in the method of storing hydrogen by refuelling with hydrogen at high pressure catalytic composite material containing as a source of hydrogen with organic substrate capable of reversible reactions hydrogenation-dehydrogenation and catalytic hydrogenation-dehydrogenation and hydrogen from catalytic composite material when it is heated under reduced pressure, according to the invention, as a catalytic composite material using any of the materials described above, filling his conduct when contacting the organic substrate and a heterogeneous catalyst at a temperature of from 50 to 180°and the hydrogen pressure from 1 to 100 ATM and hydrogen gas is carried out at the contacting hydrogenated during charging of the organic substrate with the same catalyst at a temperature of from 200 to 350°C at atmospheric pressure.

The filling and release of hydrogen, it is advisable to carry out without mixing the composite material.

In the proposed method the stage of filling the system with hydrogen in the hydrogenation of polycyclic aromatic compounds (or other organic is ubstrates) 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 heterogeneous catalyst contains from 0.1 to 15 wt.% active metal, preferably from 0.5 to 5 wt.%. 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)2H2PtCl6or H2PdCl4followed 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 noble metal 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 that is necessary for both the biscuits high speeds of the reactions 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.

According to the invention, as a carrier you can use other neutral or weak acid media type silicon oxide or aluminum oxide. Use as carriers acidic media type aluminosilicates (zeolites) limited, as in the conditions of the reactions of hydrogenation/dehydrogenation possible course of adverse reactions of cracking and opening cycle, leading to irreversible stages.

The catalytic composite material for hydrogen storage may also contain structural modifier or matrix, in which dispersed the hydrogen source (organic matter) and the catalyst. As such a structural matrix can be used, for example, block the catalyst (for example, on the basis of cordierite) coated with an active metal (platinum), then this block is allocated to the hydrogen source (for example, hydrogenated biphenyl).

According to the invention, the object hydrogenation (substrate) at the stage of filling the catalytic system hydrogen used organic compounds (aromatic hydrocarbons the odes, including condensed polycyclic polyunsaturated aromatic oligomers and polymers such as polyacetylenes, polyamory)capable of reversibly and repeatedly gidrirovaniya to degidrirovaniya. Preferably use terphenyl, for example in the form of a mixture of ortho-, meta-, and para-isomers.

As the substrate instead of terphenyl you can also use the biphenyl, naphthalene, anthracene, and low molecular weight polymers such as polystyrene with an average molecular weight of 1000, although it is possible to use more high molecular weight substrates.

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.

Below are the physico-chemical properties of terphenyl isomers.

o-terphenyl: TPL = 58-59°; so bales. = 337°

m-terphenyl: TPL = 86-87°; so bales. = 379°

p-terphenyl: TPL = 212-213°; so bales. = 389°C.

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

Limitations on the use of biphenyl related to the fact that the biphenyl and its gidrirovannoe derived (bicyclohexyl) have a boiling point (BP. biphenyl 255° (C)being in the range of the temperature requirements of the second stage of the proposed method (the release of hydrogen during dehydrogenation, see below), which may lead to partial ablation of the substrate with a stream of hydrogen.

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 source substrate (such as terphenyl) and heterogeneous catalyst containing highly dispersed metal, for example platinum, metal 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 80-180°S, preferably 100 to 150°C, hydrogen pressure of 5-100 bar, preferably 5 to 20 MPa, and the ratio of substrate:catalyst = 10:1 to 1,000:1, preferably from 20:1 to 100:1.

2. the stage of evolution of hydrogen from the system when getting in touch already providerone in the first stage of the substrate, such as terphenyl, with the same to what talization at temperatures 220-340° With, preferably 270-320°and atmospheric pressure.

The amount of hydrogen that can accumulate catalytic system by the proposed method can reach a value of 7.5 to 8.0 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, such as polycyclic aromatic hydrocarbons or oligomer, dissolved hydrogen and hydrogen adsorbed on the catalytic centre (metal particles of Nickel, platinum or palladium).

