• 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:
    Catalysts as prepared by impregnating a carbon support with a halogen-containing compound of Ru, reducing the Ru to metal with hydrogen, and then depositing an alkali metal and a barium compound. The catalysts may be used for ammonia production.
    公开号:SU1433394A3
    申请号:SU843815214
    申请日:1984-11-15
    公开日:1988-10-23
    发明作者:Джеймс Мак Кэррол Джон；Роберт Теннисон Стефен；Филип Уилкинсон Николас
    申请人:Дзе Бритиш Петролеум Компани П.Л.С. (Фирма)；
    IPC主号:
    专利说明:


    O1
    The invention relates to methods for p) riveting the deposited low-temperature catalysts for ammonia synthesis deposited on coal,
    The purpose of the invention is the preparation of a catalyst with increased activity at 300-450 ° C due to a change in the sequence of operations and the use of a carrier with certain physicochemical parameters.
    Example 1. Coal used as a carrier is prepared from Deguss commercially available extruded activated carbon under the name Katepon BKIV. This has the shape of extrudates 4 mm in diameter and typical values of the specific surface measured by the BET method, the main plane and the edge, 939, 182 and 32 m / g, respectively.
    Activated carbon is subjected to heat treatment as follows, the gels are heated from room temperature in a stream to temperature for 1 h. After reaching the temperature. ø temperatures, the coal is cooled in a flow of gels to 25 ° C. Then the coal is heated in an air atmosphere in a muffle furnace at a temperature of approximately the time required to obtain a weight loss of 20% by weight. Then the coal is heated in an atmosphere of helium to a temperature of 1800-1850 C, as in the heating stage in helium. Coal is cooled to k4 ambient temperature in the atmosphere
    G € | LIA,
    : Graphite-containing coal has barely the characteristics: specific venus | brychny according to the BET method 710 specific surface area, measured by the main plane method, 389 m / g specific surface area, measured according to the crust method, 2.3 MVr; the ratio of specific surfaces measured by BET methods and the main plane 1.8; specific surface ratio
    ti, measured by the method of the main plane, to the surface by the edge method 169,
    Coal is impregnated with an aqueous solution of ruthenium trichloride in order to apply the amount of ruthenium trichloride corresponding to 10 May, h, Ru and per 100 ma.h. coal The water from the coal is evaporated in a rotary evaporator and the coal is then dried in
    j 0
    5 o
    Q
    five
    45
    50
    55
    the furnace at, then it is restored by the flow of hydrogen at for 2 hours,
    After cooling, the carbon is impregnated with an aqueous solution of potassium nitrite and barium in the ratio indicated in Table 1,
    Then, the impregnated coal is crushed and particles of 16-30 mesh (1.19-0.59 mm) are used in the ammonia production experiments. A sample (1.6 cm) of the impregnated coal, obtained in accordance with the method described above, is placed in a cylindrical microreactor adapted to supply a gas stream to it. Impregnated coal is activated by passing a stream of hydrogen over it with a flow rate of 60 ml / min, raising the temperature from 3 C / min to 450 C. and keeping it at 450 ° C for 1.25 hours. After that, the water is terminated.
    Then a mixture of hydrogen and nitrogen at a molar ratio of 3: 1 is passed over the resulting activated catalyst. mash at a pressure of 5 bar (), temperature 320 C and gas hourly space velocity (GHSU) 1300 h
    The activity values, measured as the amount of ammonia in the gas stream leaving the reactor, are shown in Table 1,
    Examples 2-4. The catalyst was prepared as in Example 1, only using different ratios of potassium and barium nitrite.
    The results of testing the catalysts and their composition are given in Table 1,
    For example, the catalyst is prepared as in example 1, only potassium nitrite is replaced with cesium nitrate.
    Example 6. A catalyst is prepared analogously to example 3, but is tested on a mixture of hydrogen and nitrogen at a molar ratio of 1: 1, bar (abs.) And a space velocity of 30,000 h,
    The test results and the composition of the catalyst are given in Table 2.
