• 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:
    The invention relates to catalytic chemistry, in particular to a catalyst component (QD) for the conversion of methyl alcohol, and can be used to produce hydrocarbons. An increase in the selectivity of QD is achieved through the use of phosphorus-containing crystalline aluminosilicate (PCA). A PCA treated with dilute acid or ammonium chloride and calcined has the following composition, wt%: sodium oxide 0.02-0.03; alumina 0.98-1.05; phosphorus oxide O, 49-0,53 {silica 89.5-89.7; crystallization water up to 100, and a certain diffraction pattern. The methanol conversion test (and a volumetric rate of 3.1) shows an increase in the yield of hydrocarbons to 31%. 2 tab. sh (l
    公开号:SU1324680A1
    申请号:SU853868331
    申请日:1985-03-21
    公开日:1987-07-23
    发明作者:Бааке Михаэль；Кляйншмит Петер
    申请人:Дегусса Аг (Инофирма)；
    IPC主号:
    专利说明:

    eleven
    The invention relates to phosphorus-containing crystalline aluminosilicates, which can serve as components of catalysts for the conversion of methyl alcohol to hydrocarbons,
    The purpose of the invention is phosphorus-containing crystalline aluminosilicate, the use of which as a component of the catalyst makes it possible to increase the selectivity of the latter due to a certain chemical composition of the new structure of the above-mentioned aluminosilicate ..
    Example 1. 2.5 g of alumina trihydrate are dissolved in 50 ml of 6.2N. NaOH and added to a suspension of 120 g of precipitated silicic acid (89% Sic,) a solution of 25 g
    BUjP - (CHj) j - PBUgBrj in 750 ml. The mixture is stirred for 20 minutes at 50 ° C, transferred to a steel autoclave and stirred at 100 ° C for 310 hours. At the end of the crystallization, the crystals are filtered, washed with water and dried 12 h at 120 ° C. Example 2. Carried out by
    measure 1, but instead of alumina trihydrate, the same amount of sodium aluminate is used, the amount of NaOH is reduced to 3.5 g and stirred for 200 hours at 130 ° C.
    Example H. In contrast to Example 1, g of alumina trihydrate is used, 16,, 5 g of NaOH and 100 g of precipitated silicic acid and stirred for 50 hours at 160 ° C.
    Example 4. Unlike example 1, 6.5 g of alumina trihydrate, 25 g of NaOH, 310 g of precipitated silicic acid, 60 g of BujP - (CHj) - PBu.jBrj are used. Crystallization is carried out for 14 hours at 175 ° C.
    In Examples 1-4, PZ1 aluminosilicate is well crystallized, the composition of which is given in Table 1.
    The X-ray diagram of the structural analysis of the PZ1 aluminoscigate shows mainly the following ge lines.

    I / I, 100
    9.18
    7.31 5.15 4.84 4.55 4.23 3.68 3.56 3.44 3.30 3.15 2.15 1.88 1.83
    17
    13
    14 59
    30 28
    18 3 6
    where 1 / 1o
     interstate distances and their relative intensities.
    0
    Example 5. 50 g of PZ1 according to example 2 in 500 ml of 1N. HCl stirring: 2 hours at 80 ° C, filtered, washed with water until neutral and dried for 17 hours at.
    35 Example 6. 30 g of PZ1 from example 2 in 300 ml of 5N. the solution is stirred for 2 hours at 80 ° C, filtered off, washed with water until the Cl is removed, dried for 4 hours at and calcined at 550 ° C for 16 hours.
    40
    In Examples 5 and 6, PZ2, a well-crystallized aluminosilicate, whose composition is shown in Table 1, is prepared. one.
    The compositions of the initial mixtures for the synthesis of aluminosilicate, as well as the analysis of the products of examples 1-6 are presented in table. one.
    The X-ray diagram of structural analysis of aluminosilicate PZ2 mainly shows the following lines.
    d, A 13.48
    1 / 1s 100
    7.34
    24
    3.40 1.85
    It is removed by standard methods using a diffractometer with a scintillation counter for Cu – Kd radiation. . h l 10 Example 7 (application; about 50 g
    powdered aluminosilicate according to example 5 or 6 is mixed with 15 ml of 40% kieselzol and 15 ml of water to a paste, which is formed into granules. After drying (4 hours at 170 ° C) the granules are calcined at 440 ° C and then dissipated. A fraction of 0.5-1.5 mm is used to convert
    methanol.
