• 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 precursor units, e.g. for ammonia synthesis catalysts, comprise an iron oxide composition in the form of sintered shaped units of substantially uniform cross section having a plurality, e.g. 13 to 50 or more, through passages of substantially uniform cross section. The passages preferably have a diameter of less than 1.5, particularly less than 0.7, mm.
    公开号:SU1544175A3
    申请号:SU864028561
    申请日:1986-11-06
    公开日:1990-02-15
    发明作者:Тистлетвейт Теренс；Херман Хендрик Тер Маат Йохан；Джон Дэвидсон Питер
    申请人:Империал Кемикал Индастриз Плс (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to catalysts based on sintered iron oxide with promoters of different shape, and can be used in the production of ammonia.
    The aim of the invention is to increase the activity of the catalyst on the basis of the proposed precursor for making estimates of the latter in the form of a certain shape with appropriate geometrical dimensions providing a certain volume of void and density.
    Example 1. Hematite is ground to a fine powder with an average particle size of 3 microns, all particles having a size less than 10 microns. 958 g of milled hematite powder is mixed with 31 g of aluminum oxide trihydrate (А12Оз ЗНгО) and 11 g of calcium carbonate, both of which are pre-crushed to a similar degree of dispersion.
    10 g of a high molecular weight polysaccharide (Zusiplast PSI, supplied
    cl
    s
    Zschimtner und Schwarz, Lahnstein am Rhein, Germany), About g maize starch (Kardek, variety G08010, supplied by CPC W Ltd, Industrial Division, Trafford Park, Manchester, UK) and 130 ml of an aqueous solution containing 96 g of potassium carbonate (, and mixed to a homogeneous paste. The mixture is then extruded at room temperature through a shank extrusion head having 13 wires 0.7 mm in diameter suspended as rods. A cylindrical extrudate having 13 longitudinal holes is cut into sections, dried at 30 ° C for 1. h in an atmosphere with adjustable humidity, after It is heated to 00CC at a rate of 200 ° C / h and maintained at 00 ° C until the starch is completely baked. The molded parts are then treated at 1300 ° C from the air atmosphere for Dh, and then cooled to ambient temperature for b h
    The speckled shaped blocks are cylinders with a length of 6.5 mm and a diameter of 6.5 mm with 13 holes with a diameter of 0.6 mm, a particle density of 4.2, as determined with reference to their volume in mercury at atmospheric pressure, and porosity 0, cm3-g-1.
    Chemical analysis shows that

    The special units have the following composition, mas:
    Fe703 96.9
    CaO0,6
    A1703 2.0
    KaO0,5
    Twelve blocks (approximately 10 grams) are mixed with 65 grams of fused alumina crumbs with an average particle size of 2, -3.35 mm and loaded into the reactor to form a dilute layer 90 mm long and 28 mm in diameter. The speckled blocks are then activated by gradually heating up to 75 ° C for 8 hours and maintaining at this temperature s for 6 hours, at an absolute pressure of 150 bar of a hydrogen-nitrogen mixture (3: 1). The volumetric rate of EO ° recovery is 2ROGO cm3-h-1-h-1,
    The activity of the catalyst for ammonia synthesis reactions is estimated by measuring the concentration of ammonia in the gas leaving the reactor at different
    ,
    ,
    S

    0
    volumetric speeds Reaction conditions: temperature 50 ° С, absolute pressure 150 bar, hydrogen – nitrogen mixture (3: 1).
    The described procedure is repeated using shaped blocks in exactly the same way, except that the extrusion die does not contain suspended wires and, therefore, the shaped blocks do not have through channels.
    The results are shown in Table. one.
    The data table. 1 show the effectiveness of end-to-end channels in increasing the catalytic activity.
    EXAMPLE 2 The procedure of Example 1 is repeated, except that 12 g of ground graphite is introduced into a powder mixture of hematite, aluminum oxide trihydrate and calcium carbonate, and sintering and subsequent cooling is carried out in an atmosphere essentially free of oxygen
    The composition of the obtained sintered shaped blocks is similar to the composition of the blocks of example 1, except that iron oxide is present in the form of magnetite (Fe304). The speckled blocks exhibit activity similar to that shown in Example 1, however, after recovery, it is significantly higher.
    The specimens of examples 1 and 2 have a BET surface area below 1, traces of particles below 20 μm in size, pore volumes of at least 0.02 cm3 with a radius below 10 μm. After recovery, the pore volumes are much higher, at least 0.02 cm3-g-1 have pores with a radius of 0.1-10 microns.
    EXAMPLE 3. The speckled blocks are manufactured according to Example 1, however, with the elution of different relative contents of magnesium alumina spinel, ground to similar hematite, dispersity, into a mixture of hematite - alumina - calcium carbonate.
    In order to evaluate the recovery characteristics of the sintered blocks, a series of blocks are loaded into a cylindrical reactor with a diameter of 27.5 mm and a length of 70 mm to form a randomly compacted layer with a volume of about AO cm3.