    Example. The catalyst was prepared analogously to example 5, test conditions similar to example 6.
    Examples 8-9. The catalysts were prepared as described in example 5, by varying the ratio of cerium nitrate and barite nitrite, as tested according to example 6,
    The test results and the compositions of catalysis of the ator mass are presented in Table 2,
    Example 10 (comparative). The catalyst is prepared according to a known method, i.e. using successively aqueous solutions containing 2 wt.%. Ba calculated on carbon in the form of Ba (COe), 4 wt.% Ru calculated on carbon in the form of RuCla, and 12 wt.% K calculated on carbon in the form of KOH. The coal is dried after each step of deposition, but also using heat treated carbon instead of activated carbon as a carrier.
    The starting material for the obtained heat-treated coal is the commercially available Degussa activated carbon called Katepon VK 16, which is extruded with a diameter of 1.6 mm and typical specific surfaces measured using the BET methods of the main plane and the edge one, 1214, 164 and 32, respectively The charcoal is heat treated in a stream of nitrogen in a furnace at a temperature of about 1700 ° C (residence time in the hot zone is approximately 45 minutes), and then rapidly cooled to room temperature. The coal is then heated in an air atmosphere in a rotating tube furnace to a maximum temperature of 540 ° C with a total residence time of approximately 5 hours to obtain a total weight loss of 20 May. The heating stage in nitrogen is then repeated to a temperature of about 1850 ° C.
    After heat treatment, the coal has the following properties: specific surface according to the BET method 535 specific gravity on the surface, measured according to the method of the guilty plane, 223 specific surface measured using the regional method,, 7; the ratio of specific surfaces measured by the BET and main plane methods, 2.4; the ratio of the specific surface measured by the method of the main plane to the surface measured by the edge method, 131.
    This coal is activated as in example 1.
    The resulting catalyst is tested in a cylindrical microreactor as in example 1.

    ten
    15
    20
    25
    thirty
    35
    40
    45
    50
    55
    The test results are presented in table 3.
    Example 11 A catalyst is prepared as in example 1 using heat-treated coal obtained as in example 10, with the amounts of KNOj and Ba (NO) 2 and the content of ruthenium corresponding to the known method.
    The catalyst is activated and tested as in Example 1 (Table 3).
    Example 12 (comparative). Prepare the catalyst using the same base as in Example 10. The catalyst containing Ne and K is prepared using solutions of the same concentration of Ru and K as in Example 10. However, Ba was not applied to the catalyst.
    AKTiiBHOCTb catalysts investigated in the same way as in example 10,
    Table 3 gives a comparative characteristic of catalysts. Comparison of the results of Examples IO and 11 shows a significant increase in the maximum degree of ammonia conversion and a decrease in temperature required to obtain the maximum degree of conversion when using the proposed catalyst as compared to the catalyst prepared by a known method.
    A comparison of examples 10 and 12 shows that using the same support for catalysts prepared in accordance with a known method does not offer advantages over catalysts prepared using Ru and K alone.
    Example 13. Thermally treated coal is prepared as in example 10. Based on the coal, the catalyst is prepared as follows. The carbon is impregnated with an aqueous solution of ruthenium trichloride in order to obtain a theoretical content of Not 10 hours, per 100 parts of carbon. Water is evaporated from the impregnated carbon in a rotating evaporator and the impregnated coal is then dried in an oven at 100 ° C. It is then reduced in a stream of hydrogen at 200 ° C for 2 hours,
    After cooling, the carbon is impregnated with an aqueous solution containing CsNO. and Ba (NO.i) 2-HiO in the calculation of 10.5 hours
    Ba and 51 parts Cs per 100 parts carbon, then dried and heated.
    After that, the coal is crushed and particles with a size of 16-30 mesh (1.19 - 0.59 mm) are tested by ammonia in a cylindrical microfiber, as in Example 1.: The maximum ammonia content in
    The catalyst is obtained from coal as follows.