The observed technical effects - multiple refills proposed in this invention for catalytic hydrogen systems, high speed stages of hydrogenation and dehydrogenation due to the fact that the 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.

Figure 1 shows the curves of the dependence the value of the system pressure (autoclave) from the time of refuelling with hydrogen at its original pressure of 70 ATM for catalytic systems:

a - 5% Pt/Sibunit - terphenyl

b - 15% Pt/C - terphenyl

in - 0,7% Pd/Sibunit - terphenyl.

Figure 2 shows curves of the amount of hydrogen released from the time of bringing the stage for the catalytic dehydrogenation systems:

a - 15% Pt/C - terphenyl

b - 5% Pt/Sibunit - terphenyl

in - 0,7% Pd/Sibunit - terphenyl.

The invention is illustrated in the following examples:

Example 1.

2.9 g of catalyst 2% Pd/CKT-4 (activated charcoal) impregnated on capacity molten biphenyl (3.5 g) in a glass container, put the obtained catalytic system (total weight of 6.6 g) together with the capacity of the autoclave PARR-4842 (300 ml, equipped with a pressure gauge for measuring pressure), purge the autoclave with hydrogen (this operation is omitted when reusing system) and at a pressure of 50 bar is heated to 120°C for 1 hour. After cooling to room temperature, release of the system unreacted hydrogen and heat the system up to 300°measuring the amount of hydrogen gas hours. The amount of hydrogen theoretically able to stratics on hydrogenation just downloaded the biphenyl is 3,05 liters. The total amount of hydrogen released from the catalytic system during its heating (minus gas volume due to its thermal expansion), was 3.3 liters (ili,295 g).

Thus, the proposed system is able to accumulate 4.6 wt.% of hydrogen. Note that the mass loss of the catalytic system (determined by weighing) after one cycle of charging/discharging is not more than 0.5%, indicating a minor ablation of the substrate with a gas stream.

Example 2.

In the autoclave load 0.6 g of catalyst 5% Pt/Sibunit (graphitized activated carbon) and 11 g of terphenyl in example 1 and at a pressure of 70 ATM and stirring with a frequency of 500 rpm and heated the mixture up to 180°C for 1.5 hours. The amount of hydrogen theoretically able to stratics on hydrogenation just downloaded terphenyl, is of 9.55 liters. The kinetic curve of the absorption of hydrogen during hydrogenation terphenyl, based on the readings of the pressure gauge shown in figure 1(a).

Further according to the example 1 determine the total amount of hydrogen released from the catalytic system during its heating to 340°C. It was of 9.75 liters (or 0.87 g). The kinetic curve of hydrogen is shown in figure 2(b).

Thus, the proposed catalytic system total weight 11,6 g is able to accumulate to 7.5 wt.% of hydrogen.

Example 3.

The catalytic system with the difference that the catalyst used 15% Pt/C, tested in the method for storing hydrogen according to example 2. Kinetic curves is ogloszenia hydrogen during hydrogenation terphenyl and hydrogen evolution at the stage of dehydrogenation is shown in figure 1(b) and 2(a). The total amount of hydrogen released from the catalytic system during its heating to 340°S, as in example 2, was of 9.75 liters, i.e. the system is able to accumulate to 7.5 wt.% of hydrogen.

It should be noted that when using the catalyst according to example 3 significantly (compared to example 2) decrease the time of filling and full of hydrogen at the stage of dehydrogenation, which is obviously related to the different catalytic activity. So, full hydrogenation terphenyl [observed, the cessation of hydrogen absorption, see figure 1(b)] is achieved already by the 22nd minute, and the release of hydrogen ends to 90 minutes [figure 2(a)].

