Storage method for great amount of hydrogen

FIELD: storage of gases in chemical, petrochemical ,and oil-refining industries.

SUBSTANCE: proposed oxygen storage method includes partial reduction of λ-Al2O3 on specific surface area of 200 - 400 m3/g doped with up to 0.5 mass percent of Sn during synthesis and subjected to oxidizing treatment at 500 °C in oxygen stream. Reduction is made by activated molecular, hydrogen, or hydrogen-containing hydrocarbon gas at gas temperature of 100 - 750 °C, pressure of 1 - 10 at., and humidity of 10-5 - 10-1 volume percent followed by freezing water produced in the process; storage of partially reduced λ-Al2O3 in arbitrary-humidity atmosphere at up to 50 °C or in vacuum, or in inert gas atmosphere at temperature of up to 750 °C and humidity of up to 10-5 volume percent; and oxidation of partially reduced λ-Al2O3 with water vapors at temperature of 100 - 750 °C or in vacuum at humidity of 10-5 - 10-2 volume percent.

EFFECT: enhanced holding capacity of hydrogen store at enhanced safety and low cost of its storage.

1 cl, 87 ex

 

The invention relates to a method of storing gases and can be used in chemical, petrochemical and refining industries.

Known methods of storing gases in compressed, liquid, absorbed and adsorbed state and in crystallohydrates form and in the form of chemically converted surface of solids [Fastiv VG, Peter JV, Rovinsky AU Cryogenic engineering. M.,1974; Sidorenko MV Underground gas storage. M.: Nedra, 1965; BSA, M.: Owls. encyclopedia, 1970, volume 2. s; S.W. Weller and Montagna A.A. Studies of Alumina 1. Reaction With Hudrogenat Elevated Temp. - J.Catal., 1971, v.21, n 3, p.303 - 311; Y. Amenomiya Adsorption of Hydrogen and H2-D2Exchange Reaction on Alumina. - J.Catal., 1971, v.22, No. 1, p. 109 - 122.; Borisevich P., Y. Fomichev, Lewinter ON the Study of the interaction of hydrogen with the surface γ-Al2About3in the conditions of variable humidity system. THE USSR ACADEMY OF SCIENCES. Journal of physical chemistry, 1985, vol. 3; Borisevich P., Y. Fomichev, Lewinter ON the Study of the interaction of hydrogen with the surface γ-Al2About3. THE USSR ACADEMY OF SCIENCES. Journal of physical chemistry, 1981, t, VIP, s-2151; the Patent of the Russian Federation No. 2048435; Method long-term storage of hydrogen. Borisevich Y.P.; the Patent of the Russian Federation No. 2190571. The method of hydrogen storage in harsh environments. Borisevich P., Shcherbakov D.A.].

The disadvantages of these methods as applied to hydrogen are: greater is e technical complexity and high costs for liquefaction of hydrogen due to its very low boiling point, large losses in storage due to the same reason, increased fire and explosion hazards of liquid hydrogen, and the need to use in the liquefaction of either pure hydrogen or a special device for the separation of gases, condensed at higher temperatures; the compression of hydrogen is also quite difficult and expensive process, which, although it minimizes losses during storage, but does not reduce fire and explosion hazard, which adds considerable complexity in the operation of vessels working under considerable pressure and are characterized by high intensity, in addition, receiving and storing compressed hydrogen requires its original purity; storage of hydrogen adsorbed and absorbed state in the practical technique is not applied (perhaps except in the case of its dissolution in palladium), as it is characterized by low holding capacity of all known adsorbents and absorbents, many of which are rare and precious substances (e.g., noble metals), often incomplete reversibility during desorption and the impossibility of long-term storage of hydrogen in this state as a result of technical inconvenience, and as a result of air oxidation; hydrogen storage in crystallohydrates form of industrial value (the difference from hydrocarbon gases) also has no as for obtaining and storing such substances are required elusive conditions associated with high costs; storing hydrogen in the form of a partially reconstructed gamma-alumina industrial applications also have not received as either bookmark the hydrogen storage is only flowing hydrogen and only at atmospheric pressure, resulting in the total amount of hydrogen, "founded on storage, much smaller amounts of hydrogen consumed to restore the surface, and, accordingly, the amount of hydrogen, "received from the store, much less than the number of hydrogen it takes to restore the surface, or to increase "storage capacity" donate range of storage conditions.

The closest in technical essence and the achieved effect to the present invention is a method of hydrogen storage [Patent of the Russian Federation No. 2125537. The method of hydrogen storage. Borisevich P.], based on a partial recovery of gamma-alumina containing up to 3.7·10-71 m2adsorbed anions of organic acids and the last pre-oxidation treatment at 500°in a stream of oxygen or molecular active hydrogen, or hydrogen-containing hydrocarbon gas with subsequent oxidation is arnosti water vapor, accompanied by hydrogen evolution. The disadvantages of this method are fundamental limitations on the amount of hydrogen, "put in storage" and the amount of hydrogen, "retrieved from a repository" - no more than 38 l H2(N.U.) / 1 l γ-Al2About3.

The aim of the invention is to increase the "storage capacity" in relation to hydrogen while maintaining security and low costs associated with storage.