    The coal is washed twice with a 5% solution of concentrated HCl. Each time the acid is decanted, and in the end it is washed with distilled water 4 X 200 cm. Coal is dried in a flask with. open throat during the night in va
    inlet gas and temperature, with a vacuum furnace at 100 C. Then coal
    The maximum concentration of ammonia obtained is given in Table 4; EXAMPLE 14. The experiment was carried out as in Example 13, but using activated carbon according to Example 10, which was not subjected to heat treatment, and using | 0.908 g of catalyst. I The results are shown in table 4. I Example 15 (comparative) Preparing a catalyst using heat-treated as the carrier; coal used in Example 10 | Barium, ruthenium and alkali metal — coal is carbon in the same way as in the known IHOM method. However, to obtain more similar conditions, for comparison, solutions containing
    impregnated with ruthenium trichloride solution in order to precipitate ruthenium per 100 h of carbon for 10 hours.
    A solution of RuClj is obtained in distilled water, and the excess solvent is removed in a rotary evaporator, RuClo is reduced in a stream of hydrogen using normal conditions for reduction: increase
    20 temperatures at 1 ° C / min to 200 ° C and
    Store at 200 ° C for 5 h. Coal ruthenium on coal is cooled with nitrogen.
    After cooling, the carbon is impregnated with an aqueous solution so as to separate 51 hours of cesium in the form of g and 10.5 parts of barium in the form of Ea (BUT per 100 parts of carbon. Water is removed in a rotary evaporator as described above by using the Method
    | Ba (NO, j) and RuCl. Instead of solution
    1 potassium salt using a solution of CsOH, 30 higher vacuum and temperature
    containing 51 wt.% Cz by weight of coal. (vacuum 400 mbar, temperature at
    ; Used solutions of Ba (NO-,),
    ; CsOH and ruthenium trichloride choose
    so that to obtain the content of Ba -10.5 hours for 100 hours of coal, the content of Cs is 51 hours for 100 hours of coal and the content of RU 10 hours for 100 hours of coal.
    The catalyst is tested in the process.
    ammonia production as in Example 1
    selection 95 ° C).
    The catalyst is then crushed and sieved to obtain samples 315 c. .16-30 mesh (1, .6 - 0.59 mm). These samples (0.974 g) are tested for activity in the synthesis of ammonia in a tubular microreactor. The amount of catalyst used corresponds to a fixed bed volume of 1.62 cm.
    The obtained test results are shown in Table 4.
    Example 8 p 16. A carbon nasal is prepared from Katepon RK 16 activated carbon (Degussa). It is subjected to grinding to a particle diameter of 1.6 mm. Surface area, measured according to the BET method, 1214. The specific surface measured by the base plane method is 164 MVr. Specific surface 5 measured by the edge method, 32.
    The ratio of specific surfaces, measured by the BET method and the basic plane method, is 7.4. The ratio of specific surfaces, measured - by the method of the main plane and by the edge method, 5.13.
    impregnated with a solution of trichloride ruthenium in order to precipitate 10 parts of ruthenium per 100 h, carbon.
    A solution of RuClj is obtained in distilled water, and the excess solvent is removed in a rotary evaporator, RuClo is reduced in a stream of hydrogen using normal conditions for reduction: increase
    temperatures at 1 ° C / min to 200 ° C and
    Store at 200 ° C for 5 hours. Ruthenium on coal is cooled with nitrogen.
    After cooling, the carbon is impregnated with an aqueous solution so as to set aside 51 hours of cesium in the form of g and 10.5 parts of barium in the form of Ea (BUT per 100 parts of carbon. Water is removed in a rotary evaporator as described above by using the Method
     (vacuum 400 mbar, temperature at
    selection 95 ° C).
    The catalyst is then crushed and sieved to obtain samples 315 c. .16-30 mesh (1, .6 - 0.59 mm). These samples (0.974 g) are tested for activity in the synthesis of ammonia in a tubular microreactor. Amount is40
    catalyst used corresponds to a fixed bed volume of 1.62 cm.
