• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    1457820 Gas purification HOECHST AG 29 April 1974 [9 May 1973 14 March 1974] 18615/74 Heading C1A [Also in Division B1] Gas mixtures comprising carbon monoxide, hydrocarbons and oxygen are purified by combustion of the carbonaceous compounds in the presence of a catalyst comprising copper, manganese and nickel aluminates supported on alumina which is substantially free of alkali and silicates, the total amount of the aluminates being 10-45% wt. and the weight ratios copper : manganese : nickel : : 2-4 : 1-2 : 0À1-1. The catalysts may also contain cerium oxide. Examples describe the purification of a mixture containing 3% v. O 2 , 2% v. CO, 1000 p.p.m.v. hydrocarbon, 2.5% v. H 2 O and the balance N 2 .
    公开号:SU1041019A3
    申请号:SU742023736
    申请日:1974-05-08
    公开日:1983-09-07
    发明作者:Фогт Вильгельм；Глазер Херманн；Диршка Хельмут
    申请人:Кнапзак Аг (Фирма)；
    IPC主号:
    专利说明:

    (The invention relates to catalysts for carbon monoxide and hydrocarbons and to methods for producing catalysts. Catalysts for carbon monoxide and hydrocarbons contained in the exhaust pits of internal combustion engines containing manganese, meth or nickel on carrier-alumina or magnesium oxide are known. and a method for producing it, which implies that the support is impregnated with manganese salts of copper or nickel followed by thermal treatment to convert the salts to the corresponding oxides C With the closest to the proposed The essence of the technical effect and the achieved effect is catalyzed with oxides of copper, nickel and manganese on alumina carrier, in the following ratio of components, wt.%: Copper oxide Manganese oxide Nickel oxide Remaining Aluminum oxide aqueous solutions of copper, nickel and manganese nitrates, followed by decomposition of salts on the carrier by heating at 300-600 ° C and calcining the formed oxides at SOO-tZOO C for 18 h 2. However, the known catalyst is not quite stable. Known catalysts have a high activity when they are brought into contact with the gas to be oxidized in a mixture with oxygen, which has a stoichiometric or somewhat lower stoichiometric amount, but lose some of their activity when the gas mixture contains oxygen in excess. Therefore, known catalysts need to be brought into contact with the gas to be oxidized into a mixture with such amount of oxygen, which corresponds to the stoichiometry of the oxide of hydrogen and hydrocarbons in this gas, in order to maintain the catalyst in an active state and to achieve complete combustion of the gas being oxidized. Since the content of oxide and hydrocarbons in the exhaust gases of internal combustion engines constantly fluctuates, this condition can be. ig2 is made only with a large cost of hardware design. Thus, for example, the activity of a known catalyst, expressed in terms of temperature, at which 50% of carbon monoxide and H-hexane is converted to carbon dioxide and water: AND, -335 ° C 1 l I.OrOf. g .WUir. 50 hex C. After treatment of a known catalyst with a gas mixture containing 2 vol. carbon monoxide and 98 vol. | nitrogen, at kOO ° C, Qf 2QQ C, hex C. However, after heating the catalyst and the gas mixture, and applied in the experiment, when And eo 330 ° C, the subsequent cooling of 50 hex 80s. Therefore, in the oxidizing basin, a decrease in catalyst activity is observed. The aim of the invention is to increase the stability of the catalyst and increase its activity. The goal is to teM that the catalyst for the recovery of carbon monoxide and hydrocarbons, consisting of copper, nickel and manganese compounds on the carrier is alumina, containing aluminates as copper, nickel and manganese compounds, and alumina free of aluminum oxide as a carrier. compounds of alkali metals and silicates, in the following ratio of components, weight .; Copper aluminate 11.4-22.9 Nickel aluminate 0,6-h, 7 Manganese aluminate 6.3-12.6 Alumina free from alkali metal compounds and silicates Rest The catalyst additionally contains 3, E, 2% mixed cerium oxide aluminum. According to the method for preparing the catalyst by impregnating the support with aqueous solutions of copper, nickel and manganese nitrates, followed by decomposition of the salts on the support by heating at 300-600 ° C and calcining the resulting oxides at 800-1200 ° C for 18 hours, the support is impregnated for 20 hours at 1000 -1200 C. The catalyst is additionally impregnated with an aqueous solution of cerium nitrate, dried for 32 hours, decomposed with cerium nitrate first for 3 hours, and then for 10 hours during 3 hours, followed by calcination for 10 hours. The proposed catalyst in comparison with the known has a high stability and activity. (And (, РР ЗБО ° С). Subsequent treatment of the catalyst with a gas mixture containing 2% by volume of carbon monoxide and 98 hp of nitrogen does not lead to a change in activity, the introduction of cerium-aluminum mixed oxide into catalysis, increases its activity (10 ° С Thus, the proposed catalyst on a carrier is suitable for oxidizing carbon monoxide and hydrocarbons with an excess amount of an acidic type, as a result of which the complete burning of these substances can be guaranteed, since the activity of the catalyst on the carrier is practically independent of and oxygen in the gas mixture brought into contact with it. While copper, manganese and nickel aluminates are soft powders, the supported catalyst is high abrasion resistant bodies with higher compressive strength, which is achieved due to the introduction of the above metal aluminates of the 8 alumina skeleton,, The method is carried out as follows: 17 nl per 1 ml of catalyst per hour of the gas mixture used in the experiment ,. containing 3 vol.1 oxygen, 2 vol. carbon monoxide, 1000 mg / ml n-hexane, 2.5% by volume of water vapor, the rest is nitrogen, is acidified with a supported catalyst, and the gas stream used is preheated, taking into account the temperature provided in each case . In the oxidized gas, the residual content of carbon monoxide and n-hexane is determined and, based on this, the degree of conversion of these components is calculated as a percentage. As a measure of the catalyst activity, the temperature is taken, at which 50 and, respectively, 90 carbon monoxide and n-hexane are converted into carbon dioxide and ggr-Q water. Bosotex eohex. The compressive strength of the catalyst is measured in the longitudinal direction between the plane-parallel plates 9-4. Example (in accordance with the level of technology). Approximately 80 MVr of the usual commercial alumina with a grain size of 3 mm and a specific surface of the particles, determined by the BET method, are applied by impregnation with an aqueous solution of metal nitrates 5, U copper, 2, manganese and 1.57 nickel. The applied metal nitrates are heated to oxides by heating and immediately thereafter, the catalyst is calcined for 18 hours at 1000 C. Catalyst activity: 335 ° C; And, ogex + 85 C. After treatment of the obtained catalyst for 2 h with a gas mixture containing 2 vol.% Of carbon monoxide and 98 vol. nitrogen, when it has the following activity: I5oso200S; And ogex ZO C. After heating the catalyst in the gas mixture used in the experiment, with and subsequent cooling AND STOP, O, and ogex 80 ° C. Therefore, in the oxidizing gas, a decrease in catalyst activity is observed. Example2. (in accordance with the level of technology). Normal commercial sintered alumina with a particle size of 3 mm and a specific surface area of the particles, determined by the BET method, is impregnated approximately 0.25 with an analogous solution to Example 1 with an aqueous solution of metal nitrates. The applied metal nitrates are decomposed at 400 ° C and immediately after this the catalyst is calcined within 18 hours at 1000 ° C. Catalyst activity: 395С; And,. 85C. After reduction of this catalyst with a gas mixture containing 2 vol. | carbon monoxide and 98 rpm of nitrogen at 00 ° C; the activity is as follows: I5oso270 C; 4x 50s. After heating the catalyst at 600 ° C in the gas mixture used in the experiment and the subsequent cooling of I530395Hl50r.xc585C. In this case, a decrease in activity is also observed. Example 3. Clean, completely free of alkali metal compounds and silicates of alumina, obtained by hydrolysis of anhydrous aluminum chloride in Oxygen flame water, is stirred in water until a loose mass is obtained, and the resulting paste is dried in SC. Dry mass crushed into flour and after adding 5 wt. graphite, pressed into a cylindrical body with a length of 3 mm and a diameter of 3 mm. After burning graphite; additionally as an aid in pressing the agent at 650 ° C, the pressed bodies are calcined for 2Q m at. The riocfie of this cylindrical body has a specific surface area, determined by the BET method, 6.9, a pore volume of 0.32, and compressive strength in the longitudinal direction between the parallel-parallel plates 8.1 kg / mm. The cylindrical bodies obtained by the above method are impregnated with a solution of metal nitrates in the same way as in Example 1 and the nitrates are decomposed by heating. Then, the catalyst is calcined at 1000 C. The catalyst contains wt.