The problem is solved in that a method of storing large quantities of hydrogen includes partial recovery γ-Al2About3with a specific surface area of 200-400 m2/g molecular active hydrogen or hydrogen-containing hydrocarbon gas at 100-750°C, a pressure of 1-10 ATM and gas humidity 10-5-10-2vol.%, the freezing of generated water, storing partially restored γ-Al2About3in the air arbitrary humidity at temperatures up to 50°With, or vacuum or inert gas at temperatures up to 750°C and humidity up to 10-5vol.% and subsequent oxidation of the partially restored γ-Al2About3water vapor when 100-750°With inert gas at atmospheric pressure or a vacuum with a humidity of 10-5-10-2vol.%. The proposed method differs from the closest analogue of the fact that vosstanovlenie the subject γ -Al2About3, which in its synthesis was introduced to 0.5 wt.% Sn, the last pre-oxidation treatment at 500°With the oxygen flow.

The essential difference between the proposed method against known is that the first partial surface reconstruction or molecular active hydrogen, or hydrogen-containing gas after pre-oxidation treatment at 500°With the oxygen flow is subjected to a rigid body (γ-Al2About3in which stage of its synthesis was introduced to 0.5 wt.% Sn.

The novelty of the claimed technical solution is that as the storage of hydrogen is used partially restored after pre-treatment at 500°With the flow of oxygen gamma-aluminum oxide, in which at the stage of its synthesis was introduced to 0.5 wt.% Sn, with freezing released during the restoration of the water, which may then be stored in air, inert gas or vacuum, without losing the ability of hydrogen in strict compliance with a set amount of oxidation has been partially restored the surface of gamma-alumina with water vapor.

It is known that according to the law of electrostatic valence [Pauling L. The Nature of the Chemical Bond, 3rd rd., Cornell Univ. Press. Jthaca, New York, 1960, p.548] work ZAR is on a stable ionic structure must be equal to or approximately equal to zero. Because of this requirement IT is better groups, instead of oxygen, the anionic layer, which, according to energy principles, should limit the surface of crystalline gamma-alumina is preferably a hydroxyl layer.

It is known that molecular and activated hydrogen at a temperature of from 100 to 750°and the humidity of the gas from 10-5up to 10-2vol.% in flow conditions could partially restore the surface of gamma-alumina [Borisevich P. Interaction of hydrogen with the surface γ-Al2About3and its role in the processes of dehydrogenation and dehydrocyclization. The dissertation on competition of a scientific degree of Kida. chem. I. Minsk, Byelorussian Academy of Sciences, Institute of Physical organic chemistry, 1985]. Since the interaction of hydrogen with gamma-alumina is accompanied incremental dehydroxylization surface compared to calcination in vacuum or inert gas environment in the same temperature range, the resulting surface defects are fundamentally different from surface defects, obtained by degidroksilirovanie gamma-alumina in a vacuum or inert gas environment, which determines the ability of the considered oxide to act as a "repository" of hydrogen. Degidroksilirovanie gamma-alumina in an inert atmosphere or vacuum, etc the springing mechanism, proposed Peri J.B. [ Peri J.B. A Model for the Surface of γ - Alumina.- J.Phys.Chem., 1965, v.69, p.220 - 231], accompanied by the formation of the surface layer of the oxygen anions, whereas when degidroksilirovanie in a hydrogen environment, surface hydroxyl groups are removed much more of the (N2O), resulting in the exposed layer of positively charged ions of aluminum, which allows us to consider the interaction of alumina with hydrogen as the process of surface restoration.

Introduction to the structure of gamma-alumina in its synthesis of Sn (SnCl4) changes the nature of the surface, as it inevitably will change the conditions of partial restoration, and subsequent oxidation of the partially reconstructed surface, as the number of defects occurring during the surface reconstruction and their nature will be completely different. The violation of the homogeneity of the crystal lattice of gamma-aluminum oxide when introduced to him at the stage of synthesis of Sn inevitably leads to a much higher proportion of hydroxyl groups of the surface of gamma-alumina, usually stable under oxidizing treatment and the interaction with hydrogen, will lose its stability, and this will inevitably lead to the emergence of a larger number of surface defects. The increase in the number of surface defects in the data case is equivalent capacity "warehouse". The upper concentration limit of the Sn introduced into the composition of gamma-alumina in its synthesis, due to the possibilities of technology for γ-Al2About3. The lower limit of the concentration of Sn (0,001%by weight), introduced into the structure of gamma-alumina in its synthesis; due to the minimum detected the influence of tin on the increase in the number of surface defects γ-Al2About3.

For each temperature recovery the degree of removal of Oh-groups is determined by the humidity of the system. Moisture reduction system (freezing N2A) shift the equilibrium towards sustainable livelihoods restored surface. The amount of hydrogen, which potentially implies for storage increases. Increase humidity system shifts the equilibrium towards the hydration of the surface. The amount of hydrogen, which potentially implies the storage decreases. Thus, for each temperature recovery there is a limit humidity above which makes recovery impossible. With increasing temperature the recovery amount of hydrogen, which potentially implies deposited increases up to the maximum possible for the humidity system and specific surface of the sample of gamma-alumina. With the increase in specific is poverhnosti alumina "storage capacity", naturally, increased (including with splitting the sample up to the darkening of the surface during recovery. With increasing hydrogen pressure when you restore the storage capacity also increases, and the maximum capacity for the same value of the humidity system and specific surface area can be achieved at lower temperatures, because of the greater ease of removal of Oh-groups with increasing hydrogen pressure.