    The composition of the catalyst is presented in table.5.
    The catalyst is activated as a result of the restoration by a given program of a temperature change in a stream of hydrogen of 60 cm / min at a pressure of 1 bar (abs.). The temperature is increased at a rate of 5 ° C / min to 450 ° C and then maintained at this temperature for 1.25 hours. A mixture of hydrogen and nitrogen at a molar ratio of 3: 1 is passed over the catalyst at a pressure of 6 bar (abs.) And Noah gas speed of 1300 hours With different
    Temperatures determine the percentage of ammonia in the stream from the reactor.
    The results are shown in the tablob.
    /14
    Example 17 (known method). The catalyst is prepared using carbon as in the carrier of example 16, barium, ruthenium and alkali metal are deposited on carbon in a known manner. However, for a more accurate comparison with Example 1, a CZOH solution is used instead of a potassium salt solution.
    Such solutions are used to apply 10.5 bari in the form of Ba (IO) 2 10 h, ruthenium in the form of Ni, and 51 h, cesium in the form of CsOH per 100 h, carbon.
    This catalyst in the amount of 0.908 g is tested in the process of obtaining ammonia as in Example 16.
    PRI m e. P 18, the Catalyst is prepared analogously to example 16, except that. activated carbon is heat treated in



    Three stages analogously to Example 1, in accordance with which coal is heated successively in an inert, oxidizing and inert atmosphere.
    General properties for this portion of thermally treated coal: specific surface area, measured by the BET method, 560 m / g; specific surface area measured by the base plane method, 235 specific surface area, measured using the edge method of 3.4 MVr; the ratio of specific surfaces measured by the BET methods and the main plane, 2.4; the ratio of specific surfaces measured by the method of the main plane and by the edge method, 69, the Catalyst is then prepared and tested as in Example 1 6,
    Example 19 (known method) The catalyst was prepared analogously to example 17, the sequence of stages corresponds to a known method, but





    The compositions of catalysts PP used thermally treated
    the coal obtained as in example 18, j frames 16-23 and their activity are presented in table.
    EXAMPLE 20 Catalyst is prepared as in Example 18, however, the starting material for the production of thermally treated carbon is activated carbon BKTU (Degussa), /
    Coal is in the form of particles 3–4 mm in diameter and has specific surface area values measured by the BET methods, the main plane and
    50
    regional, 840, 168 and 36 m / g, respectively.
    Coal is subjected to a three-stage heat treatment (inert g az.
    55
    5 and 6,
    Example 24 A catalyst is prepared analogously to example 16, but using 10 hours, Ru, 5 hours, Cs and 5 hours, Ba, which corresponds to a total promoter content of 0.01 mol per 1 mole of carbon. The highest catalyst activity is in the region of 365-380 ° C, where the ammonia yield is 3.1%,
    As follows from the presented data, the highest yield of ammonia is reached at 370 ° C. P 7 bar (abs,), V 30,000 hours and is
    oxidation, inert gas) as in example 1,
    After heat treatment, carbon has the following characteristics: udna na. surface, measured by the BET method, 643 m / g; measured by the Vr method; on the spot
    on the surface, the main plane, 438 m on the surface, measured by the edge method, 3.4, the ratio of specific surfaces, measured by the BET methods, and the main plane, 1.5; the ratio of specific surfaces, measured by the method of the ground plane and the edge method, 129
    The coal is washed twice with a 5% -sized solution of concentrated HC1. Each time the acid is decanted and then the coal is washed with distilled water 4 X 200 cm-. Coal in an open-mouth flask overnight in a vacuum oven at,
    The impregnated solution contains 15h. KB as KNO instead of CsNO ,. The catalyst is tested in a tubular ticroreactor. The amount of catalyst used is 0.720 g, which corresponds to the volume of fixed 1.62 cm of catalyst,
    PRI me R 21 (a known method) The catalyst was prepared analogously to example 19, but instead of using CsOH, a solution of KOH at a rate of 15 parts by weight. on 100 mach., carbon.
