• 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:
    Selective production of dimethylamine in preference to mono- and trimethylamines by a catalytic vapor phase reaction of ammonia and methanol over a zeolite selected from mordenite, clinoptilolite and erionite, the improvement being characterized by the fact that the zeolite used has been contacted with steam at a temperature of 250 to 700 DEG C.
    公开号:SU1416054A3
    申请号:SU843751081
    申请日:1984-06-07
    公开日:1988-08-07
    发明作者:Асина Есиро；Фудзита Такеюки；Фукатсу Митио；Яги Дзунсуке
    申请人:Нитто Кагаку Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for producing dimethylamine by catalytic reaction in the gas phase of methanol and ammonia.
    The aim of the invention is to increase the selectivity of the process by using a catalyst that has been pretreated in a certain way.
    Example 1 (comparative).
    A 1 / 2V stainless steel tube, 800 mm long, is filled with X 4-alumina pellets with an alumina content of 18% and a mixture of ammonia and methanol containing 50 wt.% Ammonia, is introduced into this tube at 400 ° C under pressure. 18 kg / cm and with a flow rate (VS) of 1600 - 5800 h, as a result of which methylamine mixtures are obtained.
    The same catalyst is in contact with water vapor with a pressure of 15 kg / cm in the specified reaction tube at 400 ° C bulk flow rate for 10 hours, and nitrogen gas is passed in for 30 minutes, then the same mixture of ammonia-methanol is fed at 400 ° C. With under pressure of 18 kg / cm. and with a flow rate of 1000–4000 h, as a result of which a methylamine mixture is obtained.
    Methylamine was analyzed by gas chromatography using a column 5 filled with polystyrene balls impregnated with 3% KOH.
    B table, 1 shows the composition of the methyl amine mixture of example 1 and their indicators.
    Example 2 Crushed natural mordeite (100 g is refluxed in 2 liters of 2N solution for 20 hours. The operation is repeated three times with the solution renewed in each operation and the treated mordenite is dried at 130 ° C for 6 hours , followed by calcination at 450 ° C for 3 hours, as a result of which mordenite type H (Na 051%, K 0.1%, 10) is obtained. This mordenite is pressed into cylinders with a diameter of 3 mm, which are used as a catalyst in reaction proceeding using the same reaction tube as in the a significant example 1 and carried out with equal mass coli ammonia and methanol at 320 ° C under a pressure of 18 kg / cm and at a space velocity of 1500-6900 h. The same mordenite
    Type H is placed in a similar reaction. The tube is subjected to steam treatment at 400 ° C, a pressure of 15 kg / cm and a volumetric rate of about 1000 hours. When using this catalyst, the reaction proceeds under similar reaction conditions, resulting in methyl methane mixtures.
    Example 3 Reaction tests are carried out analogously to Example 1. With the difference that mordenite manufactured by industry (cylinders with a diameter of 2 mm) are used, and the reaction proceeds at 310 C.
    A commercial mordenite subjected to steam treatment, as described in Example 2, is used as a catalyst, and this reaction proceeds at 310 ° C,
    Used in this process, commercially produced mordenite may be synthetic,
    In tabl. 2 shows the compositions and their indicators in examples 2 and 3,
    Example 4, Crushed mordenite of natural origin. (100 g) is immersed in 500 ml of 1N hydrochloric acid and maintained at 40 ° C for 30 hours. Then, treated
    In this way, the mordenite is washed with water, dried and calcined at 450 ° C for 4 hours, as a result of which mordenite is obtained containing 0.7% Na, 1.4% K and small amounts
    other elements, such as Fe, and Ca. This mordenite is forced into cylinders 3 mm in diameter, which are used as a catalyst in the reaction between methanol and ammonia.
    at 320 ° C, a pressure of 18 kg / cm, a space velocity of 1000-4300 and N / C 1.9. The reaction tests are carried out in the same way as for the catalyst treated
    water vapor, under conditions similar to example 3.