Application for recovery of activated hydrogen (activation can be done either by using high-frequency discharge, or by using a phenomenon Shpillover or Jampover when using platinum mobile or platinum catalyst on the carrier, or, finally, with the help of γ-irradiation) further facilitates the process of restoring the surface of gamma-alumina due to the much higher reactivity of the activated hydrogen in comparison with the molecular allowing to achieve a single "storage capacity" for the same value of the humidity system, specific surface oxide and the pressure at much lower temperatures.

Finally, restore the surface of gamma-alumina is quite possible and the hydrogen-containing hydrocarbon gas (in the absence of oxygen in it, able in these circumstances to call back the oxidation of the surface). The degree of recovery of the surface of gamma-alumina under other equal conditions determined by the partial pressure of free hydrogen and heavy hydrocarbons can cause partial nauglerozhivaniya the surface of gamma-alumina, which reduces the storage capacity".

Of course, to shift the equilibrium oxidation ↔ restore the surface of gamma-alumina, carried out in a confined space (to conserve hydrogen) in the side surface restoration when "tab of the hydrogen storage", requires the freezing of generated moisture, which is easiest to implement on zeolites (e.g., NaX), cooled to liquid nitrogen temperature. In this case, if the flow rate of hydrogen at the surface reconstruction of gamma-alumina is not the limiting factor, the process can be carried out on duct without freezing the resulting moisture. The upper temperature limit surface reconstruction of gamma-aluminum oxide (750° (C) constrained sintering of gamma-aluminum oxide, so that the surface oxide (and, hence, "storage capacity") begin to decrease. The lower temperature limit recovery of the surface of gamma-alumina (100° (C) limited reactivity of hydrogen with respect to the alumina. The lower limit humidity gas is ri recovery of gamma-alumina (10 -5vol.%) limited technical difficulties deeper dehydration. The upper limit of the humidity of the gas in the recovery of gamma-aluminum oxide is limited by the shift in the equilibrium oxidation ↔ surface reconstruction in the leftmost position at which no surface recovery becomes impossible, even at the highest temperatures patentable range. The lower limit of the hydrogen pressure (or partial pressure of hydrogen in the case of hydrocarbon hydrogen-containing gas) - 1 ATM - limited to a minimum "storage capacity", in which this method is appropriate, with a further reduction of the pressure potential of gamma-alumina remain almost entirely unrealized. The upper limit on the hydrogen pressure (10 ATM) is limited by technical difficulties for the compression of hydrogen, and most importantly, too deep to restore the surface of gamma-alumina, in which the future of the water vapor oxidation is impeded in patenting temperature range.

After restoring the surface of gamma-alumina ("bookmark hydrogen storage") and cooling to room temperature in the recovery environment oxide completely ready for the storage of hydrogen or in the air arbitrary humidity at temperatures up to 50°or in the Vake is IU or inert gas at arbitrary temperature (up to 750° C) and humidity up to 10-3vol.%.

The upper limit (50° (C) when storing the recovered oxide in the air caused by the impossibility of any water vapor concentration to cause significant oxidation of reduced surface gamma-aluminum oxide (hydrogen gas) to a specified temperature as a result of their lack of reactivity.

The upper limit of humidity (10-5vol.%) when storing the recovered oxide in vacuum or inert gas at arbitrary temperature (up to 750° (C) due to the inability of water vapor (due to their negligible concentration) to cause substantial oxidation of the previously restored surface (hydrogen evolution) until the beginning of sintering the oxide surface.

Production of hydrogen from storage associated with the oxidation of water vapor previously restored the surface of gamma-alumina, with a fully restored original hydroxyl cover is solid. The amount of hydrogen, "received from the vault"is determined by the depth of oxidation of previously restored the surface of gamma-alumina, which is proportional to the temperature and humidity of the environment during oxidation. For each degree of recovery of gamma-alumina, there is a limit humidity, below which the CSOs oxidation becomes impossible, and the limit of 10-5vol.%, above for any degree of recovery in the temperature range of oxidation 100-750°can be obtained all hydrogen, "laid previously deposited". The lower limit of the temperature during the oxidation of the surface of the pre-restored gamma-aluminum oxide (100° (C) due to the fact that at lower temperatures, even at the highest moisture system oxidation partially restored oxide may not be complete, that is, the amount of hydrogen, "retrieved from storage will be significantly less than the number of hydrogen "laid down for safekeeping."

The upper limit of the temperature during the oxidation of the surface of the pre-restored gamma-aluminum oxide (750° (C) due to thermal stability of the surface of gamma-alumina by sintering, i.e. at higher temperatures a decrease in specific surface area gamma-alumina and, therefore, reduces the storage capacity to re-bookmark the hydrogen storage.

The lower limit humidity system in the oxidation of the surface of the pre-restored gamma-alumina (10-5vol.%) due to the reactivity of water vapour, which at lower concentrations is not able to fully oxidize the surface of gamma-alumina even at the most in the high temperatures (750° C), i.e. the amount of hydrogen, "retrieved from storage will be less than the number of hydrogen "laid down for safekeeping."