    Example 22. The catalyst was prepared analogously to example 16, only deposited May 3, h, ruthenium. on May 100, h, carbon ,,
    Example 23 A catalyst is prepared as in Example 16, only 15 mph is deposited, ruthenium at 100 May, h, carbon.
    The compositions of the catalysts PP examples 16-23 and their activity is presented in table.
    5 and 6,
    Example 24, The catalyst is ready in t analogously to example 16, but using 10 h, Ru, 5 h, Cs and 5 h, Ba, which corresponds to a total promoter content of 0.01 mol per 1 mol of carbon. The highest catalyst activity is in the region of 365-380 ° C, where the ammonia yield is 3.1%,
    As follows from the presented data, the highest yield of ammonia is reached at 370 ° C. P 7 bar (abs,), V 30,000 hours and is
    12% vs. 3.7% by a known method.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    I. A method for preparing a catalyst for ammonia synthesis, comprising; impregnation of the carbon carrier with solutions of rami of ruthenium chloride, alkali metal salts and barium, drying and reduction with hydrogen, characterized by the fact that, with the aim of preparing i 45P C, carbon-I carrier in the beginning is impregnated with ruthenium chloride solution at a rate of 3–15 May, h, ruthenium at 1OP mAh, I carbon followed by suicide and reduction with hydrogen and then chain metal - nit-; rata or potassium nitrite or cesium and
    0.061 0.052 0.039 0.031 0.015
    0.046
    According to the proposed method
    1 0.0617 0.054
    Barium nitrate - brite salts in the calculation of 0.01-0.062 mol of salts per 1 mol of carbon with a molar ratio of alkali metal and barium equal to 0.33 - 13.02: 1.
    2, Method POP.1, differing from that with the fact that a carrier with a specific surface area measured by the BET method, equal to 535-710 with the ratio of the specific surface area measured by the BET method to the value of specific surface, measured by the method of the main plane, equal to 1.5-2.4, and the ratio of the value of the specific surface, measured by the method of the main plane to the value of the specific surface, measured by the edge method, equal to 69.0 - 169.0.
    Table 1
    3.53 4.05 3.42 3.64 0.92 2.31 2.61 2.35 1.21 1.19 4.47.
    7.0 5.32
    Table 3
    33394
    I 2 Continuation of table 1
    Table2
    Table 4
    13
    143339414
    Table3
    Note, The content of ruthenium in the catalysts of Examples 16-21 is 10 hours, per 100 hours, carbon-a-1 polymers 22 and 23 contain ruthenium 3 and 15 hours per 100 hours, carbon.
    npH-jt., С / g NHjIt., С / И Гш, Тг, О / NH, and .с / янн T, с /, нн, I t, ci% tffljj t °, c / 4Hj I t, c /; i rH} j tc / .m.
    Table
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    同族专利:
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    GB1565074A|1976-11-03|1980-04-16|British Petroleum Co|Process for the production of ammonia|
    US4142993A|1977-12-07|1979-03-06|The Research Council Of Alberta|Transition metal catalyst|CA1290316C|1985-06-27|1991-10-08|Alain Louis Pierre Lenack|Aqueous fluids|
    GB8703323D0|1987-02-13|1987-03-18|British Petroleum Co Plc|Separation process|
    GB8719840D0|1987-08-21|1987-09-30|British Petroleum Co Plc|Separation process|
    EP0840646A1|1995-05-31|1998-05-13|The University Of Virginia Patent Foundation|Catalyst and process for preparing ammonia|
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    EP3872036A1|2018-10-23|2021-09-01|Tsubame BHB Co., Ltd.|Ammonia synthesis system and ammonia production method|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB838307612A|GB8307612D0|1983-03-18|1983-03-18|Ammonia production and catalysts|
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