    Molded catalyst composition,
    wt.%: crystalline aluminosilicate 89.3, silica 19.7 is first activated at 420 ° C in a stream of nitrogen. Methanol is fed to the catalyst at the reaction temperature. The following process conditions are maintained: total pressure 1.8 bar, feed CH-OH / Nj 1 mol / mol, temperature. 40b C, volumetric speed 0.4.
    Achieve complete conversion into a mixture of hydrocarbons, which has the following composition,%: C-C 50 olefins, 13 hydromatics, 37 saturated hydrocarbons.
    Comparative data on the activity and selectivity of the application of the known means and aluminosilicate PZ2. according to the invention are given in table. 2
    1324680 4
    55. high operating temperature is not practical because the catalyst
    85 is quickly deactivated. Besides,
    carrying out the process at higher temperatures is uneconomical.
    Formula
    20
    25
    thirty
    the invention
    Crystalline alromosilicate, treated with dilute acid or ammonium chloride and calcined, containing oxides of sodium, aluminum and phosphorus, silicon dioxide and water of crystallization and having the following chemical composition, wt.%:
    Sodium Oxide Alumina Oxide Phosphorus Silicon Dioxide Crystallization Water
    0.02-0.03 0.98-1.05 0.49-0.53 89.5-89.7
    Up to 100
    characterized by the following diffraction pattern
    d 1 13,48
    7.34 3.55 3.40 1.85
    I / TO 100
    24 55 85 20
    where d is the interplanar spacing
    and I / IQ relative intensity,
    as a catalyst component
    as a component of catalyzate
    MeOH conversion is carried out at 400 ° C for the conversion of methyl alcohol.
    and a volumetric rate of 3.1 hours. More
    hydrocarbons.
    the invention
    Crystalline alromosilicate, treated with dilute acid or ammonium chloride and calcined, containing oxides of sodium, aluminum and phosphorus, silicon dioxide and water of crystallization and having the following chemical composition, wt.%:
    0
    Sodium Oxide Alumina Oxide Phosphorus Silicon Dioxide Crystallization Water
    0.02-0.03 0.98-1.05 0.49-0.53 89.5-89.7
    Up to 100
    characterized by the following diffraction pattern
    d 1 13,48
    7.34 3.55 3.40 1.85
    I / TO 100
    24 55 85 20
    where d is the interplanar spacing
    and I / IQ relative intensity,
    as a catalyst component
    for the conversion of methyl alcohol
    hydrocarbons.
    Editor P.Geershi
    Compiled by V.Nohrin Tehred A. Kravchuk
    Order 2990/5
    Circulation 510 Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5
    Production and printing company, Uzhgorod, st. Project, 4
    Table 1
    table 2
    Proofreader V. But ha
    权利要求:
    Claims (1)
    [1]
    Claim
    Crystalline aluminosilicate treated with dilute acid or ammonium chloride and calcined, containing sodium, aluminum and phosphorus oxides, silicon dioxide and crystallization water and having the following chemical composition, wt.%:
    Sodium oxide 0.02-0.03 Aluminium oxide. 0.98-1.05 Phosphorus oxide 0.49-0.53 Silica 89.5-89.7 Crystallization water Up to 100 characterized by next diffraction picture d [X] 1/1 0 13.48 100 7.34 24 . 3,55 55 3.40 85 1.85 20
    where d is the interplanar spacing and 1/1 0 is the relative intensity as a catalyst component for the conversion of methyl alcohol to hydrocarbons.
    Table 1
    The initial mixture, mol Examples 2 3 4 - I 6 Na O 4,52 4.88 8.94 8.75 - ai 2 o 31 1 1 1 - SiO 2129.45 144.99 64.21 128.62 - - n about 3292 3686 1961 3949 - - Templat 3.57 4.00 2.12 3.28 -. - Composition of products % Na 2 O 2,36 2.13 3.18 2,55 0,03 0.02 SiO 288.3 89.9 89.5 88.6 89.5 89.7 Al g 0 s 1.12 1,03 2.03 1.13 0.98 1.05 0.68 0.56 0.75 0.62 0.49 0.53 Loss on ignition,% 7.54 6.38 4,54 7.10 9.00 8χ2
    table 2
    Famous means ΡΖ2 Meon,% 18.3 12 MeOMe,% 57.1 thirteen H 4 0,%  23.9 45 Hydrocarbons,% 0.7 31
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    同族专利:
    公开号 | 公开日
    DE3211433A1|1983-09-29|
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    US4481174A|1984-11-06|
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE3211433A|DE3211433C2|1982-03-27|1982-03-27|Crystalline aluminosilicate PZ 1 and process for its production|
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