![]() Catalyst for oxidation of hydrogen
专利摘要:
For the catalytic oxidation of hydrogen, a palladium alloy having a low induction period up to the catalytic reaction is used. The palladium alloy contains at least 80 % by weight of Pd, at most up to 19.9 % by weight of a further metal from Group 8 of the Periodic Table, especially Ni, and at most 10 % by weight of Cu. <IMAGE> 公开号:SU1757445A3 申请号:SU884356243 申请日:1988-07-29 公开日:1992-08-23 发明作者:Клатт Карл-Хайнц;Конрад Ральф;Венцл Хельмут;Кумар Хакраборти Амийя;Роде Юрген;Керстинг Эдмунд 申请人:Форшунгсцентрум Юлих Гмбх (Фирма);Гезельшафт Фюр Реакторзихерхайт (Грс) Мбх (Фирма); IPC主号:
专利说明:
The invention relates to catalysts for the oxidation of hydrogen in an atmosphere containing hydrogen and oxygen and can be used in a safety device for removing hydrogen from an explosive atmosphere containing hydrogen and oxygen in the event of nuclear reactors. Known alloy based on palladium, containing one or more elements selected from the group including silver, nickel and copper. The known alloy is used as a material for coatings on materials such as steel, silver, and monolith. Also known is a catalyst for the oxidation of hydrogen, used to remove hydrogen from the atmosphere of the safety tank of a nuclear reactor, which is copper oxide. The disadvantage of such a catalyst is its short service life due to its rapid poisoning by catalytic dyses. The closest solution to the technical essence and the achieved effect is a catalyst for oxidizing hydrogen in an atmosphere containing hydrogen and oxygen, which is a palladium alloy containing 2–40% by weight of one of the elements of group 1B, including copper together with 0 , 1-20.0 wt.% One of the elements of the VIH group, including nickel. y - “ The use of this catalyst, for example the composition Pd: Ni: Cu 90: 9.5: 0.5, in the process of hydrogen oxidation (0.4 bar) for the gas atmosphere of the composition, bar: air steam: CO 1.3: 1, 6: 0.005 gives the catalyst warming up to 500 ° C. Xi sl vj J SL Ca The aim of the invention is to reduce the heating temperature of the catalyst while maintaining resistance to catalytic ladders. This goal is achieved by a catalyst for the oxidation of hydrogen in an atmosphere containing hydrogen and oxygen, including a palladium-nickel-copper alloy with the following content of components, wt%: palladium 90-95; nickel4.0- 9.5; Copper 0.5-1.0, deposited on one or both sides of a carrier — a sheet material made of a metal that absorbs the reaction heat — aluminum or copper. Distinctive features of the invention are the deposition of an alloy on one or both sides of the above-mentioned carrier. This allows the catalyst to be used in a medium containing catalytic dyes, such as chlorine, water-soluble aerosols, and malo, sulfur, and carbon monoxide. The preservation of activity is indicated by an immediate increase in temperature and the achievement of its maximum value of 130-470 ° C. The use of the catalyst allows to reduce the temperature of its heating during operation by 30-370 ° C in comparison with the known catalyst. Example 1. Investigate the catalytic effect of palladium alloy, which contains 95% by weight Pd, 4% by weight Ni, 1% by weight Cu, which is deposited on one side of an aluminum sheet in the reaction chamber, into which a gas mixture composed in real ratios for accidents. In the reaction chamber, one or several sheet carriers with a remaining free-deposited surface are arranged accordingly so that both sides of the layers are available for the gas mixture obtained in the reaction chamber. In total, in the reaction chamber with a volume of 6.5 liters, there is a sheet carrier with a total surface of 240 cm2 for catalysis. For testing, a gas atmosphere is used which contains 1.3 bar of air, 1.6 bar of steam, 0.007 bar of CO. 0.4 bar of hydrogen is supplied to this gas atmosphere. After hydrogen is supplied to the gas atmosphere, a pressure of above 3.3 bar is first created in the reaction chamber. As a result of the catalytic oxidation of hydrogen that occurs, the pressure then drops for about the first 3.5 minutes to a pressure of about 3.15 bar. The pressure then remains constant, which means that the oxidation reaction during this time has already been largely completed and the bound hydrogen already exists in the form of water vapor. During the same period of time, the temperature in the sheet carrier rises from 120 ° C for 1 minute to a maximum temperature of 260 ° C. After reaching this maximum temperature, it again quickly falls. After 4 min, the sheet carrier again has the initial temperature of 120 ° C. The fact that the heat released during the catalysis can be almost completely absorbed by the sheet carrier and retracted shows a slight temperature change around the sheet carrier with a layer in the reaction chamber, the temperature in the reaction chamber rises from 120 ° C after hydrogen supply during the catalytic reaction to a maximum of 140 ° C. This maximum temperature is reached within 2 minutes after the start of the reaction. Immediately thereafter, the temperature in the reaction chamber is again compressed to its original value. Example 2. Investigate the catalytic effect of palladium alloy, which contains 90 wt.% Pd, 9.5 wt.