• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    A new zeolite material designated NU-3 having a molar composition expressed by the formula: 0.5 to 1.5 R2O : Y2O3 : at least 5 XO2 : 0 to 400 H20 wherein R is a monovalent cation or 1 /n of a cation of valency n where n is a whole number of 2 or more, X is silicon and/or germanium, Y is one or more of aluminium, iron or gallium and H20 is water of hydration additional to water notionally present when R is H, and having an X-ray diffraction pattern substantially as shown in Table 1, is prepared from a reaction mixture containing XO2 (preferably silica), Y2O3 (preferably alumina) and an optionally substituted quinuclidinium ion.
    公开号:SU1398770A3
    申请号:SU813287503
    申请日:1981-05-12
    公开日:1988-05-23
    发明作者:Дэвид Шорт Глин；Винцент Виттэм Томас
    申请人:Империал Кемикал Индастриз Лимитед (Фирма)；
    IPC主号:
    专利说明:

    :about
    CD 00
    This invention relates to methods for producing a natural levinite-type zeolite used as an adsorbent and catalyst.
    The aim of the invention is to increase the catalytic activity of the zeolite during the methanol conversion process,
    Example 1. Preparation of N-methyl-quinuclidine sodium zeolite (Nu-3).
    The reaction mixture has the following molar composition; 11.5, 17 „1 Al.jOj, 60 SiO ,, 600, and 111 g of solid silica (AKZO KS - 300-7.18 Na,., 0, 695 SiO, 226) is dispersed in 311.6 g of an aqueous solution containing 22 g of sodium hydroxide and 5.6 g of sodium aluminate (1.25 Na ,, 0, AljOj. The resulting suspension is heated with stirring to 95 ° C, after which 120 g are added with stirring - Tilquinuclidinodide “The resulting gel is subjected to reaction with stirring in a stainless steel autoclave with a capacity of 1 l for three days at 180 C. The product is filtered in suspension, twice .1 L of distilled water at 60 ° C, It is dried overnight at 120 ° C. The product is I-methyl-quinuclidine-sodium Nu-3, which has data on diffraction of reagent radiation, and the following 1-molar composition: 0.3, 1.5 Q ,, 0,, 45 SiO., 15.
    P p im er 2. The product obtained in Example 1 is calcined in air (saturated with water at 25 s) for 48 hours at 450 C. The resulting sodium hydrogen Nu-3 has X-ray data of structural analysis presented in Table 3. A suspension of calcined Nu-3 is subjected to ion exchange with 5 ml of NHC1 per g of zeolite for 1 h at 25 ° C and then washed twice with 10 ml of distilled water per g of zeolite. In conclusion, the product is dried overnight at 120 ° C. and then calcined with air for three hours. Hydrogen Wu-3 has data from p-ray structural analysis, identical to sodium-hydrogen Ni-3, and has the following molar composition (not taking hydrogen into account): 0.01 NajO, AljQ ,, 46 SiOz.
    P rim e p 3. Preparation of N-methyl-quinuclidine-sodium Nu-3, having a SiOj / M Oj ratio of 98.
    ABOUT .
    d d
    0
    five
    The reaction mixture having the following molar composition: 10, 20 QI, 100 SiO, 1200, and 163 g of KS-300 silica was dispersed in 352.4 g of an aqueous solution containing 15.4 g of sodium hydroxide. and 5 g of sodium aluminate. The suspension is heated to 95 seconds with stirring, after which 123 g of N-methylquinuclidinoidide is added with stirring. The resulting gel is subjected to reaction with stirring in a stainless steel autoclave with a capacity of 1 liter for three days at 180 ° C. At the end of the procedure, the suspension is treated as in Example 1, and the product is N-methylquinuclidine-sodium Nu-3, having the following mole composition: 0.1, 2, 98 SiO, 30 H, jO.
    P p and. M e p 4. Sample H Nu-3, obtained from Example 2, is tested as a acid catalyst for the dehydration of methane catalyst in granules approximately 0.3-3.0 mm in size - activated at 450 ° C for 3 hours in a stream of nitrogen. The catalyst temperature is maintained at 450 ° C. and a sample of methanol (0.6 μl) is passed over the catalyst bed. The analysis data for hydrocarbons C, -C of the final product are as follows, vol.% (No significant amounts of aromatic compounds are obtained).