The catalytic system was tested in the method of storing hydrogen in 4 cycles of hydrogenation/dehydrogenation. Total system capacity of hydrogen in 4 cycles is reduced by no more than 1% (assuming the maximum hydrogen capacity at 100%), with no lower velocity flow stages of hydrogenation and dehydrogenation. Some reduction in total capacity associated with fly ash from the system in the first cycles over boiling hydrocarbons (impurity biphenyl - about 1%).

Examples 4-7.

The catalytic system according to example 3 was tested in the method of storing hydrogen with the difference that at the stages of hydrogenation/dehydrogenation used other temperature, initial pressure bodoro the a and the mixing speed.

The results are given in table 1.

It is seen that at constant system capacity hydrogen depending on the temperature and initial pressure of hydrogen in the autoclave significantly change stages of hydrogenation/dehydrogenation.

Example 5 shows that the filling of the catalytic system with hydrogen during hydrogenation terphenyl and release of hydrogen in the dehydrogenation possible even without mechanical mixing. Obviously, it is very important for mobile and portable devices, hydrogen storage, in which the mixing is difficult to organize.

Examples 6, 7 show that the charging of the system is possible at lower hydrogen pressures (even 5 ATM and below).

Table 2 shows the results of tests of various catalytic systems according to the present invention.

Table 1

The test results of the catalytic system 15% Pt/C: terphenyl = 1:18,4 (mass.)
N Approx.Conditions under hydrogenationTime 50%/100% filling, minConditions under dehydrogenationTime 50%/100% hydrogen, minHydrogen capacity, wt.%
P, ATMN, R/minT °N, R/min
37018050015/2234050038/907.5
45014030028/6028030050/3207,5
550140050/4002800130/07,5
65 (const)18050050/1807,5
73018050026/100

Table 2
The results of tests of various catalytic systems
Conditions under hydrogenation: P=20 bar, T=180°C, N=500 rpm
Conditions under dehydrogenation: P=1 ATM, T=320°C, N=500 rpm
N Approx.CatalystSubstrateSubstrate/ Catalyst mass.Time 50%/100% filling, minTime 50%/100% hydrogen, minHydrogen capacity, wt.%
815% Pt/Cterphenyl2/110/1725/604,2
9"100/180/210100/3207,6
10"800/1380/900400/-7,9
113% Pt-0,25% Pd/terphenyl20/125/7070/2407,5
12" Sibunit500/1340/850520/-7,7
135% Pd/Al2O3naphthalene20/120/6055/140 is a*6,2
14"100/190/2206,3
1515% Pt/Cpolystyrene20/1 60/180the 5.7
16"Min=1000100/1110/260240/-5,8
1715 %Ni/SiO2polystyrene5/150/160140/4004,8
18"Min=100040/1200/640the 5.7
* - at the stage of dehydrogenation using naphthalene as the substrate at the outlet of the autoclave is provided by the hydrogen permeable membrane to prevent ash from hydrogen decline (the product of the hydrogenation of naphthalene)

1. The catalytic composite material for hydrogen storage, containing a source of hydrogen with organic substrate capable of reversible reactions of hydrogenation and dehydrogenation, and the catalyst for the hydrogenation-dehydrogenation, wherein as the organic substrate it contains aromatic hydrocarbon selected from the group: condensed matter, polycyclic, polyunsaturated, aromatic oligomers and polymers, and as a catalyst material contains a heterogeneous catalyst comprising carbon or oxide media with high specific surface nanese the figures on this surface, at least one metal of group VIII when the mass ratio of the substrate and catalyst is from 10:1 to 1000:1.

2. The material according to claim 1, characterized in that as polycyclic aromatic hydrocarbon contains a biphenyl or its functional derivative, or terphenyl.

3. The material according to claim 1, characterized in that as a condensed aromatic hydrocarbon contains naphthalene, or anthracene, or a functional derivative of the other.

4. The material according to claim 1, characterized in that the aromatic polymer includes polystyrene or copolymer with an average molecular weight of 1000 or polyacetylene, or policemen.