% Ni, 0.5 May,% Cu. Palladium alloy is deposited on both sides of an aluminum sheet. Sheet media has a thickness of 0.1 mm. The entire catalytic surface is 80 cm2. For testing, a gas atmosphere containing the following quantities of gases is used: (partial pressures are indicated) 1.3 bar of air, 1.6 bar of water vapor, 0.005 bar CO. 0.4 bar of hydrogen is supplied to the gas atmosphere. The catalytic reaction starts immediately after the hydrogen is introduced into the gas atmosphere. As the pressure in the reaction chamber increases with the addition of hydrogen, the temperature in the sheet carrier also increases. Catalytic oxidation of hydrogen leads to a decrease in pressure, the pressure in the reaction chamber decreases from about 3.4 to 3.1 bar. The temperature in the sheet carrier quickly rises from 120 ° C over 1 minute to a maximum of 240 ° C. After that, it falls again and reaches the initial value of 120 ° C again after 3 minutes. Hydrogen completely passes into water vapor. Based on these studies, only the start of the oxidation reaction has been established for suitable alloys, i.e. the time at which an increase in temperature in the sheet carrier is used as a result of the absorption of the reaction heat Example 3 (comparative). A palladium alloy with 90 wt.% Pd, 9.5 wt.% N1, 0.5 wt.% Cu in the form of a sheet (rolled film) is used. No special sheet carrier is used. Sheet dimensions are as follows: 200x20x0.1 mm. In the reaction chamber with a volume of 6.5 liters, the entire catalytic surface is 90 cm. In the reaction chamber there is a gas mixture with 1.3 bar of air. 0.005 bar CO, 1.6 bar water vapor. In addition, impurities of chlorine, water-soluble aerosols (silver nitrates and boronitrates) and oils are added to the gas atmosphere in order to create the most unfavorable for the catalytic reaction gas atmosphere that may arise in the event of a reactor accident in the reactor safety tank. The initial temperature in the sheet was 120 ° C. In the reaction chamber serves 0.4 bar. The catalytic effect of the palladium alloy appears without delay, the temperature increase in the sheet was spontaneous, the temperature in the palladium sheet rose to a maximum of 500 ° C. Example 4 The alloy of palladium specified in Example 3 with 90% by weight of Pd, 9.5% by weight of Ni. 0.5 wt.% Cu is applied to an aluminum sheet. A sheet carrier with a catalytic total surface of 120 cm2 is used in the reaction chamber. The gas mixture contains 1.6 bar of air, 0.005 bar CO. 0.4 bar of hydrogen is added to this gas mixture. The initial temperature in the sheet carrier 120 ° C. A decrease in pressure and an increase in temperature takes 1 minute. The temperature in the sheet carrier rises to a maximum of 325 ° C. Example 5 Palladium alloy with 94 wt.% Pd, 5 wt.% N1 and 1 wt.% Cu was sprayed on both sides onto an aluminum sheet. The thickness of the palladium alloy on both sides of the sheet carrier is 3000 A. A sheet carrier of the following sizes is used. 200x30x0.1 mm3. The total catalytic surface in the reaction chamber is 240 cm2. The catalytic reaction develops the faster, the more the catalytic surface in the reaction chamber is used. Essential for determining the catalytic surface is, however, its maximum allowable heating up to the above temperature limit, which lies below the explosion temperature of the gas mixture. Since the release of heat from a sheet or sheet carrier to the environment is crucial, the indicated specific heat transfer (heat transfer coefficient in J / m2-kgf) is also accepted. To ensure high reliability, they strive to create for gas atmosphere in the safety reactor capacity in the event of an accident as much as possible catalytic surface and put it into action as quickly as possible. A gas atmosphere of the following composition is used in the reaction chamber (partial pressures: air 1.3 bar, steam 1, 6 bar, CO 0.007 bar. The initial temperature in the sheet carrier is 120 ° C. 0.4 bar Na is passed into the reaction chamber. The catalytic reaction proceeds without delay, the maximum temperature in the sheet carrier is 280 ° C. Example 6. A palladium alloy containing 94 wt.% Pd, 5 wt.% Mi, 1 wt.% Cu is deposited on both sides on an aluminum sheet carrier with dimensions of 145x28x0.1 mm3. The reaction chamber contains a sheet of tsiteli with a catalytic surface of 180 cm2. The gas atmosphere present in the reaction chamber has the following gas composition, expressed in partial pressures: 1.3 bar of air; 1.6 bar of water vapor; 0,006 bar CO. The initial temperature in the sheet carrier is 120 ° C. Serve 0.4 bar of hydrogen. The reaction starts spontaneously, the maximum temperature in the sheet carrier is 305 ° C. Example 7. A palladium alloy with 95 wt.% Pd, 4 wt.% NJ 1 May% Cu was sprayed on both sides onto a copper sheet. In the reaction chamber, the catalyst surface is 240 cm. 0.08 bar of hydrogen (4% by volume) is fed to the atmosphere of air (1.9 bar) in the chamber. The initial temperature in the sheet carrier is approximately 100 ° C. Despite the low concentration of hydrogen, the reaction develops directly after passing the hydrogen, the maximum temperature in the sheet carrier is 130 ° C. The main results of the test are tabulated.