    The results are shown in Table 3.
    EXAMPLE 5. Using erionite of natural origin as a catalyst, extruded into cylinders with a diameter of 2 mm, the reaction of methanol with ammonia was carried out at 400 ° C, a pressure of 18 kg / cm, and
    speeds of 2000-5500 h- and N / C 1.9. The reaction tests are carried out similarly to the tests for natural erionite, used with steam treatment, under the same conditions as in Example 3,
    The results are shown in Table. 3
    EXAMPLE 6: Clinoptilolite of natural origin, sifted through a 5-6 mesh sieve. (3.3-2.8 mm), held in 500 ml of 1 and hydrochloric acid at room temperature for 20 hours, washed with water, dried and calcined at 450 ° C for 4 hours. It is used as a catalyst and the reaction Methanol with ammonia is carried out in the same reaction tube as used in Example 1, at 350 ° C, at a pressure of 18 kg / cm, flow rate 1000-4300 h and N / C 1.9. The same reaction tests are carried out for the above catalyst, which is in contact with water vapor at 450 ° C under a pressure of 8 kg / cm for 10 hours.
    The results are shown in Table. 3..
    Example 7. Mordenite of natural origin, crushed to cubes of about 6 mm in size (1 kg), is placed stationary in 5 l of 1 n hydrochloric acid for 20 hours and then washed with water and dried, after which it is calcined at 450 C for 4 hours A part of the product is placed in the same reaction tube as used in Example 1, into which ammonia-methanol mixture is introduced to carry out the reaction at 320 ° C, pressure of 18 kg / cm 2, space velocity (SV) of 1000-4300 l / h and N / C 1.9,
    In addition, a part of this product is in contact with water vapor at 400–550 ° C under a pressure of 5–15 kg / cm and at a space velocity of 1000 h for 8–72 h and using the corresponding prepared catalysts, the reaction is carried out.
    The results of the reaction tests are given in Table. four.
    PRI me R 8. Mordenite of natural origin, in an amount of 100 g, ground to square particles of 6 mm in size, is boiled under a reflux condenser of 1.5 liters 0.5 n. sodium hydroxide solution for
    4 hours, thoroughly washed with water and kept in 500 ml of 1N hydrochloric acid at 40 ° C for 24 hours. Processing in this way mordenite is washed with water, dried and calcined at 450 ° C for 4 hours, as a result get a mordenite catalyst containing 0.24% Na, 3.95% K and
    small amounts of other metals such as Ca and Mg. This catalyst is placed in the same reaction tube as used in Example 1, and the reaction is carried out by passing NITH of methanol — through this tube at 320 ° C, a pressure of 18 kg / cm, a space velocity of 1000–4200 h and N / C of 1.9 ,
    The same reaction tests
    carried out for a catalyst that is in contact with water and steam, at 400 ° C, a pressure of 13 kg / cm for
    20 h.
    The results are presented in Table 5.
    Example 9: Mordenite of natural origin, (100 g), crushed to square particles about 6 mm in size, is contained in 1N.
    ammonium nitrate at 20 ° C for 16 hours, washed with water, dried and calcined at 450 ° C for 4 hours. The resulting catalyst is placed in the same TU. Reaction tube that is used
    was called in example 1, and carried out
    reaction by feeding a mixture of ammonia-methanol at 320 ° C, a pressure of 18 kg / cm and N / C 1.9. The resulting reaction products are analyzed at a volume of
    The reagent speeds are 1000–4400 hours. After the reaction, under the same conditions at 320 ° C and a space velocity of 1000, for 700 hours, the products obtained are analyzed
    at 320 C and a flow rate of 1000-300 hours, respectively. After completion of the reaction, the water vapor passes. . Dit through the catalyst bed at 400 ° C, a pressure of 15 kg / cm and a space velocity of 1000. Then a mixture of methanol-Amsh-iaK is introduced again and the analysis is carried out, respectively, of the reaction products obtained at 320 ° C, a pressure of 18 kg / cm-2 and N / C 1.9.