5. The material according to claim 1, characterized in that as the carbon carrier contains 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 0.1 to 15% by weight of a heterogeneous catalyst.

8. The method of storing hydrogen by refuelling with hydrogen at high pressure catalytic composite material containing as a source of hydrogen with organic substrate capable of reversible hydrogenation reactions-is gidrirovaniya, and the catalyst for the hydrogenation-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, refilling his conduct when contacting the organic substrate and a heterogeneous catalyst at a temperature of from 50 to 180°and a hydrogen pressure of 1 to 100 atmospheres, and a hydrogen gas is carried out at the contacting hydrogenated during charging of the organic substrate with the same catalyst at a temperature of from 200 to 350°C at atmospheric pressure.

9. The method according to claim 8, characterized in that the filling and release of hydrogen carried out without mixing the composite material.



 

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36 cl, 2 dwg

FIELD: alternate fuels.

SUBSTANCE: in order to obtain hydrogen-containing gas, reaction mixture consisting of water steam and hydrocarbons is passed through first reaction zone to form products, which are then passed through second reaction zone containing mixture of steam CO conversion catalyst and CO2 absorbent. Reaction products formed in second reaction zone are passed through third reaction zone wherein reaction products are cooled to separate condensate from gas phase. The latter is passed through fourth reaction zone containing CO and CO2 methanization catalyst. Hydrogen-containing gas from fourth reaction zone is recovered for further use and first to fourth stages are continuously run until level of carbon-containing compounds exceeds allowable maximum. In order to regenerate absorbent, passage of reaction products from first reaction zone to second reaction zone is cut off and the same is fulfilled with reaction products from second reaction zone passed to theirs reaction zone. Thereafter, pressure in second reaction zone is leveled with regeneration agent pressure and regeneration agent is passed through second reaction zone in direction opposite to direction in which reaction products are passed in the second stage. Once regeneration of absorbent is ended passage of regeneration agent through the second reaction zone is cut off, pressure in the second reaction space is leveled with pressure of reaction products in the second reaction zone and all stages are repeated. Hydrogen thus obtained can be used in small-size autonomous fuel processor.

EFFECT: increased economical efficiency of process.

21 cl, 2 dwg, 1 tbl, 9 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: chemical or physical processes.

SUBSTANCE: method comprises binding free oxygen in the exhaust gas from the internal combustion engine by burning fuel and cleaning, cooling, and compressing the inert gas produced. The gas is partially compressed first in the internal combustion engine, and the compression ratio is controlled by the control of the expansion ratio of the exhaust gas by affecting the value of the head pressure of the internal combustion engine exhaust. The remainder compression is carried out with the use of a compressor. The device comprises the internal combustion engine, drive for permitting control of the speed of rotation of the internal combustion engine, systems for supplying air and fuel, exhaust gas system, control desk, positive-displacement compressor that is actuated by the drive, combustion chamber, finned tube, filter, gas-air heat exchanger provided with fan actuated by the drive, and scrubber, which are connected in series in the main pipeline. The main pipeline connects the exhaust system that includes the controllable valve for discharging exhaust gas to the atmosphere with the compressor provided with the by-pass line having a flow rate controller.

EFFECT: enhanced safety and efficiency .

2 cl, 1 dwg, 1 ex

FIELD: fire-fighting.

SUBSTANCE: module comprises housing that receives the space for fire-fighting powder, gas generator connected with the aerator provided with the perforated side, diaphragm pressed to the throat of the housing by means of coupling nut, member that controls the flow of gas-powder mixture, and fastening unit. The gas generator is made of changeable source of cold gas and has housing made of thin-walled cylindrical shell closed from one side by means of a lid provided with the connecting pipe with the central through opening and provided with the trancated cone from the other side. The output opening of the cone receives the cap-shaped aerator. The distance from the centers of openings of the perforation to the outlet opening of the trancated cone is less than that from the centers to the flat bottom of the aerator. The member that controls the flow of the gas-powder mixture is mounted in the inner space of the throat of the housing bottom and is made of a hollow cylindrical nozzle whose side top section is provided with tangential input openings.