%: Copper aluminate, 5 Manganese aluminate Nickel aluminate 7 Alumina Remains Catalyst activity: soco Ido, compressive strength kg / mm Catalyst treatment in a reducing atmosphere does not lead to a change in activity. PRI me R. The extruded alumina particles are prepared in the same way as described in Example 3, but calcination is performed for 20 hours at. After this, cylindrical bodies have an accessory surface defined by the method BET, 6.3, round pores 0.32 and compression strength 8.1 kg / mm. After impregnation with a solution of metal nitrates and subsequent calcination carried out according to Example 3, the catalyst has the following activity: I 5 ° C 175 ° C; And, ogeksZ Oh C. Treatment of the catalyst in a reducing atmosphere does not lead to a change in activity. If in the gas used in the experiment, the mixture of n-hexane is replaced by propylene, then the activity of the catalyst I5o "" 85 C. G | EXAMPLE 5: Pressed aluminum oxide particles were prepared as described in Example 3, however, calcination was carried out at 1200 ° C for 20 hours. After this, the cylindrical bodies have a specific surface, determined by the BET method, “jO”, about 0.24 pores and compressive strength 13.7 kg / mm. After the preparation with a solution of metal nitrates and subsequent calcination treatment carried out analogously to Example 3, the catalyst has the following activity: Iepso205C; Wc390 c. ; P p and measures 6 (comparative). A concentrated solution of copper nitrate is introduced into a suspension of pure, free of alkali metals and alumina silicates in water in such an amount that the mass, based on the content of alumina in it, has a copper content. After drying the suspension at 100-200 ° C, the resulting mass crushed into flour and after adding 5 wt. graphite as an aid to pressing, press-down cylindrical bodies with a length of 3 mm and a diameter of 3 mm. Pressed body. heated for 12 h at. Immediately after that, 2, manganese and 1.57% nickel are applied to the pressed bodies by impregnation with a solution of metal nitrates, after which the nitrates are decomposed by heating at. After calcination for 18 hours at 1000 ° C, the catalyst has a specific surface area determined by the BET method, 12.2 MVr, pore volume 0.29 cmVr, compressive strength 3.6 kg / mm and the following composition, weight,%: .. ; -. , Medi, 5 Manganese aluminate 9.3 Nickel aluminate 7 Alumina Rest Catalyst activity: r U. and riO 2604, Vg < 2 > After treatment of the catalyst for 2 hours with a gas mixture containing 2% by volume of carbon monoxide and 98% by volume of nitrogen, a change in the activity is observed: coz 230 ° C I5.3bo "e. PRI me R 7. The catalyst was prepared by the method described in Example 3, however, a solution of metallic nitrates was deposited with copper, 2% manganese, and 0.2% Nickel. The catalyst has a pore volume of 0.29, strength at. Ezhatiy 6.8 kg / mm and the following composition, weight :. Copper aluminate Manganese aluminate Nickel aluminate Alumina Rest Catalysts activity: And 1954; And ,,, 365С. Treatment of the catalyst in a reducing atmosphere (compare with example 6) does not lead to a change in activity. Example 8 The catalyst was prepared by the method described in Example 3, however, a solution of metal nitrates was coated with 8% copper,% copper, 0, and nickel. The catalyst has a volume of / 0.29, compressive strength of 2.8 kg / mm and the following composition, weight: Copper aluminate 22.9 manganese aluminate 12.6 Nickel aluminate 1.2 Alumina Remaining Catalyst activity: 225 ° C; E5, eX380 ° C. As a result of the reductive treatment of the catalyst (cf. example 6), its activity remains almost unchanged. Example 9 (comparative) The catalyst is prepared by the method described in Example 3, however, 121 MEDIUM 6% manganese, 0.6 nickel is applied to the solution of metal nitrates. The catalyst has a pore volume of 0.28; compressive strength 1.27 kg / mm and the following composition, weight: Copper aluminate G, 3 Manganese aluminate 18.9 98 Nickel aluminate 1.8 Aluminum oxide Remaining Catalyst activity: Igpt 235 ° С; And “„ ex 00С. After its reductive treatment (compare with Example 6), the catalyst activity: I5oCo215C; IddhexZb5 ° C, PRI me R 10 (comparative). Before the decomposition of nitrates, Ce (NO,) X is dried, the formed bodies are heated with air up to 500 hours, respectively, 800 ° C. Catalyst activity: And coco ZOCH; And 5 ° C; Idohexbioos .; Example 11. The catalyst obtained in accordance with Example 3 by impregnation is applied with an aqueous solution of cerium nitrate 2,4-. 6% cerium. At the same time, each kilogram of catalyst is impregnated with an aqueous solution of Ce (N03) 3 bNoO (260 cm3). Concentration of Ce (MOH) 3 bbLO in solution to obtain a 2% content of Ce 63.5 g; for H-130.6 g; for 6% Ce - 20i, 0 g. The applied cerium salt is dried for 32 hours at YO ° C and then by salt for 3 hours at 250 ° C and the salt is decomposed for 10 hours at 500 ° C. Immediately thereafter, calcined for 10 hours uri 800 ° C .. The activity and compressive strength of the catalysts obtained by this method, as well as their composition, are given in table. 1 and 2 respectively. Table 1