    Methane19.8
    Ethan0,6
    Ethan22,7
    Propane9.0
    Propane 38,6
    ieo-VutanO, 1
    n-butane0.4
    Butene-22,4
    izo-buten2,9
    trans-butene-2 2.7
    CIS-Butene-21,0
    Example 5. Reaction mixture
    has the following molar composition: 19.5, 29 QI, ,, 100 SiO, 1050. The reaction was carried out as in Example 1, except that samples were taken after three and five days. After three days, the product is from zeolite Nu-3, but after five days a significant redistribution of Nu-3 occurs in oi-quartz, so the final product contains about 70% 06 quartz.
    Example 6 A reaction mixture having the following molar composition: 5.85, 8.7 QI,. Al, jO, 30 SiO, 315 HjO and 131 g of silica KS-300 are dispersed in 427.6 g of an aqueous solution containing 15 g of sodium aluminate and 23.6 g of sodium hydroxide. The suspension is homogenized with stirring and 90 ° C for 15 minutes, then 146 g of N-methylquinuclidinoidide is added with stirring and stirring is continued for 15 minutes. Then the gel is transferred to a 1 liter stainless steel autoclave, equipped with a stirrer, and the reaction is carried out for five days at. The product in suspension is processed in the same way as in Example 1. The dried product is a Nu-3 zeolite and has the following molar composition: 0.96,, 2, ..., 20.8 SiOj, 6.9, X-ray data - structural analysis of this zeolite is presented in table 1.
    Example 7: A reaction mixture having the following molar composition: 12.01.0.002, 9.8, ,, 50 SiO, 530, as well as 49 g of potassium hydroxide and 27.4 g of potassium aluminate ( 1.5, 16) is dissolved in 468 g of water. Then, 160. g of Aerosil-300 silica (0.145 Na, 0, ,, 3000 SiO, 101 H.0) are dispersed in the solution. The suspension is heated with stirring for 30 minutes at 95 ° C, then 160 g of N-methylquinuclidinoidide is added to it with stirring. The reaction was carried out as in Example 1, except that the reaction time was 5 days at 180 ° C. The product is K-methylquinuclidine-potassium Nu-3, the X-ray structural analysis of which is presented in Table 2.
    Example8. 11 g of sodium hydroxide, used in. of Example 1, 41.3 g of cesium hydroxide are replaced. The reaction is carried out as in Example 1, except that the reaction time is seven days at 180 C. The product is N-methylquinuclidine-sodium-cesium Nu-3.
    Example9. 22 g of sodium hydroxide used in example i is replaced with 13.2 g of lithium hydroxide and, except for this, the reaction is carried out as in example I. After five days at 180 ° C, the product is N-methylquinuclidine-sodium Lithium Nu-3, the X-ray diffraction analysis of which is presented in Table 3.
    Example 10: Sample H-Nu-3, prepared as described in Example 2, was tested as an acid catalyst in the conversion of methanol. In a continuous flow apparatus, a layer of approximately 1 ml H of Nu-3, which is 500-700 L /, activated at 450 ° C in air for 16 hours and then I h in nitrogen at 450 ° C. The catalyst is maintained at 450 ° C, and methanol vapor consisting of 60% methanol and 40% nitrogen is passed over the catalyst. The hourly flow rate of methanol is 1.2 supply volumes / volume of catalyst per hour. Analysis of hydrocarbons C, -C is presented in table 4. Methanol conversion is more than 95%. Liquid hydrocarbons were not observed. EXAMPLE 11 Preparation of N-methyl-quinuclidine-sodium Nu-3 with a SiOj / Al ratio.
    A sample of Nu-3 is obtained in the same manner as in the example, except that the reaction is carried out for five days at 180 ° C and the product contains approximately 18% i-quartz as contamination. Hydrogen Nu-3 is obtained in the same manner as in Example 2, except that the ion exchange in the suspension is carried out at 60 ° C. Hydrogen Nu-3 contains 18 times more sodium than the catalyst of Example 2 and has the following molar composition (if hydrogen is not taken into account): 0.18 Na20, 43 SiO.
    Methanol conversion.