The upper limit of the humidity system in the oxidation of the surface of the pre-restored gamma-alumina (10-2vol.%) due to the reactivity of water vapor, which already at this concentration is able to fully extract the hydrogen from the storage even when not heating to the maximum temperature, so a further increase in humidity is just not practical.

The above mentioned disadvantages associated with the storage of hydrogen by conventional methods can be overcome, if storage is to use the process of oxidation - reduction of gamma-alumina, which in its synthesis was introduced to 0.5 wt.% Sn, after the oxidation treatment of the surface.

This technical solution provided in the proposed method.

Example 1. The sample (50 g) of gamma-aluminum oxide (0.2-0.5 mm) with a specific surface area of 200 m2/g in the closed volume was partially restored by molecular hydrogen (with the absorption of water formed by clinoptilolite, cooled with liquid nitrogen) when termoregulirovanija heated at 40°C/min to a temperature of 750°aged at 750°within hours, a pressure of 1 ATM and a humidity of 10-3vol.%. When the extract of sample g of the MMA-aluminum oxide at 750 ° With in an hour the pressure and humidity of hydrogen was maintained at the original level. After cooling in the recovery environment to room temperature and the two-month storage partially restored oxide in air arbitrary humidity (room conditions) at a temperature of up to 50°With the oxide was treated with water vapor in helium environment (humidity 10-2vol.%) at atmospheric pressure and termoregulirovanija (40°C/min) heated to 750°C. After an hour of exposure at 750°store received 4 l H2(N.U.)/1 l of gamma-alumina. Thus, example 1 is a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in the harsh conditions of temperature and humidity, but gentle pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 2. Unlike example 1, the recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the store received 9 l H2(N.U.)/1 l of gamma-ACS is Yes aluminum.

Example 3. Unlike example 1, the recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 6.5 liters of N2(N.U.)/1 l of gamma-aluminum oxide.

Example 4. Unlike example 1, the partial recovery of gamma-alumina was carried out at 10 ATM. Store received 10 l H2(N.U.)/1 l of gamma-alumina. Thus, example 4 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions of temperature, humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 5. Unlike example 4 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 24,5 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 6. Unlike example 4 recovery, storage and subsequent oxidation of exposed γ-Al 2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 17,5 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 7. Unlike example 1, the partial recovery of gamma-alumina was carried out at 5 ATM. From the storage was obtained 7,2 l H2(N.U.)/1 l of gamma-alumina. Thus, example 7 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions of temperature, humidity, and medium pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 8. Unlike example 7 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 15,8 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 9. Unlike example 7 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, stores the received 9,3 l H 2(N.U.)/1 l of gamma-aluminum oxide.

Example 10. Unlike example 1, the partial recovery of gamma-alumina was carried out at 100°With hydrogen, activated on aluminium oxide-platinum catalyst. From the storage was obtained 1 l H2(N.U.)/1 l of gamma-alumina. Thus, example 7 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide under mild conditions of temperature, severe humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 11. Unlike example 10 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 2.5 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 12. Unlike example 10 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 1.8 l H2(N.U.)/1 l of gamma-oxide is luminia.

Example 13. Unlike example 1, the partial recovery of gamma-alumina was carried out at 600°S. Of storage was obtained with 0.2 l of H2(N.U.)/1 l of gamma-alumina. Thus, example 7 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in the average conditions of temperature, severe humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 14. In contrast to example 13 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 0.5 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 15. In contrast to example 13 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 0,28 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 16. Unlike example 1, the partial recovery of gamma-alumina is rodilas at a relative humidity of 10 -1vol.%. From the storage was obtained 0.34 l H2(N.U.)/1 l of gamma-alumina. Thus, example 16 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in the hard conditions of temperature, softer, moisture, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 17. In contrast to example 16 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 0,73 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 18. In contrast to example 16 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 0,51 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 19. Unlike example 1, the partial recovery of gamma-alumina was carried out at a relative humidity of 10-3vol.%. Store received 1.5 l H2(N.U.)/1 l g of the MMA-alumina. Thus, example 19 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions with temperature, average humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 20. In contrast to example 19 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 3,7 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 21. In contrast to example 19 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 2,59 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 22. Unlike example 1, was used for the partial recovery of gamma-alumina with a specific surface area of 400 m2/year Of storage was obtained 8 l H2(N.U.)/1 l of gamma-alumina. Thus, example 22 also serves as a reference point (not sod is RIT the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions with temperature, severe humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 23. In contrast to example 22 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 20 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 24. In contrast to example 22 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 13,6 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 25. Unlike example 1, was used for the partial recovery of gamma-alumina with a specific surface area of 300 m2/year Of storage was obtained 6 l H2(N.U.)/1 l of gamma-alumina. Thus, example 25 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the home is aemula of the invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions of temperature, hard for humidity, and a soft pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 26. In contrast to example 25 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 14,7 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 27. In contrast to example 25 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 12,6 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 28. Unlike example 1, the partial recovery of gamma-alumina was carried out at 750°With hydrogen, activated on aluminium oxide-platinum catalyst. Store received 12 l H2(N.U.)/1 l of gamma-alumina. Thus, example 28 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in particularly harsh conditions of temperature, hard to wet the STI, and soft pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 29. In contrast to example 28 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 20 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 30. In contrast to example 28 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 16.6 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 31. Unlike example 1, the partial recovery of gamma-alumina was carried out at 600°With hydrogen, activated on aluminium oxide-platinum catalyst. From the storage was obtained on 11 l H2(N.U.)/1 l of gamma-alumina. Thus, example 31 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in a special medium conditions temperature, severe humidity, and mild pressure on the Oia, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 32. In contrast to example 31 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 18 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 33. In contrast to example 31 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 14 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 34. Unlike example 1, the partial recovery of gamma-alumina was carried out at 750°With hydrogen, activated on aluminium oxide-platinum catalyst at a pressure of 10 ATM. Store received 20 l H2(N.U.)/1 l of gamma-alumina. Thus, example 34 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in particularly harsh conditions of temperature, severe humidity, and especially hard on having the structure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 35. In contrast to example 34 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 50 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 36. In contrast to example 34 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 35 l H2(N.U.)/1 l of gamma-aluminum oxide.