    The results of the reaction are given in Table 6. Example 10s The catalyst and reaction tube described in Example 7 are used for steaming.
     . 514
    and the preparation of methylamines. Steam treatment is performed in such a way that steam is captured by the device.
    The results are shown in Table. 7
    EXAMPLE 11 For steam treatment and the production of methylamine, the catalyst and apparatus used in Example 7 is used. In this example, the steam treatment is carried out in such a way that steam is maintained at a pressure of 15 kg for 40 hours. / cm and a temperature of 400 ° C, and the resulting methylamines are carried out after steam treatment, the introduction of methanol and ammonia into the apparatus, at 300–345 ° C, a pressure of 5–30 kg / cm, N / C 0.5–46.8 and volume rate of 8201800
    For comparison, they are ta46
    the same reaction, eliminating the stage of steam treatment.
     The results are presented in Table. AT.
    权利要求:
    Claims (1)
    [1]
    The invention The method of producing dimethylamine by reacting ammonia and methanol in the gas phase phase at 300-380 ° C, yielding
    lenia 5-30 atm, the ratio N / C 0.5 -1
    4.8 and a volumetric rate of 820-6360 h, in the presence of a catalyst, a zeolite selected from the group including mordet, clinoptilolite, zionite, characterized by the fact that. In order to increase the selectivity of the process, the process is carried out in the presence of a catalyst pre-treated with steam at 350-550 ° C, with a partial vapor pressure of 5-30 atm for 8-300 H.
    Table 1
    Catalyst:
    alumina
    1600 -99.3
    Reactions: 18 kg / x: m2, N / C 1.9
    2030 98.8
    3100 97.1
    Volumetric speed 1000 h
    5800 87.9
    Time 20 h
    1000
    97.9
    1330
    94.5
    200.0
    86.1
    4,000
    68.7
    24.8
    24.3
    50.9.
    23.0
    22.9
    54.1
    21.1
    19.8
    59.1
    20.7
    17.0
    62.3
    1570
    99.5
    Reaction: 320 C N / C 1.9
    2110
    99.1
    Water vapor treatments:
    3160
    97.0
    400 ° C, 15kg / / .cm2
    6470
    86.6
    1500
    98.4
    WITH,
    2110
    96.4
    3410 89.6
    table 2
    Example 4
    Catalyst; mordenite
    1070
    98.6
    Reaction: 320 ° С, 18 kg / cm2 N / C 1.9
    1430
    Steam treatment, 400 ° С, 15 kg / / cm2 2140 Volume rate 1000 h
    Time 20 h
    4280
    74.4
    Example 5
    Catalyst: erionite
    2120
    98.4
    2760
    96.2
    4240 87.0
    Volumetric speed 1000 h 5490
    Time 20 h, Example 6
    .Catalyst:
    clinoptilolite 1060
    Reaction: 350 ° C
    18 kg / cm2
    N / G 1.9 1410
     Processing in
    by steam: 450 ° С, 5 KG / CM2
    2120
    88.2
    Volumetric speed 1000 h
    4220 72.1
    Time 20 h
    (Without processing)
    400 15
    20
    400
    20
    400
    48
    400
    72
    550
    20
    T a b l and c a
    ,
    1010
    82.9
    1420
    73.4
    2060
    63.7
    Table 5
    Table 8
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    同族专利:
    公开号 | 公开日
    JPH022876B2|1990-01-19|
    JPS59227841A|1984-12-21|
    KR850000383A|1985-02-27|
    BR8402769A|1985-05-14|
    EP0130407B1|1986-08-13|
    US4582936A|1986-04-15|
    DE3460476D1|1986-09-18|
    EP0130407A1|1985-01-09|
    KR910002943B1|1991-05-11|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP58100949A|JPH022876B2|1983-06-08|1983-06-08|
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