• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Catalyst for the synthesis of ammonia from hydrogen comprises (1) as support on graphite containing carbon having (a) a basal plane surface area of at least 100 m 2/G (b) a ratio of BET surface area to basal plane surface area of not more than 5:1 and (c) a ratio of basal plane surface area to edge surface area of at least 5:1 and (ii) as active component (a) 0.1 to 50% by weight of a transition metal and (b) 0.1 to 4 times by weight of (a) of a modifying metal or ion selected from the alkali or alkaline earth metals or ions. The modifying metal or ion is actively associated with the transition metal rather than the support.
    公开号:SU904505A3
    申请号:SU772541696
    申请日:1977-11-03
    公开日:1982-02-07
    发明作者:Айвор Фостер Алан；Гордон Джеймс Питер；Джеймс Маккэрролл Джон；Роберт Теннисон Стефен
    申请人:Дзе Бритиш Петролеум Компани Лимитед (Инофирма)；
    IPC主号:
    专利说明:

    (54) CATALYST FOR. SYNTHESAMMIAKA
    one
    This invention relates to catalysts for the synthesis of ammonia.
    It is known that in the Haber processes, for which nitrogen and hydrogen are used as raw materials, along with other 5 promoters, such as alumina, a potassium-promoted iron catalyst is used. These catalysts are reduced from powdered iron oxides before application and used under severe conditions, for example, at pressures up to 300 atm and temperatures of 450-500 ° C SP.
    The reaction Nj + 3Hj 2NH.j is high exotherm-IS, and thus the equilibrium is shifted to the right at lower temperatures. However, the lack of activity of the iron catalysts at low temperatures (400 ° C) does not allow 20 to achieve equilibrium in the short time during which the reactants are in contact with the catalyst.
    The closest to the proposed technical sui; and the effect is achievable is a catalyst for the synthesis of ammonia, which contains: at least one alkali metal from group 1A of the Periodic Table of the Elements at least one compound, preferably halide, oxide or transition metal sulfide from groups 4B, 5B, 6B, 7B and 8; graphite. In the known catalyst, the alkaline promoter is present in a free metallic state and acts as an electron donor, and graphite is an acceptor. At a pressure of -0.8 atm and a ratio of N, / N 1/3 for a known catalyst, the ammonia content in the exhaust gas is 0.13% t23.
    A disadvantage of the known catalysts is the presence in their composition of an alkaline promoter in the form of a metal, which makes them very sensitive to moisture and air, and the investigator;
    but, unstable. In addition, the preparation of such a catalyst involves the time-consuming operation of dispersing the alkali metal in vacuum, in an inert gas atmosphere, or evaporating from a solution in liquid ammonia.
    The aim of the invention is to increase the activity and stability of the catalyst.
    This goal is achieved by the fact that the catalyst for ammonia synthesis, including a transition metal compound and a promoting additive on graphite-containing carrier, contains as a transition metal compound 1-20 wt.% Ruthenium or 10 wt.% Rhodium or 10 wt.% Cobalt, as alkaline or alkaline earth metals or metals from the actinide group in the amount of 0.1–4 h, based on the weight of the transition metal; and, as a carrier, graphite-containing coal, having a ratio of the total specific surface to the main planar surface of from 8: 1 to 1: 1 and the total surface of 150-1300 m / g, in an amount up to 100 wt.%.
    The present invention contemplates the use of a carrier with well-defined surface characteristics and the use of promoter additives in the form of ions, and not in the form of metal, which allows the promoter to be introduced by conventional impregnation. The interaction of the transition metal with the promoter ions and with the carrier, which has strictly defined surface characteristics, provides an increase in the activity and stability of the catalyst. Thus, the ammonia content at the outlet at a pressure of 5.4 atm for the catalyst according to the invention is 4.50% and, in addition, the catalyst is resistant to impurities of carbon monoxide and moisture.