    Sample H-Nu-3, prepared according to this example, is used in the conversion of methanol. In a continuous-flow reactor, a layer of approximately 1 ml of H-Nu-3 with a particle size of 500-700 / c is activated at 450 ° C in air for 16 hours and then in nitrogen at 450 ° C for 1 hour. The catalyst is maintained at 450 C and 60% methanol in a flask is passed over the catalyst. The methanol feed rate is 1.1 times the feed volume / volume of the analyzer / hour. The analysis of hydrocarbons -C is presented in Table 5, and no hydrocarbons are detected.
    Methanol conversion is more than 95%.
    Example 12, A sample of N-methiquinuclidine-nitride Nu-3, prepared in Example 6, is calcined into air for 72 hours at 450 ° C. Calcined Nu-3 in the form of a slurry under (vertical exchange with 10 ml N / I HCl per g of zeolite, for 1 hour, is then washed with 50 ml of distilled water per g of zeolite, then the product is dried overnight at 120 ° C,
    Sample NH-3 is used as an acid catalyst in the conversion of methanol. In a continuous reactor, approximately i ml of a catalyst with a particle size of 500-700 r is activated at 450 ° C in air for 16 h and then 1. h in nitrogen at 450 ° C. The temperature is maintained at 450 ° C and 60% methanol in azo; They are passed over the catalyst, a method for the production of zeolite of the type of solid levinite, which includes the interaction of the components of an aqueous mixture containing sources of alkali metal oxide, aluminum oxide, silicon oxide and nitrogen-containing organic matter at elevated temperature.
    drying characterized by
    owl volume velocity is 1.2 vol-
    , „,. “Followed by filtration, washing and feed rate / catalyst volume / h. Ana-25; „„ „„ „„ „„
    LIZ of C4-C4 hydrocarbons is given in tab. B, no liquid hydrocarbons were detected. The conversion of methanol is more than 90% in the first hour and is priblichto, in order to increase the catalytic activity of the zeolite in the process of methanol conversion, the N-mixtures of Induclidine dihydrogen is used as the nitrogen-containing organic substance, and the aqueous mixture has The following 1e molar ratio of components:
    clearly 50% in the second hour.
    Example 13. 100 g of silica are stirred in 705 g of water With 20.5 g of sodium aluminate. The suspension is heated to and then 108 g of N-methylquinucl adiniodil is added with stirring in a two-liter stainless steel autoclave at 180 ° C for five days. The product is treated as in Example 1, to obtain pure zeolite, Nu-3.
    PRI me R 14. 77.25 g of pure silica is stirred in 1152 g of water with 17.6 g of sodium hydroxide and 4.62 g of sodium aluminate. The suspension is heated to 95 ° C and 92.7 g of N-methynequinuclidine iodide are added with stirring. The mixture was mixed with agitation in a two-liter stainless steel autoclave for 263 hours. The product was treated as in Example I, producing very pure Nu-3 zeolite.
    In the known method, the degree of methanol conversion does not reach 90%.
    Table 7 shows the molar ratios in the reaction mixtures according to the examples.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for producing a zeolite of the type of natural levinite, comprising the interaction of the components of an aqueous mixture containing sources of alkali metal oxide, aluminum oxide, silicon oxide and nitrogen-containing organic matter at elevated temperature.
    ,
    drying characterized in that.
    subsequent filtration, washing and; „„ „„ „„ „„
    that, in order to increase the catalytic activity of the zeolite in the process of methanol conversion, the N-trashInIlclide diide is used as the nitrogen-containing organic substance, the reaction is carried out at 95-180 ° C, and the aqueous mixture has the following 1 molar ratios of the components:
    Zyug / M Oz30-100
    , 0-G, 63
    35.1-175.4
    HjO / SiO,
    OH / SiO,
    10-30 0.2-0.4
    where M is an alkali metal ion; Q - N-methyl quinidine ion; Z is an acid radical forming a salt with quinuclidene-iodide ions; OH - total alkali.
    T ow “2
    Total olefins
    61,361,857,457,1
    Total Su + S Olefins
    63.5
    139877010
    Table 5
    58.2
    60.5
    eleven
    Editor I. Shulla
    Compiled by T. Chipikina
    Tehred A. Kravchuk Proofreader L. Pililenko
    Order 2609/58
    Circulation 446
    VNIIPI USSR State Committee
    for inventions and discoveries 113035, Moscow, Zh-35, Rau Ska nab., 4/5
    1398770
    12 Continuation of table 7
    Subscription
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB8015890|1980-05-13|
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