EFFECT: enhanced reliability and efficiency.

9 cl, 3 dwg

FIELD: chemical or physical processes.

SUBSTANCE: device comprises housing that receives initiating member, delay system, main gas-generating charge, and at least one additional gas-generating charge which is mounted in the housing for permitting initiation of it and the delay system by a single pulse from the initiating member. The additional gas-generating charge can be mounted axially symmetrically between the initiating member and the delay system and is provided with the axial passage that can receive delay system or delay system and main gas-generating charge.

EFFECT: enhanced reliability.

5 cl, 2 dwg

FIELD: chemical industry; methods of production of hydrogen.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of hydrogen. The method of start up of the evaporation installation for formation of the hydrocarbon-air mixture decomposed in the reformer for production of hydrogen contains the combustion/mixing chamber, in which through a device with inlet openings the air is fed; the porous evaporating medium and the first heating device added to it; the tool of a surface ignition for inflaming of hydrocarbon-air mixture present in the combustion/mixing chamber. The method includes the following stages: a) heating and evaporation of the liquid hydrocarbon or the hydrocarbon-containing liquids; b) mixing of the vapor produced at the b) stage with the air; c)inflaming of the mixture produced at the b)stage for starting up of a combustion procedure of the mixture; d)keeping up of the combustion procedure up to the end of the given duration of time and-or until the given temperature will be reached in one or several given zones of the installation; e) the termination of the combustion process after the given duration of time and-or after reaching the given temperature. The invention ensures an increase of efficiency of the process due to the temperature drop in the zone of the catalytic reaction.

EFFECT: the invention ensures an increase of efficiency of the process due to the temperature drop in the zone of the catalytic reaction.

7 cl, 2 dwg

FIELD: organic synthesis; devices of processing of a gaseous hydrocarbon raw.

SUBSTANCE: the invention is pertaining to the field of organic synthesis, in particular, to devices of processing of a gaseous hydrocarbon raw. The high-production module type generator of synthesis gas works according to a method of a high-temperature partial oxidation-combustion of the hydrocarbon gases with the industrial oxygen or air at the nominal pressure of 0.2-10.0 MPa and consumption of the oxygen or the air of 0.2-0.4 as compared to stoichiometry (1.0) with usage of the steam and CO2 for correction of the synthesis gas composition by a molar ratio of H2/CO. The basis of the offered design of the synthesis gas generator is a typical module of a combustion chamber with productivity of hydrocarbon gas in terms of methane within the limits of 0.375-3.75 tons per hour. The synthesis gas generator includes from two to several tens modules of the combustion chambers combined in the vertical or horizontal packets with the common cooled body and the common gas withdrawing collecting main. The invention presents the formulas for calculation of the diameter and the length of the active channel, losses of pressure on its inlet and outlet. Usage of the given invention ensures no less than tenfold increase of the volumetric productivity of the synthesis gas generator as compared with its known analog.

EFFECT: the invention ensures no less than tenfold increase of the volumetric productivity of the synthesis gas generator as compared with its known analog.

3 cl, 3 dwg

Hydrogen generator // 2266157

FIELD: power equipment; generation of hydrogen both in stationary plants and in transport facilities.

SUBSTANCE: proposed hydrogen generator is made in form of chemical reactor generating hydrogen by hydrolysis, i.e. by decomposition of water by use of solid reagent and hydrolysis reaction of heterogeneous nature proceeding on solid agent surface. Hydrogen thus generated shall be used in power plants working on fuel elements. Hydrogen may be also used for cutting and welding of metals. Hydrogen generator working on hydrolysis exothermic reaction includes reaction vessel with hydrogen supply main and heat exchanger for removal of reaction heat. Generator is also provided with two hydrogen accumulators fitted with pressure sensors; each hydrogen accumulator is pneumatically connected with reaction vessel through inlet valve and with hydrogen supply main through outlet valve; hydrogen accumulators are made in form of hermetic reservoirs partially filled with water and hydraulically interconnected through heat exchanger used for removal of reaction heat and water flow regulator connected with pressure sensors fitted in hydrogen accumulators. Provision is made for autonomous operation of generator which may be cooled in automatic mode.