Examples 35 and 36 show extreme differences between the claimed essential features from the known. No other method does not allow to lay on the storage of such large amounts of hydrogen.

Example 37. Unlike example 1, the partial recovery of gamma-alumina was carried out at 750°With hydrogen, activated on aluminium oxide-platinum catalyst at a pressure of 5 ATM. Store received 15 l H2(N.U.)/1 l of gamma-alumina. Thus, example 37 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with already swetnam storage "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in particularly harsh conditions of temperature, hard on humidity and medium pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 38. In contrast to example 37 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 35 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 39. In contrast to example 37 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 25 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 40. Unlike example 1, the partial recovery of gamma-alumina was carried out hydrogen-containing hydrocarbon gas (85% vol. H2and 15 vol.% CH4). From the storage was obtained 3,75 l H2(N.U.)/1 l of gamma-alumina. Thus, example 40 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions with temperature, severe humidity and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature, but soft on the humidity.

Example 41. In contrast to example 40 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 8,2 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 42. In contrast to example 40 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 5,5 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 43. Unlike example 1, part restored alumina was kept for 1.5 years. From the storage was obtained 3,95 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 44. In contrast to example 43 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 8,92 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 45. In contrast to example 43 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, keep the searching was obtained 6,46 l H 2(N.U.)/1 l of gamma-aluminum oxide.

Example 46. Unlike example 1, partially restored alumina was kept in vacuum (P=0.1 mm Hg). From the storage was obtained in (4.1 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 47. In contrast to example 46 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 9,2 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 48. In contrast to example 46 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 6,56 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 49. Unlike example 1, part restored alumina was kept in an environment of helium at random (750° (C) the temperature and humidity of the system up to 10-5vol.%. From the storage was obtained in (4.1 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 50. In contrast to example 49 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 9,2 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 51. In contrast to example 49, and rehabilitation is blenio, storage and subsequent oxidation were subjected to γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 6,56 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 52. Unlike example 1, the production of hydrogen from the storage was carried out at a relative humidity of 10-5vol.%. From the storage was obtained 0,22 l H2(N.U.)/1 l of gamma-alumina. Thus, example 52 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions with temperature, severe humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were harsh temperatures and severe humidity.

Example 53. In contrast to example 52 to the recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 0,55 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 54. In contrast to example 52 to the recovery, storage and subsequent oxidation of exposed γ-Al2About3, the composition of which the synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 0,38 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 55. Unlike example 1, the production of hydrogen from the storage was carried out at a relative humidity of 10is 3.5vol.%. From the storage was obtained 1,3 l H2(N.U.)/1 l of gamma-alumina. Thus, example 52 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions with temperature, severe humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were hard on temperature and medium humidity.

Example 56. In contrast to example 55 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 3,25 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 57. In contrast to example 55 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 2.3 l H2(N.U.)/1 l of gamma-OK the IDA aluminum.

Example 58. Unlike example 1, the production of hydrogen from the storage was carried out at termoregulirovanija heated to 100°and exposure at 100°C for 1 hour. From the storage was obtained 0,01 l H2(N.U.)/1 l of gamma-alumina. Thus, example 58 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions with temperature, severe humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were mild temperatures and severe humidity.

Example 59. In contrast to example 58 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the store received 0,l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 59A. In contrast to example 58 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 0,017 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 60. In the profile is from example 1, production of hydrogen from the storage was carried out at termoregulirovanija heated to 400°and the exposure at 400°C for 1 hour. From the storage was obtained 1,85 l H2(N.U.)/1 l of gamma-alumina. Thus, example 60 also serves as a standard (does not contain the whole set of essential features, reflected in the claims) to compare the claimed invention with the known method of storing "laid" hydrogen under mild conditions on the temperature after the restoration of the oxide in severe conditions with temperature, severe humidity, and mild pressure, without the introduction of the γ-Al2About3at the stage of synthesis of tin; the oxidation conditions were average temperature, and hard to moisture.