    In the first series of experiments (A), when passing a mixture of hydrogen and azo5 .1
    that containing 75 wt.% of hydrogen, through the bed at a rate of 250 l-h-1, the bed temperature is raised to 350 ° C over 3 hours and then raised to 475 ° C over 8 hours.
    In the second series of experiments (B), the layer is heated to 4-75 ° C by passing nitrogen through the layer at a rate of 250 lH-1, and then the nitrogen stream is replaced with a mixture of hydrogen and nitrogen containing 75 masad of hydrogen and kept at this temperature until complete reduction of iron oxide to iron.
    In both series of experiments, after cooling the mixture of hydrogen to nitrogen to room temperature, the latter is replaced by nitrogen flowing at a rate of 200 l / h, and then for 30 minutes the nitrogen is gradually replaced by air. After that, the blocks are examined.
    The results are shown in Table. 2
    For comparison, compositions are also prepared in which aluminum-magnesium magnesium spinel is replaced by magnesia.
    When the recovery method A is carried out on blocks that do not contain lime, the blocks are intact.
    PRI me R 4. Extrudates get analogously to example 1, but using a composition containing 1 wt.% The spinel of magnesium aluminum oxide. A head with 50 wire cores arranged in concentric circles of 29, 14 and 6 around the central rod is used. The head and cores are of such dimensions that, after agglomeration, the extruded blocks have a length and diameter of 8.5 mm, through channels with a diameter of 0.48 mm. Particle density is 4.0 g-cm-, blocks with through channels have a relative pore volume of 0.16, a geometric surface area (GWP) of about 20, and a GWP / (A.HGP) value (where A is the solid surface area cylinder, GP - geometrical porosity of the block), is equal to 17.7. There are 88 holes per 1 cm2 cross section of the block.
    The blocks have the following chemical composition, wt.%:
    Fea0396,4
    A1a032.3
    CaO0,6
    MgO0,3
    KaO0,4
    Q
    0
    five
    5 0 5 0
    five
    1756
    An adiabatic reactor is used to evaluate the activity of each type of catalyst. The bed volume is 23.7 liters and fills the annulus with an outer diameter of 203 mm, an internal diameter of 8 mm and a length of 1015 mm. The starting materials of the catalyst are reduced at a pressure of 80 bar with a gas mixture containing hydrogen and nitrogen at a molar ratio of 2.35 and a flow rate of 300 m3 hr (under normal conditions). The inlet gas temperature is 350 ° C, then it is raised to maintain a water concentration below 2000 ppm. from volume. When the reduction is complete, the inlet temperature is lowered to 350 ° C, and after the steady state is established, the ammonia concentration of the gas leaving the bed is measured as the temperature of the entire bed rises.
    The results are shown in Table. 3
    Measure 5: The procedure of Example 4 is repeated. The size of the blocks obtained, the number and diameter of the through channels, the number of channels per 1 cm2 of the block cross-sectional area and the geometric volume of voids, calculated from the sizes of the blocks and the number and diameter of the through channels, calculated effective activity The randomly laid layer of the blocks relative to the layer of the sintered blocks that do not have through channels are listed in Table. 4. The experimental results obtained in Examples 2 and 5 are in good agreement with the relative activities deduced.
    PRI me R 6 (comparative). Evaluate their own activity, sintering catalysts for ammonia synthesis “
    9bOg of magnetite ore is mixed with 16.0 g of calcined alumina (o / -A1703), 8.24 g of anhydrous potassium carbonate (), 10.8 g of calcium carbonate (CaCOe) and 10 g of magnesium stearate as a binder. . The mixture is homogenized and ground using a vibratory ball mill to a fine powder. All particles have a size below 20 microns and over 50% by weight of particles have a size less than 10 microns. The powder is compacted between two opposing spinning rolls to obtain elongated, (almost cylindrical) blocks with a diameter of about 4.0 mm and a length of about 50 mm. Elongated
    blocks are crushed into shorter lengths of approximately mm. All the resulting short blocks are passed through a 75 mm sieve, and more than 99% of their mass is retained on a 3.35 mm sieve. The blocks are then calcined in air to 1300 ° C to effect agglomeration and, therefore, compaction. As measured by the movement of mercury at atmospheric pressure, the density of the sintered blocks is 4.3 g with a porosity of 0.037 cm3-g 1.
    Chemical analysis of the blocks gives the following composition of the catalyst, May .: CaO0,6
    K-jO0, M)
    , 7
    MR00.27
    3
    Fe703 Else The intrinsic catalyst activity of the sintered products is evaluated by crushing the sintered material to particles between 0.6-1 mm in size. The obtained coarse powder is loaded into a laboratory reactor with a catalyst bed 32 mm long and mm in diameter.