权利要求:
Claims (1) [1] Invention Formula A catalyst for the oxidation of hydrogen in an atmosphere containing hydrogen and oxygen, including palladium-nickel-copper alloy with the following content of components, wt.%: Palladium 90-95; nickel 4,0- 9,5; copper 0.5-1.0, characterized in that, in order to reduce the heating temperature of the catalyst while maintaining resistance to catalyst women, said alloy is applied on one or both sides of the carrier — a sheet material made of a metal that absorbs the reaction heat — aluminum or copper.
类似技术:
公开号 | 公开日 | 专利标题 SU1757445A3|1992-08-23|Catalyst for oxidation of hydrogen EP0306945B1|1993-04-14|Oxidation of carbon monoxide and catalyst therefor US3243387A|1966-03-29|Palladium-silver-iron oxide on alphaalumina catalyst composition for the selective hydrogenation of acetylene EP0987054B1|2004-06-16|A method and apparatus for selective removal of carbon monoxide DE69913037T2|2004-09-02|reforming reactor RU1779224C|1992-11-30|Catalyst for removing hydrogen from gas mixture CN1004610B|1989-06-28|Process for removal of arsenic from gases US5928985A|1999-07-27|Copper catalysts US4111689A|1978-09-05|Method of storing hydrogen EP0239111B1|1990-07-04|Process for removing metal carbonyls from gaseous streams US5268091A|1993-12-07|Method for removing arsenic and phosphorus contained in liquid hydrocarbon cuts, nickel based retaining material AU634563B2|1993-02-25|A nickel based retaining material for removing arsenic and phosphorus contained in liquid hydrocarbon cuts US1962485A|1934-06-12|Gas purification US1366176A|1921-01-18|Treatment or purification of mixtures of hydrogen and carbon monoxid for the separation therffrom of the latter US4054642A|1977-10-18|Process for the treatment of gases containing various derivatives of sulphur RU2099137C1|1997-12-20|Catalyst for oxidizing hydrogen in atmosphere containing hydrogen, oxygen, and water vapor US3459657A|1969-08-05|Process for the selective hydrogenation of pyrolysis gasoline HU188289B|1986-03-28|Method for producing catalyst for hetereogeneous catalysis US4431566A|1984-02-14|Conversion of methanol into hydrogen and carbon monoxide US4112053A|1978-09-05|Dry method for the denitrification of exhaust gas containing nitrogen oxides US20030044330A1|2003-03-06|Solid material and process for adsorption and desorption of nitrogen oxides in exhaust gases of internal combustion engines KR100427678B1|2004-04-30|Highly activated hydrogen containing material and method for producing the material US3391089A|1968-07-02|Catalyst for the stream reforming of naphtha and related hydrocarbons US2111469A|1938-03-15|Manufacture of formaldehyde JP2000061307A|2000-02-29|High dispersion type steam reforming catalyst and method for producing hydrogen
同族专利:
公开号 | 公开日 EP0301536B1|1997-09-10| EP0301536A2|1989-02-01| DE3725290C2|1990-09-27| CA1314277C|1993-03-09| DE3725290A1|1989-02-16| EP0301536A3|1993-07-28| JPH01176045A|1989-07-12| JP2723544B2|1998-03-09| DE3856023D1|1997-10-16| RU1782326C|1992-12-15|
引用文献:
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申请号 | 申请日 | 专利标题 DE3725290A|DE3725290C2|1987-07-30|1987-07-30| 相关专利
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