EFFECT: enhanced operational reliability at simple control algorithms.

1 dwg

FIELD: substance treatment methods.

SUBSTANCE: particles composed either of a single element selected from group consisting of silicon, titanium, nickel, and samarium or of carbon fluoride are arranged relative to each other such as to enhance wave energy intrinsic to element or carbon fluoride in order to create power field between particles wherein energy is concentrated. Resulting activating structure is capable of generating hydrogen by liberating it from hydrogen bonds of water or hydrocarbons and also capable of removing injurious substances from gas under no external energy supply conditions. Invention is appropriate for use in food processing, chemical, pharmaceutical industries, and agriculture.

EFFECT: expanded substance treatment possibilities.

55 cl, 23 dwg, 4 tbl, 29 ex

FIELD: chemistry.

SUBSTANCE: device has body, solution injector, chlorine injector and throttle valve. Chlorine injector is placed under solution injector. Inside generator body, guide for gas flow is st, forming a channel together with side wall of body. Jets of solution and chlorine flow move in the channel downwardly in same direction to one side of guide. Output of flow of singlet oxygen from solution jets is performed with turn for 180° upwards and by further movement of singlet oxygen flow through throttle valve to other side of guide. Pipe of injector of solution pass through apertures in chlorine injector, while ends of pipes of solution injector exit below openings for output of chlorine jets. Such input of chlorine decreases destruction of solution jets by chlorine jets at starting and working portions of jets and excludes solution getting into chlorine injector.

EFFECT: higher efficiency, higher reliability.

2 cl, 3 dwg

FIELD: power equipment; generation of hydrogen in stationary plants and on transport facilities.

SUBSTANCE: proposed hydrogen generator operates on reaction of hydrolysis with solid reagent granules; hydrogen generator includes reaction reservoir filled with solid reagent granules, hydrogen supply main, liquid reagent supply main and heat exchanger for removal of reaction heat. Generator is also provided with loading bin with hatch which is hermetically sealed during operation of generator; arranged inside loading bin are starting heater and heat-transfer agent main connected to heat exchange loop for removal of reaction heat at its outlet. Operation of hydrogen generator includes loading the solid reagent granules from loading bin into liquid reagent reaction reservoir, heating the reagents for starting the generator, cooling the reagents in stationary mode, draining the reaction products from reaction reservoir and repeating all above-mentioned operations. Prior to loading the solid reagent granules into reaction reservoir, they are heated in loading bin to temperature of reaction; after discharge of solid reagent granules into reaction reservoir, bin is filled with next portion of solid reagent granules which are heated with heat of reaction. Multi-purpose loading bin is used as important component of generator temperature control system.

EFFECT: enhanced efficiency; fast response due to reduced power requirements and starting time; enhanced compactness.

3 cl, 1 dwg

FIELD: production of hydrogen and carbon oxide referred to as synthesis gas by selective catalytic oxidation of hydrocarbon raw material in presence of oxygen-containing gases.

SUBSTANCE: proposed method includes bringing the starting material in contact with catalyst at hourly volume rate of gas within 10,000-10000000 h-1; mixture contains organic material and oxygen or oxygen-containing gas in the amount ensuring ratio of oxygen to carbon no less than 0.3; electric current is passed through at least part of catalyst. Used as catalysts are complex composites including metallic carriers.

EFFECT: possibility of quick and safe ignition of catalyst; increased degree of conversion and selectivity under conditions of change of load in wide range.

24 cl, 7 ex

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