    The crushed material is activated by reducing in a mixture of hydrogen - nitrogen (3: 1) at an absolute pressure of 50 bar, raising the temperature to (75 ° C for 12 hours and maintaining this temperature for 3 hours. The catalyst obtained is used to synthesize ammonia in the reactor at absolute pressure 50 bar and a temperature of 50 ° C with a volumetric gas velocity of 0000 cm3 per 1 g of unrestored crushed material (i.e., starting material of the catalyst) per hour, and the concentration of ammonia in the gas leaving the reactor is measured. moment computed are other ob- sp ace speed initial rate constant per unit weight of the catalyst starting material.
    To assess the degree of decrease in activity, the method of accelerated aging is adopted by raising the temperature to 550 ° C and maintaining this temperature for 6 hours. The temperature is then lowered to 450 ° C and the conversion is measured at various flow rates. Thereafter, the final rate constant per unit weight of the starting material of the catalyst is calculated.
    The catalytic activity of a standard fused catalyst is also determined using the above procedure. In each case, three samples of the test material are used and constant velocities are found from the mean of the determined concentrations of ammonia.
    In tab. 5, the initial and final relative activities are the ratio of the initial and final constant speeds to the initial constant speed of the standard fused catalyst.
    From the data table. 5, it is clear that sintered materials not only exhibit a higher initial activity than standard fused materials, but a decrease in their activity during aging is much smaller.
    The technological scheme, producing about 1000 tons of ammonia per day and using a standard fused catalyst with a particle size of 6-9 mm, includes a synthesis loop operating at a pressure of 131 bar abs. with a circulating intensity of about 26,000 kgmol / h. In such a flowchart, the power required for compression in the circulation of synthesis gas and for cooling in order to reduce the ammonia product is typically 18.6 MW, the heat release from the synthesis is about 30, t MW, the heat released It is usually used to cover this energy requirement and to provide the power and / or heat required to produce synthesis gas.
    Due to the increasing activity when using a multi-hole catalyst instead of a standard fused catalyst, the circulation speed required to obtain the same amount of ammonia can be reduced to 22,000 kg-mol / h while reducing the circuit pressure to 116 bar abs. As a result, the energy requirements for compressing and circulating synthesis gas, as well as for cooling, are reduced to 16.9 MW, and the heat release increases to 30.9 MW. By modifying the circulation pump to allow the circulation rate to decrease to 21,000 kg-mol / h and at the same time, the pressure of the circuit to increase to 121.5 bar abs, can be obtained
    an even more efficient process, since the energy requirements for compressing and circulating the synthesis gas and also for cooling are only 16.1 MW, while the heat output rises to 31 1 MW.
    权利要求:
    Claims (3)
    [1]
    1. A catalyst precursor for the synthesis of ammonia in the form of a catalyst shaped block based on special oxide of iron with promoters selected from the group of aluminum oxides, calcium, potassium and magnesium, and having a constant cross-section, in order to increase activity, the block is made in the form of a cylinder with a diameter of a circle of cross-sectional area
    0
    five
    0
    75yu
    block, corresponding to 6, 5 mm, with a ratio of block length to its diameter 1, and has through channels of constant cross section with a diameter of 0.2-0.6 mm, arranged longitudinally to the block in the calculation of 0-1b7 channels per 1 cm2 area block cross section while maintaining a geometric volume of block voids of 5-22%.
    [2]
    2. Precursor of catalyst pop.1, characterized in that the through channels of the block have a circular cross section with a length-to-diameter ratio of 10.8-32.5.
    [3]
    3. A catalyst precursor according to claims 1-2, characterized in that its density corresponds to, 0-, 2 g-cm-h.
     Percentage by weight of a mixture of hematite - alumina - carbonate, calcium.
    Table 1
    Table 2
    eleven
    Sample
    Without channels6,6
    With 50 channels8,3
    Channels
    Diameter, mm
    Number
    8.0-0001
    6, 61340112.1
    6.50.537112222.5
    6.5 0.33711282.5
    6,50,25516752,7
    8,00,550100202,5
    8, 485088162.4
    9.50,55071112.4
     Example 1. Example 4.
    i
    Table 5
    Sample Concentration No. e waste - Relative to auxiliary gas, masd, amortization
    flow rate
    40000 cm3-g-1hPool- Konechna
    I- - ---- ---- - -on the End „-...- ...
    5.50 5.20
    Fused 5.50 5.20 -1.0 0.86 5.75 5.50
    6.10 6.00
    Special 6.10 6.10 -1.34 1.25 6.40 6.05
    From the rest of T. Belova Yudo va Editor I. Rybchenko Tehred A. Kravchuk Proofreader A. Obruchar
    Order 409 Circulation 407 Subscription
    VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5
    Production and Publishing Combine Patent, Uzhgorod, st. Gagarin, P1
    1544175
    Table
    12
    Ammonia concentration, May. %
    71 95
    Table4
    lo 1 cm2
    The calculated geometric volume of voids,%
    Relative effective activity
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    法律状态:
    优先权:
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