    The carrier used in the proposed catalyst can be obtained by a known 1z1 method, which includes the following operations: initial heat treatment of activated carbon in an inert atmosphere at 900-3000 C, oxidation stage at 300-1200С and subsequent heat treatment in an inert atmosphere at SOOO-ZOO S, mainly at 4OOh2100 ° С, the Initial activated carbon has a common surface (according to BET) 500,; This method results in a carrier having the main
    the planar surface determined by the heat of adsorption of n-dotriacontan from a solution in n-heptane is not less than 100 m / g, the ratio between the total surface determined by the BET method and the main plane surface is not more than 5: 1 and the ratio between the main plane surface and the edge surface defined by heat
    adsorption of N-butanol from n-heptane, not less than 5: 1.
    An example. Activated charcoal is heated to 900 ° C
    0 in nitrogen (to remove unwanted, organic impurities), and then heat treated to 1500 ° C in argon and oxidized in air at up to 23% weight loss of 5. The oxidized carbon is further heated to 1700 ° C in argon and crushed to 16-30 mesh.
    The carrier obtained has a total surface (BET) of 565 m / g, a main plane surface of 218 m / g and an edge 8.
    The catalyst is then prepared according to the following technology.
    The carrier is impregnated with a 0% aqueous solution of ruthenium trichloride. The water produced is evaporated in a rotary evaporator, the material is dried in an oven at 110 ° C and then reduced in a stream of hydrogen at 450 ° C for 2 hours.
    The impregnation and recovery operations are then repeated.
    Potassium is added by impregnation with a 20% potassium nitrate solution followed by evaporation and drying.
    The resulting catalyst contains 16.6 wt.% Ruthenium and 9.6 wt.% Potassium.
    The catalyst is then used in the reaction for the formation of ammonia from a stoichiometric mixture of nitrogen and hydrogen under various conditions of temperature, volumetric velocity and pressure.
    The results obtained for the catalyst of example 1 and the known industrial iron catalyst are shown in Table 1. Example 2.5% by weight of ruthenium is added to activated carbon thermally treated at 2600 ° by single-step impregnation according to the method described in example I. After reduction operation, 10 weight, 7, rubidium is added from an aqueous solution of carbonic rubid. After drying, the catalyst is further heat treated to nitrogen. The catalyst is then restored in a stream of water (0 ml / min) by programmed raising the temperature to 450 ° C at a rate of Io C / min. At 450 ° C, hydrogen is replaced by a mixture in the ratio of 3: 1 at a pressure of 5.17 atm. On a catalyst bed weighing g at a space velocity of 1000 h, the yield of ammonia is 3.48Z at 360 ° C. Example 10 wt.% Rubidium from an aqueous solution of rubidium carbonate is added to activated carbon thermally treated at 2600 ° C. After drying and heat treatment, 5% by weight of ruthenium from a toluene solution of ruthenium III acetylacetonate III (Acac) is added under nitrogen and reduced in hydrogen at. The catalyst was tested as in example 2. The yield of ammonia was 4.27% at CJSC. EXAMPLE 4-15. Examples 4-15 show the effect of metals in groups 1A, 2A and the lanthanide-actinide series as promoters, the results of the research are presented in Table. 2 Catalysts are prepared by analogy with example 3, i.e. the promoter is added first, and ruthenium from the toluene solution of Ru (Acac) is second. All catalysts except for those specified in examples 12–15 s ;; they contain 5 wt.% Ruthenium and 0.12 mol.% Promoter, equivalent to 10 Bes.% Rb. Examples 16-21. Examples 16-21 show the effect of carbon carrier parameters. As the starting material, activated charcoal was used, which is modified by heat treatment to IPOOC in argon, followed by oxidation in air at up to 20% weight loss and secondary heat treatment in argon to 1500-1700 ° С. Rubidium and ruthenium are added as in Example 3 in order to obtain catalysts containing 5 wt.