Example 61. In contrast to example 60 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the storage was obtained 4,6 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 62. In contrast to example 60 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 3,25 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 63. Unlike example 1, the hydrogen production and the warehouse was carried out in vacuum at the same humidity system. Store received 4 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 64. In contrast to example 63 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.5 wt.% Sn. As a result, from the store received 9 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 65. In contrast to example 63 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.25 wt.% Sn. As a result, from the storage was obtained 6.5 liters of N2(N.U.)/1 l of gamma-alumina

Example 66. Unlike example 1, the recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 4,001 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 67. Unlike example 4 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 10,0012 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 68. Unlike example 7 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced 0,001 the AC.% Sn. As a result, from the storage was obtained 7,001 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 69. Unlike example 10 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 1,0005 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 70. In contrast to example 13 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained with 0.2 l of H2(N.U.)/1 l of gamma-aluminum oxide.

Example 71. In contrast to example 16 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 0.34 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 72. In contrast to example 19 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 1,5001 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 73. In contrast to example 22 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage C is thesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 8,0015 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 74. In contrast to example 25 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 6,001 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 75. In contrast to example 28 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 12,001 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 76. In contrast to example 31 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 11,001 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 77. In contrast to example 34 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 20,002 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 78. In contrast to example 37 recovery, storage and subsequent oxidation of exposed γ-Al2About3which structure in studiesinto was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 15,0015 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 79. In contrast to example 40 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 3,7505 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 80. Unlike example 1, the recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 3,9505 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 81. In contrast to example 46 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 4,1005 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 82. In contrast to example 49 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 4,1005 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 83. In contrast to example 52 to the recovery, storage and subsequent oxidation of exposed γ-Al2About3in which to study the synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 0,22 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 84. In contrast to example 55 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 1,3 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 85. In contrast to example 58 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 0,01 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 86. In contrast to example 60 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 1,85 l H2(N.U.)/1 l of gamma-aluminum oxide.

Example 87. In contrast to example 63 recovery, storage and subsequent oxidation of exposed γ-Al2About3, which at the stage of synthesis was introduced to 0.001 wt.% Sn. As a result, from the storage was obtained 4,001 l H2(N.U.)/1 l of gamma-aluminum oxide.

The examples 1-87 data obtained by laboratory study of the processes of oxidation - reduction real samples of gamma-alumina

From the above examples we can draw the conclusion that advantages of the proposed method when storing large quantities of hydrogen obvious.

The method of storing large quantities of hydrogen, including partial recovery γ-Al2About3with a specific surface area of 200-400 m2/g of activated molecular hydrogen or hydrogen-containing hydrocarbon gas at 100-750°C, a pressure of 1-10 ATM and gas humidity 10-5-10-1vol.%, the freezing of generated water, storing partially restored γ-Al2About3in the air arbitrary humidity at temperatures up to 50°With, or vacuum, or inert gas at temperatures up to 750°C and humidity up to 10-5vol.% and subsequent oxidation of the partially restored γ-Al2About3water vapor when 100-750°With inert gas at atmospheric pressure or a vacuum with a humidity of 10-5-10-2vol.%, characterized in that the restoration is subjected to γ-Al2About3, which in its synthesis was introduced to 0.5 wt.% Sn, the last pre-oxidation treatment at 500°With the oxygen flow.



 

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FIELD: polymer materials and ceramics.

SUBSTANCE: invention provides a novel method for preparing silicon carbide-based powder material suitable for manufacturing ceramic products. Material is prepared by mechanochemical treatment of organosilicon polymer for 10 to 90 min on planetary ball mill in inert atmosphere (pressure 1-5 atm), wherein 50-150 g grinding balls are used per 1 g polymer and acceleration of balls is 20-60 g. Preferably grinding balls are 3-12 mm in diameter.

EFFECT: facilitated powder preparation procedure, achieved powder particle size of the order of several nanometers, and increased yield of ceramics.

3 cl, 1 tbl, 2 ex

FIELD: mining industry and heating engineering.

SUBSTANCE: liquid phase of high-temperature hydrothermal heat carrier is subjected to ageing during which polymerization of silicic acid takes part to form colloidal silica particles. Metal cations, in particular magnesium cations, are then added while increasing pH of solution to 10-12 and thereby initiating coagulation, flocculation, and sedimentation of floccules in the form of sludge. The latter is dried and thermally treated to give magnesium silicate.

EFFECT: enabled control of silicon compound precipitation kinetics, control of residual silicon compound concentration, and sedimentation of material rich in metal from hydrothermal heat carrier.

1 dwg, 1 tbl, 4 ex

FIELD: carbon materials.

SUBSTANCE: invention is designed for use in manufacture of hydrosols, organosols, and suspensions in oils. Nano-size diamond powder is charged into ultrasonic disperser and water and modifier, in particular organic ligand such as EDTA or ethylenebis(oxyethylenenitrilo)tetraacetic acid are then added. Resulting suspension is separated on centrifuge into dispersion medium and precipitate. The latter is treated with water to form suspension, which is centrifuged to give precipitate and hydrosol, which are concentrated separately by heating in vacuum into powderlike form. When concentrating hydrosol, depending on desire, following finished products may be obtained: concentrated hydrosol, cake, or dry black powder. When concentrating precipitate, clear nano-size diamond powder is obtained. Thus obtained products are appropriate to prepare sedimentation-resistant hydrosols and organosols with no ultrasound utilized, which products have no tendency to aggregate upon freezing and thawing, boiling and autoclaving, and which can be repetitively dried and reconstituted. Surface pollution of nanoparticles is reduced.

EFFECT: enabled preparation of hydrosols with precise concentration of nano-size diamonds.