    The catalyst is Ce CuA1204 | mpA120 M | A120 | CeAUzOrmep 12. Pure, - not containing alkali metal compounds and silicates, alumina is mixed with water until a paste is obtained, which is dried at. The dried mass is crushed and after adding 5% by weight of graphite, it is pressed into cylindrical granules with a length of 3 mm and a diameter of 3 mm. After burning, no graphite is calcined while the granules are heated for 20 hours, after which mechanically stable molded granules are obtained. Impregnated with a solution of metal nitrate,% copper, 2.9t% manganese and 1.571 nickel are applied to these granules. The metal nitrates applied are decomposed by heating to form metal oxide. Immediately thereafter, the catalyst is calcined for 18 hours at 800 ° C. Catalyst activity: AND AND .. P p, and meper 13 The catalyst is prepared analogously to example 12, however, the deposited metal nitrates are decomposed into metal oxides at 600 ° C. sateM calcined for 18 hours at. Catalyst activity: spgl 200; C; . P p and measures 1h. The catalyst was prepared analogously to example 12, however, after decomposition from the nitrates of the ortals, heating the catalyst was calcined for 18 h at. Catalyst activity: And - ,, gd310 C; I5 hex 70C. PRI me R 15 (in accordance with the present invention). The catalyst is prepared analogously to example 12, only after decomposition of the metal nitrates deposited on the mold granules by heating, the catalyst is calcined at 1200 ° C for 18 hours. HSOCO ZOC Catalyst activity: Ivohex / OC
    权利要求:
    Claims (5)
    [1]
    * 1. The catalyst for the survival of carbon monoxide and hydrocarbons, consisting of copper, nickel and manganese compounds on a support - alumina, characterized in that, in order to increase the stability of the catalyst, it contains copper as compounds , nickel and manganese, their aluminates, and as a carrier, alumina, free from alkali metal compounds and silicates, in the following. weight, D: Aluminate Aluminate Aluminate
    Coal-free alumina
    eleven; 4-2 * 2.9
    0.6-4.7 manganese nickel copper 6.3-12.6 times alkaline metals and silicates
    [2]
    2. The catalyst according to π. 1, characterized in that, in order to
    - increase the activity of the catalyst, 4 it additionally contains 3.1-9.2% of mixed ceria-aluminum oxide.
    [3]
    3. A method of producing a catalyst according to π. 1 by impregnating the carrier with aqueous solutions of copper, nickel and manganese nitrates, followed by decomposition of salts on the heating medium;
    . lowering at 300–600 ° C and calcining the formed oxides at 800–12 ° C for 18 h, due to the fact that, when the catalyst is readily baked, the support is calcined for 20 h at 1000–1200 ° C FROM.
    [4]
    4. The method according to PP. 2-3, characterized in that, in order to obtain a catalyst for the survival of carbon monoxide and hydrocarbons with increased activity, the catalyst is additionally impregnated with an aqueous solution of cerium nitrate, dried at.
    '140 ° C for 32 hours, decompose cerium nitrate. First at 250 ° C for 3 hours, and then at 500 ° C for 10 hours, followed by calcination at 800 ° C for 10 hours.
    Priority on points:
    05/09/73 1 and 3
    03/14/74 for PP. 2 and 4 liters and with the aim of a half-elevated stapered front impregnated with SU "1041019
    J to aluminum manganese nickel copper
    [5]
    5.1
    2.94
    1,67
    Rest
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    同族专利:
    公开号 | 公开日
    BR7403750D0|1974-12-03|
    CS194704B2|1979-12-31|
    NL7405848A|1974-11-12|
    PL94707B1|1977-08-31|
    IL44733A|1976-08-31|
    NL171128C|1983-02-16|
    FR2228539A1|1974-12-06|
    ATA376674A|1977-07-15|
    IL44733D0|1974-06-30|
    GB1457820A|1976-12-08|
    CH595136A5|1978-01-31|
    FR2228539B1|1980-12-12|
    RO71152A|1980-10-30|
    DD111234A5|1975-02-05|
    IT1011404B|1977-01-20|
    JPS5715934B2|1982-04-02|
    AT342011B|1978-03-10|
    US3923690A|1975-12-02|
    SE396018B|1977-09-05|
    JPS52113391A|1977-09-22|
    CA1022529A|1977-12-13|
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    US20070060472A1|2003-04-29|2007-03-15|Johnson Matthey Public Limited Company|Manganese ozone decomposition catalysts and process for its preparation|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19732323262|DE2323262C3|1973-05-09|Supported catalyst|
    DE19742412162|DE2412162C3|1974-03-14|Supported catalyst|
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