% Ru and 10 wt.% Rb. The results are presented in Table. 3 Examples 22-25. The effect of carrier parameters on the activity of catalysts containing 10% Ru / / 10% K and prepared according to Example 2 is shown in Table. 4. Examples 26-30. The examples show the effect on the activity of the various starting compounds from which a promoter additive is applied using sodium as a promoter. The catalysts contain 2.7% by weight of sodium and 5% by weight of ruthenium and are obtained according to Example 3. The results obtained are presented in Table. 5. Examples 29 and 30 show the importance of removing ions of a halide compound, in particular chloride, if used in the preparation of the catalyst. PrimrrZ. Catalyst resistance to carbon monoxide and water poisoning. A catalyst containing 5% Ru / 10% Rb at AU / 2600 is prepared analogously to Example 3. The catalyst used is an ammonia yield of 4.3% at a pressure of 5.17 atm and a stoichiometric cootHomeHHH Na / Hj l: 3. The feed is then changed to volumes / min of carbon monoxide. After 3 days no deterioration in catalyst activity was observed (4.3% NH, with). For comparison, the activity of the extracted magnetite catalyst under similar conditions drops from 1.32% NH, to 0.18% NH, in those NH to 0.18% NHj 100 min. Resistance against boi poisoning is investigated on the same catalyst (5% Ru / 10% Rb). Withstand general reaction conditions (5.17 bar, 40 ° C) and get a yield of ammonia of 4.2%. The water in the reactor is then reduced. 100 ml of water is introduced into the gas mixture. When the pressure is raised again, the output of the miak drops slightly, but returns to its original value after 15 minutes. Examples 32-41. Examples 32-41 show the use of other transition metals besides ruthenium. 790 Catalysts are prepared using AU / 2600 C as a carrier. PeroxonHbfH metal is introduced first from an aqueous solution. The catalyst is then dried and reduced under a stream of hydrogen. The promoter is added with this from an aqueous solution and the catalyst is heat treated in nitrogen at 500 ° C (the Table concentration of 2 58 motors in these examples is 0.12 mol.%). The results of the experiments are summarized in Table. 6. Examples 42-60, In table. 7 shows the activity of catalysts with different ruthenium and rubidium contents. In each example, the catalyst is prepared analogously to example I. Table I
     Pack corresponds to the temperature at which maximum conversion is achieved.
    Table 3
    II
    90450512
    Table 6
    Table 7
    权利要求:
    Claims (3)
    [1]
    1. US Patent No. 3472794, cl. 252-459, publ. 1969.
    [2]
    2. The patent of England R 1367112,
    cl. With I And, pub. 1971 (prototype)
    [3]
    3. The UK patent number 1468141, cl. C 3 P, published. 1975.
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    同族专利:
    公开号 | 公开日
    DE2748972A1|1978-05-11|
    CS225807B2|1984-02-13|
    NO773743L|1978-05-05|
    IN146975B|1979-10-20|
    ES464035A1|1978-07-16|
    NZ185598A|1980-04-28|
    FR2369872B1|1984-10-12|
    IE46074B1|1983-02-09|
    AU515799B2|1981-04-30|
    JPS5916816B2|1984-04-18|
    PT67232B|1979-04-16|
    BE860440A|1978-05-03|
    ZA776369B|1979-06-27|
    JPS5357193A|1978-05-24|
    CA1097887A|1981-03-24|
    BR7707354A|1978-06-20|
    MX147295A|1982-11-10|
    AU3022577A|1979-05-10|
    FR2369872A1|1978-06-02|
    IT1143770B|1986-10-22|
    PT67232A|1977-12-01|
    US4250057A|1981-02-10|
    NO148984C|1984-01-25|
    NL7712072A|1978-05-08|
    IE46074L|1978-05-03|
    US4163775A|1979-08-07|
    PL116384B1|1981-06-30|
    NO148984B|1983-10-17|
    PL201877A1|1978-06-19|
    DE2748972C2|1990-05-17|
    GB1565074A|1980-04-16|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB45711/76A|GB1565074A|1976-11-03|1976-11-03|Process for the production of ammonia|
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