3 cl, 1 tbl, 5 ex

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: chemical industry and special-purpose technique; manufacture of large-sized blanks of shaped articles for chemical and heat-exchange apparatus.

SUBSTANCE: starting coke-filler is mixed with coal-tar pitch and is impregnated with it; then mixture is calcined at temperature of 1100°C and ground to size not exceeding 1.25 mm at content of particles of no more than 0.07 mm in the amount not exceeding 50%. For obtaining fine-grained materials, grinding is continued till particles of 0.5 mm have been obtained. Powder thus obtained is mixed with pitch and blanks are molded from hot coke-pitch mass by extrusion through tip or in mold, after which blanks are subjected to roasting and graphitization. After roasting and graphitization, blanks may be again impregnated with coal-tar pitch and subjected to repeated roasting. Density of material thus made ranges from 1.65 to 1.78 g/cm3, compressive strength ranges from 30.0 to 51.3 Mpa and bending strength ranges from 16 to 26.4 Mpa.

EFFECT: avoidance of rejects.

3 cl, 3 ex

FIELD: carbon materials.

SUBSTANCE: powderlike catalyst is continuously fed into tubular reactor and displaced along reactor axis. Following composition of catalyst can be used: 70-90% Ni and 10-30% MgO or 40-60% Co and 40-60% Al2O3, or Mo, Co, and Mg at molar ratio 1:5:94, respectively. Process is carried out continuously at countercurrent catalyst-hydrocarbon contact. In the first zone(s) catalyst is activated by gases leaving hydrocarbon pyrolysis at 450-600°C. Residence time of catalyst ranges from 5 to 180 min. Activated catalyst is passed into pyrolysis zone(s) at 550-1000°C. Into the same zone(s), hydrocarbons, e.g. methane, are countercurrently passed. Residence time of catalyst in pyrolysis zone(s) ranges from 0.5 to 180 min. Invention can be used in sorbent, catalyst, and composite manufacturing processes.

EFFECT: enabled continuous manufacture of layered nanotubes or bent hollows fibers, reduced number of stages and consumption of reagents.

4 cl, 2 dwg, 7 ex

FIELD: alternate fuels.

SUBSTANCE: invention relates to generation of synthesis gas, containing hydrogen and carbon monoxide, for use in synthesis of gasoline, methanol, or dimethyl ether. Process includes following stages: removing solely hydrogen sulfide form natural gas; containing hydrogen sulfide and carbon dioxide, by passing natural gas through hydrogen sulfide-removal apparatus filled with hydrogen sulfide adsorbent; and adding carbon dioxide and water steam H2S-free natural gas thereby producing gas blend. Gas blend is then fed into reaction tube of reforming plant to carry out steam reforming reaction in gas blend. According to invention, natural gas is passed through convection section communicating with radiation combustion chamber of reforming plant to heat natural gas to temperature suitable to reaction between hydrogen sulfide (in natural gas) and hydrogen sulfide adsorbent.

EFFECT: enabled selective removal of hydrogen sulfide from natural gas.

6 cl, 2 dwg

FIELD: nuclear power engineering.

SUBSTANCE: proposed method includes passage of flow of "light" and "heavy" water mixture under pressure through one or several holes of dielectric element, acting on this mixture by magnetic field and dividing it into three flows: two flows having different ions by electrical sign and chemical properties are electrically insulated, accelerated and directed to collimators. "Light" and "heavy" water mixture at specific resistance of about 109 ohms·m is taken at ratio required for control of nuclear reaction. Device proposed for realization of this method has housing which is dielectrically resistant to cavitation emission and is used for receiving the mixture. Insert mounted in housing is made from dielectric material liable to cavitation emission and provided with one or several holes for passage of mixture. Housing is also provided with electrically insulated branch pipes for receiving the ionized flows. Located in way of ionized flows are control electrodes and contactors; collimators with contactors are mounted at the end of ionized flow.

EFFECT: possibility of production hydrogen from "light" and "heavy" water mixture in amount sufficient for practical use.

3 cl, 1 dwg

FIELD: methods of production of hydrogen, electrical power and the hydraulically purified products out of hydrocarbon raw materials.

SUBSTANCE: the invention is pertaining to the method of production of hydrogen, electrical power and, at least, one hydraulically purified product out of the hydrocarbon raw material containing at least a fraction, which has the same range of boiling-out or higher, than the temperature range of boiling of a hydraulically purified product, which will be produced; this method includes the following operations: treatment of the hydrocarbon raw material with hydrogen at presence of the applied catalyst; at that hydrogen at least partially is produced from fraction of the hydraulically purified raw material having the temperature range of boiling different from the temperature range of boiling of the fraction of hydrocarbon raw material, from which will be produced a hydraulically purified product or at least from a part of the indicated product of the hydraulical purification; separation of the hydraulically purified product from the hydraulically purified raw material, when the hydraulically purified product is necessary to separate; a part or the whole rest hydraulically purified raw material and hydraulically purified product, if it will not be separated to produce hydrogen; a part or all hydrogen, which is not used for treatment of hydrocarbons, is subjected to processing with production of electrical power; or a part of the hydraulically purified raw material and the hydraulically purified product, if it will be not separated, is subjected to processing with production of an electrical power; and the rest is directed to processing with production of hydrogen. The invention allows to produce simultaneously hydrogen, electrical power, and at least one hydraulically purified hydrocarbon product.

EFFECT: the invention allows to produce simultaneously hydrogen, electrical power, and at least one hydraulically purified hydrocarbon product.

18 cl, 1 dwg, 9 ex

FIELD: heat treatment of solid carbon-containing materials for production of activated carbon.

SUBSTANCE: proposed method includes heating and carbonization of raw material in horizontal rotary furnace at continuous mode for 1.0-3.0 h at temperature of 650-850°C and rate of heating not exceeding 10°C/min; method includes also delivery of formed carbonisate to vertical activation furnace by batches without cooling them; activation of each batch is continued for ≤30 min at temperature of 750-950°C in mode of layer suspended by jet of gaseous activating agent; new batch of carbonisate is delivered after unloading the batch of finished product; proposed method includes also delivery of vapor-and-gas mixture from activation furnace to carbonization furnace in counter-flow of material being carbonized, directing the vapor-and-gas mixture from carbonization furnace to waste-heat boiler for after-burning, generation of low-pressure steam required for preparation of activating agent and decontamination of flue gases formed in waste-heat boiler.

EFFECT: intensification of heat-exchange process; improved quality of activated carbon; improved economical parameters due to saving of fuel; reduction of technological process duration.

5 cl, 1 dwg, 2 tbl, 4 ex

FIELD: powder metallurgy.

SUBSTANCE: starting powders of silicon, 40 to 400 mcm, and niobium, below 63 mcm, are taken in proportion (1.33-1.38):1 to form monophase product and in proportion (1.44-1.69):1 to form multiphase product. Powders are subjected to mechanical activation in inert medium for 0.5 to 2 min, ratio of powder mass to that of working balls being 1:20. Resulting powder is compacted and locally heated under argon atmosphere to initiate exothermal reaction producing niobium silicide under self-sustaining burning conditions. Process may be employed in metallurgy, chemistry, mechanical engineering, space, nuclear, and semiconductor engineering, and in electronics.

EFFECT: found conditions for monophase and multiphase crystalline niobium silicide preparation.

2 ex

FIELD: synthesis of zeolites.

SUBSTANCE: the invention is dealt with synthesis of zeolites, in particular, with a composition containing in the capacity of raw material a lime product of incineration or aluminum silicate, to which is added a water alkaline solution, and the mixture is heated up, treated with the help of a mixer producing an agitated mixture in the form of a suspension or a mash. The agitated mixture is continuously relocated and exposed to a direct radiation by electromagnetic waves with a frequency within the range of 300 MHz - 30 GHz, and so transforming it into zeolite. Zeolite is cleaned by means of a cleaning machine and dried in a drum-type steam drying installation. The indicated method may be used for production of synthetic zeolite. The production is characterized by a decreased amount of the applied and removed alkali at decreased power input and operational time.

EFFECT: the invention ensures production of synthetic zeolite using a decreased amount of the applied and removed alkali at reduced power input and operational time.

3 cl, 3 dwg, 3 ex

FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

FIELD: carbon materials.

SUBSTANCE: invention relates to technology of manufacturing porous carbon materials based on fine-size compositions preferably for use as filter elements in micro- and ultrafiltration processes. According to invention, pore agent is dispersed via diluting it with high-dispersed carbonaceous powder in joint grinding-and-mixing process and resulting mixture is added to charge. Carbonaceous powder utilized is either carbon black or colloidal graphite with particle size not larger than 0.5 μm and pore agent-to-diluent ratio is between 1:1 and 1:2.

EFFECT: increased permeability of materials.

4 cl, 2 tbl, 2 ex

FIELD: carbon materials.

SUBSTANCE: invention concerns manufacture of diamond films that can find use in biology, medicine, and electronics. Initial powder containing superdispersed diamonds with level of incombustible residue 3.4 wt %, e.g. diamond blend, is placed into quartz reactor and subjected to heat treatment at 600-900оС in inert of reductive gas medium for 30 min. When carbon-containing reductive gas medium is used, heat treatment is conducted until mass of powder rises not higher than by 30%. After heat treatment, acid treatment and elevated temperatures is applied. Heat treatment and acid treatment can be repeated several times in alternate mode. Treated powder is washed and dried. Level of incombustible impurities is thus reduced to 0.55-0.81 wt %.

EFFECT: reduced level of incombustible impurities.

4 cl, 3 ex

FIELD: carbon materials.

SUBSTANCE: weighed quantity of diamonds with average particle size 4 nm are placed into press mold and compacted into tablet. Tablet is then placed into vacuum chamber as target. The latter is evacuated and after introduction of cushion gas, target is cooled to -100оС and kept until its mass increases by a factor of 2-4. Direct voltage is then applied to electrodes of vacuum chamber and target is exposed to pulse laser emission with power providing heating of particles not higher than 900оС. Atomized target material form microfibers between electrodes. In order to reduce fragility of microfibers, vapors of nonionic-type polymer, e.g. polyvinyl alcohol, polyvinylbutyral or polyacrylamide, are added into chamber to pressure 10-2 to 10-4 gauge atm immediately after laser irradiation. Resulting microfibers have diamond structure and content of non-diamond phase therein does not exceed 6.22%.

EFFECT: increased proportion of diamond structure in product and increased its storage stability.

2 cl

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